&EPA
United States
Environmental Protection
Agency
Office of Research and
Development
Washington, DC 20460
EPA 600/R-93/242
October 1993
Assessment and
Remediation of
Contaminated Sediments
(ARCS) Program
Quality Assurance Program
Plan
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5 EPA/600/R-93/242
) October 1993
ASSESSMENT AND REMEDIATION OF CONTAMINATED
SEDIMENTS (ARCS) PROGRAM
QUALITY ASSURANCE PROGRAM PLAN
by
Brian A. Schumacher
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Exposure Assessment Research Division
Las Vegas, Nevada 89193
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89193-3478
U.S. EnviroUmental f rejection ARency ^ Printed on Recycled Paper
Region 5, Library (p|_-12J)
77 West Jackson Boulevard, 12th Flonr
Chicago, !L 60604-3590
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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), performed and funded the research decribed here. It has been peer reviewed
by the Agency and approved as an EPA publication. Mention of corporation names, trade names,
or commercial products does not constitute endorsement or recommendation for use.
It should be noted that the formal ARCS quality assurance program was initiated shortly after
the EPA Environmental Monitoring and Systems Laboratory in Las Vegas (EMSL-LV), Nevada, with
the assistance from Lockheed Environmental Systems & Technologies Company (LESAT) in Las
Vegas, Nevada, under Contract No. 68-CO-0049, were identified and tasked with the implementation
and daily operation of the ARCS QA program. EMSL-LV and LESAT first became involved in the
ARCS QA program in January, 1990. However, the ARCS program was initiated in fiscal year 1989
and thus, some sample collection and experimentation had occurred prior to the establishment of
a formal QA program by the Great Lakes National Program Office. Therefore, it should be noted
that the following laboratories and their respective activities were performed using whatever QA/QC
program was in place at the laboratory at the time the activity was undertaken:
1) U.S. Army Corps of Engineers - Buffalo, Chicago, and Detroit districts; sediment collection
for Engineering/Technology workgroup from the Buffalo River, Saginaw River, and Indiana
Harbor areas of concern,
2) Environmental Research Laboratory in Duluth, MN; sediment homogenization for the
Engineering/Technology workgroup's samples from the Buffalo River, Saginaw River, and
Indiana Harbor areas of concern, and Toxicity Identification Evaluation (TIE) sediment
testing,
3) Large Lakes Research Station in Grosse He, MI; sediment sample collection from the
Buffalo River, Saginaw River, and Indiana Harbor areas of concern for the
Toxicity/Chemistry workgroup,
4) Battelle-Marine Sciences Laboratory in Sequim, WA; inorganic and organic chemistry of
sediment, elutriate, and pore waters from the Buffalo River, Saginaw River, and Indiana
Harbor areas of concern,
5) Michigan State University in East Lansing, MI; bioassay testing of samples from the
Indiana Harbor area of concern,
6) National Fisheries Contaminant Research Center in Columbia, MO; bioassay testing in
samples from the Buffalo River, Saginaw River, and Indiana Harbor areas of concern, and
7) Wright State University in Dayton, OH; bioassay testing in samples from the Buffalo River,
Saginaw River, and Indiana Harbor areas of concern.
Since these activities were performed prior to the initiation of the formal ARCS QA program, the data
generated by the laboratory will only be verified using the laboratory's QA program and not the
ARCS QA program requirements. These differences will be clearly noted in the final data verification
reports that will accompany the submitted and accepted databases from these laboratories. All
sampling and laboratory efforts performed after the initiation of the formal ARCS QA program will
be reviewed and subjected to the QA program presented in this document.
The correct citation of this document is:
Schumacher, B.A. 1993. Quality Assurance Program Plan for the Assessment and Remediation
of Contaminated Sediments (ARCS) Program. EPA/600/R-xx/xxx. U.S. Environmental Protection
Agency, Las Vegas, Nevada.
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Foreword
On November 16, 1990, President George Bush signed into law the Great Lakes Critical
Programs Act of 1990 (GLCPA). The GLCPA extends the ARCS program by one year and stipulates
a number of activities to be conducted immediately. Since this QAPP was in preparation during the
passage of the act, it does not necessarily reflect all the mandated changes in the Act.
in
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Abstract
The Assessment and Remediation of Contaminated Sediments (ARCS) program is a
congressionally mandated program, by the 1987 amendments to the Clean Water Act, Section
118(c)(3), designed to address the concern over the presence of polluted bottom sediments in the
Great Lakes. ARCS is an integrated program for the development and testing of assessment and
remedial action alternatives for contaminated sediments. Five areas of concern were specified in
the Clean Water Act as requiring priority consideration in locating and conducting demonstration
projects: Saginaw Bay, Michigan; Sheboygan Harbor, Wisconsin; Grand Calumet River, Indiana;
Ashtabula River, Ohio; and Buffalo River, New York. It will be in these areas that the efforts of the
ARCS program will be concentrated. While the ARCS program is not a cleanup program and will
not solve the contaminated sediment problems at the five areas of concern, it will provide valuable
experience, methods, and guidance that could be used by other programs to actually solve the
contamination problem.
To accomplish the goals of contaminated sediment assessment and remediation, the Great
Lakes National Program Office in Chicago, Illinois, will create two committees, one non-technical
workgroup, and three technical workgroups. The two committees, namely, the Management Advisory
Committee and the Activities Integration Committee, will be formed to provide oversight for the
ARCS program and to develop the ARCS quality assurance program. The non-technical workgroup,
the Communication/Liaison workgroup, will be responsible for the dissemination of up-to-date
information regarding the ARCS program and related activities to elected officials, government
agencies, and the interested public.
The three technical workgroups, namely, the Toxicity/Chemistry, the Engineering/Technology,
and the Risk Assessment/Modeling workgroups, are responsible for the generation of data and
subsequent documents to fulfill the goals of the ARCS program. The Toxicity/Chemistry workgroup
will be responsible for developing and testing sediment assessment methods as well as producing
maps of the contaminated sediments. The primary responsibilities of the Engineering/Technology
workgroup will be to evaluate and test available removal and remedial technologies for contaminated
sediments, to select promising new technologies for further testing, to demonstrate alternatives at
priority consideration areas, and to estimate contaminant losses during remediation. The Risk
Assessment/Modeling workgroup will be responsible for the evaluation of environmental and human
health impacts resulting from contaminated sediments and the development of techniques for
assessing the environmental impacts resulting from the implementation of remedial alternatives
including the "no-action" alternative.
This document will address the design and implementation of the quality assurance program
and the validation/verification of the resultant analytical database for the entire ARCS program.
Individual sections addressing sampling strategy, field and laboratory operations, quality assurance
objectives, quality assurance implementation, assessment and reporting of data quality, development
of a quality assurance/quality control evaluation scale for historical databases, data quality
assessment and reporting, as well as the database management system have been included to
provide an overview of the ARCS quality assurance program.
This quality assurance management plan is submitted in partial fulfillment of contract number
68-CO-0049 by Lockheed Engineering and Sciences Company, Las Vegas, Nevada, to the U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Las Vegas, Nevada,
under the sponsorship of the U.S. Environmental Protection Agency, Great Lakes National Program
Office, Chicago, Illinois.
IV
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Table of Contents
Page
Notice jj
Foreword jjj
Abstract iv
List of Figures viii
List of Tables ix
Acknowledgments x
List of Acronyms xi
1. Introduction 1 of 2
1.1 Directives 1 of 2
1.2 Sources of Information 1 of 2
2. Project Description 1 of 36
2.1 Project Overview 1 of 36
2.2 Project Objectives 4 of 36
2.3 Project Organization 5 of 36
2.3.1 Management Advisory Committee 5 of 36
2.3.2 Activities Integration Committee 7 of 36
2.3.3 Toxicity/Chemistry Workgroup 10 of 36
2.3.4 Risk Assessment/Modeling Workgroup 17 of 36
2.3.5 Engineering/Technology Workgroup 27 of 36
2.3.6 Communication/Liaison Workgroup 35 of 36
3. Sampling Strategy 1 of 6
3.1 Selection of Areas of Concern 1 of 6
3.2 Toxicity/Chemistry Workgroup Sampling Strategy 1 of 6
3.2.1 Selection of Master Stations 2 of 6
3.2.2 Selection of Priority Master Stations 2 of 6
3.2.3 Selection of Extended Priority Master Stations 2 of 6
3.2.4 Selection of Reconnaissance Stations 3 of 6
3.3 Risk Assessment/Modeling Workgroup Sampling Strategy 3 of 6
3.3.1 Mini-Mass Balance/Synoptic Surveys 4 of 6
3.3.2 Sediment Transport Studies 5 of 6
3.3.3 Hydrodynamic Studies 5 of 6
3.4 Engineering/Technology Workgroup Sampling Strategy 6 of 6
4. Field and Laboratory Operations 1 of 31
4.1 Field Operations 1 of 31
4.1.1 Toxicity/Chemistry Workgroup Field Operations 1 of 31
4.1.1.1 Master Stations 2 of 31
4.1.1.2 Reconnaissance Stations 3 of 31
4.1.1.3 Sediment Mapping 5 of 31
4.1.1.4 Fish Collection for Tumor and Abnormality Studies 6 of 31
4.1.2 Risk Assessment/Modeling Workgroup Field Operations 6 of 31
4.1.2.1 Mini-Mass Balance/Synoptic Survey Sampling 6 of 31
4.1.2.2 River Characterization Studies 9 of 31
4.1.3 Engineering/Technology Workgroup Field Operations 10 of 31
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Table of Contents (cont.)
Page
4.2 Analytical Laboratory Operations 11 of 31
4.2.1 Toxicity/Chemistry Workgroup Laboratory Activities 15 of 31
4.2.1.1 Inorganic Chemistry 15 of 31
4.2.1.2 Organic Chemistry 18 of 31
4.2.1.3 Bioassay 20 of 31
4.2.1.4 Fish Bioaccumulation Assays 24 of 31
4.2.1.5 Fish Tumor and Abnormalities 24 of 31
4.2.2 Risk Assessment/Modeling Workgroup Laboratory Activities 24 of 31
4.2.3 Engineering/Technology Workgroup Laboratory Activities 28 of 31
4.3 Sample Custody 31 of 31
5. Quality Assurance Objectives 1 of 18
5.1 Overview of Quality Objectives 1 of 18
5.2 Design Characteristics 2 of 18
5.2.1 Analytical Replicate Samples 4 of 18
5.2.2 Field Duplicate Samples 4 of 18
5.2.3 Reagent Blanks 5 of 18
5.2.4 Reference Materials 10 of 18
5.2.5 Matrix Spikes and Matrix Spike Duplicates 11 of 18
5.2.6 Surrogate Spikes 12 of 18
5.2.7 Ongoing Calibration Check Samples 12 of 18
5.3 Description of Measurement Quality Objectives 13 of 18
5.3.1 Field Sampling and Mapping 14 of 18
5.3.1.1 Precision and Accuracy 14 of 18
5.3.1.2 Representativeness 15 of 18
5.3.1.3 Completeness 16 of 18
5.3.1.4 Comparability 16 of 18
5.3.2 Laboratory Analysis 16 of 18
5.3.2.1 Detectability 16 of 18
5.3.2.2 Precision and Accuracy 17 of 18
5.3.2.3 Representativeness 17 of 18
5.3.2.4 Completeness 18 of 18
5.3.2.5 Comparability 18 of 18
6. Quality Assurance Implementation 1 of 8
6.1 Control of Data Quality 1 of 8
6.1.1 Field Sampling and Characterization 1 of 8
6.1.1.1 Precision and Accuracy 1 of 8
6.1.1.2 Representativeness 1 of 8
6.1.1.3 Completeness 2 of 8
6.1.1.4 Comparability 2 of 8
6.1.2 Laboratory Analysis 2 of 8
6.1.2.1 Detectability 2 of 8
6.1.2.2 Precision and Accuracy 3 of 8
6.1.2.3 Representativeness 3 of 8
6.1.2.4 Completeness 3 of 8
6.1.2.5 Comparability 3 of 8
6.1.3 ARCS Audit Program 4 of 8
6.1.3.1 Audit Samples 4 of 8
6.1.3.2 Performance Audits 5 of 8
6.1.3.3 System Audits 5 of 8
6.1.3.3.1 Field System Audits 5 of 8
6.1.3.3.2 Laboratory System Audits 6 of 8
vi
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Table of Contents (cont.)
Page
6.2 Data Validation/Verification 6 of 8
6.2.1 Data Validation 6 of 8
6.2.1.1 Field Sampling and Characterization Data 7 of 8
6.2.1.2 Analytical Laboratory Data 7 of 8
6.2.2 Data Verification 8 of 8
7. Data Quality Assessment and Reporting 1 of 3
7.1 Statistical Design 1 of 3
7.1.1 Assessment of Detectability 1 of 3
7.1.2 Assessment of Precision 1 of 3
7.1.3 Assessment of Accuracy 2 of 3
7.1.4 Assessment of Representativeness 2 of 3
7.1.5 Assessment of Completeness 2 of 3
7.1.6 Assessment of Comparability 2 of 3
7.2 Quality Assurance Reports to Management 3 of 3
7.2.1 Status Reporting 3 of 3
7.2.2 Formal Reporting 3 of 3
8. Quality Assurance/Quality Control of Historical Databases 1 of 2
8.1 Objectives 1 of 2
8.2 Evaluation Scale 1 of 2
9. Data Management System 1 of 4
9.1 Ocean Data Evaluation System (ODES) 1 of 4
9.2 Overview of the Databases 1 of 4
9.2.1 Field Sampling Data 2 of 4
9.2.2 Analytical Laboratory Data 2 of 4
9.3 Data Base Processing. Validation, and Verification 2 of 4
References 1 of 3
Appendix
A. Analytical Laboratory Pre-Award Evaluation Scoring Sheet 1 of 7
VII
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List of Figures
Figure Section Page
1 ARCS Priority Areas of Concern 2 2 of 36
2 Areas of Concern on the Great Lakes as Identified by the IJC .... 2 3 of 36
3 ARCS Management Structure 2 6 of 36
4 T/C Workgroup Organizational Chart 2 11 of 36
5 T/C Workgroup Analytical Matrix by Sampling Station Type 2 13 of 36
6 Risk Assessment/Modeling Workgroup Organizational Chart 2 18 of 36
7 Components of Phase I and II Exposure Modeling Efforts 2 21 of 36
8 Engineering/Technology Workgroup Organizational Chart 2 28 of 36
9 ARCS Sample Identification Coding System 4 4 of 31
VIII
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List of Tables
Table Section Page
1 Treatment Technologies to be Demonstrated at the Priority Consideration
Areas 2 33 of 36
2 Preferred and Alternate Methods Accepted for Analyses in the
ARCS Program 4 12 of 31
3 Organic Compounds to be Identified and Quantified for the ARCS
Program 4 19 of 31
4 Bioassays to be Performed as a Collaborative Effort Under the
Direction of WSU 4 22 of 31
5 Measurement Quality Objectives for Inorganic and Organic Chemistry
Analyses for the ARCS Program 5 6 of 18
6 Measurement Quality Objectives for Bioassays and Fish
Bioaccumulation Studies for the ARCS Program 5 8 of 18
IX
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Ackno wledgements
External peer reviews of this document by the following individuals are gratefully
acknowledged: Dave Cowgill, Great Lakes National Program Office (Chicago, IL); Rick Fox, Great
Lakes National Program Office (Chicago, IL); Joe Hudek, USEPA Region II (Edison, NJ); Margo Hunt,
USEPA Region II (Edison, NJ); Lloyd Kahn, USEPA Region II (Edison, NJ); John Piper, Great Lakes
National Program Office (Chicago, IL); Pranas Pranckevicius, Great Lakes National Program Office
(Chicago, IL); Philippe Ross, The Citadel (Charleston, SC); Kathy Schroer, Great Lakes National
Program Office (Chicago, IL); George Schupp, USEPA Region V (Chicago, IL); Marc Tuchman, USEPA
Region V (Chicago, IL); Steve Yaksich, U.S. Army Corps of Engineer-Buffalo District (Buffalo, NY).
The following individuals are acknowledged for their technical assistance during the
development of this document: Jim Allen, U.S. Bureau of Mines (Salt Lake City, UT); Gerald Ankley,
Environmental Research Laboratory-Duluth (Duluth, MN); Danny Averett, U.S. Army Corps of
Engineers-Waterways Experiment Station (Vicksburg, MS); G. Allen Burton, Wright State University
(Dayton, OH); Eric Crecelius, Battelle-Marine Sciences Laboratory (Sequim, WA); John Filkins, Large
Lakes Research Station, Grosse He, MI; Steve Garbaciak, U.S. Army Corps of Engineers-Chicago
District (Chicago, IL); John Giesy, Michigan State University (East Lansing, MI); Chris Ingersoll,
National Fisheries Contaminant Research Center (Columbia, MO); Wilbert Lick, University of
California-Santa Barbara (Santa Barbara, CA); Simon Litten, New York State Department of
Environmental Conservation (Albany, NY); Michael Mac, National Fisheries Research Center-Great
Lakes (Ann Arbor, MI); Russell Moll, University of Michigan (Ann Arbor, MI); John Rogers,
Environmental Research Laboratory-Athens (Athens, GA); Ron Rossman, the University of Michigan
(Ann Arbor, MI); Harish Sikka, State University College of New York at Buffalo (Buffalo, NY); Frank
Snitz, U.S. Army Corps of Engineers-Detroit District (Detroit, MI); and Tom Wagner, Science
Applications International Corporation (Cincinnati, OH).
Finally, the support of my technical monitor (when I was employed at Lockheed Engineering
& Sciences Company), Wes Kinney, U.S. Environmental Protection Agency, Environmental Monitoring
Systems Laboratory (Las Vegas, NV) and my ARCS project officer, Paul Horvatin, Great Lakes
National Program Office (Chicago, IL) are gratefully acknowledged.
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List of Acronyms
AA
AET
AIC
AOC
ARCS
ASTM
AVS
BCD
B.E.S.T.
BOM
CDF
CF
CRM
CSO
CSS
CVAA
CVAF
C/L
DDT
DO
DOC
DQO
EC
ECD
EDTA
EMSL-LV
ERL-A
ERL-D
E/T
FID
FPD
FY
GC
GFAA
GLCPA
GLNPO
HPLC
ICP
IDL
IJC
INHS
LC
LESAT
LLRS
LOEL
LTS
MAC
MDL
MQO
MS
MSG
MSL
MSU
atomic absorption spectrometry
apparent effects threshold
Activities Integration Committee
area of concern
Assessment and Remediation of Contaminated Sediments
American Society for Testing and Materials in Philadelphia, Pennsylvania
acid volatile sulfides
base catalyzed destruction
basic extraction sludge technology
Bureau of Mines in Salt Lake City, Utah
confined disposal facility
critical fluids
certified reference material
combined sewer overflow
chemical solidification/stabilization
cold vapor atomic absorption
cold vapor atomic fluorescence
communication/liaison
1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane
dissolved oxygen
dissolved organic carbon
data quality objective
effective concentration
electron capture detector
ethylenediamine tetraacetate
Environmental Monitoring Systems Laboratory at Las Vegas, Nevada
Environmental Research Laboratory in Athens, Georgia
Environmental Research Laboratory in Duluth, Minnesota
engineering/technology
flame ionization detector
flame photoionization detection
fiscal year
gas chromatography
graphite furnace atomic absorption
Great Lakes Critical Program Act
Great Lakes National Program Office in Chicago, Illinois
high pressure liquid chromatography
inductively coupled plasma spectroscopy
instrument detection limit
International Joint Commission
Illinois Natural History Survey in Champaign, Illinois
lethal concentration
Lockheed Environmental Systems & Technology Company in Las Vegas, Nevada
Large Lakes Research Station in Grosse lie, Michigan
lowest observable effect level
low temperature thermal stripping
Management Advisory Committee
method detection limit
measurement quality objective
mass spectrometry
Michigan Sea Grant College Program
Marine Science Laboratory
Michigan State University in East Lansing, Michigan
XI
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List of Acronyms (cont.)
NAA
NBS
NCC
NFRC-GL
NFCRC
NIST
NOAA
NOEL
NYSDEC
ODES
O&G
PAH
PCB
PI
PID
QA
QAPP
QAPjP
QC
QE
RA/M
RAP
RPD
RREL
RSD
SAIC
SDL
SER
SLT
SOP
SOT
SRM
SUC-B
TCLP
TIC
TIE
TOC
TSS
T/C
UCSB
USAGE
USEPA
USFWS
WASP4
WES
WSU
XRF
neutron activation analysis
National Bureau of Standards
National Computer Center
National Fisheries Research Center-Great Lakes in Ann Arbor, Michigan
National Fisheries Contaminant Research Center in Columbia, Missouri
National Institute of Standards and Technology
National Oceanic and Atmospheric Administration
no observable effect level
New York State Department of Environmental Conservation in Albany, New York
Ocean Data Evaluation System
oil and grease
polynuclear aromatic hydrocarbon
polychlorinated biphenyl
principal investigator
photoionization detection
quality assurance
quality assurance program plan
quality assurance project plan
quality control
quality evaluation
risk assessment/modeling
remedial action plan
relative percent difference
Risk Reduction Engineering Laboratory in Cincinnati, Ohio
relative standard deviation
Science Applications International Corporation in Cincinnati, Ohio
system detection limit
solvent extractable residue
serial leaching test
standard operating procedure
sediment quality triad
standard reference material
State University College of New York at Buffalo in Buffalo, New York
toxicity characteristic leaching procedure
total inorganic carbon
toxicity identification evaluation
total organic carbon
total suspended solids
toxicity/chemistry
University of California at Santa Barbara in Santa Barbara, California
United States Army Corps of Engineers
United States Environmental Protection Agency
United States Fish and Wildlife Service
water quality analysis program
Waterways Experiment Station in Vicksburg, Mississippi
Wright State University in Dayton, Ohio
X-ray fluorescence
XII
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Section No.: 1
Revision: 1
Date: January 21, 1993
Page: 1 of 1
Section 1
Introduction
1.1 Directives
The quality assurance policy of the United States Environmental Protection Agency (USEPA)
requires that every monitoring and measurement project to have a written and approved quality
assurance (QA) program and project plan (Costle, 1979a and 1979b). This requirement applies to
all USEPA Regional Offices, Program Offices, USEPA Laboratories, and States and includes all
monitoring and measurement efforts mandated or supported by USEPA through regulations, grants,
contracts, or other formalized means not currently covered by regulation. The purpose of this
Quality Assurance Program Plan (QAPP) is to specify the policies, organization, objectives, and the
quality assurance and quality control (QC) activities needed to achieve the data quality requirements
of the Assessment and Remediation of Contaminated Sediments (ARCS) program. These
specifications are used to assess and control measurement errors that may enter the system at
various phases of the project, e.g., during sediment sampling, preparation, and analysis.
1.2 Sources of Information
The USEPA Quality Assurance Management Staff guidelines (Stanley and Verner, 1985) state
that the QAPP and Quality Assurance Project Plans (QAPjPs) should address in detail or by
reference, each of the following 14 items:
1) project description,
2) project organization and responsibilities,
3) quality assurance objectives for measurement data in terms of precision, accuracy,
completeness, representativeness, and comparability,
4) sampling procedures,
5) sampling custody,
6) calibration procedures and frequency,
7) analytical procedures and calibration,
8) data reduction, validation, and reporting,
9) internal quality control checks,
10) performance and system audits,
11) preventative maintenance procedures,
12) calculation of data quality indicators,
13) corrective actions, and
14) quality assurance/quality control reports to management.
Additionally, each QAPP and QAPjP must have a title page with provisions for approval signatures
and a table of contents.
Each individual laboratory generating any form of data (i.e., field sampling, field descriptions,
analytical results, sediment maps, etc.) for the ARCS program is required to prepare a QAPjP for
their individual part of the ARCS program. These individual laboratory QAPjPs will address each of
the 14 items in detail, however, a discussion of the fourteen points as they relate to the overall
ARCS program will be presented in the rest of this document. Copies of the approved QAPjPs for
the ARCS program will be maintained at the Great Lakes National Program Office (GLNPO) in
Chicago, Illinois, and by the Environmental Monitoring and Systems Laboratory in Las Vegas,
Nevada (EMSL-LV).
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Section No.: 2
Revision: 1
Date: January 21, 1993
Page: 1 of 36
Section 2
Project Description
2.1 Project Overview
The 1987 amendments to the Clean Water Act, in Section 118(c)(3), authorizes the USEPA Great
Lakes National Program Office to coordinate and conduct a 5-year study and demonstration project
relating to the control and removal of toxic pollutants in the Great Lakes, with emphasis on removal
of toxic pollutants from bottom sediments. Five areas were specified in the Clean Water Act as
requiring priority consideration in locating and conducting demonstration projects: Saginaw Bay,
Michigan; Sheboygan Harbor, Wisconsin; Grand Calumet River, Indiana; Ashtabula River, Ohio; and
Buffalo River, New York (Figure 1). In response, GLNPO has initiated the Assessment and
Remediation of Contaminated Sediments Program. ARCS is an integrated program for the
development and testing of assessment and remedial action alternatives for contaminated
sediments. Information from ARCS program activities will be used to guide the development of
Remedial Action Plans (RAPs) for the 42 Great Lakes Areas of Concern (AOCs) as identified by the
International Joint Commission (IJC), as well as Lakewide Management Plans (Figure 2). The ARCS
program is scheduled to be performed from fiscal year (FY) 1988 through 1992.
While the Clean Water Act specifies that priority consideration should be given to the
Ashtabula River, Buffalo River, Grand Calumet River, Saginaw Bay, and Sheboygan Harbor, it does
not preclude considering other areas in the Great Lakes. The ARCS program will take advantage
of ongoing sediment-related activities in these other locations where it would be beneficial. Some
of the priority considerations areas are the sites of intensive work by other programs. Both the
Ashtabula River and Sheboygan Harbor are being addressed under the USEPA Superfund Program.
Rather than duplicate efforts in these areas, the ARCS program will follow these activities to utilize
the information gained and will focus its resources only on factors that are not being addressed by
the Superfund activities.
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Section No.: 2
Revision: 1
Date: January 21. 1993
Page: 2 of 36
ARCS1 PRIORITY
AREAS OF CONCERN
GREAT LAKES AREAS OF CONCERN
1. SHEBOYGAN HARBOR
2. GRAND CALUMET/INDIANA HARBOR
3. SAGINAW RIVER/BAY
4. ASHTABULA RIVER
5. BUFFALO RIVER
1 Assessment and Remediation of Contaminated Sediments
KILOMETERS
US ENVIRONMENTAL PROTECTION AGENCY
OREATLAKEt NATIONAL PROOAAM OFFICE
Figure 1. ARCS Priority Areas of Concern.
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Section No.:
Revision:
Date:
Page:
2
1
January 21, 1993
3 of 36
GREAT LAKES
AREAS OF CONCERN
LAKE SUPERIOR
(1) Peninsula Harbor
(2) Jackfish Bay
(3) NiptgonBay
(4) Thunder Bay
(5) St Louis River
(6) Torch Lake
(7) Deer Lake-Carp Creek
-Carp River
LAKE MICHIGAN
(8) Manistique River
(9) Menominee River
(10) Fox River/Southern
Green Bay
(11) Sheboygan
(12) Milwaukee Estuary
(13) Waukegan Harbor
(14) Grand Calumet River
/Indiana Harbor Canal
(15) Kalamazoo River
(16) Muskegon River
(17) White Lake
LAKE HURON
(18) Saginaw River
/Saginaw Bay
(19) Collingwood Harbor
(20) Penetang Bay
to Sturgeon Bay
(21) Spanish River Mouth
LAKE ERIE
(22) Clinton River
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
LAK
(31)
(32)
(33)
(34)
(35)
(36)
(37)
Rouge River
Raisin River
Maumee River
Black River
Cuyahoga River
Ashtabula River
Wheatley Harbor
Buffalo River
E ONTARIO
Eighteen Mile Creek
Rochester Embayment
Oswego River
Bay of Quinte
Port Hope
Toronto Waterfront
Hamilton Harbor
CONNECTING CHANNELS
(38) St Mary's River
(39) St Clair River
(40) Detroit River
(41) Niagara River
(42) St Lawrence River
&ETOVK
US ENVIRONMENTAL PROTECTION AGENCY
GREAT LAKES NATIONAL PROGRAM OFFICE
Figure 2. Areas of Concern on the Great Lakes as Identified by the IJC.
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Section No.: 2
Revision: 1
Date: January 21, 1993
Page: 4 of 36
2.2 Project Objectives
The overall objectives of the ARCS program are to:
assess the nature and extent of bottom sediment contamination at selected Great Lakes
Areas of Concern,
evaluate and demonstrate remedial options, including removal, immobilization, and
advanced treatment technologies, as well as the "no action" alternative, and
provide guidance on the assessment of contaminated sediment problems and the selection
and implementation of necessary remedial actions in the Areas of Concern and other
locations in the Great Lakes.
The primary aim of the ARCS program is to develop guidelines that can be used at sites
throughout the Great Lakes. Site-specific factors at the five priority consideration areas will need
to be considered in conducting assessments and choosing appropriate remedial alternatives for
those locations. The varying characteristics at the five areas should provide a range of conditions
applicable to other Great Lake sites. The five sites are to be viewed as case studies of the
application of the procedures developed under the ARCS program.
Another important aim of the ARCS program is that the procedures developed and
demonstrated be scientifically sound, and technologically and economically practical. The intent is
to provide the environmental manager with methods for making cost-effective, environmentally sound
decisions. As a result, application of existing techniques will be stressed over basic research into
new technologies. Some developmental work will, however, be undertaken.
To completely assess the causes and effects of contaminated sediments and to fully evaluate
the remedial options available, a mass balance of each of the AOCs, including quantification of
contaminant loadings from point and non-point sources would be desirable. Unfortunately, such
characterizations could cost several millions of dollars for each priority area. The ARCS program
intends to use the available resources to develop a basic framework for site characterization. More
in-depth evaluation may be performed if additional funds become available.
It is important to stress at the outset that the ARCS program is not a cleanup program and
will not solve the contaminated sediment problems at the five priority consideration areas. The
ARCS program will, however, provided valuable experience, methods, and guidance that could be
used by other programs to actually solve the identified problems.
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2.3 Project Organization
To accomplish the objectives of the ARCS program, two committees, one non-technical
workgroup, and three technical workgroups will be established. The names of the individual
workgroups and their basic responsibilities are as follows:
Management Advisory Committee: To advise the GLNPO Director on their perceptions of the
overall progress of the ARCS program and to review annual work and funding plans for the
ARCS program.
Activities Integration Committee: To oversee the ARCS program, including the technical
activities of each of the workgroups, to develop and coordinate the QA/QC program, and to
coordinate the data management activities of the ARCS program.
Toxicity/Chemistry Workgroup: To assess the current nature and extent of contaminated
sediment problems by studying the chemical, physical, and biological characteristics of
contaminated sediments and their biotic communities, to demonstrate cost-effective
assessments techniques at the priority consideration areas that can be used at other Great
Lakes AOCs, and to produce three-dimensional maps showing the distribution of contaminated
sediments in the priority areas.
Risk Assessment/Modeling Workgroup: To assess the current and future hazards presented
by the contaminated sediments to all biota (aquatic, terrestrial, and human) under the "no
action" alternative and other remedial alternatives at the priority consideration areas, as well
as to develop a ranking scheme for site comparison.
Engineering/Technology Workgroup: To evaluate and test available removal and remedial
technologies for contaminated sediments, to select promising technologies for further testing,
and to perform field demonstrations on as many of the promising technologies as possible.
Communication/Liaison Workgroup: To facilitate the flow of information from the technical
workgroups and the overall ARCS program to the interested public and to provide feedback
from the public to the ARCS program on needs, expectations, and perceived problems.
An organizational flow chart of the primary management structure is provided in Figure 3.
2.3.1 Management Advisory Committee
The Management Advisory Committee (MAC) is responsible for the overall guidance of the
ARCS program. The MAC is chaired by the Director of GLNPO and composed of members from
numerous participating agencies with interests in the Great Lakes region. The participating agencies
include the U.S. Army Corp of Engineers (USAGE), the U.S. Fish and Wildlife Sen ice (USFWS), the
National Oceanic and Atmospheric Administration (NOAA), other USEPA Headquarter Offices, USEPA
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MANAGEMENT ADVISORY COMMITTEE
Chaired by GLNPO Director
ACTIVITIES INTEGRATION COMMITTEE
Chaired by GLNPO Staff Chief
TOXICITY/
CHEMISTRY
WORK GROUP
RISK ASSESSMENT/
MODELING
WORK GROUP
ENGINEERING/
TECHNOLOGY
WORK GROUP
COMMUNICATION/
LIAISON
WORK GROUP
Figure 3. ARCS Management Structure.
Regions II, III, and V, Great Lakes State Agencies, universities, and public interest groups. Input
by the MAC members may reflect both personal and professional opinions and/or the position of
member's organization with respect to technical or policy issues. The advice of this committee will
be used by the GLNPO Director to implement the recommendations of the AIC or amend them, as
necessary. The MAC is also responsible for the review of ARCS work and funding plans to ensure
the maximum utility of the products of the ARCS program.
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2.3.2 Activities Integration Committee
The Activities Integration Committee (AIC) has three primary objectives which are as follows:
1. to coordinate and provide oversight of the technical aspects of the ARCS program
including the activities of each of the workgroups,
2. to development and coordinate the QA/QC program for the ARCS program, and
3. to establish the ARCS data management program.
Coordination and oversight of the technical aspects of the ARCS program (objective 1) will be
performed through a minimum of annual AIC workgroup meetings which include the chairpersons
of each of the four workgroups listed above, the ARCS QA officer or representative, as well as,
representatives from EMSL-LV, USEPA Region II, and USEPA Region V. As the ARCS program
progresses and the decision making and data review processes become critical, more frequent
meetings of the AIC will be held and weekly conference calls will be held to discuss important
issues.
To achieve the second objective, the ARCS AIC will have overall oversight responsibility for the
ARCS QA/QC program. The USEPA Environmental Monitoring and Systems Laboratory in Las Vegas,
Nevada, with the assistance from Lockheed Engineering & Sciences Company, will be responsible
for the implementation and daily operation of the ARCS QA/QC program. EMSL-LV and LESAT first
became involved in the ARCS QA program in January, 1990. The primary tasks of EMSL-LV and
LESAT are as follows:
1) assist in the development of program and project Data Quality Objectives (DQOs),
2) review QAPjPs submitted by the principal investigators (PI),
3) develop a laboratory and field audit program,
4) development of a quality assurance/quality control evaluation scale for historical datasets,
5) prepare a final QA report and appropriate sections/chapters for the case studies and
guidance documents to be produced by the three technical workgroups, and
6) to act as an intermediate data repository for the ARCS program which includes database
conversion, manipulation, and QA/QC validation.
Each of these tasks will be discussed in more detail in the following paragraphs.
Upon initial entry into the ARCS program in January 1990, a list of pertinent questions relating
to the DQOs of the ARCS program will be developed and distributed to the ARCS management and
each of the workgroups (excluding the Communication/Liaison workgroup since no measurement
data will be generated by members of the workgroup) to satisfy task 1. The DQO questions will be
formulated to stimulate the program participants into thinking about the objectives of the overall
ARCS program and how their individual projects fit into the ARCS program. The questions will also
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make the Pis think about what type of data will be generated, its particular relevance to the ARCS
program, and how much error is allowable in their measurements (i.e., develop Measurement Quality
Objectives - MQOs) such that their data would not compromise the overall objectives of the ARCS
program.
The participating Pis are required to prepare QAPjPs for their projects to satisfy the DQOs and
have their QAPjPs reviewed and approved by the QA staff at LESAT and EMSL-LV prior to the start
of sample analyses (task 2). The signature/approval list for each QAPjP will include the PI,
laboratory's QA officer, workgroup chair, ARCS QA officer, EMSL-LV QA officer, project officer, and
ARCS program manager. The purpose of the QAPJP is to specify the policies, organization,
objectives, and the quality assurance and quality control activities needed to achieve data of a
"known and acceptable" quality for the ARCS program which meets the overall ARCS objectives.
These specifications are used to assess and control measurement errors that may enter the system
at various phases of the project, e.g., during sediment sampling, preparation, and analyses.
Adherence to an overall Quality Assurance/Quality Control program is essential for a large, multi-
participant program, such as ARCS, to ensure that the data collected by individual investigators will
be comparable and congruous.
At EMSL-LV and LESAT, the QAPJP review process will consist of the following steps:
1) initial review by three scientists with at least one specializing in the area of quality
assurance and one in the area of the principal type of analyses that are being performed
(i.e., inorganic or organic chemistry, bioassay, etc.),
2) return of review comments to the PI for QAPjP revision, if necessary,
3) additional reviews by same three scientists to ensure appropriate modifications and
clarifications have been made,
4) if acceptable, the QAPjP is then reviewed by the EMSL-LV QA officer for compliance with
USEPA policy and for completeness of the document,
5) if approved by the EMSL-LV QA officer, the document is started through the approval
signature cycle, and
6) upon receipt of the completely signed QAPjP, copies are made and distributed to the PI,
ARCS program manager, workgroup chairs, EMSL-LV, and LESAT.
The review of the QAPjP will include checking for the inclusion and discussion of the sixteen general
requirements for a QAPjP as specified by Stanley and Verner (1985). Specific checking for conformity
of the laboratory and field specified MQOs to the ARCS-defined MQOs will also be performed. The
review for the laboratory specified MQOs includes checking for acceptable instrument detection
limits (IDLs), appropriate acceptance limits and frequency of use for accuracy, precision, blank, and
spiked samples, suitable initial and ongoing calibration procedures, comparable analytical
methodologies, satisfactory sample handling and preservation techniques, and the correct sample
holding times for given sample types. Specific checking of the field activities in the ARCS program
includes checking for proper and comparable field sampling techniques, sample handling procedures,
sample preservation methods, and the appropriateness of instrumentation and QA/QC measures
to be used during field sampling.
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To ensure that the QAPjPs are being followed properly by the analytical laboratories, EMSL-LV
will develop and perform a on-site system audit program (task 3) for both field and laboratory
activities. In addition, EMSL-LV will periodically distribute pre-analysis audit samples and routine
audit samples to participating laboratories at the request of GLNPO or the workgroup chairs. Audit
samples of known toxicity or chemical concentration in an appropriate matrix (i.e., water or
sediment/soil) will be prepared by the LESAT staff and distributed to the analytical laboratory as
single-blind samples (i.e., the sample identity is known to the laboratory but the analyte
concentrations are not).
EMSL-LV and LESAT will create and distribute to members of the Risk Assessment/Modeling
workgroup and the ARCS management after their review, a quality assurance/quality control
evaluation scale for historical datasets (task 4). The evaluation scale will help establish the
confidence level the workgroup members can place in their resultant baseline hazard evaluations and
may also be used to possibly explain some of the data outliers that may result from their modeling
efforts. A point system in which the all essential QA/QC practices will be given numerical values
by parameter group, such as inorganic metals, pesticides/PCBs, PAHs, etc., will be used. The
historical data will then be rated on the sum total of various categories. Categories include
accuracy, precision, spiked samples, detection limits, blank usage, calibration procedures, sampling
technique, holding times, and other properties that might influence the integrity of the sample or the
quality of the resultant data. If deficiencies in the received data are noted, additional QA/QC data
will be requested from the analytical laboratory. If the deficiencies remain, flags will be attached
to the parameter groupings. The flags will allow the data user to assess the value of the received
data as is (actual rating) and the potential value of the data (assuming that if the flag indicates
missing information, that the analytical laboratory properly and successfully performed the missing
QA/QC measurements).
A final report for the ARCS program, the final QA report as listed for task 5, will be prepared
by the ARCS QA Officer. The final QA report will provide discussions of the project organization, QA
program (its successes and failures with possible explanations, where possible), audit program,
data verification, an overview of the database structure and tracking, assessments of the success
of the QA/QC protocols for detectability, accuracy, precision, representativeness, and comparability,
as well as include a conclusion and recommendation section which addresses how well the program
did from a QA/QC standpoint and provides guidance for future improvements on projects of a similar
nature to those involved in the ARCS program. The final QA report will be initiated upon completion
and receipt of the final database.
Appropriate sections or chapters for the case studies and guidance documents to be prepared
by the three technical workgroups will be written by EMSL-LV and LESAT (task 5). For the case
studies, the QA/QC sections to be provided by EMSL-LV and LESAT will include detailed descriptions
of the QA/QC program that was applicable to all analyses performed by all laboratories whose data
are used and presented in the particular case study. The guidance document chapter will include
an idealized QA program, for the appropriate analyses, that will allow researchers, program
planners, decision makers, etc., to be able to apply appropriate QA/QC measures during their future
testing program(s).
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EMSL-LV and LESAT will act as an intermediate data repository for the ARCS program (task
6). This responsibility will include the collection of all data from the analytical laboratories, creating
computer programs to perform QA/QC checks on the data, conversion of the data from the received
format to an Ocean Data Evaluation System (ODES) acceptable format, development of a cross-
referencing system to track hardcopy data to its corresponding computer file, and to submit the final
database on floppy disk to the ODES personnel for uploading onto the mainframe computer at the
National Computer Center (NCC) in Research Triangle Park, North Carolina. A more complete
discussion of the data management and the ODES system is provided in the section 9.0.
2.3.3 Toxicity/Chemistry Workgroup
The Toxicity/Chemistry (T/C) workgroup is responsible for developing and testing sediment
assessment methods. An organizational chart displaying the laboratory name, laboratory location,
the dominant type of analyses to be performed at the laboratory, and the principal investigator is
presented in Figure 4. This workgroup will assess the nature and extent of contaminated sediments
and their biotic communities. The workgroup will demonstrate effective assessment techniques for
aquatic life at the priority consideration areas. Finally, it will use the information obtained to
produce contamination maps of the priority areas.
To accomplish these goals, the following activities will be needed:
1) general characterization, sampling, and mapping of sediment deposits,
2) toxicity testing of sediment samples,
3) broader spectrum toxicity testing on a selected subset of sediment samples,
4) chemical analysis of sediment, sediment extracts, and fish tissue samples,
5) fish tumor and abnormality surveys,
6) fish bioaccumulation assays, and
7) mutagenicity testing of sediment extracts.
Upon completion of these tasks, the T/C workgroup will develop a guidance document that will
indicate the most accurate and cost-effective methodologies which can be used to identify
contaminated sediments under various contamination scenarios for future investigations.
In order to properly evaluate the nature and extent of sediment contamination in the AOCs,
each of the areas will be characterized for physical, chemical, and biological parameters, including
mapping the distribution of bottom sediments and sediment contaminants (goal 1). It is desirable
to have information on the physical and spatial characteristics of the sediments and some basic
indicator parameters to help select the stations that will be subjected to more intensive testing and
characterization.
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I
Battelle MSI
Sequim, WA
Chemistry
Eric Crecelius
Global Geochemistry
Canoga, CA
Michigan State University
East Lansing, Ml
Bioassays
John Giesy
USFWS NFRC - GL
Ann Arbor, Ml
Fish Tumor & Abnormality
Studies
John Cannon
Twin Cities Testing
St. Paul, MN
NOAA CLERL
Ann Arbor, Ml
P. Landrum
USEPA LLRS
Sampling, Indicator
Parameters
Michael Mullin
USFWS NFCRC
Columbia, MO
Bioassays, Mutagenicity,
Benthic Community Structure
Christopher Ingersoll
Wright State University
Dayton, OH
Bioassays
G. Allen Burton, Jr.
-f
University of Minnesota
St. Paul, MN
M. Henry
\
Memphis State University
Memphis, TN
S. Klaine
^Illinois Natural History Survey i
Champaign, IL
I L. Burnett
Figure 4. T/C Workgroup Organizational Chart.
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There will be four kinds of sampling stations to be used for the ARCS program sediment
testing:
Reconnaissance stations,
Master stations,
Priority master stations, and
Extended priority master stations.
Figure 5 shows the types of tests done at the various stations in each category. Sediment
sampling and mapping are two of the primary responsibilities of the Large Lakes Research Station
(LLRS) located in Grosse He, Michigan. A more complete description of the sampling activities of
the LLRS is provided in Section 4.1.
Sediment surveys at each area of concern will be conducted in five phases. The five phases
should be conducted in the following sequence:
1) pre-survey phase,
2) reconnaissance survey phase,
3) inter-survey phase,
4) supplemental survey phase, and
5) post-survey phase.
In the pre-survey phase, existing information on sediment contamination at each priority
consideration area should be obtained and reviewed. Based on this information and discussions
with various investigators who have worked in the area, a transect/station grid will be prepared to
guide sampling and sediment profiling throughout the AOC. An initial set of ten master station
surficial sediment samples will be collected using a Ponar grab sampler or box corer. Detailed
analyses, including testing for both inorganic and organic contaminants will be performed on these
samples. This data will then be correlated with the results of the reconnaissance stations where
only a limited number of "indicator parameters" are run (described in following text).
During the reconnaissance survey phase, acoustical soundings will be made to map the
physical distribution of sediments to aid in selecting sampling sites. Numerous sediment core
samples (100 to 200 per area) will be collected at this time to be tested for a set of indicator
parameters which can be run relatively quickly and inexpensively on a large number of samples. The
core horizons will be visually characterized and photographed during the core collection process.
The core samples obtained during the reconnaissance survey will be analyzed during the inter-
survey phase for the following indicator parameters at the LLRS laboratory:
Ammonia (in sediment elutriates),
Conductivity (in sediment pore waters)
Metals (cadmium, chromium, copper, iron, lead, nickel, and zinc),
Microtox (Photobacterium phosphoreum) bioluminescence assay (in sediment elutriates),
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TYPES OF ANALYSES
INDICATOR PARAMETERS
BENTHIC COMMUNITY
DETAILED CHEMISTRY
TIERED BIOASSYAS
o Photobacterium
o Selenastrum
o Daphnia
o Chironomus riparius
o Hyalella
o Pimephales
AMES AND MUTATOX
COMPARATIVE BIOASSAYS
o Photobacterium
o Selenatrun
o Daphnia
o Hyalella
o Ceriodaphnia
o Lemna
o Pimephales
o Hydrilla
o Diaporeia
o Hexagenia
o Panagrellus
o Bacterial enzymes
BIOACCUMULATION
TYPES OF SAMPLING STATIONS
Reconnaissance
Stations
.§/?;<
'"',-'>"" *--' '; -
Wasfer
Stations
*
:.',-
f
' ;
,
-';;
' '*'
Priority
Master
Stations
-
- -
\
t
*
-
- :^:
"
x
.. . .. '^ .
\ ./
" >
Extended
Priority
Master
Stations
-
-
'
' r '
" ' " ' "-
A^'Jt '*,\ ', .
, '
.: "K - - -:-. '
;;- ''"..':'::'
, '-.;..' .. ;
Figure 5. T/C Workgroup Analytical Matrix by Station Type.
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Organohalogens (Br, Cl, and I),
PH,
Sediment grain size fractions,
Solvent extractable residue,
Total/volatile solids, and
Total organic carbon.
In principle, the indicator parameters will correlate with other measurements of contamination and
toxicity. Therefore, use of the indicator parameters will allow the detailed analyses from the few
master stations to be extrapolated throughout the site, based on correlations between
reconnaissance and master station data. Information from these analyses and from profiling data
obtained during the reconnaissance survey will be used to prepare three-dimensional contamination
maps during the post-survey phase. Maps of bottom topography and sediment layer thickness will
also be prepared.
Based on the results of the bottom profiling and indicator parameters, an additional second
set of ten master stations per AOC will be identified for sampling during the supplemental survey
phase (resources permitting). Sediments from the second set of ten master stations will be
collected, homogenized, and shipped to the same analytical laboratories for physical, chemical, and
biological characterization as in the pre-survey phase.
Toxicity testing and a broader spectrum of toxicity testing (goals 2 and 3) will be performed
using various bioassays in a tiered approach to make efficient use of analytical resources. The
results of analyses at one tier are used to select which samples will undergo testing at the next tier.
Fewer samples are analyzed in each successive tier since the tests become increasingly more time-
consuming and costly. Tier I testing focuses on acute toxicity testing, benthic community structure
and mutagenicity testing while Tier II focuses on partial life-cycle toxicity. Tier III testing focuses
primarily on full life-cycle toxicity and bioaccumulation. The primary laboratories involved in the
bioassay and toxicity testing are Michigan State University (MSU) in East Lansing, Michigan, the
National Fisheries Contaminant Research Center (NFCRC) in Columbia, Missouri, and Wright State
University (WSU) in Dayton, Ohio. Bioaccumulation studies will be performed at MSU and the
National Fisheries Research Center-Great Lakes (NFRC-GL) in Ann Arbor, Michigan.
Tier I testing includes the use of the following methods on elutriates of the sediment samples
obtained from all the initial ten master stations:
Daphnia magna. 48-hr mortality test,
Microtox (Photobacterium phosphoreum). 15-min luminescence test, and
Selenastrum capricornutum. 24-hr carbon-14 uptake test.
Tier I testing also includes the use of chemical extracts obtained from sediment samples to assess
any mutagenic activity using the Ames Salmonella microsome test as well as the determination of
benthic community structure. In addition, selected invertebrates, fish, and amphibians may also be
tested including midge (Chironomus tentans and Chironomus riparius). amphipods (Hvalellaazteca).
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ctadocerans (Ceriodaphnia dubia). fathead minnows (Pimephales promelas). rainbow trout (Salmo
gairdneri). or bluegill sunfish (Lepomis macrochirus).
Approximately one-half of the samples undergoing Tier I testing are selected for Tier II testing
which consists of the Hvalella azteca. 7- and 14-day whole sediment growth, survival, and
reproduction tests. Approximately one-quarter of the samples undergoing Tier I testing will also go
through Tier III testing. Tier III testing consists of the following two tests:
Hvalella azteca: 28-day whole sediment growth test, and
Pimephales promelas: 10- and 28-day whole sediment bioaccumulation test.
Selection of samples for Tiers II and III are made to satisfy two conditions. Sediments with
low acute toxicity form the majority of the selections, while some with moderately acute and highly
acute toxicity are included to provide and appropriate range over which to evaluate the tiered testing
system. Other bioassays may be added as deemed necessary by the T/C workgroup.
In order to provide guidelines for future contamination surveys, it is necessary to compare the
results of the limited suite of bioassays to a larger set of bioassay methods. Therefore, a selected
number of sediment samples will undergo a broader spectrum of bioassays. The additional
bioassays, their various endpoints, and phases to be tested on the selected samples include:
Microtox (Photobacterium phosphoreum). 15-min luminescence, elutriate,
Selenastrum capricornutum: 48- and 96-hr growth, elutriate,
Daphnia magna: 96-hr mortality, elutriate,
Daphnia magna: 7-day reproduction, sediment,
Chironomus tentans: 10-day mortality, sediment,
Chironomus tentans: 10-day growth, sediment,
Chironomus riparius. 14- and 28-day mortality, sediment,
Chironomus riparius: 14-day growth, sediment,
Hyalella azteca: 7- and 14-day mortality, sediment,
Hvalella azteca: 14-, and 28-day reproduction, sediment,
Ceriodaphnia dubia: 7-day mortality, sediment and elutriate,
Ceriodaphnia dubia: 7-day reproduction, sediment and elutriate,
Lemna minor: 4-day frond growth, sediment,
Lemna minor: 4-day chlorophyll-a, sediment,
Pimephales promelas: 7-day mortality, sediment,
Pimephales promelas: 7-day growth, sediment,
Pimephales promelas: 7-day terata, sediment,
Hydrilla verticillata: 14-day root length growth, sediment,
Hydrilla verticillata: 14-day shoot length growth, sediment.
Hydrilla verticillata: 4-day chlorophyll-a, sediment,
Hvdrilla verticillata: 4- and 7-day dehydrogenase activity, sediment,
Diporeia sp.: 20-day mortality, sediment,
Diporeia sp.: 20-day avoidance, sediment,
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Diporeia sp.: 20-day uptake, sediment,
Hexagenia limbata: 10-day mortality, sediment,
Hexagenia limbata: 10- and 28-day growth (molting frequency), sediment,
Hexagenia limbata: 10-day uptake, sediment,
Panagrellus redivivus: 96-hr mortality, elutriate,
Panagrellus redivivus: 96-hr growth (development), elutriate,
Bacterial enzymes: 2-hr activity, sediment, and
Artificial substrates: 28-day community indices, sediment.
The resulting information to be obtained from this effort will be compared with tho results of the
limited suite of bioassays. Several of these bioassays also yield dose-response inforr..i,or., which
will be useful in the Risk Assessment/Modeling workgroup's assessment efforts. This broader
spectrum testing on a limited number of samples also provides a check on the effectiveness of the
tiered testing system.
Samples of sediments, sediment extracts (elutriates and pore waters), and fish tissue (from
the bioaccumulation assays) collected in the ARCS program will be subjected to numerous chemical
analyses to satisfy the fourth goal of the T/C workgroup. These analyses include a wide variety of
inorganic and organic chemicals important to understanding sediment contamination problems in
the AOCs. The bulk of the chemical analyses for the T/C workgroup will be performed by Battelle-
Marine Science Laboratory (MSL) located in Sequim, Washington. The chemical parameters include:
Total organic carbon (TOC) in the sediment,
Free and acid volatile sulfides (AVS),
Extractable metals,
Metals (silver, arsenic, cadmium, chromium, copper, iron, mercury, manganese, nickel, lead,
selenium, and zinc),
Organo-metals (methylmercury and tributyltin),
Polynuclear aromatic hydrocarbons (approximately 16 compounds),
Polychlorinated biphenyls (total and approximately 20 congeners),
Chlorinated pesticides,
Chlorinated dioxin and furan congeners, and
Semi-volatile chlorinated compounds.
A more complete list of the organic compounds to be analyzed is presented in section 4.2.
Fish tumor and abnormality identification on the brown bullhead (Ameiurus nebulosus) will also
be performed as part of the T/C workgroup testing program (goal 5). The brown bullhead has been
selected as the primary fish due to its intimate contact with the bottom sediments. The white
sucker (Catostomus commersoni) or carp (Cvprinus carpio) will serve as secondary fishes. Surveys
will be conducted in the Buffalo, Ashtabula, and Saginaw Rivers to determine the incidence of
external abnormalities and internal tumors. A goal of eighty-five individual fish will be collected and
targeted for field necropsy and histopathological examination at each area.
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At a very limited number of master stations, the extended priority stations, a 10-day fathead
minnow (Pimephales promelas) bioaccumulation assay will be conducted using bulk sediment
samples. Upon completion of the assay, chemical analyses of the fish tissue will be conducted to
determine the update of sediment contaminants into the organism. Chemical analyses will include
all the tests described for satisfying the fourth goal of the T/C workgroup.
2.3.4 Risk Assessment/Modeling Workgroup
The Risk Assessment/Modeling workgroup (RA/M) is responsible for the evaluation of
environmental and human health impacts resulting from contaminated sediments and the
development of techniques for assessing the environmental impacts resulting from the
implementation of remedial alternatives. An organizational chart displaying the laboratory name,
laboratory location, the dominant type of analyses to be performed at the laboratory, and the
principal investigator is presented in Figure 6. A mini-mass balance approach will be taken to
provide the predictive capabilities necessary to determine such impact. The assessments will serve
to identify and develop techniques and tools for performing sediment-related hazard evaluations.
Assessments will consider the difficult task of separating the effects of sediments from those of
the water column or other sources. A system for prioritizing sites with contaminated sediments will
be developed and applied to the five priority consideration areas to provide a comparative framework
for assessing multiple sites in need of remediation.
The primary objectives of the RA/M workgroup are:
1) hazard evaluation, and
2) prioritization system development.
Both of these objectives will be discussed with the tasks needed to accomplish the objectives in the
following text.
The phrase "hazard evaluation" refers to the overall evaluation of impacts to all receptors of
concern resulting from exposure to sediment contaminants and consists of several discrete
assessments (objective 1). The ultimate purpose of the hazard evaluation is to determine the
existing and future health risks and effects (e.g., carcinogenic, reproductive, or systemic effects,
community structure impacts, etc.) presented to human and environmental receptors (aquatic, avian,
mammalian) from direct or indirect contact with sediment contaminants under different remedial
options. The hazard evaluation is comprised of four assessments, namely, exposure, human health
risk, aquatic hazard, and wildlife hazard assessments. The exposure assessment is an integral part
of the human health risk assessment and the aquatic and wildlife hazard assessments, and is not
usually separated out as such. However, since the activities involved in performing the exposure
assessment are different than those involved in performing a risk or hazard assessment, the
separation has been made in this document.
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Chair Marc Tuchman
NYSDEC
Albany, NY
TSS & Limnological
Parameters
Simon Litten
University of California
Santa Barbara, CA
Sediment Resuspension &
Modeling
Wilbert Lick
SUC @ Buffalo
Buffalo, NY
Synoptic Survey - Buffalo
River
Harish Sikka
USEPA ERL Duluth
Duluth. MN
TIE
Gerald Ankley
Michigan Sea Grant
Ann Arbor, Ml
Synoptic Survey - Saginaw
River
Russell Moll
Michigan State University
East Lansing, Ml
Organic Chemistry
John Ciesy
University of Michigan
Ann Arbor, Ml
Inorganic Chemistry
Ron Rossman
Saginaw Valley Stale
College
Saginaw, Ml
Sampling
Gail Kantak
Figure 6. Risk Assessment/Modeling Workgroup Organizational Chart.
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Two levels of evaluation are proposed in this program plan, namely, baseline and
comprehensive hazard evaluations. Baseline human health hazard evaluations will be performed for
all five priority demonstration areas and will be developed from available site-specific information.
The baseline hazard evaluations will describe the hazards to receptors under present site conditions
or the "no action" alternative. This baseline assessment will examine all potential pathways by
which humans may incur risk from exposure to sediments at a given location.
Comprehensive hazard evaluations will be performed for the Buffalo River and Saginaw Bay
areas. These evaluations will describe the hazards to receptors under different remedial
alternatives. A variety of remediation scenarios will be examined as part of the comprehensive
evaluation. These will include examining selective removal or capping of "hot spots", source control,
or dredging of an entire river, among others. Additionally, the comprehensive risk assessment will
examine risk from losses of selected remedial alternatives. The following remedial alternatives may
be considered in this phase of the comprehensive evaluation:
Capping,
Immobilization/stabilization,
Extraction,
Chemical treatment,
Biological treatment, and
Confined disposal.
These remedial alternatives will be considered by the Engineering/Technology (E/T) workgroup, which
will determine the input of contaminants, after remediation, presented by each alternative. The RA/M
workgroup will use these contaminant loading estimates to estimate exposure and hazards to
receptors and compare them to the "no action" alternative.
As a component of both the human health risk assessment and the aquatic and wildlife
hazard assessments, the exposure assessment strives to describe or predict the receptor's
exposure to sediment-related contaminants. The assessment of direct or indirect exposure to
sediment contaminants by receptors of concern will vary with the type of receptor considered
(human, aquatic, avian, or mammalian), the exposure route (ingestion, inhalation, and/or dermal
uptake) and the exposure parameters (exposure magnitude, duration, and frequency).
Probable human exposure routes which may need to be addressed in this assessment include:
(1) intake of sediment contaminants through the consumption of aquatic and avian wildlife into
which sediment contaminants have bioaccumulated, (2) intake of sediment contaminants through
ingestion of sediments (particularly in children between the ages of two and eight), and (3) dermal
uptake of sediment contaminants resulting from recreational use of nearshore contaminated areas.
Other exposure routes, such as inhalation of volatile contaminants in sediments or ingestion or
inhalation of contaminants from drinking water supplies tainted by sediment contaminants may also
be important on a site-specific basis.
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Exposure assessments for aquatic biota will be evaluated in part by work being performed for
the T/C workgroup. A suite of bioassays on the toxicological effects of sediment contaminants are
planned by the T/C workgroup, including those to provide dose-response information. These data,
along with existing information, will be the basis for the aquatic biota hazard assessment.
Exposure assessments for piscivorous avian and mammalian wildlife will focus mainly on the
uptake of sediment contaminants through the consumption of biota into which sediment
contaminants have bioaccumulated. Other routes of exposure may also be of importance such as
intake of contaminated suspended particles in whole water or direct uptake of sediment
contaminants dermally. The feasibility of analyzing these routes will be considered.
The input needed to perform the exposure assessments will be provided by existing
information, information obtained from the T/C workgroup, though the RA/M workgroup's modeling
efforts, and through the performance of selected field exposure studies.
The purpose of exposure modeling is to provide a predictive tool to evaluate future exposures
(and consequently hazards) if present conditions are maintained ("no action") or if cleanup actions
are undertaken. The development and validation of models will proceed in two phases (Figure 7).
Phase I will focus on developing modeling tools using existing information.
Phase II will validate the approaches developed in Phase I by obtaining current synoptic
information about the area via five or six sampling days on a given river system. Data will be
collected on flows, contaminant loadings, and concentrations in the water column of both the
particulate and dissolved phases. This work will be conducted on the Buffalo and Saginaw Rivers.
The State University College at Buffalo (SUC-B) in Buffalo, New York will conduct the sample
collection on the Buffalo River while a team of Universities in Michigan (a consortium of the
University of Michigan in Ann Arbor, Michigan, Michigan State University located in East Lansing,
Michigan, and Saginaw Valley State University in University Center, Michigan) will conduct the
sampling program on the Saginaw River. To support the food chain model (to be discussed), fish
species will also be collected and analyzed. For the Buffalo River, the food chain model will
concentrate on carp, while for the Saginaw River, the walleye (Stizostedion vitreum) fishery and other
forage fishes will be sampled and analyzed. These data will then be used to calibrate the exposure
models. Without calibration, there would be little confidence in the exposure models results.
The contaminants to be selected for modeling purposes will be chosen based on fish
advisories, concerns cited in the respective remedial action plans, and results obtained from Toxicity
Identification Evaluation (TIE) of the sediments as part of the ARCS program. TIE involves the
manipulation of the extracted pore waters from the sediments followed by toxic it y testing. The
manipulations of the pore water are intended to change the toxicity of the sample and subsequent
toxicity tests using either Pimephales promelas or Ceriodaphnia dubia as test organisms. Based
on the manipulations, inferences can then be drawn about the physical-chemical characteristics of
the toxicants. The TIE work will be performed by the Environmental Research Laboratory in Duluth,
Minnesota (ERL-D) and WSU.
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Phase I
1) Compilation, review and analysis of all pertinent environmental
information.
2) Development of a sediment transport, deposition and resuspension
model.
3) Use of Toxidty Identification Evaluation (TIE) approach where the
cause(s) oftoxicity (e.g., the particular chemicals) have not been
identified.
4) Development of load/response relationships for the chemicals of con-
cern based on existing information about loadings to the system.
Phase II
1) Measures contaminant loadings to the system, such as:
o Upstream loadings
o Tributary loadings
o Combined sewer overflows
o Hazardous waste site discharges.
2) Sample fish.
3) Measure flow characteristics of river.
4) Measure conventional parameters.
5) Characterize sediment deposits.
6) Perform a Toxidty Identification Evaluation (TIE) on selected
Samples.
Figure 7. Components of Phase I and II Exposure Modeling Efforts.
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The parameters that will be examined in the Buffalo River priority consideration area by SUC-B
include the following contaminants:
Total polychlorinated biphenyls (PCBs),
DDT,
Dieldrin,
Chlordane,
Benzo(a)pyrene,
Benzo (a) anthracene,
Benzo(b)fluoranthene,
Benzo(k)fluoranthene,
Chrysene,
Pb, and
Cu.
The contaminants to be analyzed and modeled for the Saginaw River AOC will be:
Total PCBs,
Pb,
Cu, and
Zn.
The primary objectives of the mass balance modeling studies include the demonstrations of
available mass balance techniques and how they may be used as an aid in addressing management
questions concerning the remediation of contaminated sediments. The mass balance studies will
be designed to allow estimates of the effects of remedial alternatives, using information provided
from other ARCS programs, in order to estimate the response of the AOCs to these alternative
remedial actions in terms of toxicity and concentrations of contaminants in the water, sediment, and
biota. In the mass balance approach, the law of conservation of mass is applied in the evaluation
of the sources, transport, and fate of contaminants. The approach requires that the quantities of
contaminants entering the system, less quantities stored, transformed, or degraded in the system,
must equal the quantities leaving the system. Once a mass balance budget has been established
for each pollutant of concern, the approach can be used to provide quantitative estimates of the
effects of changes in that budget.
A mass balance model is the means by which the mass balance approach is applied to a
natural system. The application of the mass balance method involves the quantification of the
sources, transport, and fate of contaminants. The specific components of the exposure modeling
study are described below.
1) Hvdrodvnamic Model Application: The complex interaction of flows in the Great Lakes (due
to upstream inflows and changes in lake elevation) requires that a hydrodynamic model
be applied in order to estimate flows. For the systems of concern in the ARCS modeling
studies, the model will be multi-dimensional in order to provide resolution of lateral as well
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as possible vertical gradients in addition to longitudinal gradients in transport
characteristics.
2) Sediment Transport Model: A model of cohesive sediment transport will be applied in
order to predict the interactions between transport, deposition, and resuspension
processed under various meteorological and hydrological conditions. This model will
provide predictions for use in the transport of sorbed contaminants and resuspension of
toxic sediments. The model will aid in assessing the "no-action" alternative by providing
estimates of burial rates and the effects of dredging on the system by providing estimates
of sediment transport and times required to refill dredged areas. The application of a
sediment transport model is of particular importance in these studies due to the lack of
historical sediment data.
3) Contaminant Exposure Model: Time variable exposure models will be applied in order to
predict the effects of water and sediment transport, as well as the effects of sorption and
kinetic processes such as volatilization and degradation, on the concentrations of certain
critical contaminants. Modeling studies will be conducted concurrently of the riverine
portions of the systems and affected bays or lakes. The contaminant exposure model will
assess the effects of loading and various remedial alternatives on the system. The
models will be applied to estimate load/response/uncertainty relationships, which will aid
in addressing the study objectives. The models will also provide information that will be
used by the food chain model to estimate the contaminant body burdens in fish species
due to varying exposure concentrations in water and sediment.
4) Toxicitv Model: Since it may not be possible to relate exposure concentrations to toxic
effects, it will be necessary to construct a toxic unit model of the system in order to
estimate the probability of toxicity in response to various meteorological and hydrological
conditions to evaluate the impacts of proposed remedial alternatives. The toxic unit model
will utilize information from the hydrodynamic and sediment transport models as well as
data from sediment transport models to estimate the probability of toxic events.
5) Food Chain Model: A model of the food chain will be utilized to estimate the response of
varying exposure concentrations on contaminated concentrations in the biota. The model
will use data collected as part of the study in order to construct a simple food chain model
as well as evaluate certain hypothetical food chains (due to reintroduction of some
species) using information obtained from the other studies.
The study will utilize existing models and methods. The model which will be used as a
framework for the study is the Water Quality Analysis Program - WASP4 (Ambrose et al., 1988).
This model will be used to integrate predictions from other models (e.g., hydrodynamic and sediment
transport) in order to estimate contaminant concentrations in the water, sediment, and biota. The
WASP4 model provides a consistent modeling framework for eutrophication, toxics transformation
and transport, bioaccumulation, and food chain effects. It is maintained and distributed by the
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Center for Exposure Assessment Modeling in Athens, Georgia and has been widely distributed
throughout the world.
Field sampling programs will be designed to provide information required for the application
of mass balance models. Synoptic surveys are planned for six sampling days for the lower Buffalo
and Saginaw Rivers by SUC-B and MSG, respectively. Data will be collected on two low flow days,
representative of low flow steady-state conditions. Samples will also be collected during a high
flow event lasting 3 to 4 days. The sampling stations will be selected to allow estimates of
pollutant influxes to and effluxes from the AOCs. Samples will be integrated over the width of the
river system and possibly over depth. Where significant stratification is encountered, samples will
be taken at discrete depths at several locations. The data collected during the synoptic Surveys will
include flows, loading and concentration data for solids and chemicals in both water and suspended
solids. Studies of selected conventional parameters will be collected at a greater frequency in order
to aid in the calibration of the hydrodynamic and sediment transport model and in order to aid in
estimating yearly loadings. Data on sediment contamination will be collected as part of the studies
of other ARCS workgroups. The types of data to be obtained are briefly described below.
1) Hvdrodynamic Data: Data for the calibration of the hydrodynamic model will include
historical data as well as data collected as part of the field studies. Historical data are
available on flows, water surface elevations at the mouth of the Buffalo and Saginaw
Rivers, meteorological data, and concentrations of some conventional constituents such
as temperature, conductivity, etc. These data will be obtained concurrently with field
studies. In addition, water surface elevation data, velocity and discharge measurements,
and wind velocity and direction data will be obtained.
2) Sediment Transport Data: Data for the calibration of the sediment transport model will
rely on historical data, such as U.S. Army Corps of Engineers dredging records. Data on
sediment characteristics (e.g., grain size, water content, etc.) will be collected during the
sediment surveys. Further, suspended solids will be collected concurrently with the river
sampling and suspended solids data will be collected either during high flow events on the
Buffalo River or hourly during certain periods on the Saginaw River in order to support the
sediment transport model. Finally, "shaker" studies will be conducted to estimate the
resuspension characteristics of the bottom sediments in the Buffalo River by the University
of California at Santa Barbara (UCSB) located in Santa Barbara, California.
3) Contaminant Exposure Data: Historical ambient water, sediment, loading, and food chain
data will be used for the calibration of the exposure model, whenever possible. In
addition, surveys will be conducted to identify spatial variability in the system during
certain low flow periods. Further studies will be conducted to identify pollutant loadings
and ambient pollutant concentrations in water, sediments, and biota.
a. Pollutant Loadings: Pollutant loading will be estimated and/or measured from point and
non-point sources. Historical data will be assessed to estimate loadings from point
sources as well as measurements acquired concurrently with the ambient water quality
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studies. Loadings from combined sewer overflows (CSOs) will be estimated based on
a limited field sampling program (24 samples at 10 CSOs) and storm water modeling
in the Buffalo River study. CSOs were not identified as a significant pollutant loading
source in the Saginaw River and will therefore not be sampled. Loadings for
contaminants and suspended solids from upstream tributaries will be based on six daily
averaged measurements. Historical contaminant, suspended solids, and flow data, as
well as data from the suspended solid survey, will be used to extrapolate these
measurements to annual loading rates. An analysis of the uncertainty of these
estimates will also be performed.
b. Ambient Water Concentration: Ambient data for particulate and dissolved contaminants
as well as conventional parameters will be obtained over the six scheduled sampling
days.
c. Sediment Data: Data for sediment concentrations will be collected as part of separate
sampling studies planned for the RA/M workgroup.
4) Food Chain Data: Data will be collected for carp in the Buffalo River and their stomach
contents analyzed in order to establish a relationship between carp contaminant
concentrations and their benthic forage. Carp were selected for analysis for two reasons.
First, there are presently advisories in effect for consumption of carp in the Buffalo River.
Second, the available resources limit the possibility of collection data to support an
evaluation of fish species with a more complex food chain. Data will be collected for a
minimum fifteen carp (divided into three age classes) for analysis. Sampling in the
Saginaw River will concentrate on walleye and its food chain due to the importance of the
walleye fishery in the area.
The final phase of this approach will be to verify and calibrate the models in Phase I using
the site-specific data collected during Phase II.
The activities involved in the preparation of the individual risk and hazard assessments vary
depending upon the area evaluated, the receptors, and the endpoints considered. It is primarily a
paper exercise combining information on exposure to and toxicity of sediment contaminants. The
baseline assessments will use existing data while the comprehensive assessments will use the
results obtained from the exposure modeling work to predict future risk.
Cancer risks and non-cancer hazards potentially incurred resulting from direct and indirect
exposure to sediment contaminants will be considered. Risks and hazards will be calculated using
methods recommended by the USEPA risk assessment guidelines of 1986 and other generally
recognized risk assessment procedures. Uncertainties in the risk assessment will be stated, as will
the assumptions, and discussion on the overall meaning of the risk assessment will be developed.
Toxicological information required to calculate risks or hazards may not be available for all chemicals
found in the demonstration areas. Therefore, the baseline risk assessment will identify information
which is required for the evaluation but not available, and such needs will be recommended to the
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AIC for resolution. As part of the comprehensive evaluations planned for the Buffalo River and
Saginaw Bay, target sediment concentrations (i.e., chemical concentrations below that associated
with unacceptable risks and hazards) will be calculated for chemicals identified as responsible for
the majority of the risk or hazard.
One of the more potentially important impacts of some chlorinated organic compounds, such
as PCBs, are their potential adverse developmental effects upon infants and children. Recent
epidemiological evidence exists that suggests developmental effects have occurred in young children
whose mothers were heavy consumers of Great Lakes fish. Given the relationship between
sediment and fish contamination, this toxicological endpoint should be assessed in the ARCS
program. However, this endpoint is not easily assessed in a quantitative fashion using the existing
risk assessment methodology commonly employed by the USEPA. This arises from the hypothesis
that the contaminants, to which the infant or child is exposed through placenta! transfer and breast-
feeding, is the result of the mother's body burden of the chemical. This maternal body burden is
the result of her lifetime of contaminant intake, not only that occurring during pregnancy.
Assessment would require complex pharmacokinetic modeling, an approach which is not well
developed in the environmental assessment field.
Given the difficulties which exist in quantifying this hazard, it is beyond the scope of the ARCS
program to address this issue in any great depth. However, ARCS would be remiss if it did not
address the issue at all. Therefore, the RA/M workgroup will pursue the option to develop the
existing epidemiological information, discuss the relationship between sediments, fish consumption,
human body burden, and human-to-human chemical transfer, and discuss the inadequacies of
present assessment techniques to describe the problem.
A numerically-based ranking system which synthesizes assessment variables and produces
objective priorities will be designed to allow remedial priorities to be set for each of the Great Lakes
AOCs (objective 2). Development of numerically-based ranking systems will provide a method for
integrating hazard and risk assessments within and between individual AOCs. The result will be a
prioritization procedure that can be used in a comprehensive strategy for the management of
contaminated sediments by Federal, State, and Provincial governments to guide the development
of RAPs and Lakewide Management Plans.
During the ARCS program, a database for each of the five priority consideration areas will be
obtained and will contain assessment variables which range from site-specific factors (e.g.,
measurements and/or predictions of heavy metal and organic contaminants, acute and chronic
toxicity, mutagenicity, bioaccumulation potential, benthic species composition, and resuspension
potential) to broad scale factors (e.g., fish tumor incidence rates, fish and waterfowl consumption
advisories, loading to receiving waters, beach closings, drinking water hazards, human risk from fish
consumption, and socioeconomic considerations). These factors will be integrated for use in a
decision-making framework to determine which site(s) should be targeted for remedial action. As
much as possible, this assessment will be based on a minimum data set common to all five priority
consideration areas obtained by the three technical workgroups.
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For the decision-making process, assessment factors will be synthesized to evaluate the sites
with regard to remediation. For remedial evaluation, a ranking system will be used which (1) is
numerically-based, (2) accommodates a multi-disciplinary database (chemical concentrations,
ecotoxicity, model predictions, human risk, cost, etc.), (3) synthesizes and reduces the database to
an understandable context, (4) produces objective output, (5) illustrate quantifiable differences
between sites, and (6) established remedial priorities. The priorities established by the ranking
system will then be viewed in terms of remedial goals, the likelihood of successful remediation, cost-
benefit, and the technologies available to achieve these goals.
The following tasks anticipated for this activity provide site ranking and integration of
information about individual sites or AOCs:
1) investigate methods of ranking and decision support analysis to determine what other
approaches should be incorporated for the ARCS program,
2) develop a ranking method to integrate measures of hazard, risk, and cost,
3) develop a method of ranking sites which can be applied to the Great Lakes region, by
State and Provincial jurisdictions, or smaller sub-regions (i.e., individual lake watersheds),
and
4) calibrate and test the ranking procedure and integration procedure on the five priority
consideration areas being investigated during the ARCS program.
This work will be closely coordinated with the data collection and assessment activities of the
T/C workgroup. Data collection and toxicology studies will be specifically designed to provide
information for the integration and ranking system selected.
2.3.5 Engineering/Technology Workgroup
The primary responsibilities of the Engineering/Technology workgroup will be to evaluate and
test available removal and remedial technologies for contaminated sediments, to select promising
new technologies for further testing, to demonstrate alternatives at priority consideration areas, and
to estimate contaminant losses during remediation. An organizational chart displaying the
laboratory name, laboratory location, the dominant type of analyses to be performed at the
laboratory, and the principal investigator is presented in Figure 8. The E/T workgroup will seek
technologies that are available, implementable, and economically feasible. Both removal and in situ
alternatives will be considered.
To fulfill these responsibilities, the following tasks will be required:
1) review of technical literature,
2) evaluation of applicability of technologies for bench-scale studies,
3) develop recommendations for pilot-scale demonstration,
4) estimate contaminant losses during remediation,
5) collect sediments for bench-scale testing,
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Engineer!
vfKf ,MU,«fes.j,<>*,*>Mj!:ias
USAGE - Buffalo District
Buffalo, NY
Sediment Sampling
Stephen Yaksich
Chair Stephen Yaksich f
USAGE - Detroit District
Detroit, Ml
Sediment Sampling
Frank Snitz
US Bureau Of Mines
Salt Lake City, UT
Inorganic Treatment /
Recovery
James Allen
USEPA ERL - Duluth
Duluth, MN
Sediment Homogenization
Phil Cook
USEPA ERL - Athens
Athens, GA
Bioremediation
John Rogers
USAGE - WES
Vicksburg, MS
Solidification / Stabilization
Danny Averett
SAIC
Cincinnati, OH
Bench & Pilot Scale
Treatment Technologies
Thomas Wagner
Figure 8. Engineering/Technology Workgroup Organizational Chart.
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6) store and analyze sediments,
7) bench-scale testing of selected treatment technologies,
8) treatment technologies for inorganic contaminants,
9) workshop on bioremediation technologies,
10) evaluation of solidification/stabilization technologies,
11) conduct pilot-scale demonstrations, and
12) development of options for priority consideration areas.
Each of these tasks will be discussed individually in the following text.Existing literature on
contaminated sediment treatment technologies will be reviewed for the ARCS program focusing on
the updating of present knowledge on the selection and use of technologies for removal and
transport of contaminated sediments, placement/disposal of material at disposal sites, treatment
technologies, as well as in situ techniques (task 1). Previous technology assessments and field
demonstration studies conducted by the USEPA, USAGE, and other laboratories will be reviewed for
applicability.
The applicability of treatment technologies to priority consideration areas will be evaluated
based upon the nature and degree of contamination at the site (task 2). Treatment technologies
identified in Task 1 will be matched with the contaminants present at a given site, the level of
contamination, and volume of sediments to which technology can be applied to remediate the
sediments. Each technology will be evaluated based on cost, effectiveness, volume of material to
be handled, level of existing contamination and levels of cleanup required.
The E/T workgroup will develop recommendations for the selection of sites and technologies
for pilot-scale demonstrations (task 3). The selection of technologies which are available for pilot-
scale demonstration may be limiting since there will probably not be enough time to scale-up
developmental techniques which require elaborate physical or mechanical plants. All proprietary
vendors that already have portable pilot-scale plants available for demonstration will be considered.
A few technologies can be demonstrated using commercially available equipment.
Another limiting factor that must be considered during the recommendation development
process is the availability of sites for the demonstrations. Site availability may be the major
determinant as to which technologies can be demonstrated during the ARCS program. Most pilot-
scale demonstration are performed at the site of contamination. The site of a demonstration must
be secure so that accidents, spills, or emissions can be controlled. The use of existing, operational
confined disposal facilities (CDFs) will be selected as the most viable sites for demonstrations since
the land acquisition and site preparation processes for demonstrations is a very time-consuming
process and requires resources beyond the scope of the ARCS program. Other options, such as
close collaboration with Superfund projects and/or the Superfund SITE program, will be explored.
Contaminant inputs that may occur to the environment during and after implementation of the
remedial alternative will be assessed (task 4). Models available to calculate losses during dredging,
volatilization losses, leaching losses, runoff and effluent concentrations will be reviewed. Models
will be selected to calculate the annual losses to the environment resulting from each treatment
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technology evaluated. These contaminant loads to the environment will be supplied to the RA/M
workgroup who will assess the human and environmental health impacts associated with each of
the remedial alternatives. These tasks will be accomplished the USAGE Waterways Experiment
Station (WES) located in Vicksburg, Mississippi and the USEPA Environmental Research Laboratory
in Athens, Georgia (ERL-A).
The bench-scale tests (to be discussed) require sediments for testing from the five priority
consideration areas (task 5). The "same" sediment samples will be used to evaluate and compare
similar demonstration projects. Therefore, it is necessary to collect, characterize, and preserve large-
volume sediment samples from each of the areas. Sediment samples will consist of homogenized,
moist composites of samples from a contaminated region within the priority consideration area.
Sediments will be collected for all five areas for bench-scale studies. Additional samples will be
collected for the pilot demonstration projects.
The sediment samples will be homogenized and split into representative subsamples in a wet
condition during the operations of task 6. The wet subsamples will be provided in a variety of
convenient sizes for use by the various investigators. The procedure to accomplish this task will
be the same that has been previously applied to sediments from Lake Ontario and the Fox
River/Green Bay (Great Lakes National Program Office, 1989), and has been validated for organic
carbon and organochlorine contaminant homogeneity. Wet samples will be stored in a cold room
at 4° C.
The basic characterization of the sediment will be performed by ERL-D and will include the
following parameters:
Total organic carbon,
Total inorganic carbon,
Particle-size distribution,
Density of the dry material,
Total sulfur content,
Acid volatile sulfides,
Oil and grease,
Total PCBs,
Polynuclear aromatic hydrocarbons (PAHs),
Metals, and
Hg.
Particularly promising technologies identified in Task 3 will be evaluated in bench-scale tests
using sediment from the priority consideration areas (task 7). As used here, bench-scale tests are
defined as tests that are done on a few grams to kilograms of sediment. The selection of which
technology to use on which priority consideration area will depend upon matching the characteristics
of each technology to the contamination present at the given area. A brief description of the
technologies available for remediation of contaminated sediments will be provided in later text in this
section.
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Bench-scale testing will provide preliminary feasibility data and design data for pilot-scale
demonstrations of selected technologies. As used here, pilot-scale tests are those that involve up
to several cubic meters of sediments. Several laboratories/companies have been identified to
perform various portions of the bench-scale testing program and will thus receive contaminated
sediment samples for the priority consideration areas dependant upon the expected results of their
remedial process.
Science Applications International Corporation (SAIC) of Cincinnati, Ohio, under the direction
of the Risk Reduction Engineering Laboratory (RREL) in Cincinnati, Ohio, will be contracted to test
the B.E.S.T extraction process, two different varieties of low temperature thermal stripping (LTS),
wet air oxidation, and incineration remedial processes. Sediments from the Sheboygan River,
Ashtabula River, and Grand Calumet Harbor will be tested by the USEPA's RREL-Cincinnati
laboratory using the Base Catalyzed Destruction (BCD) process for removal of PCBs. Sheboygan
River sediments will also be sent to ECO-Logic in Ann Arbor, Michigan, for testing with their
hazardous waste destructor. Sediments from the Buffalo, Saginaw, Grand Calumet, and Ashtabula
priority consideration areas will be sent to Chemical Waste Management, Inc. located in Riverdale,
Illinois, for their solvent extraction procedure.
The treatment technologies for the remediation of inorganic contaminants (task 8) will be the
primary responsibility of the Bureau of Mines (BOM) - Salt Lake City research facility in Salt Lake
City, Utah. The BOM will examine the treatment options that include the extraction and recovery of
metals from the contaminated sediments. These techniques include physical separation processes
using gravity, magnetic properties, and flotation processes. Treatment options will be evaluated
using sediment samples from three of the priority consideration areas with metal contamination
problems, namely, Buffalo River, Grand Calumet River, and Saginaw Bay.
A workshop on bioremediation processes (task 9) will be conducted by ERL-A in which
presentations will be made describing site characterizations of the five ARCS priority AOCs located
in the United States and for Hamilton Harbor, Ontario. Once the overviews of these areas have been
presented, the remainder of the workshop will be devoted to discussing related laboratory and field
studies and the applicability of biological remediation processes of sediment-based contaminants,
in particular, for the degradation of organic compounds. The workshop will be conducted to arrive
at a consensus on the direction bioremediation testing should take for the ARCS program, due to
the relative diversity of approaches being attempted in this field, and the high potential of this form
of remedial action.
Besides removal and disposal, chemical solidification/stabilization (CSS) techniques are
probably the most proven techniques for remediation of contaminated sediments. CSS techniques
will be investigated for the Buffalo River sediments to accomplish task 10. The scope of the study
will involve laboratory preparation of CSS samples using Buffalo River sediment and one of the
following binders/additives: portiand cement, lime/fly ash, kiln dust, and portland cement with
powdered activated carbon. A range of binder-to-sediment ratios will be screened and an optimal
ratio will be selected for detailed evaluation. Effectiveness will be measured by comparing leaching
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results, unconfined compressive strength, and durability under wet/dry and freeze/thaw cycles at
WES.
Pilot-scale demonstrations will be scheduled to start in FY1991 and continue through FY1992
(task 11). The scale of the pilot demonstrations will be several hundred cubic yards of sediment.
Full-scale demonstrations would address in the range of 5000 to 10000 cubic yards of sediment.
Pilot-scale demonstrations will only show the unit process (e.g., extraction). They will not include
the full treatment train (e.g., dredging, storage, sorting, dewatering, extraction, destruction of extract,
solidification, and final disposal) that a full-scale demonstration would. Pilot-scale demonstrations
could be performed either on-site or at an off-site location.
Based upon the information gained in the earlier tasks, concept plans for sediment remedial
options (task 12) will be developed for each priority consideration area. The costs of applying the
selected options will be calculated. In addition, estimates will be made on the losses of
contaminant that might result from applying the remedial actions. The RA/M workgroup will use this
and other information to evaluate the hazards associated with each remedial option. These plans
will also serve to identify data gaps that need to be filled in order to complete the process of
selecting the best remedial options for each priority consideration area. The concept plans to be
developed will present three different remediation scenarios for each priority consideration areas.
These plans will provide useful information to the State and local groups responsible for the
development of sediment RAPs.
A brief description of each of the remedial technologies that are under consideration or are
part of the ARCS program and presented in Table 1 follows:
Solidification/stabilization: The addition of binding materials to produce a more stable
solid material that is more resistant to the leaching of contaminants. Typical binding
materials used include portland cement, fly ash, kiln dust, blast furnace slag, and
proprietary additives.
Inorganic treatment/recovery: The physical or chemical separation of sediments into
different fractions that may be more or less contaminated. Since sediment contaminants
usually associate themselves with fine-grained particles like silts and clays, their
separation from the bulk sediment could significantly reduce the volume of material
requiring advanced treatment.
Bioremediation: The use of microorganisms such as bacteria to reduce the toxicity of
sediment contaminants by degrading them through biological action. Bioremediation has
been used in the treatment of waste waters and contaminated soils.
Base catalyzed destruction (BCD) process: This chemical process, formerly call KPEG
nucleophilic substitution, reduces the toxicity of chlorinated hydrocarbons (such as PCBs)
by removing chlorine atoms and replacing them with alkali metals such as potassium.
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Table 1. Treatment Technologies to be Demonstrated at the Priority Consideration Areas.
TECHNOLOGIES
Solidification/
Stabilization
Inorganic Treatment/
Recovery
Bioremediation
KPEG Nucleophilic
Substitution
B.E.S.T. Extraction
Process
CF Systems
Solvent Extraction
Incineration
Low Temperature
Thermal Stripping
Wet Air Oxidation
Eco-Logic
Destruction Process
In-Situ Stabilization
Acetone Extraction
(Rem-Tech)
Aqueous Surfactant
Extraction
Taciuk Thermal
Extraction
Sediment Dewatering
Methods
PRIORITY CONSIDERATION AREAS
and Scale of Demonstration
ASHTABULA
RIVER
Bench3
BUFFALO
RIVER
Bench0
Bench
Bench*
Bench
Bencha
GRAND
CALUMET
RIVER
Bench*
Bench13
Bench
Bencha-e
Bench3
Bench3
Bench*
SAGINAW
BAY
Benchb
Bench3
Bench3
SHEBOYGAN
HARBOR
Benchd
Pilotd
Bench3
Bench'
Benchd
Pilotd
Benchd
Benchd
Benchd
Benchd
Legend: a = performed for ARCS Program by contractor
b = performed for ARCS Program by Bureau of Mines
c = performed for ARCS Program by Army Corps of Engineers/Waterways Experiment Station (WES)
d = performed by Superfund Potentially Responsible Parties
e = performed for U.S. Army Corps of Engineers by Indiana University - N.W. or Corps' WES
f = performed for Canada
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Basic extraction sludge technology (B.E.S.T.) extraction process: This extraction separates
contaminated sediments into three fractions: a solid fraction that contains the inorganic
contaminants (such as heavy metals); and oil fraction that contains the organic
contaminants (such as PCBs); and a water fraction that may contain residual amounts of
the original sediment contaminants. Alone, B.E.S.T. does not destroy any contaminants
but may significantly reduce the volume of material requiring advanced treatment.
Critical fluids (CR systems solvent extraction: This extraction performs the same
functions as the B.E.S.T. process, but instead of the solvent used by B.E.S.T., the CF
System's process utilizes gases at critical temperature and pressures (propane and carbon
dioxide), which reduces the cross-contamination of the end products with the solvent. The
propane is simply exposed to normal pressure and temperature where it returns to its
gaseous state.
Incineration: Incineration involves the high temperature destruction of organic
contaminants in a furnace. It has been used for the disposal of municipal and hazardous
wastes.
Low temperature thermal stripping: ITS removes volatile organic contaminants by heating
the sediments to temperatures lower than those used in the destructive incineration
process. This process is not intended to permanently destroy contaminants but may result
in a sediment that is more easily disposable.
Wet air oxidation: Organic contaminants are destroyed by exposing them to elevated
temperature and pressures. This process was developed over 30 years ago and has been
successfully used to treat municipal sewage sludge.
Low energy extraction: This extraction separates contaminated sediments into the same
fractions as described for the B.E.S.T. process. It uses a combination of solvents to
remove PCBs and other organic contaminants from the sediment.
ECO-Logic destruction process: A thermochemical process that uses high temperature
and hydrogen gas to destroy organic contaminants.
in Situ stabilization: This process involves the covering or armoring of sediment deposits
with geotextiles, plastic liners, or graded stone. It thus prevents the disturbance and
resuspension of contaminated sediments which could lead to a release of sediment
contaminants back into the water column.
Acetone extraction (Rem-Tech): Acetone is used as a solvent to extract PCBs from
contaminated sediments.
Aqueous surfactant extraction: This process is similar to the low energy extraction
process previously described. Instead of applying acetone, however, this process uses
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aqueous surfactant to remove PCBs. Ultrasonics may be employed to improve extraction
efficiencies.
Taciuk thermal extraction: A thermal separation process similar to low temperature
thermal stripping. The sediments are heated in a oxygen-free atmosphere which aids in
the removal of organic contaminants.
Sediments dewaterinq methods: These techniques to remove water from contaminated
sediments include air drying, consolidation, and filter processes. They may be necessary
prior to the application of a treatment technology that works inefficiently in the presence
of water.
2.3.6 Communication/Liaison Workgroup
The role of the quality assurance program in the Communication/Liaison (C/L) workgroup is
nonexistent since this workgroup generates no measurement data. However, since the C/L
workgroup is an integral part of the ARCS program, a brief overview of their activities is presented
here.
The Communication/Liaison Workgroup is responsible for the dissemination of up-to-date
information regarding the ARCS program and related activities to elected officials, government
agencies, and the interested public. This workgroup will also provide feedback from those interested
parties to the technical workgroups and other ARCS committees.
These responsibilities will be accomplished by the completion of the following tasks:
1) continual workgroup interaction,
2) preparation and dissemination of general and site-specific information materials on the
ARCS program and on contaminated sediments in general,
3) mailing list compilation and maintenance,
4) solicitation of public input through news updates, press releases, questionnaires, public
meetings, and informal dialogue,
5) development and maintenance of library repositories for contaminated sediment and ARCS
program materials in the five priority areas,
6) on-site coordination of public meetings and press briefings,
7) slide show preparation and dissemination,
8) video preparation and dissemination, and
9) guidelines for public participation and community outreach plans, when appropriate.
The C/L workgroup will prepare press releases, fact sheets, and other such materials for
dissemination to interested Federal and State agencies, elected officials, and the public at regular
intervals. Quarterly ARCS updates will be produced and published. They will provide information
not only on the ARCS program activities, but also on cooperative efforts and information sharing
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with other projects (such as USEPA's Superfund program, Environment Canada's contaminated
sediment research, etc.) and on more general topics, such as current scientific research that relates
contaminated sediments to ecological impacts on the Great Lakes. Updates on activities specific
to the priority consideration areas will be included in the fact sheets or produced and disseminated
separately, as needed. Press releases will be coordinated and issued by the C/L workgroup member
representing USEPA's Office of Public Affairs.
Representatives from the C/L workgroup will travel to the priority consideration sites to inform
the public and media about the ARCS program, ongoing field work, research activities and results.
Public meetings will be held at all five of the ARCS program site locations. Based on the experience
gained in dealings at the five priority consideration areas, the C/L workgroup will produce guidelines
for public involvement for future contaminated sediment demonstration projects.
A slide show will be developed to aid in the discussion of contaminated sediments. The
narrative developed in conjunction with the slide show will discuss current contaminated sediment
problems, pollutants, ARCS objectives, and remedial options.
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Section 3
Sampling Strategy
3.1 Selection of Areas of Concern
Forty-two areas of concern have been identified by the International Joint Commission (a
binational organization composed of commissioners from Canada and the United States) in the
Great Lakes Basin Ecosystem (Figure 2). These AOCs are sites where general or specific objectives
of the Great Lakes Water Quality Agreement are not met and such failure has caused or is likely
to cause impairment of beneficial use or of the area's ability to support aquatic life. Impairment
of beneficial use means a change in the chemical, physical, or biological integrity of the Great Lakes
ecosystem sufficient enough to cause any of the following: restrictions on fish and wildlife
consumption; tainting of fish and wildlife flavor; degradation of fish and wildlife populations; fish
tumors or other deformities; bird or animal deformities or reproductive problems; degradation of
benthos; restriction on dredging activities; eutrophication or undesirable algae; restrictions on
drinking water consumption, or taste and odor problems; beach closings; degradation of aesthetics;
added costs to agriculture or industry; degradation of phytoplankton or zooplankton populations;
or loss of fish and wildlife habitat.
From the original list of forty-two AOCs selected by the IJC, five AOCs were named in the
authorizing legislation for testing in the ARCS program The five selected ARCS AOCs (Figure 1) are:
Sheboygan Harbor,
Grand Calumet River/Indiana Harbor,
Saginaw River/Bay,
Ashtabula River, and
Buffalo River.
Of the five selected AOCs, two are currently undergoing testing/remediation through the Superfund
program, namely, Sheboygan Harbor and Ashtabula River. Since there is a considerable amount of
Superfund work in ongoing and due to limitations of funding, these two sites will undergo minimal
testing in the ARCS program. Therefore, the ARCS program will concentrate its resources and
efforts on the remaining three AOCs.
3.2 Toxicity/Chemistry Workgroup Sampling Strategy
The T/C workgroup will analyze four different levels/types of samples in order to satisfy the
original goals of its part of the ARCS program. These levels are the master station, priority master
station, extended priority master station, and reconnaissance station. Some of the different sample
types require unique samples to be obtained while other samples are differentiated by the amount
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of testing that will be performed on the sediment. A more detailed description of the different
sample types and their site selection is provided in the following text.
3.2.1 Selection of Master Stations
In general, the selection of master station locations will be determined by the members of the
T/C workgroup. Three primary considerations that will be used during the selection process will be:
1) the availability of historical sediment contaminant concentration data and contaminant
maps from each AOC,
2) input from local authorities, including discussions of present and future public uses as well
as present and historic contaminant discharges or sources, and
3) a desire to provide some degree of complete geographic coverage of the entire AOC.
Stations will usually be positioned along the sides of the dredged shipping channel since these
shallow areas are usually the location of sediment deposition zones. Areas of soft sediment will
preferably be selected due to sampling considerations. When possible, samples will be collected
in each AOC that represent a gradient of contaminant concentrations ranging from stations
considered to be relatively uncontaminated to known "hot spots" of high pollutant content as
identified from work performed for the first two considerations.
3.2.2 Selection of Priority Master Stations
Approximately one-half of the master stations will be selected to be designated as priority
master stations. These stations will be selected to represent sediments with a wide range in the
degree of contamination present in each AOC. The priority master station sediments would thus
include samples with little to no appreciable quantities of contaminants as well as from "hot spot"
where notably high contaminant concentration levels have been identified. These sediments will
undergo the same testing that is performed for the master stations with an additional suite of
comparative bioassays (Figure 5). The additional suite of bioassays will be used to assist in the
selection of optimal sediment toxicity test assays (i.e., which organisms are most sensitive to the
presence of given contaminants or suites of contaminants), to provide comparisons with the IJC
recommended test battery, and to aid determinations of biologically significant contaminant levels
in "grey" areas where contaminant levels are likely to produce some acute and chronic toxicity
effects.
3.2.3 Selection of Extended Priority Master Stations
Most, if not all, of the sediments selected as priority master stations will undergo a
bioaccumulation assay using Pimephales promelas. Upon completion of the assay, the actual
sediment used in the bioaccumulation assay will undergo chemical analysis. If the potential exists
for the bioaccumulation of a contaminant or suite of contaminants identified in the sediment, the
priority master station will be designated as an extended priority master station and the fish tissue
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will then undergo analysis for the suspected bioaccumulated contaminants. The extended priority
master station sediments will most likely be an area of high contaminant levels (i.e., the "hot spot")
in each AOC.
3.2.4 Selection of Reconnaissance Stations
In general, the locations of the indicator stations will be chosen to give a more complete
coverage of the AOC than could be provided by the sampling of the master stations. Selection of
the reconnaissance stations will be based on historical data plus the interpretation of the results
from sub-bottom profiling (a more detailed description of the sub-bottom profiling may be found in
section 4.1.1.3). The profiling tracings will be examined for indications of soft sediment, sediment
layering, physical discontinuities, and other features of interest which can be used to separate
distinct depositional episodes and, thus, possibly different contamination levels.
The profiling and coring scheme for the AOCs will be designed to accomplish two goals,
namely, (1) to conduct a "zone reconnaissance" of sediment quality throughout the whole study area
and (2) to perform a more detailed "site mapping" of a known "hot spot" depositional area.
Chronologically, the sub-bottom profiling of the area will be conducted first, accompanied by the
more or less simultaneous interpretation of the profiling tracings. After review of the tracings,
sediment cores will be collected using a Vibra-corer system (to be discussed in more detail in
section 4.1.1.2). Approximately 60 cores will be collected from each AOC.
For the "zone reconnaissance" sampling, samples will be collected throughout the AOC from
positions generally across the river channel from each other with an occasional core being collected
from the center of the navigation channel. The zone reconnaissance will also involve collecting cores
at the initial master stations so that correlations can be made between the detailed analyses
performed on the master stations and the indicator parameter analyses that will be performed on
the reconnaissance stations. The correlated data will then be used to produce three-dimensional
mapping of contamination and toxicity from each AOC.
The site mapping will involve the intensive collection of cores throughout the area of the "hot
spot". Approximately 30 cores (one-half of the cores to be collected per AOC) will collected on a
grid system that covers the entire "hot spot". The potential sites will be about 25 m apart along
seven transects between the navigation channel and one bank of the river. The intensive sampling
of the "hot spot" will provide detailed information on the contaminant levels and distribution should
the area be selected for a limited remediation demonstration.
3.3 Risk Assessment/Modeling Workgroup Sampling Strategy
Sampling for the RA/M workgroup will consist predominantly of the collection of samples to
support the mini-mass balance/synoptic surveys on the Buffalo and Saginaw Rivers. These efforts
will include the collection of the water column samples, simultaneous measurements of river
discharge and associated water quality parameters, and sampling of fish populations. For the
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Buffalo River system, the sampling of combined sewer outfall (CSO) discharges will also be
undertaken. CSOs were not identified as a contaminant source for the Saginaw River and therefore
will not be sampled. Two additional river characterization studies will be conducted on the Buffalo
River AOC by the RA/M workgroup. The rationales for the various RA/M workgroup surveys and
studies will be discussed separately in the following text.
3.3.1 Mini-Mass Balance/Synoptic Surveys
The basic goal in the sampling design for the mini-mass balance/synoptic surveys is to collect
information about the river system during several periods of low flow (or quasi-steady state)
conditions as well as during at least one high flow event (after a major storm system has passed
through the AOC or during the spring snow melt). These data will provide information on the relative
importance and amplitude of point and non-point pollutant sources to the AOC on both a temporal
and a spatial scale. These same data will also serve as a primary information source for the mass-
balance, near-field dispersion, far-field dispersion, and food chain models to be used oy the RA/M
workgroup. Samples will be collected from fixed stations (six in the Saginaw River AOC and 7 within
the Buffalo River AOC) for all sampling events to measure pollutant influxes to the AOC, ambient
concentrations within the AOC, and effluxes to the lake, harbor, or bay.
Under low flow conditions, numerous measurements will be taken throughout the AOC to
determine dissolved contaminant concentrations in the water column and on the suspended
sediment. Additional measurements of the river flow conditions (i.e., flow velocity and direction,
sediment load, thermal stratification, etc.) and water quality parameters (such as pH, conductivity,
temperature, dissolved oxygen, chlorophyll-a content, etc.) will be made simultaneously with the
collection of the water column samples.
Samples collected during the high flow event will undergo the same basic measurements as
the samples collected under low flow condition and will be collected at the same station locations.
Data derived from these samples will be used to give an indication of the variation in pollutant
concentration with discharge.
Combined sewer outfalls will be sampled to quantify the input of contaminants from the storm
waters that drain the City of Buffalo. CSOs have been identified as a potential source of inorganic
and organic contaminants in the Buffalo River RAP (NYSDEC, 1989). Ten CSOs will be selected and
sampled to give a coverage of the Buffalo River AOC. The criteria used in the selection of these
sites include:
1) the ability to obtain samples from a manhole up-pipe of the outfall,
2) runoff inputs from major land use categories present in the AOC,
3) good spatial resolution within the AOC,
4) outfalls representing a large contributing area and have a pipe diameter of greater than
61 cm, and
5) the past use of the given outfall in the model to be applied to the AOC.
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Selected CSOs will be collected during one storm overflow event. Samples will be taken during at
least two additional CSO events at a selected outfall to provide a preliminary assessment of
pollutant level variability from different storm events.
Fish samples will be collected at both the Buffalo and Saginaw River AOCs. Fish will be
collected throughout the entire stretch of the river that has been designated as the AOC. Carp will
be collected as the primary fish in the Buffalo River while walleye will be sampled in the Saginaw
River. Carp were chosen to be sampled in the Buffalo River due to their abundance and
representativeness of the river's bottom feeders. Walleye was selected in the Saginaw River AOC
due to its abundance, the importance of the walleye fishery at the AOC, and past use of the walleye
in bioaccumulation studies thereby allowing for comparison of results and modeling efforts through
time. Fish samples will be collected and analyzed to determine the bioaccumulation of the
contaminants in the food chain of the AOC. A minimum of 45 from each AOC will be collected and
separated into three representative age classes to allow for the determination of bioaccumulation
rates and variability through the life-cycle of the selected species. These data will then be correlated
to the quantities of contaminants in the water column and suspended sediments to determine biotic
uptake rates and bioaccumulation potentials.
3.3.2 Sediment Transport Studies
The sediment transport studies involve the determination of the resuspension potential of the
bottom sediments. The sampling strategy involves collecting samples and testing resuspension
potential throughout the entire AOC. Actual sampling sites will be selected after discussion with
the members of the field crew from LLRS that has sampled both master and reconnaissance
stations on the Buffalo River and has done preliminary mapping of the Buffalo River. The primary
consideration will be to perform tests at sites with muddy bottom sediments since these sediments
are most easily resuspended by natural high flow events. Sites will be divided into two classes,
namely, deep (greater than 10 feet deep) and shallow (less than 10 feet deep) waters, if muddy
bottom sediments can be identified in each class.
3.3.3 Hydrodynamic Studies
This study involves the collection of total suspended solids data and other limnological
parameters, such as water temperature, conductivity, and velocity, during high flow events in the
river. These data will be used in the calibration of hydrodynamic and sediment transport models
to be employed by the RA/M workgroup modelers. The primary goal of this exercise will be to obtain
data from the upper and lower boundaries of the Buffalo River during an event large enough to
initiate bottom scour of the river bed. Samples will be collected from bridges over the Buffalo River
and Cazenovia Creek (the major tributary to the Buffalo River in the AOC) at the upper reaches of
the AOC and from a bridge near the mouth of the river.
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3.4 Engineering/Technology Workgroup Sampling Strategy
The E/T workgroup's sampling strategy consists of simply gathering enough sediments from
one or two locations within an AOC to supply all the bench scale remediation processes with the
same initial sediment after it has been homogenized. Therefore, all remedial activities will be
starting from the same baseline contaminant concentrations to allow for the determination and
comparison among the effectivenesses of the remedial processes in the removal of a given class
or classes of contaminants (i.e., RGBs, PAHs, and/or metals). The sediments to be collected will
be grossly contaminated with a given class or classes of contaminants. The collected samples
should contain several representative contamination scenarios that have been identified in the Great
Lakes basin so that the results can then be applied to the remediation of not only the AOC but other
sites as well. Site selection will be based on historical data, the results of the sediment
characterization from the T/C workgroup efforts, and discussions among members of the three
technical workgroups.
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Section 4
Field and Laboratory Operations
This section outlines the operational and logistical operations required for the sampling,
sample preparation, and analyses of the sediments for the ARCS program. Specific information on
the step-by-step action will be presented in the QAPjPs prepared by the participants in the ARCS
program. This section is divided into two parts, namely, field and laboratory operations. Further
subdivisions will be made by workgroup since the sampling and laboratory activities and goals are
different for each of the three technical workgroups.
4.1 Field Operations
Field operations will be undertaken for all three technical workgroups. Written SOPs will be
provided for all sampling activities and will be included in the QAPjP submitted in conjunction with
the sampling effort. The goals of sample collection for the T/C workgroup will include the collection
of sediments from all the master stations to be used for sediment characterization (including both
chemical and physical properties of the sediment) and toxicity testing. The T/C workgroup will also
be responsible for the collection of the reconnaissance station sediment samples that will be used
in the quantification of indicator parameters. Further, maps of the bottom sediments will be
generated from the field data obtained using seismic and resistivity mapping techniques by the T/C
workgroup. The field operations for the RA/M workgroup will include sampling for the synoptic
surveys (mini-mass balance surveys) on the Buffalo and Saginaw Rivers, sediment resuspension
potential determinations, and total suspended solids measurements (including miscellaneous flow
and water quality parameters) to be used in the modeling efforts of the RA/M workgroup. The E/T
workgroup's field operations will include the collection of bulk sediments to be used and distributed
to various laboratories during the testing of the selected remedial technologies. Discussion of the
personnel involved in the field operations, sample preparation/homogenization techniques, sample
storage and custody procedures, and a brief overview of the methods to be used in obtaining
samples for the ARCS program will be presented in the following text. The rationale for the
selection of the sampling locations has already been presented in Section 3 of this document.
4.1.1 Toxicity/Chemistry Workgroup Field Operations
The Large Lakes Research Station at Grosse He, Michigan will be responsible for the collection
of all the sediments for the T/C workgroup. This sampling includes the collection of all the master
and reconnaissance stations as well as mapping the contaminated sediments. The project officer
of the LLRS effort is Dr. Michael D. Mullin of the USEPA. Field operations will be under the direction
of John C. Filkins of the USEPA and Joseph Rathbun of AScI Corporation. AScI Corporation is a
primary subcontractor to the USEPA at the LLRS research field station. More detailed information
on the sampling efforts of the T/C workgroup will be presented in the LLRS QAPjP.
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4.1.1.1 Master Stations
The general locations of the master stations will be determined by the T/C workgroup prior
to the field crew actually going to the AOC. The exact locations of the sampling sites will be
determined in the field by the sampling crew which will have two considerations in the site selection
process. The two considerations will be (1) the presence of soft sediments and (2) the ease of
relocating the station at a later date should it become necessary. For logistical reasons, it is
occasionally necessary to move a station from its intended location to a more practical position.
At each master station, the sampling process will consist of four steps. These steps are as
follows:
1) site location,
2) benthos sample collection,
3) bulk sediment collection, and
4) sample preparation, labeling, and storage.
The first step will be to obtain the exact location of the collection site. Location information
will be obtained after the sampling vessel has been securely anchored by a minimum of a three-way
anchoring system. Site coordinates will be obtained using the Loran C navigation or the global
positioning system. In addition, triangulation observations will be made at each station using local
landmarks. Both sets of coordinates will be recorded in a bound logbook along with the date, time,
weather conditions, and any pertinent comments.
The second step in the field sampling program will be to obtain the samples to be used to
determine the benthic community structure. Five individual Ponar grab samples will be collected and
sieved through a 500 /urn sieve. Prior to the taking of the replicate grab samples, the sampler will
be moved to avoid collection from the same spot. All material remaining on the sieve will be placed
in an uniquely labeled (on both the outside of the jar as well as on paper inside the jar) canning jar
and preserved with a 10% buffered formalin solution. Prior to shipping these samples to NFCRC-
Columbia for determination and quantification of the benthos, the jars will be filled approximately
two-thirds full or to cover the material with formalin, whichever is greater.
Collection of the bulk sediment sample (step 3) will be performed using either a Van Veen or
Ponar grab samplers. Approximately 15 liters of sediment at master stations and approximately 120
liters of sediment at priority master stations will be required. Multiple grabs will therefore be
required. To avoid the sampling of the same spot and to assure the collection of true surficial
sediments, the sampler and sampling vessel will be moved slightly during the sampling process.
Movement of the vessel will consist of changing the position along two or three of the anchor lines
which will allow the vessel to shift its position slightly downstream. The sediment from the grabs
will be transferred to 5-gallon plastic-bag lined buckets. Upon completion of sampling at a given
site, all sampling equipment will be thoroughly rinsed with river water to remove any residual
sediments.
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Upon completion of the sampling effort, the sediments will be transported to the shore to be
homogenized. Homogenization will consist of mixing the sediments in a cement mixer for 15
minutes. Homogeneity will be checked visually in the field. If the sediments appear to be
heterogeneous after the first 15 minutes, an additional 15 minutes mixing in the cement mixer will
be used. The mouth of the cement mixer will be covered with plastic sheeting to help limit the loss
and exposure of the sampling crew to any volatile organic compounds present in the sediment.
Once the sediment is determined to be homogeneous, the sample will be transferred to labeled,
high-density polyethylene bottles. A 2-inch headspace will be left in each bottle to allow for later
sample homogenization at the analytical laboratories. The bottles will be place in ice chests and
surrounded with ice packs. Ice packs will be replaced as needed to maintain the samples in a
chilled condition as near to 4° C as possible. Upon completion of sampling at a given site, all
sampling equipment will be thoroughly rinsed with clean tap water to remove any residual
sediments. Just prior to shipping, fresh ice packs will be placed inside the ice chests along with
a shipping manifest indicating sample numbers, sample volumes, and collection dates. Samples
will be shipped by next-day delivery to the LLRS laboratory for storage. Samples will be maintained
at the LLRS laboratory in walk-in coolers at 4 ± 2° C in the dark.
A unique sample identification coding scheme, developed at LLRS, will be used to clearly label
and identify the numerous sediment samples that are part of the program. The coding scheme
consists of a unique 11-digit sample number. The number can be used to identify the collection site,
survey number, transect number, station number, sample type, replicate, and sample fraction (Figure
9). This number will be assigned to each sediment, fish, or benthos sample and will be recorded
in the field log and on the sample container. This number is the only number that will be used and
will be accepted for the reporting of the final data in the ARCS program.
4.1.1.2 Reconnaissance Stations
The location of the reconnaissance stations will be determined in the field and selected to
achieve two primary goals, namely, to obtain as complete as possible coverage of the entire AOC
and to obtain a zone of intensive sampling around a known "hot spot". Indicator station locations
will be chosen based on historical data plus the interpretation of the results from the sub-bottom
profiling (to be discussed). A more complete discussion of the rationale and sampling design used
for the selection of reconnaissance stations was presented in section 3.2.4.
The sampling process at each reconnaissance stations will consist of two primary steps. The
steps are (1) site location and (2) sediment core collection. The first step will be to obtain the exact
location of the collection site. Location information will be obtained after the sampling vessel has
been securely anchored by a minimum of a three-way anchoring system. Site coordinates will be
obtained using the Loran C navigation or the global positioning system. In addition, triangulation
observations will be made at each station using local landmarks. Both sets of coordinates will be
recorded in a bound logbook along with the date, time, weather conditions, and any pertinent
comments.
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I H
1
0 1
0 1
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(Note: supplemental information is
recorded on the field data sheets)
Sample Fraction:
Surface grab - 00
Core intervals - 01, 02, 03, etc.
Sample Replicate: Single sample -1
Replicate No. - 2, 3, 4, etc.
Sample Type: G, Grab (box core, dredge)
C, Core (piston, gravity, vibra-)
F, Fish
B, Benthos
Station Number: Sequential on each transect
Transect Number: Sequential at each site
Survey Number: Sequential at each site
Site code: IH, Indiana Harbor
BR, Buffalo River
SR, Saginaw River
Figure 9. ARCS Sample Identification Coding System.
The second step in the field sampling program will be to obtain the core samples to be used
to determine the indicator parameters. Once the sampling vessel is firmly anchored, core samples
will be obtained using a Vibra-core unit. The core tube will be lined with a plastic core sleeve and
secured at one end. The core tube will be securely attached to the vibrating motor head and
lowered into the water. The vibrator unit will be activated upon contact with the sediments and the
core will be pushed into the sediment until it is "refused". Upon retrieval of the core tube, the core
sleeve will be removed and placed on a work table. The core sleeve will be cut and the core sliced
in half lengthwise. Observations of sediment color, texture, smell, and layering will be made and
recorded in the field logbook. Video tapes of each core will also be made while the core is laid out
on the work table. The field crew will then slice the core laterally into approximately 2-foot sections
which will be kept as individual samples. These samples will be placed in 4-liter polyethylene bottles
and kept on ice until transported back to LLRS for laboratory analysis. Upon completion of sampling
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at a given site, all sampling equipment will be thoroughly rinsed with river water to remove any
residual sediments. Homogenization for the reconnaissance station samples will consist of mixing
the sediments until visually homogeneous (i.e., uniform color, texture, and water content) at the LLRS
laboratory. Samples will be maintained at the LLRS in walk-in coolers at 4 ± 2° C in the dark.
The same unique sample identification coding scheme, as discussed for the master stations,
will be used to clearly label and identify the numerous sediment samples that are part of the ARCS
program. This number will be assigned to each sediment sample and will be recorded in the field
logbook and on the sample container. This number is the only number that will be used and will
be accepted for the reporting of the final data in the ARCS program.
4.1.1.3 Sediment Mapping
The objectives of the sediment mapping program are to spatially map the extent and thickness
of post-glacial bottom sediments in selected AOCs and to determine the degree of hardness of the
surficial sediments. The mapping effort will be a part of the LLRS project under the direction of Dr.
Michael D. Mullin with assistance from Dr. Robert W. Taylor of the University of Wisconsin,
Milwaukee, Wisconsin. Ideally, the sediment mapping will be performed prior to the collection of
the reconnaissance stations to help identify areas with soft bottom sediment deposits for potential
core sampling. However, due to time constraints on the sampling surveys, the mapping of the
sediments prior to sampling may not be possible and will thus be performed nearly simultaneously
with sample collection of the reconnaissance stations.
Sediment mapping will be conducted using seismic and resistivity profiling equipment. The
seismic profiling for the T/C workgroup will be performed using a Datasonics Model SBT-220 sub-
bottom transceiver and a model TTV-120 towed transducer vehicle with transducer array. Resistivity
data will be obtained using a current transmitter with a 1.5 kilowatt output at an 8 second period.
Electrical resistivity potentials from a 20 electrode Schulumberger array will be collected and used
to determine sediment clay content.
In portions of the AOC which are less than 100 meters wide, three equally spaced lines parallel
to shore line will be surveyed. In wider stretches of the river, harbor, or bay, an additional series
of diagonal lines forming a diamond pattern will overlay the parallel lines. Resistivity profiles may
only be feasible along the parallel tracks due to instrument/system limitations. Time permitting,
additional longitudinal tracks will be planned down the channel and along both sides of the river.
The seismic data will be used to map the thickness and extent of the bottom sediments. The
resistivity unit will measure the electrical resistivity of the pore water in the sediment which can be
directly related to the physical characteristics of the sediment, such as clay content, and be used
as a auxiliary procedure for the seismic system. The profiling equipment will be connected to the
Loran C navigation or global positioning systems which will periodically record the geographic
position of the unit on the strip chart and computer record. The strip chart records of the
distribution of the soft and consolidated sediments and water depth will be used to create a map
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of soft sediment deposition areas and a three-dimensional distribution map of the sediment layers.
When necessary, core samples will be collected to aid in the interpretation of the profiling results.
4.1.1.4 Fish Collection for Tumor and Abnormality Studies
Brown bullheads (Ameiurus nebulosus^ will be collected from the Indiana Harbor/Grand
Calumet River system by electroshocking. This method allows capture of live fish necessary for
pathological examination yet is non-destructive to non-target species. Depending upon the depth
of water, some supplementary sampling with gill nets, trawls, and/or trap nets may be necessary.
The NFRC-GL, under the direction of Dr. John E. Gannon, will be responsible for the collection of the
fish samples. If the brown bullheads are not found or are in insufficient number, the white sucker
(Catostomus commersoni) will become the target species of bottom dwelling fish. The target
number of fish to be collected is 85 with a minimum of 50 fish being considered adequate for the
estimation of tumor frequency, although at a reduced confidence level.
4.1.2 Risk Assessment/Modeling Workgroup Field Operations
The State University College at Buffalo (SUC-B) in Buffalo, New York will be responsible for
the collection of all the samples for the synoptic or mini-mass balance surveys to be conducted on
the Buffalo River. This effort will include the collection of the Buffalo River water column,
simultaneous measurement of river discharge and field-collected limnological parameters, and
sampling of fish populations. SUC-B will also be responsible for the sampling of combined sewer
outfall (CSO) discharges into the Buffalo River. The project officer of the SUC-B effort will be Dr.
Harish C. Sikka of the Division of Environmental Toxicity and Chemistry. More detailed information
on this portion of the sampling efforts of the RA/M workgroup will be presented in the SUC-B QAPj'P.
The members of the Saginaw River team, a cooperative agreement among the University of
Michigan, Michigan State University, and the Saginaw Valley State University, will be responsible for
the collection of all the samples for the synoptic survey to be conducted on the Saginaw River. This
effort will include the collection of the Saginaw River water column, simultaneous measurements
of river discharge and field-collected limnological parameters such as water temperature, flow rates,
pH, conductivity, etc., as well as the sampling of fish populations. The project officer of the MSG
effort will be Dr. Russell A. Moll of the Center for Great Lakes and Aquatic Sciences at the University
of Michigan in Ann Arbor, Michigan.
4.1.2.1 Mini-Mass Balance/Synoptic Survey Sampling
For the synoptic surveys, the field-collected limnological parameter list includes conductivity,
water temperature, pressure (depth), dissolved oxygen, pH, percent light transmission, fluorescence
(chlorophyll-a), and total incident radiation to the water surface. Field-collected parameters will be
determined during each day of sampling at the sampling stations. More frequent measurements
may be necessary to better characterize the river water and flow conditions in the synoptic survey
AOCs. In the Buffalo River, the field-collected limnological parameters will be measured using the
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Sea-Bird* Model SBE-25 Sealogger automated measurement system. In the Saginaw River and Bay,
the Sea-Bird Electronics SEACAT SBE-16* recorder fitted with a Sea Tech Transmissometer will be
used to measure conductivity, temperature, and light transmission. The HydroLab Surveyor II* field
unit will be used in conjunction with the SEACAT recorder to collect data for water temperature,
conductivity, pH, and dissolved oxygen in the Saginaw River. Total incident radiation will be
measured using a LI-COR* system for both surveys. In addition to the field-collected limnological
parameters, meteorological conditions will also be noted and recorded daily during sampling events.
Current velocity, direction, and water surface elevation will be made to determine river
discharge at both AOCs. Current velocity and direction will be determined as a function of depth
using a March-McBirney Model 301 Flow Velocity Meter in the Buffalo River while both Price and
Weathermeasure current meters will be used in the Saginaw River. Water surface elevations will
be read from staff gauges installed along the river banks or bridges by the USAGE. A map of the
bottom profile will be made using either a depth finder or be obtained from the USAGE. This data
used in combination with the measured currents will provide the discharge of the river at each
station.
Prior to the sampling of the water column in the Buffalo River, determinations will be made
as to whether the river is stratified or not. The direction of current flow will be the primary
parameter used to determine if stratification of the river exists. The river will be considered stratified
if the vertical velocity profile indicates reverse flow and the temperature profile (to be used as a
confirmatory analysis) shows the presence of a thermocline. If the river is not stratified, water
samples will be composited horizontally (width-integrated) along a transect at mid:depth. If the river
is stratified, one horizontally composited water sample will be taken above the thermocline and
another horizontally composited sample will be taken below the thermocline. Both samples will be
maintained as unique and separate samples for analysis. Water column samples in the Saginaw
River will only be composited horizontally (width-integrated) at mid-depth since stratification is not
a concern at this AOC.
Water column samples for metals analysis will be collected using a Sigma streamline pump
sampler, or equivalent. These samplers are designed to limit sample contamination and the intake
rates have been approved by the USEPA. Prior to sampling at each transect, the intake line of the
sampler will be rinsed at least three times or purged for 10 minutes with river water to help eliminate
cross-contamination of samples between river transects. Each collection bottle will be rinsed three
times with river water before filling with sample water. Approximately 1-liter of river water will be
collected to satisfy the volume requirements for the metals analyses. Both filtered and unfiltered
samples (note: unfiltered samples will be collected and analyzed to provide confirmation of the
contaminant mass-balances) will be collected in the Buffalo River while only filtered water samples
will be collected in the Saginaw River. Sample filtration will occur immediately after the water is
collected. A 0.45 jL/m membrane filter will be used in the Buffalo River while a 0.50 pm Teflon filter
will be used in the Saginaw River synoptic survey. Filters containing the particulate matter will be
stored in precleaned polyethylene vials or precleaned aluminum foil envelopes and frozen (-20° C)
for the Saginaw River and Buffalo River surveys, respectively. The contribution of contaminants
bound on the particulate matter in the Buffalo River will be determined by subtraction of the
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contaminants present in the filtered sample from those quantified in the unfiltered sample. Water
samples collected for metals will be stored in polyethylene bottles. Water samples will be preserved
by the addition of ultrapure nitric acid to reduce the pH to 2 or less. All water samples will be
stored at 4 ± 2° C.
Water column sampling for organic analyses of pesticides, PCBs, and PAHs will require the
collection of approximately 60-liters of river water. River water will be collected using the Sigma
streamline pump sampler, or equivalent and will be collected in three 20-liter glass carboys. At each
sampling station and depth, a portion of the samples will be pumped into each of the three carboys
to approximate a composited sample in each carboy. After a transect has been sampled, the water
will be transported to a clean room or laboratory where the water sample will be separated into two
components, namely, the suspended particulate matter and a dissolved organic phase. The
particulate matter will be isolated by passing the water sample through a penta-plate filter system
containing ashed Whatman 293 mm GF/F filters. After filtration is complete, each filter is removed
from the penta-plate and returned to a washed aluminum foil wraps. The dissolved organic phase
will be isolated by drawing the filtered sample through a pre-prepared glass column containing XAD-
2 resin. The filters and sealed XAD-2 columns will be placed in ice chests with the temperatures
being maintained at 4 t 2° C in the dark. As soon as possible after filtration, the filters will be
frozen and stored at -20 ± 5° C until extraction and analysis.
Fish will be collected from the entire river within the AOC by electroshocking. Depending upon
the availability of fish, some supplementary sampling with gill nets, trawls, and trap nets may be
necessary. In the Buffalo River, carp will be collected and aged in the laboratory by scale analyses
and divided into three age classes. Three samples of each age class will be taken, each sample
being defined as the composite of five fish. A total of 45 fish will be taken to allow for further
determination of the variability within a given age class. Stomach contents and muscle samples
will be separated from each fish and shipped frozen (-20° C) to Battelle-MSL for subsequent
analysis. In the Saginaw River, walleye, alewife, gizzard shad, and yellow perch will be collected
and individually wrapped and stored frozen. These fish will be composited into groups of at least
5 fish and ground whole in the laboratory at the University of Michigan and 200 gram samples will
be frozen and shipped to MSU for PCB analysis.
Additional samples will be collected at each site to provide water and particulates for
miscellaneous limnological analyses. All the additional samples will be collected using the Sigma
streamline pump sampler or an equivalent system. Limnological analyses to be performed by the
Saginaw River team include determinations of alkalinity, hardness, suspended solid content, total
organic carbon, and chlorophyll-a content, as well as the collection of zooplankton. Four liters of
river water will be collected and stored in polyethylene bottles to satisfy these needs. Water
samples will be filtered through a GF/C filter to separate the particulate fraction from the water
sample. Filters will be stored frozen (-20 ± 5° C) while the water samples will be kept at 4 ± 2° C.
For the synoptic survey performed on the Buffalo River, additional samples will be collected
for the determination of the following limnological parameters: sulfides, chlorides, TOC, dissolved
organic carbon (DOC), hardness, alkalinity, and total suspended solids (TSS). Approximately 250
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ml of water will be collected in amber glass bottles with teflon-lined polypropylene caps. These
samples will be preserved with 4 drops of 2N zinc acetate per 100 ml of sample. Immediately after
the addition of the zinc acetate, the pH of the samples will be checked and raised to a value greater
than 9 through the addition of sodium hydroxide. Chloride and alkalinity analyses require the
collection of 500 ml of water each in polyethylene bottles. TOC and DOC determinations require the
preservation of the sample using H2SO4 to reduce the sample pH to 2 or less. Approximately 1 liter
will be collected for the TOC and DOC analyses in amber glass bottles with subsequent analyses
on both filtered (using pre-washed 0.45pm glass fiber filters) and unfiltered samples. TSS analyses
will require the collection of 1 liter of water in a polyethylene bottle. All the samples for the
limnological parameters to be determined on the Buffalo River will be maintained at 4 ± 2° C.
The final sampling effort of the RA/M workgroup to support the mini-mass balance/synoptic
surveys will be the collection of the CSOs on the Buffalo River. CSO sampling will be undertaken
by field teams from SUC-B and the Buffalo Sewer Authority. Grab samples will be obtained using
the Sigma streamline pump sampler that was used in the river survey. Flow velocity of the
combined sewage will be measured subsequent to sampling using electric flow meters so that
discharge and pollutant loadings can be determined. Grab samples will be collected by lowering
the pump sampler intake through the street-level manhole into the flow. Additionally, an automated
sampler will be placed at one of the selected CSOs. The automated sampler will collect a flow-
proportioned sample to provide a best estimate of the "average" pollutant concentration and will be
used to provide preliminary data for loading estimates. At least two additional storm overflow
events will be monitored using the automated station. Correlations between the data generated
from the grab samples and from the automated station sampling will be performed to determine
if the two types of data can be used together in the modeling efforts. The collection of the CSO
samples will follow the same sampling protocols as described for the river survey.
4.1.2.2 River Characterization Studies
In addition to the two synoptic surveys, two river characterization studies will be conducted
by the RA/M workgroup. The first characterization study involves the determination of the
resuspension potential of sediments while the second study involves the collection of TSS and other
limnological data.
The sediment resuspension project will be performed under the direction of Dr. Wilbert Lick
of the Department of Mechanical and Environmental Engineering from the University of California
at Santa Barbara, Santa Barbara, California. Yaojun Xu and Joe McNeil will be responsible for the
field work. This study basically involves resuspending the bottom sediments with a shaker. Two
different shear stresses will be applied to the sediment at 8 to 12 different sites within the AOC.
At least 4 of the sites will be located in deep water (greater than 10 feet deep) and at least 4 in
shallow water (less than 10 feet deep). Sites will be selected from predominantly muddy bottom
areas after consultation with the field crew from LLRS that has collected the T/C workgroup master
and reconnaissance stations.
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At each selected site for the resuspension study, the location of the site will be determined
using the global positioning system or the Loran C navigation system. Sediment cores will be
obtained by diver or by pole from on board ship. Cores will have 11.7 cm diameters and contain
approximately 5 to 10 cm of sediment. The cores will then undergo the resuspension testing.
Additional samples will be collected in polyethylene bottles for particle-size analysis. No sample
preservation is required for particle-size analysis.
The New York State Department of Environmental Conservation (NYSDEC) will be responsible
for conducting the second study. This study involves the collection of TSS data and other
miscellaneous limnological parameters such as water temperature, conductivity, and water velocity
(to be used to calculate discharge rates) on the Buffalo River. Simon Litten of the NYSDEC office
in Albany, New York will be the principal investigator and John McMahon of the NYSDEC Region 9
office will be in charge of the sampling operations.
Samples to be collected for the second study will concentrate on high flow events with
discharges of 6000 cubic feet per second at the river mouth. Discrete point samples will be taken
with a P-72 point integrating sampler if water velocities are high enough to prevent the deployment
of a Van Dorn sampler. Samples will be collected at 0.2 and 0.8 times the depth of the water at the
sampling station. Similar to the circumstances of the synoptic surveys, thermal stratification is a
concern at the mouth of the Buffalo River. If stratification exists, samples will be collected at 0.2
and 0.8 times the depth of each stratum. Stratification will be determined on the basis of
temperature and conductivity profiles with depth. Temperature and conductivity measurements will
be made in the field using a HydroLab Surveyor II* unit. Water velocities will also be determined
at each site using the standard Gurley meter. The total water required for TSS measurements is
approximately 0.4 liters. No special sample preservation techniques or bottle types are required for
TSS analyses.
4.1.3 Engineering/Technology Workgroup Field Operations
The E/T workgroup's field operations will include the collection of bulk sediments to be used
and distributed to various laboratories during the testing of the selected sediment remedial
technologies. Sample collection is the responsibility of the USACE division or district offices for the
Buffalo River, Grand Calumet River/Indiana Harbor, and Saginaw River/Bay AOCs. Samples to tested
for remediation potential from the Ashtabula River and Sheboygan Harbor will be collected as part
of the ongoing Superfund effort. Site locations will be marked on USACE sounding charts after
determination via triangulation. Bulk samples will be collected from the toe of the channel using a
crane barge bucket operation. Approximately 1 to 3 cubic yards of sediment will be retrieved per
bucket. Sediments will then be scooped or shoveled from the bucket, working from top to bottom,
to fill the appropriate number of 5 gallon plastic buckets. Approximately 100 gallons will be collected
from each selected area within each AOC except for the potential resampling of a "hot spof'/master
station on the Saginaw River, in which only 50 gallons wili need to be collected. Samples will be
shipped to ERL-D by motor freight at ambient temperatures. Degradation of organic compounds
is not a major concern during shipping since these compounds are highly resistant to breakdown
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and will be requantified prior to any treatment study being performed on the sediment. Sample
compositing and homogenization will be performed at ERL-D using a cement mixer. Sediments will
be deemed homogeneous by visual inspection of texture, color, and water content. After
homogenization, samples will be stored at 4 ± 2° C in the dark.
4.2 Analytical Laboratory Operations
The sample analysis will be conducted through contracts/grants/interagency agreements to
numerous analytical laboratories. This section will identify the general laboratory operations that
will be required of all laboratories participating in the ARCS program. All analytical laboratories that
have been identified at this time, the Pis responsible for the analysis and reporting of the final data,
and which parameters will be analyzed by their laboratories will be presented. The prescribed
methodologies to be used in the ARCS program will be presented (Table 2) and exceptions, with
explanation, will be discussed, where known. If standardized methods or method references are
not available, the PI will be responsible for having a written standard operating procedures (SOP)
for the method available for review either in the QAPjP or during a laboratory system audit (to be
discussed). Detailed analytical laboratory operations will be presented in the QAPjP that each
participating laboratory is required to prepare for the ARCS program.
All laboratories participating in the ARCS program will be expected to follow good general
laboratory practices as they relate to sample handling and tracking, filter preparation, sample
preparation, instrument operation, bottle washing, storage and preparation of standards, etc. For
laboratories performing bioassays, bioaccumulation studies, and/or fish tumor and abnormality
studies, good general laboratory practice relating to animal health care (i.e., handling, feeding, and
testing) will also be followed. SOPs related to these points will be available for inspection in the
written QAPjP and/or during laboratory system audits.
For the ARCS program, required containers (i.e., glass, polyethylene) and lids (i.e., teflon-lined),
preservation techniques, and holding times for collected samples will follow the protocols
established in USEPASW-846 (USEPA, 1986). Holding times at the laboratory will begin upon receipt
of the samples from the field sampling crews. It is recognized that although as much as a week
may pass since the samples were collected at the AOC, the analytical laboratories will not be held
responsible for the elapsed time.
Initial instrument calibration, where appropriate, for all analyses performed in the ARCS
program should be completed using a minimum of a three point curve or following the instrument
manufacturer's instructions. The acceptance criteria for the initial three point calibration curve,
where used, is that all points used in the determination of the calibration curve should have a
calculated coefficient of determination (R2) of > 0.97. All instruments used in the ARCS program
must be calibrated prior to analysis of any ARCS samples.
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Table 2. Preferred and alternate methods accepted for analyses in the ARCS program8.
Parameter
Metals
preparation^,^,
preparation,,.^
Ag
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
Organometals
Methylmercury
Tributyltin
Preferred Method"
3050
200.3
7761
7061
7081
7131
7191
7211
7381
7471
7461
6010
7421
7741
7951
.
GC/CVAFd
GC/FPDd
Alternate Methods"
200.4
XRFd
6010
200.7
XRFd
6010
200.7
XRFd
6010
200.7
6010
200.7
XRFd
6010
200.7
XRFd
6010
200.7
XRFd
7470
6010
200.7
200.7
XRFd
6010
200.7
XRFd
6010
200.7
XRFd
Reference(s)0
USEPA, 1986 | USEPA, 1983
Nielson and Sanders. 1983
USEPA. 1990
USEPA, 1986 | USEPA, 1986
USEPA. 1983
USEPA, 1986 | Nielson and
Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA. 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1986 | USEPA. 1986
USEPA, 1983
USEPA, 1986 | USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
USEPA, 1986
USEPA, 1986 | USEPA, 1986
USEPA, 1983
Nielson and Sanders, 1983
Bloom, 1989
SOP"
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Table 2 (cont.). Preferred and
alternate methods
accepted for analyses in the ARCS proaram*.
Parameter Preferred Method" Alternate Methods" Reference (s)c
Organics
Dioxins/furans
PAHs e)drac,|0n
cleanup
analysis
confirmation
PCBd/congenerextractlon/cleanup
analysis
PCBd/aroclorextractlon
cleanup
cleanup
analysis
Pesticidesaxtractlon
cleanup
cleanup
analysis
TOC/DOCd
Water Quality Parameter^
Alkalinity
Conductivity
Dissolved oxygen
Hardness0
Ca
Mg
8280
3540
3630
8100
8250
HPLCd
GC/ECDd
3540
3620
3660
8080
3540
3620
3660
8080
9060
310.1
120.1
360.1
130.2
7140
7450
USEPA, 1986
USEPA, 1986
USEPA, 1986
8310 USEPA. 1986 |
8270 USEPA, 1986 |
USEPA, 1986
USEPA, 1986
Krahn et al., 1988
NOAA, 1985
USEPA, 1986
USEPA, 1986
USEPA, 1986
USEPA, 1986
USEPA, 1986
USEPA, 1986
USEPA, 1986
USEPA 1986
5310C USEPA, 1986 |
combustion SOP8
USEPA, 1983
meter USEPA, 1983 |
360.2 USEPA, 1983 |
130.1 USEPA, 1983 j
215.1 USEPA, 1986 |
242.1 USEPA, 1986 |
APHA, 1985
Rhoades, 1982
USEPA, 1983
USEPA, 1983
USEPA, 1983
USEPA, 1983
Treatment Technology Parameter^
Compressive strength
Density
Moisture content
Oil & Grease
SLTd
TCLPd
Total inorganic carbon
Total sulfur
C 109-88
D 2216-80
9070
413.2
ASTM, 1987
SOPe
ASTM, 1987
USEPA, 1986 | USEPA, 1983
SOP"
40 CFR, 1987
SOP9
SOP6
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Table 2 (conU. Preferred and alternate methods accepted for analyses in the ARCS program8.
Parameter Preferred Method" Alternate Methodsb Reference(s)c
Miscellaneous Parameters
Ammonia
AVSd
Chlorides
Chlorophyll-a
Lipid content
Particle-size analysis
PH
350.3
GC/PIDd
325.2
gravimetric
sieve/gravimetric
9045
USEPA, 1983
Cutter and Oatts, 1987
325.1 USEPA, 1983 | USEPA, 1983
Strickland and Parsons, 1972
Folch et al., 1957
sieve/laser SOP8 | SOP"
150.1 USEPA, 1986 | USEPA, 1983
meter Plumb, 1981
Organohalogens
Solvent extractable residue
Sulfides
Total solids
Total suspended solids
Total volatile solids
NAAd
gravimetric
376.2
160.3
160.2
160.4
208D
208D
209F
SOP8
SOP8
USEPA 1983
USEPA, 1983 |
USEPA 1983
USEPA 1983 I
| APHA 1985
APHA 1985
I APHA 1985
a - parameter groupings (e.g., metals, organometallics, etc.) are for organizational purposes only.
Parameter group headings do not indicate a suite of parameters that are commonly analyzed
together as a unit by the analytical laboratory. Parameter groupings analyzed for a given project
are presented in Section 4.2.
b - where non-standard methods are used, a very brief description of the basic quantification
technique is presented.
c - where multiple references appear on the same line and are separated by the symbol |, the first
method listed is the reference for the preferred method while the second method listed is for
the alternate method presented.
d - AVS = acid volatile sulfides; DOC = dissolved organic carbon; GC/CVAF = gas
chromatography/cold vapor atomic fluorescence; GC/ECD = gas chromatography/electron
capture detection; GC/FPD = gas chromatography/flame photoionization detection; GC/PID =
gas chromatography/photoionization detection; HPLC = high pressure liquid chromatography;
NAA = neutron activation analysis; PAH = polyaromatic hydrocarbons; PCB = polychlorinated
biphenyls; SLT = serial leaching testing; TCLP = toxicity characterization leaching procedure;
TOC = total organic carbon; XRF = X-ray fluorescence analysis.
e - SOP = standard operating procedure prepared by the analytical laboratory performing the
specified analysis.
f - these parameters are generally associated with bioassays and fish bioaccumulation studies
performed by the T/C and RA/M workgroups for the ARCS program.
g - hardness can either be determined by titration or through the determination and summation of
Ca and Mg contents. Both results are presented as mg/L CaCO3.
h - these parameters are generally associated with the tests performed by the E/T workgroup during
remedial process testing for the ARCS program.
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The samples received by the laboratories may or may not have undergone some form of
homogenization by the parties responsible for their original collection and shipping. Subsequently,
during shipment, the sample material within each container may segregate by particle-size, density,
or some other related property. Therefore, all laboratories will be required to homogenize the
samples prior to the removal of an aliquot for analysis. Homogenization can be performed either
by manual or mechanized stirring of the sample in the bottle until visual homogeneity is obtained.
A sample will be deemed visually homogeneous when no variation in color, water content, texture,
etc. can be seen. All samples, extracts, pore waters, and standards for the ARCS program will be
stored at 4 ± 2° C in the dark until extraction or final analyses unless otherwise specified. In cases
where fish tissue, either whole fish homogenates or homogenates of various organs (i.e., stomach
contents or muscle), samples will be maintained at -20 ± 5° C until extracted or digested for
analysis. All temperature data will be kept in a bound logbook.
4.2.1 Toxicity/Chemistry Workgroup Laboratory Activities
Numerous chemical and biological parameters will need to be measured for the T/C workgroup
to satisfy their goals established in section 2.3.3. In brief, the T/C workgroup is responsible for
developing and testing sediment assessment methods through the determination of inorganic and
organic chemistry parameters, bioassays (including benthic community structure determinations and
mutagenicity tests), fish bioaccumulation studies, and fish tumor and abnormality surveys. The
following text is divided into five sections, namely, inorganic chemistry, organic chemistry, bioassays,
fish bioaccumulation assays, and fish tumors and abnormalities. For the bioassay and fish
bioaccumulation sections, a discussion of water quality parameters that will be measured to ensure
organism health prior to testing and to ensure that any toxic effects are due solely to the sediment,
pore water, or elutriates during testing will be presented. It should be noted that physical
parameter measurements, such as particle-size analysis and total solids, will be included in the
discussion of inorganic chemical analyses.
4.2.1.1 Inorganic Chemistry
Inorganic chemical analyses will be performed on a variety of different media including pore
waters, elutriates, sediments, and fish tissues for the T/C workgroup. Prior to the discussion of
which parameters will be determined, the definition of the various media needs to be clearly stated.
Pore water will be defined as the water separated from sediments strictly by centrifugation without
the addition of extra water or chemicals. Pore water will therefore represent only the chemical
phases that are in equilibrium with the sediment and not sorbed onto the sediment. Elutriates will
be prepared from a 4:1 watensediment (v/v) mixture that has been shaken, allowed to settle, and
filtered to remove any remaining suspended particles. The elutriates will represent the water
extractable phase of the chemical contaminants. Sediments will be simply defined as the solid
phase material in a given sample.
As mentioned in the project description, Battelle-MSL will be one of the two primary
laboratories used in the determination of inorganic chemical analyses for the T/C workgroup. The
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Battelle-MSL operations for the ARCS program will be under the direction of Dr. Eric A. Crecelius.
Battelle-MSL will perform chemical analyses on sediments collected from the master stations, pore
waters and sediment elutriates prepared and shipped from NFCRC, and tissue samples as a result
of the fish bioaccumulation studies.
The second laboratory used in the determination of inorganic chemical analyses for the T/C
workgroup will be LLRS. The LLRS laboratory operations for the ARCS program will be under the
direction of Or. Michael D. Mullin. LLRS will perform both chemical and physical analyses on
sediments collected at the reconnaissance stations as well as elutriates prepared from the
sediments.
Inorganic chemical parameters to be analyzed for the T/C workgroup include the following
parameters:
Metals including Ag, As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn,
PH,
Ammonia,
Total and volatile solids,
Conductivity,
AVS,
Organometals (methylmercury and tributyltin),
Lipid content,
Solvent extractable residue,
Organohalogens (Cl, Br, and I), and
Particle-size analysis.
Battelle-MSL will perform analyses for Ag, As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Zn, AVS, and
the organometals as well as determining lipid content from the fish tissue samples. LLRS will
perform analyses for Cd, Cr, Cu, Fe, Ni, Pb, Zn, pH, ammonia, conductivity, organohalogens, solvent
extractable residue, and particle-size analysis.
For the ARCS program, metals analysis, excluding Hg, should be performed using a hot
nitric/hydrochloric acid digestion of the sediment (USEPA, 1986; SW-846 method 3050). Water
matrices (e.g., pore water or from the water column) and elutriates may be aspirated with no
additional preparation other than sample preservation with nitric acid to a pH <2.0. Fish tissues
will be digested following USEPA (1990) method 200.3 for subsequent metals analysis.
Quantification of the metals should be done by inductively coupled plasma (ICP) spectroscopy
(USEPA, 1986; SW-846 method 6010) or graphite furnace atomic absorption (GFAA) spectroscopy
(USEPA, 1986; SW-846 method 7000 or USEPA, 1983; method 200.7) or their equivalents. GFAA is
the preferred method for metals quantification. Alternately, As and Se may be quantified using SW-
846 methods 7061 and 7741 (USEPA, 1986), respectively, which employ gaseous hydride generation
techniques. Mercury analysis should be performed by cold vapor atomic absorption (CVAA)
following SW-846 method 7471 (USEPA, 1986). Alternate methods to those described here must first
meet the approval of the ARCS QA Officer and T/C workgroup.
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One known exception to the prescribed metal analytical procedures is that Battelle-MSL will
digest the sediment samples using a nitric, perchloric, and hydrofluoric acid regime in a teflon
pressure vessel. This analysis follows USEPA (1983) method 200.4. Quantification of the metals
will be performed using the GFAA method as described above. The resultant digest will produce
the total elemental contents for the metals while the nitric/hydrochloric digestion will yield the
quantities of extractable metals (all the metals excluding the intercrystalline metals). Energy-
dispersive X-ray fluorescence (XRF) analysis of undigested sediment samples will also be used
during the quantification of total elemental metal contents by Battelle-MSL following the methods
of Nielson and Sanders (1983).
The determination of pH of sediments will be done electrometrically using a pH probe and
meter system following the method described by Plumb (1981), USEPA SW-846 method 9045 (USEPA,
1986), or USEPA method 150.1 (USEPA, 1983). Ammonia content of the elutriate will be determined
potentiometrically using an ion selective probe and meter following USEPA method 350.3 (USEPA,
1983) or equivalent. Ammonia determination at LLRS laboratory will be performed following the
instrument's instruction manual. USEPA methods 160.3 and 160.4 (USEPA, 1983), or their
equivalents, will be used in the determination of total and volatile solids, respectively. Total and
volatile solids will be determined gravimetrically after sample drying at 60° C and ashing at 550°
C, respectively. Conductivity of the pore water will be determined following USEPA method 120.1
(USEPA, 1983) by measuring the specific conductance of the pore water at 25° C. LLRS will
determine conductivity using the method of Rhoades (1982) which is an equivalent method.
The following methods do not, at this time, have a standardized USEPA approved
methodologies. Laboratories employing these methods will be required to provide written SOPs or
provide a published reference for the method. Acid volatile sulfides analysis will be performed
following the method described by Cutter and Oatts (1987). This method basically involves the
selective generation of H2S in an acidic regime and subsequent gas chromatography
(GC)/photoionization detection. Methylmercury and tributyltin (organometals) will be determined
following SOPs developed at Battelle-MSL. Methylmercury will be analyzed in sediment, water, and
tissue by ethylation followed by cryogenic GC with cold vapor atomic fluorescence detection (Bloom,
1989). Butyltin species will be determined in environmental samples by solvent extraction, followed
by hexylation and quantification by GC with flame photometric detection. Lipid contents of the fish
tissue submitted to Battelle-MSL from the NFRC-GL will be determined by the chloroform-methanol
extraction procedure of Folch et al. (1957) and gravimetrically quantified.
Solvent-extractable residue (SER) will be determined gravimetrically from whole sediment after
extraction with dichloromethane in a mixed sediment/anhydrous sodium sulfate mixture. The SER
analyses will be performed at LLRS. The extracted samples will then undergo analysis for
organohalogen content by neutron activation analysis (NAA). In brief, NAA measures organically-
bound halogen concentrations by measuring the characteristic gamma-ray energy spectrum emitted
by neutron-bombed elements.
Particle-size analysis will be performed at LLRS on sediment samples gravimetrically after
separating the sample into five fraction via sieve analysis. The fractions will be divided at 1 mm,
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250 fJtm, 63 pm, and 38 /vm. The finest fraction (<38 fim) will be determined gravimetrically after
sample aggregation, filtration, and drying at 105° C overnight.
4.2.1.2 Organic Chemistry
Four basic categories of organic compounds will be analyzed for the T/C workgroup, namely,
pesticides, PCBs, PAHs, and dioxins/furans. Total organic carbon will also be determined to
normalize the concentrations of the organic compounds in the samples. Organic chemical analyses
will be performed on a variety of different mediums including pore waters, elutriates, sediments, and
fish tissues.
The analysis of organic contaminants for the T/C workgroup will be the sole responsibility of
Battelle-MSL Table 3 provides a base listing of the organic compounds that will be looked for and
quantified by Battelle-MSL. Organic analyses will be performed on sediments collected from the
master stations, pore waters, and tissue samples as a result of the fish bioaccumulation studies
as well as sediment elutriates prepared and shipped from NFCRC.
A majority of the organic compounds will be analyzed following the protocols established in
USEPA SW-846 (USEPA. 1986). Pesticides and PCBs will be extracted following method 3540
(soxhiet extraction) and quantified following method 8080 which involves quantification by GC with
an electron capture detector (ECD). Sample cleanup may be necessary to remove interferences and
will follow method 3620 using a Florisil column and method 3660 to remove elemental sulfur from
the sample. Congener-specific PCBs will be analyzed following the method of Krahn et al., (1988)
and NOAA (1985), which involves a methylene chloride/anhydrous sodium sulfate extraction, a high
pressure liquid chromatography (HPLC) carbon column cleanup, and quantification by GC/ECD.
PAHs and chlorinated benzenes will be prepared by soxhiet extraction (method 3540) and quantified
following method 8100. Concentrations of these compounds will be performed using a GC
separation followed by flame ionization detector (FID). Secondary confirmation or the need to
resolve PAH pairs may warrant the use of GC separation with mass spectroscopy (MS)
quantification (methods 8250 or 8270). To remove interferences in the sample, the use of a silica
gel cleanup will be used following method 3630. Dioxins and furans will be determined following
method 8280 which involves the use of a high-resolution capillary column gas chromatography/low-
resolution mass spectrometry technique. Sample cleanup procedures will be dependant upon the
matrix and analytes to be quantified.
Total organic carbon will be analyzed by both LLRS and Battelle-MSL using an CHN analyzer
that employs sample combustion to liberate carbon dioxide which is subsequently quantified by a
thermal conductivity detector. TOC will be performed following the LLRS laboratory SOP which will
be provided in their QAPjP for the ARCS program. At Battelle-MSL, TOC will be measured in a similar
manner as at LLRS except following the protocols established in USEPA SW-846 (USEPA, 1986)
method 9060.
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Table 3. Organic compounds to be identified and quantified for the ARCS program.
Pesticide/Afoclor PCBs
Aldrin
a-BHC
/S-BHC
A-BHC
Chlordane
4.4.DDD
4.4.DDE
4.4.DDT
Oieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Lindan* ( -BHC)
Toxaphene
PCB 1016
PCB 1221
PCB 1232
PCB 1342
PCB 1248
PCB 1254
PCB 1260
PCB Congeners
2.4'-dichlorobiphenyl
2,2',5'-trichlorobipheny1
2,4,4'-trichlorobiphenyl
2,2',3,5'-tetrachlorobiphenyi
2.2',5.5'-tetrachlorobiphenyl
2,3',4,4'-tetrachlorobiphenyl
3,3',4,4'-tetrachlorobiphenyl
2,2',4.5.5'-pentachlorobiphenyl
2,3.3',4.4'-pentachlorobiphenyl
2,3',4,4',5-pentachlorobiphenyl
3,3',4,4',5-pentachlorobiphenyl
2,2',3,3',4,4'-hexachlorobiphenyl
2,2'.3.4,4',5'-hexachlorobiphenyl
2,2',4,4',5.5'-hexachlorobiphenyl
2,2',3,3',4,4',5-heptachlorobiphenyl
2,2',3,4,4',5,5'-heptachlorobipheny1
^^.S.^'.S.S'.e-heptachlorobiphenyl
2 2' 3 3' 4 4* 5 6-octachlorobJDhenvl
2 2' 3 3' 4 4' 5 5' 6-nonachlorobiphenyl
Decachlorobiphenyl
PAHs and Chlorinated Benzenes
1,4-Dtehlorobenzene
Naphthalene
2-Methylnaphthalene
Dimethyl Phthalate
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Butylbenzylphthalate
bis-(2-ethylhexyl)phthalate
Chrysene
Di-n-Octylphthalate
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indo(1.2,3-cd)pyrene
Benzo(ghi)perylene
Dioxins/Furans
2378-TCDF
Total TCDF
2378-TCDD
Total TCDD
12378-PeCDF
23478-PeCDF
Total PeCDF
12378-PeCDD
Total PeCDD
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
Total HxCDF
123478-HxCDD
123678-HxCDD
123789-HxCDD
Total HxCDD
1234678-HpCDF
1234789-HpCDF
Total HpCDF
1234678-HpCDD
Total HpCDD
OCDF
OCDD
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4.2.1.3 Bloassays
To examine the toxicity of the sediments and its pore water, as well as the potential toxicity
of the sediment from elutriates to living organisms in the Great Lakes, numerous bioassays will be
performed on the sediments from the master stations as well as Microtox being performed on
sediments from the reconnaissance stations at LLRS. Discussion of bioassay testing will be divided
into two parts, namely, the actual bioassay and the water quality parameters. Water quality
parameters are important and used to ensure that the response seen in the test organism was due
exclusively to the contaminants and not to organism stress from the culture or laboratory water
used during testing. Each of these two topics will be addressed separately in this section.
The primary laboratories involved in the bioassay and toxicity testing are Michigan State
University in East Lansing, Michigan, the National Fisheries Contaminant Research Center in
Columbia, Missouri, and Wright State University in Dayton, Ohio. Each of the laboratories involved
in the bioassay testing program and which tests will be performed at their laboratories will be
presented in the following text.
The efforts of the USFWS NFCRC will be under the direction of Dr. Christopher G. Ingersoll.
NFCRC will be performing the following bioassays on elutriates prepared from a 4:1 watersediment
mixture:
Daphnia magna.
Microtox, and
Selenastrum capricornutum.
Daphnia magna will be exposed to a sediment elutriate dilution series in a 48 hour test.
Selenastrum capricornutum will also be exposed to a dilution series of sediment elutriates using 24
hour carbon fixation (14C accumulation) test. Microtox will be applied in a 15 minute sediment
elutriate toxicity test.
Solid phase testing on the sediments at NFCRC will be conducted for the amphipod Hyalella
azteca and two midge species, Chironomus tentans and Chironomus riparius. Amphipod tests start
with juvenile animals (<3rd instar) and may continue up to 28 days until reproductive maturation.
Chironomus tentans tests start with second instar larvae (10 day old) and continue for 10 days until
the fourth instar larval stage. Chironomus riparius tests start with first instar larvae (<24 hours old)
and may continue up to 28 days through adult emergence.
NFCRC testing will also include the use of chemical extracts (extracted by Battelle-MSL in
methylene chloride, subjected to gel permeation chromatography, and transferred into DMSO)
obtained from sediment samples to assess any mutagenic activity using the Ames Salmonella
microsome test. Four strains of Salmonella will be exposed to varying doses of sediment extracts
in the presence and absence of rat liver S9. Mutagenic activity is indicated when the number of
colonies on test plates is £ 2 times the number of spontaneous revertants on negative control
plates.
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Benthic community structure will be determined at NFCRC. All collected invertebrates will be
taxonomically identified to the lowest possible classification. A multivariate approach in the analysis
of invertebrate species abundance and biomass will be incorporated into a factor analysis of the
resultant data. Principal component analysis will be used to help determine the underlying variance
in species relative abundance. Shifts in "clusters" of species as a function of both physical and
chemical differences in their habitat, provide information on the integrated response of aquatic
communities to contaminants.
Tests being performed with Daphnia magna. Selenastrum capricornutum. Hvalella azteca.
Chironomus riparius. and Chironomus tentans will follow the USEPA (1985, 1989) and ASTM (1989)
toxicity test methods. Microtox, Ames mutagenicity testing, and benthic community structures will
be performed following written SOPs provided in the QAPjP. The last three test methods have
undergone peer-review and have been published in scientific periodicals.
A majority of the bioassay testing will be performed under the direction of Dr. G. Allen Burton
at WSU. Dr. Burton will be responsible for the collaboration of five universities and/or organizations
who will be performing the actual bioassays. The collaborating investigators include the Illinois
Natural History Survey (INHS) in Champaign, Illinois, the University of Minnesota in St. Paul,
Minnesota, Memphis State University in Memphis, Tennessee, NOAA - Great Lakes Environmental
Research Laboratory in Ann Arbor, Michigan, and WSU. The individual tests, the parties responsible
for running the bioassay, the test length and endpoints, and the test media are presented in Table
4.
Toxicity test methods will adhere to USEPA (1985, 1989) protocols for testing of Pimephales
promelas. Daphnia magna. Ceriodaphnia dubia. and Selenastrum capricornutum. Methods for the
toxicity testing using Hvalella azteca. Lemna minor, and microbial activity assays will be presented
as SOPs in the submitted QAPjP. These methods will follow previously reported methodologies in
peer-reviewed periodicals. The methods for the remaining bioassay tests will be presented as SOPs
in the submitted QAPjP.
Bioassays to be performed at MSU will be under the direction of Dr. John P. Giesy. MSU will
be running bioassays using Ceriodaphnia dubia. Daphnia magna. Pimephales promelas. Selenastrum
capricornutum. Chironomus tentans. and Microtox. Two media will be used during the bioassays
at MSU, namely, pore water and sediment. Pore water testing using Ceriodaphnia dubia. Daphnia
magna. and Microtox tests will be performed to try to determine the efficiency and effectiveness
of the use of pore water for bioassays as compared to using whole sediment for predicting toxic
responses. Assays being performed with Ceriodaphnia dubia. Daphnia magna. Pimephales
promelas. Selenastrum capricornutum. and Chironomus tentans will follow the USEPA (1985, 1989)
and ASTM (1989) toxicity test methods. Microtox testing will be performed following methods that
have undergone peer-review and have been published in scientific periodicals. Written SOPs will be
provided in the QAPjP or be available for inspection during a laboratory system audit.
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Table 4. Bioassavs to be performed as a collaborative effort under the direction of WSl>.
Assay Organism/Community* Length of Test Endooint
Test Medium" Responsible Party'
Pimephates promelas
Pimeohales promelas
Daphnia maona
Daphnia maana
Ceriodaphnia dubia
Hvalella azteca
Hvalella azteca
Panagrellus redivivus
Pontoporeia hovi
7 day Larval growth
7 day Embryo survival
48 hour Survival
7 day Survival/Reproduction (3 brood)
7 day Survival/Reproduction (3 brood)
7 day Survival
10 day Survival
96 hour Survival
Development
20 day Survival
Avoidance
S. E
S. E
S. E
S. E
S
S
S
E
wsu
wsu
wsu
wsu
wsu
wsu
wsu
INHS
NOAA
Hexaaenia limbata
Selenastrum capricornutum
Lemna minor
Hvdrilla verticillata
Microtox
Alkaline phosphatase
Dehydrogenase
0-Galactosidase
0-Glucosidase
Rapid Bioassessment II. Ill
10 day
96 hour
24 hour
4 day
14 day
15 minute
2 hour
2 hour
2 hour
2 hour
28 day
Uptake
Survival
Molting Frequency
Uptake
Growth
MC uptake
Growth (frond number)
Chlorophyll-a
Chlorophyll-a
Dehydrogenase Activity
Shoot Length
New Growth
Luminescence
Enzyme Activity
Enzyme Activity
Enzyme Activity
Enzyme Activity
Community Indices (10)
S. E
E
E
E
E
S
S
S
S
E
S, E
S. E
S. E
S. E
S
U. Minn.
WSU, INHS
WSU
Memphis
INHS
WSU
WSU
WSU
WSU
WSU
a - Alkaline phosphatase, dehydrogenase, j8-galactosidase, and 0-glucosidase are all part of the bacterial activity as
described in the project description.
b - S = sediment; E = elutriate.
c - U. Minn. = University of Minnesota; Memphis = Memphis State University.
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The bioassays to be performed at MSU using Ceriodaphnia dubia and Daphnia magna as test
organisms will be run for 48 hours with an endpoint of organism survival. Daphnia magna will also
be tested in pore waters for 7 days to again test for survival but also for organism fecundity.
Chironomus tentans bioassays will be performed for 10 days on the sediment noting survival and
growth. Pimephales promelas testing for survival and, ultimately, bioaccumulation of contaminants
will be assayed for 28 days. Microtox will be performed for the standard 15 minutes in a serial
dilution series examining bioluminescence as an endpoint. Selenastrum capricornutum will be tested
in a serial dilution series for 24 hours noting UC uptake.
Microtox testing on elutriates from the reconnaissance stations will be performed at LLRS.
The Microtox test will be performed following the SOP provided to LLRS from NFCRC, thereby,
maintaining comparability among the laboratories performing the same bioassay test.
Water quality parameters in bioassay testing will be used to ensure organism health prior to
exposure to contaminants in the sediments, elutriates, or pore waters. Further, water quality
parameters will be used to ensure that the responses identified in the organisms are due entirely
to the contaminants in the sample. Water quality parameters include:
Hardness,
Alkalinity,
Dissolved oxygen (DO),
PH,
Conductivity, and
Temperature.
Additional water quality parameters such as ammonia, chloride, sulfate, and turbidity may be
monitored at the discretion of the PI if these parameters are a concern at their laboratory. Light
intensity and photoperiod, where appropriate, will be monitored during each bioassay at all
laboratories participating in the ARCS program.
Water quality parameter measurements will be made following USEPA test methods (1983)
or following the instrument manufacturer's instructions unless otherwise cited. Hardness will be
tested following method 130.2, or equivalent, which involves the sample titration after Ca and Mg
complexation using ethylenediamine tetraacetate (EDTA). Alkalinity, a measurement of the water's
capacity to neutralize acid, will be determined by titration to an endpoint of pH = 4.5 will follow
method 310.1 or equivalent. Dissolved oxygen will be measured electrometrically using a probe
(method 360.1) or using a modified Winkler procedure (method 360.2). Measurement of pH will be
performed using a pH electrode following USEPA (1983) method 150.1, USEPA (1986) SW-846 method
9045, manufacturer's instruction, or their equivalents. Conductivity, a measure of the electrical
conductance within a sample, will be tested using a self contained conductivity meter employing
USEPA (1983) method 120.1 or equivalent. Temperature will be measured using either NIST (National
Institute of Standards and Technology, formerly the National Bureau of Standards - NBS) traceable
thermometer or using a temperature probe. Due to the simplicity of this measurement, no standard
method needs to be followed for the ARCS program.
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4.2.1.4 Fish Bioaccumulation Assays
Fish bioaccumulation assays will be performed as part of the ARCS program to assess the
buildup of contaminants in fish tissue due to exposure to contaminated sediments. Ten day tests
using Pimephales promelas as the test organism will be performed at NFRC-GL under the direction
of Dr. John E. Gannon. A 28 day bioaccumulation assay using Pimephales promelas will be
performed at MSU under the direction of Dr. John P. Giesy. Water quality parameters will be
monitored during these assays following the methods/techniques presented in the bioassay section
(section 4.2.1.3). Quantities of accumulated contaminants in the fish tissues will be determined at
Battelle-MSL following the procedures presented in sections 4.2.1.1 and 4.2.1.2.
4.2.1.5 Fish Tumor and Abnormalities
The NFRC-GL, under the direction of Dr. John E. Gannon, will conduct surveys of tumors and
other physical abnormalities in bottom fish from the Grand Calumet River. Types and incidences
of tumors will be determined on the brown bullhead (Ameiurus nebulosus). preferably, after field
necropsy and preservation of tissues and histological examination. If brown bullheads are not
found, or are in insufficient number, the white sucker (Catostomus commersoni) will become the
target species of bottom dwelling fish. Biological data such as external abnormalities, age, sex, and
size will also be obtained from the sampled fish.
4.2.2 Risk Assessment/Modeling Workgroup Laboratory Activities
Numerous chemical parameters will need to be measured for the RA/M workgroup to satisfy
their goals established in section 2.3.4. The RA/M workgroup laboratory activities will be geared
towards providing data for the mini-mass balance synoptic surveys as described in section 2.3.4 and
various modeling efforts such as the hydrodynamic, sediment transport, and food chain models.
Additionally, as a preliminary evaluation of sediment toxicity and potential contamination, TIE will
be performed on the sediments.
Toxicity identification evaluation analyses and bioassays will be performed at ERL-D under the
direction of Dr. Gerald T. Ankley and at WSU under the direction of Dr. G. Allen Burton. TIE basically
involves the manipulation of the extracted pore waters from the sediments followed by toxicity
testing. The manipulations of the pore water are intended to change the toxicity of the sample.
These manipulations include:
A baseline test,
pH adjustment to pH 3 and 11,
pH adjustment and aeration,
pH adjustment and filtration,
pH adjustment and solid phase extraction through C18 columns,
EDTA chelation,
Oxidant reduction, and
Graduated pH testing.
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Bioassays are subsequently performed on the manipulated pore waters, after being adjusted back
to their initial pH values (except in the graduated pH test in which no readjustment of the pore water
will be made), using Pimephales promelas and Ceriodaphnia dubia as test organisms.
Bioassays using Pimephales promelas and Ceriodaphnia dubia will be performed following
protocols defined by the USEPA (1985,1989) or their equivalents. Pimephales promelas testing will
occur for up to 96 hours in a serial dilution test monitoring organism survival. Ceriodaphnia dubia
testing will monitor survival during a 48 hour period in a serial dilution test.
During the bioassay testing, the water quality parameters of hardness, pH, conductivity, and
DO will be monitored to ensure that the identified organism response is due solely to the
contaminants present in the sediment pore waters. Hardness will be measured either indirectly via
titration following USEPA (1983) method 130.2, or its equivalent, or by direct measurement by flame
atomic absorption spectrometry (AA) of calcium and magnesium following USEPA (1983) method
215.1 and 242.1, USEPA (1986) SW-846 methods 7140 and 7450, or their equivalents. Measurement
of pH will be performed using a pH electrode following USEPA (1983) method 150.1, USEPA (1986)
SW-846 method 9045, manufacturer's instruction, or their equivalents. Conductivity, a measure of
the electrical conductance within a sample, will be tested using a self contained conductivity meter
employing USEPA (1983) method 120.1 or equivalent. Dissolved oxygen will be measured
electrometrically using a probe (USEPA, 1983; method 360.1 or equivalent).
ERL-D will also perform quantification of the ammonia content of the pore waters as well as
the metals concentrations if the manipulation tests in TIE indicate that toxic effects are due to either
of these two contaminants. Ammonia will be determined using an ion selective electrode following
USEPA (1983) method 350.3 or equivalent. Metal concentrations of As, Cd, Co, Cr, Cu, Mn, Ni, and
Zn will be quantified, after sample preservation to a pH <2 using concentrated reagent grade nitric
acid, using GFAA (USEPA, 1986; SW-846 method 7000 or equivalent).
In support of the mini-mass balance synoptic survey efforts, chemical analyses will be
performed on particulates (or suspended sediment) and waters from the Buffalo and Saginaw
Rivers. The State University College at Buffalo in Buffalo, New York under the direction of Dr. Harish
C. Sikka will conduct the analyses on the Buffalo River samples while the members of the Michigan
Sea Grant College Program, under the direction of Dr. Russell A. Moll will conduct the sample
analysis program for the Saginaw River. Each synoptic survey's laboratory activities will be
discussed separately in the following text.
The parameters that will be examined in the Buffalo River priority consideration area by SUC-B
include the following contaminants:
Total PCBs,
DDT,
Dieldrin,
Chlordane,
Benzo(a)pyrene,
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Benzo (a) anthracene,
Benzo(b)fluoranthene,
Benzo (k)fluoranthene,
Chrysene,
Pb, and
Cu.
All organic compounds will be analyzed following the protocols established in USEPA (1986)
SW-846. Pesticides and PCBs will be quantified following method 8080 which involves quantification
by GC/ECD. Sample cleanup may be necessary to remove interferences and will follow method 3620
using a Florisil column and method 3660 to remove elemental sulfur from the sampla. PAHs
(benzo(a)pyrene, benzo(a)anthracene, benzo(b)f luoranthene, benzo(k)f luoranthene, and chrysene) will
be quantified following method 8100 or 8310. Concentrations of these compounds will either be
performed using a GC separation followed by flame ionization detection or HPLC with a fluorescence
detector. To remove interferences in the sample, the use of a silica gel cleanup wili be used
following method 3630.
Metals analysis will be performed using a hot nitric/hydrochloric acid digestion of the
particulates (USEPA, 1986; SW-846 method 3050). Quantification of the metals will be done by GFAA
following USEPA (1986) SW-846 method 7000, USEPA (1983) method 200.7, or their equivalents.
GFAA is the preferred method for metals quantification for the ARCS program.
In addition to the contaminants previously discussed, a series of "conventional" river
parameters will be measured for the Buffalo River waters. These conventional parameters include:
Sulfides,
Alkalinity,
Hardness,
Chlorides,
TOG,
DOC, and
TSS.
Sulfides in the river water will be determined colorimetrically after reaction with dimethyl-p-
phenylenediamine to produce methylene blue following USEPA (1983) method 376.2 or equivalent.
Alkalinity will be determined by titration to an endpoint of pH = 4.5 will follow USEPA (1983) method
310.1 or equivalent. Hardness will be measured directly by flame AA of calcium and magnesium
following USEPA (1983) method 215.1 and 242.1, USEPA (1986) SW-846 methods 7140 and 7450, or
their equivalents. Chloride contents will be examined using the colorimetric/automated ferricyanide
system (USEPA, 1983; method 325.2 or equivalent). The quantification of TOC and DOC will follow
the protocols established in USEPA (1986) SW-846 method 9060 which involves the conversion of
organic carbon, by combustion, to carbon dioxide and the subsequent detection and quantification
of the CO2 by an infrared detector. TSS will be determined gravimetrically after filtration and drying.
USEPA (1983) method 160.2 or equivalent is appropriate for this analysis.
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The contaminants to be analyzed in water and particulate samples collected in the Saginaw River
AOC by MSG will be:
Total PCBs,
Pb,
Fe,
Cu, and
Zn.
All four metals in the particulate fraction will be quantified after sample digestion using concentrated
nitric acid and hydrogen peroxide (30%) and GFAA analysis (USEPA SW-846 method 7000, 1986, or
equivalent). The method for sample digestion proposed by MSG is a variant on USEPA (1986) SW-
846 method 3020 and should be acceptable for the ARCS program. A written SOP for this method
will be available for review during a laboratory system audit. Filtered water samples will be tested
for Cu, Pb, and Zn using GFAA techniques following USEPA (1986) SW-846 method 7000, or
equivalent, after sample concentration by freeze-drying. A written SOP of the freeze-drying technique
will be provided in the MSG QAPjP.
Total PCB contents will be determined on the XAD-2 resin column and the filter papers
obtained from the field processing of the river waters. These samples will be extracted following
USEPA (1986) SW-846 method 3540, or equivalent, which uses a Soxhlet extraction procedure. PCBs
will be quantified following USEPA (1986) SW-846 method 8080 which involves quantification by GC
with an electron capture detector (ECD). Sample cleanup may be necessary to remove interferences
and will follow method 3620 using a Florisil column and method 3660 to remove elemental sulfur
from the sample (USEPA, 1986). PCB concentrations in fish tissue and zooplankton samples will
also be determined following these methods.
Similar to the synoptic survey to be performed on the Buffalo River, "conventional" river
parameters, including determinations of alkalinity, hardness, TSS, TOC, and chlorophyll-a content,
will also be determined by MSG. TSS will be determined gravimetrically after filtration and drying.
TOC quantification will follow the protocols established in USEPA (1986) SW-846 method 9060 which
involves the conversion of organic carbon, by combustion, to carbon dioxide and the subsequent
detection and quantification of the CO2 by an infrared detector. Alkalinity and hardness
determinations will be made using USEPA (1983) methods 130.2 and 310.1, or equivalents,
respectively. Chlorophyll-a contents will be performed employing the method described by Strickland
and Parsons (1972).
Two additional studies that will be conducted to support the sediment transport modeling
effort will be performed at UCSB and by the NYSDEC. Testing done by UCSB will be done under
the direction of Dr. Wilbert Lick while work performed by the NYSDEC will be under the direction of
Dr. Simon Litten. Both laboratories will be performing TSS quantification analyses. TSS will be
determined following method 208D in Standard Methods (APHA, 1985), or equivalent. Particle-size
analysis will be performed at UCSB using a combination of sieving for larger particles (> 0.25
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and the Malvern particle-size analyzer for the finer fraction (512 to 1 /mi). The remaining particle
sizes will be determined by difference. Written SOPs will be available at the laboratory for
inspection or will be provided upon request.
4.2.3 Engineering/Technology Workgroup Laboratory Activities
The primary laboratory activities of the Engineering/Technology workgroup will be to evaluate
and test available removal and remedial technologies for contaminated sediments. The laboratory
activities of the E/T workgroup can be divided into two sections, namely, preliminary sediment
sample characterization and remediation process efficiency testing. Each of these categories will
be discussed separately in the following paragraphs.
The basic preliminary characterization of the sediment will be performed by ERL-D and will
include the following parameters:
TOG,
Total inorganic carbon (TIC),
Particle-size distribution,
Density of dry material,
Total sulfur content,
AVS,
Oil and grease (O&G),
Total PCBs,
PAHs, and
Metals including Cd, Cr, Cu, Fe, Hg, Ni, Pb, and Zn.
Most of the methods used in the preliminary characterization of the sediments at ERL-D will follow
protocols described in USEPA (1986) SW-846. Exceptions include the analyses of total inorganic
carbon, particle-size, density, total sulfur, and AVS, for which written SOPs or references for these
methods will be provided in the QAPjP submitted by ERL-D. TOC and O&G will be analyzed using
methods 9060 and 9070, or equivalents, respectively. Total PCBs will be quantified following method
8080 which involves quantification by GC/ECD. Sample cleanup may be necessary to remove
interferences and will follow method 3620 using a Florisil column and method 3660 to remove
elemental sulfur from the sample. PAHs will be quantified following method 8100. Concentrations
of these compounds will be determined using GC/FID. Secondary confirmation or the need to
resolve PAH pairs may warrant the use of GC separation with mass spectroscopy quantification.
To remove interferences in the sample, the use of a silica gel cleanup will be used following method
3630. Metals, including Cd, Cr, Cu, Fe, Hg, Ni, Pb, and Zn, will be analyzed using a hot
nitric/hydrochloric acid digestion of the sediment (method 3050) with the exception of Hg.
Quantification of the metals should be done by ICP (method 6010) or GFAA (method 7000) or their
equivalents. GFAA is the preferred method for metals quantification. Mercury analysis should be
performed by CVAA following method 7471.
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To satisfy the E/T workgroup's responsibilities numbers 8 and 10 (treatment technologies for
inorganic contaminants and evaluation of solidification/stabilization technologies, respectively) as
listed in the project description in section 2.3.5, two specific laboratories will be used to assess the
efficiency of the remedial alternatives selected. A general description of the analytical laboratory
activities required to satisfy E/T workgroup responsibility number 7 (bench-scale testing of selected
treatment technologies) will be provided for those remedial techniques that degrade organic
contaminants such as PCBs and PAHs.
The treatment technologies for the remediation of inorganic contaminants (task 8) will be the
primary responsibility of the Bureau of Mines under the direction of Mr. James P. Allen. The BOM
will examine the treatment options that include the extraction and recovery of metals from the
contaminated sediments. Samples that are submitted to the BOM will undergo particle size
separations prior to chemical analysis using a variety of techniques, such as sieving and cycloning,
froth flotation, gravity separation, and magnetics. SOPs for the separation technologies will be
available for inspection during laboratory system audits.
Metals to be quantified in the untreated and treated (or remediated), fractionated sediments
include Ag, As, Ba, Cd, Cr, Hg, Pb, Sb, and Se. Metals analysis will be performed using a hot
nitric/hydrochloric acid digestion of the sediment (USEPA, 1986; SW-846 method 3050) with the
exception of Hg. Quantification of the metals will be performed by GFAA or flame AA (USEPA, 1986;
SW-846 method 7000) or their equivalents. GFAA is the preferred method for metals quantification.
Alternately, Se may be quantified using USEPA (1986) SW-846 method 7741, respectively, which
employ gaseous hydride generation techniques. Mercury analysis should be performed by cold vapor
atomic absorption following USEPA (1986) SW-846 method 7471.
WES under the direction of Mr. Daniel E. Averett will perform remedial tests on sediments from
the Buffalo River employing chemical solidification/stabilization (CSS) techniques which are probably
the most proven techniques for remediation of contaminated sediments. The scope of the study
will involve laboratory preparation of CSS samples using sediment and one of the following
binders/additives: portland cement, lime/fly ash, kiln dust, and portland cement with powdered
activated carbon. A range of binder-to-sediment ratios will be screened and an optimal ratio will
be selected for detailed evaluation. Effectiveness will be measured by comparing leaching results,
unconfined compressive strength, and durability under multiple wet/dry and freeze/thaw cycles at
WES.
Written SOPs for the wetting/drying and freezing/thawing test procedures will be provided in
the WES QAPjP. The determination of unconfined compressive strength will be performed following
ASTM (1987) method C 109-88. Two leaching procedures will be used at WES, namely, serial
leaching test (SLT) and toxicity characterization leaching procedure (TCLP). TCLP will be performed
following the method described in 40 CFR Part 268 (1987). A written SOP for the SLT will be
provided in the WES QAPjP.
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Upon the selection of the "ideal" binder-to-sediment ratio, bench scale testing will be performed
in which the following chemical analyses will be performed to assess the methods efficiencies for
the removal of contaminants from the system:
Metals including Cr, Cu, Ni, Pb, and Zn,
PAHs (including base, neutral, and acid extract able s),
PH,
Conductivity,
Moisture content,
Total volatile solids, and
O&G,
TOC.
Metals to be analyzed at WES include Cr, Cu, Ni, Pb, and Zn. Metals will be extracted using nitric
acid and hydrogen peroxide following USEPA (1986) SW-846 method 3050, or their equivalents.
Quantification of Cr, Pb, Cu and Ni will be made using GFAA (USEPA, 1986; SW-846 methods 7191
and 7421 and USEPA (1983) methods 220.2 and 249.4, respectively). Zn will be analyzed by ICP
following USEPA (1986) SW-846 method 6010.
PAHs will be quantified at WES following the protocols established in USEPA (1986) SW-846
method 8270 which utilizes a capillary column GC/MS technique. The measurement of pH and
conductivity will also be performed following USEPA (1986) SW-846 methods 9040 and 9050,
respectively. Moisture content and total volatile solids will be determined gravimetrically (ASTM,
1987; methods D 2216-80 and APHA (1985) Standard Methods 209F, respectively). USEPA (1983)
method 413.2 will be used for the determination of O&G in the sediments. This method uses
infrared spectrophotometric techniques in the quantification process. TOC will be analyzed using
APHA (1985) Standard Methods 5310C using sample combustion followed by thermal conductivity
detection of the released/generated carbon dioxide.
In general, for the remedial processes in the ARCS program that are aimed at the degradation
of organic compounds such as pesticides, PCBs, and PAHs, a quantification of the concentrations
of these compounds must be made prior to remediation and then after the remedial process. For
the ARCS program, the quantification of these compounds should be performed using the following
established protocols presented in USEPA (1986) SW-846. Pesticides and PCBs will be quantified
following method 8080 which involves quantification by GC with an electron capture detection.
Sample cleanup may be necessary to remove interferences and will follow method 3620 using a
Florisil column and method 3660 to remove elemental sulfur from the sample. PAHs will be
quantified following method 8100. Concentrations of these compounds will be performed using
GC/FID methods. Secondary confirmation or the need to resolve PAH pairs may warrant the use
of GC/MS quantification (methods 8250 or 8270). To remove interferences in the sample, the use
of a silica gel cleanup will be used following method 3630.
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4.3 Sample Custody
No formalized chain-of-custody is required for the ARCS program. Sample recipients will be
notified by telephone of the number and identity of samples shipped at the time of shipment from
LLRS or ERL-D, whichever source is appropriate. Sample recipients should in return, notify LLRS or
ERL-D that the samples have been received and the condition of the samples received (i.e., if the
samples leaked, broken bottle, etc.) in the event that additional sample is required by the analytical
laboratory. Records will be maintained of sample collection dates, labeling, handling, transport,
tracking, and laboratory analyses performed on the sediment samples at a given analytical
laboratory.
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Section 5
Quality Assurance Program
This section describes the QA program which is designed to allow both control and
assessment of measurement uncertainty during the sampling, sample preparation, and analysis
phases of the ARCS program.
5.1 Overview of Quality Assurance Objectives
The data collection criteria provide a balance between constraints of time and cost and the
quality of data necessary to achieve the ARCS program research objectives. The ARCS QAPP is
designed to accomplish the following objectives:
Establish the QA/QC criteria used to control and assess data collection in the ARCS
program,
Provide comparable sampling, preparation, and analytical methods and procedures,
Utilize assessment samples and procedures to verify the quality of the data,
Perform field and on-site laboratory system audits to ensure that all activities are properly
performed and that discrepancies are identified and resolved, and
Evaluate the data and document the results in a final QA report to GLNPO management.
To aid in this effort, it is necessary to identify both qualitative and quantitative estimates of
the quality of the data needed by the ARCS data users. Guidelines established by the USEPA
Quality Assurance Management Staff (Stanley and Verner, 1985) encourage the data users to clearly
identify the decisions that will be made and to specify the calculations, statistical and otherwise,
that are to be applied to the data.
The raw data for the ARCS program will be collected during three major operational phases
consisting of sediment mapping, sampling, and analysis. A certain amount of data measurement
uncertainty is expected to enter the system at each phase. The sampling population itself is a
source of confounded uncertainty that is extremely difficult to quantify. Generally, the data quality
objectives encompass the overall allowable uncertainty from sample measurement and from the
sampling population that the data users are willing to accept in the analytical results (Taylor, 1987).
Because of the many confounding sources of uncertainty, overall DQOs for the ARCS program have
not been defined.
This QAPP focuses on the definition, implementation, and assessment of measurement quality
objectives that are specified for the entire sample preparation and analysis phases of data collection
as well as for the verification of the field sampling phase. The MQOs are more or less specific
goals defined by the data users that clearly describe the data quality that is sought for each of the
measurement phases. The MQOs are defined according to the following six attributes:
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Detectability - the lowest concentration of an analyte that a specified analytical procedure
can reliably detect,
Precision - the level of agreement among multiple measurements of the same
characteristic,
Accuracy - the difference between an observed value and the "true" value of the parameter
being measured,
Representativeness - the degree to which the data collected accurately represents the
population of interest,
Completeness - the quantity of data that is successfully collected with respect to the
amount intended in the experimental design, and
Comparability - the similarity of data from different sources included within individual or
multiple data sets; the similarity of analytical methods and data from related projects
across AOCs.
Initial MQOs were established by the principal laboratories performing a given type of
measurement (i.e., inorganic or organic analyses, bioassays, etc.) after discussion and approval by
the members of the T/C and/or E/T workgroups. In most cases, if not all, the initial proposed QA
program and MQOs were equivalent to the QA program routinely implemented at the analytical
laboratory. Upon the initiation of the formal QA program within the ARCS program, the existing
MQOs were either accepted or modified with additional requirements to ensure data quality in the
ARCS program, where necessary. The resultant MQOs were then applied to all parameters in the
process of being analyzed and to all future analyses. It will be these MQOs that will be reported
in the remainder of this section. Discrepancies to the stated ARCS program MQOs will be described
in the final QA report to be submitted to GLNPO by EMSL-LV and LESAT upon completion of the
ARCS program.
If the data quality goals cannot be met during the course of the project, the actual level of
quality will be used to reassess the intended use of the data. A lower than desired attainment of
data quality could require different approaches to be used in data analysis or may result in
modifications to the levels of confidence assigned to the data. These points will be addressed in
the final QA report to be submitted to GLNPO by EMSL-LV and LESAT upon completion of the ARCS
program.
5.2 Design Characteristics
An important part of the QA program for the ARCS program consists of the use of various QC
samples. The QC samples enable the laboratory to control measurement error and meet the MQO
requirements. In order to assess the MQOs, a series of different sample types must be analyzed
together with the routine samples in a manner that is statistically relevant and in which conclusions
concerning the quality of the data can be drawn.
In order to produce data of consistently high and known quality, the participating laboratories
are required to analyze certain types of QC samples that are known to the laboratory staff and that
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can be used by the analysts to identify and control analytical measurement uncertainty. Each QC
sample has certain specifications that must be met before data for that parameter is considered
acceptable. These specifications include acceptance limits and frequency of sample use
requirements. The QC samples are non-blind samples to assist the laboratory in meeting laboratory
MQOs and include sediment, sediment extracts (including pore water and elutriates), water column
samples, and fish tissue samples, e.g., analytical replicates, as well as non-sediment, non-water,
or non-fish tissue based samples, e.g., reagent blanks. The QC samples are analyzed by each
laboratory and allow the PI and laboratory QA staff to assess whether the physical, chemical, and
biological testing is under control.
The overall QA program presented is applicable throughout the ARCS program (i.e., for all three
technical workgroups) and for all media (i.e., sediment, river water, pore water, elutriate, or fish
tissue) in which the contaminants are to be investigated. The acceptance limits and frequency of
use criteria may vary slightly between different workgroups, due to size of analytical batches and/or
the usage of the resultant data, but the quality of the data for its intended use will not be
compromised. For example, in the testing of a sediment that has undergone a remediation process
that is supposed to remove organic compounds for the E/T workgroup, the accuracy, precision, and
detection limits for the inorganic metals, monitored strictly for mass balance purposes, may not be
as strict as for the analyses of metals performed for the T/C workgroup where sediment
characterization is the workgroup's primary objective. Where these exceptions are known to exist,
they will be noted in the appropriate section.
For the purposes of the following discussions, several definitions of a batch or sample set are
required dependent upon the type of investigation being conducted. A batch or sample set for
inorganic and organic chemistry parameters, excluding the analogous tests performed to indicate
water quality for bioassays and bioaccumulation studies, will be defined as 20 or fewer routine
samples to be analyzed for a given contaminant within a given medium. In other words, a batch
being analyzed for PCBs in sediment and pore water extracted from the same sediment constitutes
two different analytical batches even though they are from the same bulk sample. A different
definition for a batch needs to be defined for the bioassays and fish bioaccumulation studies. A
batch for these studies will be defined as all tests being performed simultaneously for a given assay
in a given media (sediments, elutriates, or pore waters) from a given AOC. Fish tumor and
abnormality survey batches will include all fish collected from a given AOC during a given sample
collection trip.
The following sections will describe the types of QC samples, their acceptance limits, and
required frequencies of use by parameter or parameter group (i.e., PCBs, PAHs, etc.) required in the
ARCS program. Section 5.3 will discuss the quality assurance objectives of precision, accuracy,
representativeness, comparability, and completeness.
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5.2.1 Analytical Replicate Samples
A triplicate subsample of a routine sample is required for all inorganic and organic analyses
with the exception of the inorganic analyses used to check water quality conditions during
bioassays or fish bioaccumulation studies. For the water quality parameter testing used in
conjunction with bioassay or fish bioaccumulation testing, duplicate analyses will be required. The
selection of the replicate sample is to be at random from all the samples in a given batch. These
samples will be used to ensure that within-batch precision MQOs are being satisfied (i.e., an
estimate of the degree/extent of homogeneity obtained within the sample). Precision is calculated
as a relative percent difference (RPD) or relative standard deviation (RSD) and is evaluated to ensure
that the results are within acceptable limits set forth in this document (section 5.3) and submitted
QAPjPs. If the precision objectives for the analytical replicate are not met, corrective actions should
be initiated to determine the cause for the poor resultant precision. These corrective actions can
include a recalculation of the data, recalculation of the RPD or RSD, reanalysis of the samples,
and/or reanalysis of the entire sample batch. Notification of the laboratory QA officer should be
done immediately upon identification of any problem.
For the bioassays and fish bioaccumulation studies, all samples to be tested are run in
triplicate at a minimum. Routinely, four or more replicates of each sediment, pore water, or elutriate
are tested per organism. Precision for the fish tumor and abnormality studies will be achieved by
cross-checking approximately 10% of the samples by another fish pathologist.
One known exception to the use of triplicate analyses exists in the ARCS program. At the
LLRS laboratory, duplicate analysis will be performed during the determination of the indicator
parameters. These duplicate samples will be performed on one in every ten routine samples instead
of once per batch. The more frequent, but less reliable, duplicate samples are required to maintain
control of analytical measurement uncertainty during the processing of the numerous
reconnaissance station samples collected during each reconnaissance and mapping survey.
5.2.2 Field Duplicate Samples
Field duplicate samples will be applied to the collection of reconnaissance station samples
collected for the T/C workgroup and during the mini-mass balance synoptic surveys performed for
the RA/M workgroup. During the collection of the reconnaissance stations, a duplicate core sample
will be collected, described, and analyzed by LLRS on each sampling day. The duplicate cores will
be collected by slightly moving the vibra-core unit and coring a separate sample. Duplicate water
column, particulate, and CSO samples (where collected) will be collected during the synoptic
surveys. Field duplicates will be collected at a rate of one duplicate per sampling day. Precision
is calculated as a relative percent difference between the two samples for each analyzed parameter.
Precision for the field duplicate should have an RPD of <. 30%. Individual pairs will be used to
assess the overall within-batch precision and to provide the data user with an estimate of the
natural variability in the distribution of contaminants within the sediments or other media sampled.
These estimates will be pooled to provide the within-batch component of the overall system
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measurement uncertainty. If the precision objectives for the field duplicates is not met, corrective
actions should be initiated to determine the cause for the poor resultant precision. These corrective
actions will be primarily based upon the recalculation of the data and recalculation of the RPD (to
ensure proper calculations have been performed) due to the expected highly varied nature of the
sediments. For the water column and particulate samples, however, reanalysis of the samples or
reanalysis of the entire sample batch may be warranted after recalculations have been performed.
5.2.3 Reagent Blanks
For physical and chemical analytical methodologies that require sample preparation, a reagent
blank for each batch of samples processed is prepared and analyzed. A reagent blank is defined
as a sample composed of all the reagents, in the same quantities, used in preparing an actual
routine sample for analysis. The reagent blank will undergo the same digestion and extraction
procedures as an actual routine sample. For liquid samples, the reagent blank will be either
distilled/deionized water or the combination of reagents used during extraction/digestion. For solid
samples, the reagent blank will be the weighing dish or sample holder without the addition of any
sediments. These reagent blanks are used to check for significant baseline drift and potential
contamination within a batch of samples. The MQOs (presented in Table 5) for all reagents blanks
in the ARCS program are that the blanks must have a measured concentration ^ method detection
limit (MDL). Reagent blanks are to be run at the beginning, middle, and end of the batch for
inorganic analyses and at a rate of 1 per batch for organic analyses. If the MQOs for the reagent
blanks are not met, a new reagent blank is to be prepared and analyzed. All samples associated
with the "high" blank should be reprocessed and reanalyzed after the contamination source has been
identified and eliminated.
During the bioassay and bioaccumulation studies, the "reagent blank" is better known as the
control sample. This sample simply consists of the water in which the organisms have been either
cultured or raised. Control samples can not be performed in solid phase (whole sediment)
bioassays, due to the nature of these tests. Control samples should be assayed at a rate of at
least one per sample batch. The control sample in these tests will be used to assess organism
health during the given assay period and the influence of the "clean" water on the organism. The
response of the organisms in the control samples must equal or exceed the response limits for each
of the bioassays presented in Table 6.
An additional form of "reagent blank" will be used during fish bioaccumulation studies.
Preexposure samples of the fish population will be performed to establish a background
concentration of contaminants in the test organism. Preexposure fish may have detectable levels
of some contaminants, but should be below the levels identified in the exposed fish.
Control charts, with ± 2 and 3 a values (the 95 and 99 percent confidence intervals) as warning
and action limits, respectively, will be created and updated after each day of analysis to control any
systematic bias that may be adding to the overall measurement uncertainty for a given parameter.
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1
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6 of 18
Parameter
Metals*
except Ag
Cd
Hg
Ca
Mg
Methylmercury
Tributyltin
PAHs
Pesticides
PCB/congener
PCB/aroctor
Dtoxins/Furans
TOC/DOC
O&G
pH
Ammonia
AVS
Organohalogens1
Sulfides
Total S
Chlorides
Alkalinity
Hardness"
Sediment
(MQ/kg)
2000
100
100
100
10
10
200
10
0.5
20
0.002
0.03%
10000
N/A
1000
30 ng
10000
ftjm b
IVlLJL.
Tissue Elutriate
(pg/kg) (/jg/L)
2000
100 1
100 1
100 0.01
10 0.0001
50 0.01
200
4
1
0.002
N/A
360
Water
1
10
1
2
0.05
0.01
0.01
0.01
1000
N/A
360
10
200
1000
2000
""** «*n»iiiiau Y
Accuracy0
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
±20%
± 0.1 unit
±20%
N/A
±20%
±20%
±20%
±20%
±20%
±20%
Frequency
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
N/A
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
Precision"
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
± 0.1 unit
£20%
£20%
£20%
£20%
£20%
£20%
£20%
£20%
iatam .
Frequency
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
1/batch
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Table 5 (cont). MQOs for inorganic and organic chemistry analyses for the ARCS program*.
MDL"
Parameter
Sediment Tissue Elutriate Water Accuracy' Frequency Precision" Frequency
DO
Conductivity
Chlorophyll-a
10
N/A
± 0.5 mg/L 1/batch
± 1 pS/cm 1/batch
± 0.1 mg/L 1/batch
t 2 /jS/cm 1/batch
100
±20%
1/batch
Total solids
Volatile solids
TSS
PSA"
SER
Moisture content
Lioid content
O.OOIg
O.OOIg
0.001Q
O.OOIg
0.002g
O.OOIg
O.OOIg N/A
windows
±20%
±20%
N/A
N/A
N/A
1/batch
1/batch
N/A
1/batch
N/A
N/A
£20%
£20%
£20%
N/A
£20%
£20%
£20%
1/batch
1/batch
1/batch
£20%
1/batch
£20% 1/batch
1/batch
1/batch
1/batch
a - MQOs presented do not apply to the measurement of water quality parameters associated with bioassays or
fish bioaccumulation studies.
b - MDLs for water include pore water and water column samples. Units presented in subheading are applicable
to all parameters unless otherwise noted. If no MDL is presented, then that parameter is not measured in
that given matrix. N/A = not applicable.
c - accuracy determined from CRM, SRM, or standard and is measured from the known concentration.
d - precision is calculated as %RSD. It should be noted that LLRS will only be performing duplicate analyses,
therefore, the limit will be calculated as a RPD. Precision requirements listed here are for analytical
replicates only, field duplicates are required to have a RPD £ 30%.
e - metals include Ag, As. Cd, Cr, Cu, Fe. Hg, Mn, Ni, Pb, Se, and Zn. Exceptions are noted where different
methodologies are used during the metals quantitation. Ca and Mg are used by SUC-B for determination
of water hardness.
f - the MDL for Cl and Br is 30 ng while the MDL for I is 10 ng.
g - hardness determined titrimetrically.
h - PSA = particle-size analysis; a soil sample with acceptance windows per size fraction was provided by LESAT
to LLRS for use as an accuracy standard.
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Table 6. Measurement quality objectives for bioassavs and fish bioaccumulation studies for the ARCS program.
Assay Organism/Community
Pimephales promelas
Daphnia maona
Ceriodaphnia dubia
Hvalella azteca
Chironomus riparius
Chironomus tentans
Panaarellus redivivus
Diporeia sp.
Hexaoenia limbata
Selenastrum capficornutum
Lemna minor
Hvdrilla VBrticillata
Microtox'"
Endpoint*
Survival
Larval growth
Survival
Reproduction
Survival
Reproduction
Survival
Survival
Survival
Survival
Development
Survival
Avoidance
Uptake
Survival
Molting Frequency
Uptake
Growth
"C uptake
Growth
Chlorophyll-a
Chlorophyll-a
Dehydrogenase Activity
Shoot Length
New Growth
Luminescence
Response limit (mean)6
80%
0.25 mg
90%
60 young
90%
15 young
80%
70%
70%
80%
80%
80%
80%
80%
80%
80%
80%
200000 @ 96 hrs
200000 © 96 hrs
50% increase
50% increase
80%
80%
80%
80%
N/A
Precision"
Reference ToxicantWx & Accuracy
1CR
25% or 1 CR
45%
1CR
30%
1CR
25%
25%
25%
25%
25%
25%
25%
25%
25%
25%
25%
30% or 1 CR
30% or 1 CR
65% or 1 CR
65% or 1 CR
20%
20%
20%
20%
25%
60%
60%
40%
40%
30%
40%
40%
60%
60%
40%
40%
40%
40%
40%
40%
40%
40%
85%
85%
40%
40%
60%
60%
60%
60%
60%
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Table 6 (conU. Measurement quality objectives for bioassavs and fish bfoaccumulation studies for the ARCS program.
Assay Organism/Community
Ames Assay (Salmonella)
Alkaline phosphatase
Dehydrogenase
0-Galactosidase
0-GlucosRJase
Benthic community structure
Raoid Bioassessment II. Ill
Endpoint*
Revertant Colonies
Enzyme Activity
Enzyme Activity
Enzyme Activity
Enzyme Activity
Abundance of species
Communftv Indices MO)
Response limit (mean)"
N/A
20%'
20%*
20%*
20%'
N/A
N/A
Reference Toxicant'
25%
25%
25%
25%
25%
N/A
N/A
Precision"
& Accuracy
N/A
80%
80%
80%
80%
N/A
80%
a - for bioassays in which survival is the primary endpoint, MQOs are only presented for the survival endpoint. The additional
endpoints, such as avoidance, uptake, development and molting frequency, will be recorded by the Pis.
b - the response limit is presented as the mean of the test replicates in the control or blank sample. For Certodaphnia dubia
and Daohnia maona the reproduction response limit is the cumulative total of 3 broods. N/A - not applicable.
c - CR - concentration range in the serial dilution assays. The percentages are the maximum %RSD of EC50 and LC50 values
allowed among the replicates.
d - precision values presented are the maximum %RSDs allowed among the replicate tests. Accuracy limits presented are the
maximum %RSDs compared through time for a given test.
e - background (non-biologically induced response) should by £ 20% of the control response.
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A value outside the control limits is considered unacceptable, hence, the instrument should be
recalibrated and the samples in that batch should be reanalyzed. If bias for a given analysis is
indicated, i.e., at least seven successive points occurring on one side of the cumulative mean,
sample analysis should cease until an explanation is found and the system is brought under control.
For several of the parameters to be measured in the ARCS program, reagent blanks are not
applicable due to the nature of the test. For the inorganic parameters of conductivity, DO, pH and
TSS, reagent blanks do not exist or are not applicable. Further, reagent blanks are not applicable
to the fish tumor and abnormality studies, the determination of benthic community structures, nor
community indices to be performed at the NFRC-GL and NFCRC laboratories. Finally, reagent blanks
are not applicable to whole sediment toxicity tests.
5.2.4 Reference Materials
Certified reference materials (CRMs) or standard reference materials (SRMs) will be analyzed
in the ARCS program to assess the accuracy of measurements being made at the analytical
laboratories. These materials are to be purchased by the laboratory from known supply houses
such as NIST and the USEPA If CRMs and SRMs are not available for a given parameter, the
laboratory will assess accuracy of the analysis using a standard of known concentration created
by the QA officer or QA staff of the analytical laboratory and/or through the use of the ongoing
calibration check sample (to be discussed) and/or matrix spike recoveries (to be discussed), where
appropriate. The reference materials will be used to control bias and reduce between-batch
components of measurement uncertainty. Data for these samples will be evaluated by batch to
ensure that the results are within acceptable accuracy limits as defined in this document (section
5.3) and the laboratory's submitted QAPjP. If the reference material does not meet the accuracy
window criteria, corrective actions should be taken. These corrective actions can include a
recalculation of the data, reanalysis of the samples, and/or reanalysis of the entire sample batch.
Notification of the laboratory QA officer should be done immediately upon identification of any
problem. It should be noted that reference material are not applicable to the fish tumor and
abnormality surveys.
For bioassays and bioaccumulation studies, two forms of reference materials will be used to
assess the "accuracy" of organism responses. The first will be to expose the organism to a
"reference toxicant" that will have a known and quantifiable response in the organism. The reference
toxicants are used to test the organisms sensitivity to waterborne contaminants. The reference
toxicants that will be used for these assays will include cadmium chloride, sodium chloride, or
copper sulfate for all bioassays and bioaccumulation studies excluding Microtox. Phenol will be
used as the reference toxicant during the Microtox testing. The reference toxicants will be used
to control bias and assess the within- and between-batch components of the measurement
uncertainty.
The second reference material for assessing the "accuracy" of the bioassay and
bioaccumulation studies is the use of a reference sediment. The reference sediment is a fine silt
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clay-sized mineral soil that has been used extensively in sediment toxicity testing (Adams et al.,
1985; ASTM, 1989). The reference sediment, also known as the Florissant soil, will expose the
organism to a similar matrix to that of the sediments but without the contaminants being present.
The acceptability of the toxicity tests will be assessed by the response (survival or growth) of the
control organisms to the reference sediment.
Control charts for the reference materials, with ± 2 and 3 a values (the 95 and 99 percent
confidence intervals) as warning and action limits, respectively, will be required to be created and
updated after each day of analysis to control any systematic bias that may be adding to the overall
measurement uncertainty for a given parameter. A value outside the control limits is considered
unacceptable, hence, the test result should be recalibrated and the samples in that batch may need
to be reanalyzed. If bias for a given analysis is indicated, i.e., at least seven successive points
occurring on one side of the cumulative mean, sample analysis should cease until an explanation
is found and the system is brought under control. For the bioassay and fish bioaccumulation tests,
control charts of the effective concentration (EC), lethal concentration (LC), no observable effect
level (NOEL) or lowest observable effect level (LOEL) values will be prepared.
5.2.5 Matrix Spikes and Matrix Spike Duplicates
Matrix spike samples will be used to assess the efficiency of the extraction technique and as
a form of accuracy testing. Matrix spike analyses are to be reported as the percent spike recovery
of the known quantity added to the sample for each analyzed parameter. Selection of the sample
to be spiked should be at random from the routine samples to be tested. The concentration of the
matrix spike samples must not exceed the linear range of the instrument. If necessary, dilution of
the spiked sample is permitted. The MQOs for the matrix spike are that the recoveries for inorganic
analyses, including TOC and DOC, must be ± 15% of the known added concentration. For organic
analyses, the matrix spike should have recoveries within ± 30% of the known added concentration.
Matrix spikes should be analyzed at a rate of 1 per batch. It should be noted that matrix spikes are
not applicable to analysis of sulfides, chlorides, alkalinity, hardness (if determined titrimetrically),
conductivity, DO, pH nor TSS. Further, matrix spikes are not required during bioassays, fish
bioaccumulation testing, nor for the water quality parameter determinations associated with these
assays.
For liquid samples, e.g., pore waters and elutriates, one matrix spike sample is to be prepared
for each analyte to be tested by spiking an aliquot of a solution with a known quantity of analyte
prior to analysis. The spike concentration should be approximately 1 to 1.5 times the expected
concentration of the sample. Further, the volume of the added spike should be negligible, i.e., less
than or equal to one percent of the sample aliquot volume.
For solid samples, e.g., sediments, one matrix spike will be prepared for each analyte by
adding a known weight of material containing the analyte of interest (i.e., for TOC) or a known
volume of the analyte with a known quantity of the analyte into the sediment prior to sample
extraction or digestion. The spike concentration should be approximately 1 to 1.5 times the expected
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concentration of the sample. If a solid phase spike is added, its weight should be considered
negligible for the purposes of quantifying the spike recovery.
A matrix spike duplicate will be prepared and analyzed for the treated solids obtained as a
result of the testing of remedial technologies by the E/T workgroup. The matrix spike duplicate will
be used to check the reproducibility of the remedial technology results and provide an additional
confirmation of the extraction technique efficiency. The matrix spike duplicate will be prepared only
for the organic contaminants, namely, the PCBs and PAHs, for which the remedial technology is
supposedly degrading and/or removing from the sediment. The matrix spike duplicate should be
prepared and analyzed on the same sample selected at random for the matrix spike, in the same
manner as the matrix spike, and at the same frequency as the matrix spike previously discussed
in this section. The acceptance limits for the matrix spike duplicate recoveries are the same as for
the matrix spike and the RPD between the matrix spike and matrix spike duplicate should be < 30%.
If the MQO criteria established for matrix spike recoveries or matrix spike duplicates are not
satisfied, corrective action should be implemented. These corrective actions can include a
recalculation of the data, recalculation of the percent recovery, respiking of the sample followed by
subsequent requantification, and/or reanalysis of the entire sample batch. Notification of the
laboratory QA officer should be done immediately upon identification of any problem.
5.2.6 Surrogate Spikes
Surrogate spike analyses are only applicable to the organic analyses of PCBs, pesticides,
PAHs, and dioxins/furans. A surrogate spike is defined as the addition of an organic compound
which is similar to analytes of interest in chemical composition, extraction, and chromatography, but
which are not normally found in the environmental sample (USEPA, 1986). These compounds are
spiked into all blanks, standards, samples, and spiked samples prior to extraction. Percent
recoveries are calculated for each surrogate compound.
The MQO for the surrogate spike analysis is that the surrogate spike recovery should be ± 30%
of the known added concentration. If the criteria established for surrogate spike recoveries are not
satisfied, corrective action should be implemented immediately. These corrective actions can include
a recalculation of the data, recalculation of the percent recovery, respiking of the sample followed
by subsequent requantification, and/or reanalysis of the entire sample batch. Notification of the
laboratory QA officer should be done immediately upon identification of any problem.
5.2.7 Ongoing Calibration Check Samples
The ongoing calibration check sample is analyzed to verify the calibration curve prior to, during,
and after any routine sample analyses. The concentration of the ongoing calibration check samples
should be about mid-calibration range for the given analyte. The MQO for the ongoing calibration
check samples is that the measured concentration should be ± 10% of the known concentration.
Ongoing calibration check samples should be run at a the beginning, middle, and end of each batch
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of inorganic analyses and at the beginning, every 12 samples, and the end for organic analyses.
Corrective actions if the ongoing calibration check samples does not meet its MQO can include a
recalculation of the data and recalibration of the instrument followed by the reanalysis of the sample
batch associated with the "bad" ongoing calibration check sample. Notification of the laboratory
QA officer should be done immediately upon identification of any problem.
Control charts for the ongoing calibration samples, with ± 2 and 3 a values as warning and
action limits, respectively, will be required to be created and updated after each day of analysis to
control any systematic bias that may be adding to the overall measurement uncertainty for a given
parameter. A value outside the control limits is considered unacceptable, hence, the instrument
should be recalibrated and the samples in that batch should be reanalyzed. If bias for a given
analysis is indicated, i.e., at least seven successive points occurring on one side of the cumulative
means, sample analysis should cease until an explanation is found and the system is brought under
control.
The ongoing calibration check sample is not applicable to the gravimetric analyses (such as
TSS, total solids, etc.). Ongoing calibration check samples are also not applicable to the bioassays,
fish bioaccumulation studies, or the water quality parameters to be examined in conjunction with
these assays, as well as for the fish tumor and abnormality surveys.
5.3 Description of Measurement Quality Objectives
The following text will describe the DQOs and MQOs as they apply to the sampling and
analytical phases of the ARCS program. Implementation'of the MQOs during the ARCS program
will be described in section 6.
The structure of the MQO table for the physical, inorganic, and organic analyses (Table 5) is
as follows:
Parameter - contaminant being analyzed,
Reporting units - analytical units in which the laboratory data should be reported,
MDL - method detection limit expressed in reporting units by media in which the sample
is to be analyzed,
Accuracy - limits of acceptance for CRM, SRM, and other standards and their required
frequency of use, and
Precision - limits of acceptance for analytical replicates and their required frequency of use.
The structure of the MQO table for the bioassays (including benthic community structure
determinations) and fish bioaccumulation studies (Table 6) is as follows:
Assay organism/community - test being performed,
Endpoint - result being measured or observed,
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Response limit - limits of acceptance for the mean of the replicate samples for the control
blanks,
Reference toxicant - limit of acceptance for organism response to known toxicant, and
Precision & Accuracy - limit of acceptance for among test replicates and organism
response limits to use of the reference sediment.
5.3.1 Field Sampling and Mapping
Sediment sampling includes the physical removal of sediment samples from the core tube,
grab sampler, bucket sampler, etc., as well as the characterization of the sediment and the sampling
site for the T/C and E/T workgroups. Members of the T/C workgroup will also be collecting fish
tissue samples for contaminant level determinations and whole fish for tumor and abnormality
classification and quantitation. Members of the RA/M workgroup will be involved in the collection
of water column and suspended sediment/particulates, CSOs, and fish samples to support their
modeling efforts. In addition to sample collection, the T/C workgroup will also be mapping sediment
depths and layering for each of the sampled AOCs. Since the MQOs developed for the laboratory
operations are not applicable to the sampling and mapping efforts, specific objectives for sediment
and water sampling have been developed to ensure that field operations, e.g., sampling, will be
conducted in a consistent manner. The objectives are intended to reduce the errors inherent in
collecting sediment data and to provide an estimate of the variability within the sediment.
The goals of the ARCS program sampling programs are to describe and collect sediment,
water column, CSO, and fish samples from representative sites. Multiple fish samples will be
collected and used to represent the typical population found in the sampled AOC. The field sampling
programs produce both qualitative data from sediment characterizations and mapping as well as
quantitative data from the analysis for the sediment samples, fish tissue, water, and river flow
conditions.
5.3.1.1 Precision and Accuracy
Due to the subjective nature of sediment characterization, values for precision and accuracy
cannot be determined. However, attempts to control precision and accuracy will be made by having
one person be responsible for performing all of the qualitative sediment characterization for the
ARCS program. An additional form of control and assessment of the sediment characterization will
be accomplished through the videotaping of each reconnaissance station sample and through
various auditing techniques for all stations discussed in a later section. Precise site locations will
also be determined using the LORAN-C coordinate system, the global positioning system, and
through triangulation observations in the event that a resampling of the site is necessary.
Precision and accuracy MQOs have not been established for the sediment mapping program
due to the experimental nature of the program. However, precision can be assessed for the profiling
results using readings taken from the tie points in the sampling pattern (see section 4.1.1.3 for more
detail). The tie points are those positions at the intersection of different profiling passes which
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result in the duplicate readings being taken at the same location. Accuracy will be assessed
through comparison between the results obtained from the electronic bottom profiling systems and
the results observed in core sample collected at the same locations.
Field sampling precision will be assessed for the reconnaissance stations using the data from
the field duplicate samples to estimate the system measurement uncertainty and comparing this
uncertainty to that identified in the analytical samples. The field samples are expected to contain
the largest amount of confounded error of the QC samples. The MQOs for precision of the chemical
and biological (Microtox assay) parameters associated with the indicator parameter field duplicate
should have an RPD of ^ 30%. These duplicate samples will be collected at a rate of one per day
per sampling trip. Duplicate samples will be collected for all major depositional horizons/layers
identified in the replicate core sample by the field crew. It should be noted that the MQOs
established for field sampling are not intended to control field sampling error but are used to assess
this error component and to control within-laboratory error occurring at the analytical laboratory.
5.3.1.2 Representativeness
For the collection of master stations for the T/C workgroup, samples were collected in bulk
at locations determined at the consensus of the workgroup. Selection of the sampling sites was
based on historical sediment contaminant concentrations, input from local authorities on known
contaminant discharges and sources, and a desire to provide some degree of complete geographic
coverage of the entire AOC. Further, sampling sites were selected in each AOC that represent a
gradient of contaminant concentrations, ranging from stations considered to be relatively
uncontaminated to known "hot spots" of high pollutant content, thereby, representing all sediment
condition scenarios present within the given AOC. During the actual sample collection of the
surficial sediments, the boat will be moved periodically to ensure that only surficial sediments are
being collected.
During the collection of the reconnaissance stations for the T/C workgroup, sampling locations
will be collected throughout the entire designated AOC with a concentrated effort being made at a
known "hot spot". Samples and bottom profiles will be collected to give the best possible
geographic coverage of the AOC. The intensive sampling of the "hot spot" will provide detailed
information on the contaminant levels and distribution. Additional samples will also be collected at
the ten initial master sites so that correlations can be made between the detailed analyses to be
performed on the master stations and the indicator parameter analyses that will be performed on
the reconnaissance stations.
The basic premise in the collection of samples for the RA/M workgroup during the mini-mass
balance/synoptic surveys is to collect information about the river system during several periods of
low flow (or quasi-steady state) conditions as well as during at least one high flow event (after a
major storm system has passed through the AOC or during the spring snow melt). These events
will, hopefully, represent conditions commonly found in the river system.
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Representativeness is not a major concern for the field sampling efforts of the E/T workgroup.
The primary goal for the E/T workgroup sampling is to collect a bulk sample that is grossly
contaminated with a given class or classes of contaminants. The collected samples will, hopefully,
contain several representative contamination scenarios that have been identified in the Great Lakes
basin.
Both the qualitative and quantitative data collected are intended to be representative of the
sediments, fish, or water conditions at each AOC.
5.3.1.3 Completeness
The completeness objective for field sampling is set at 90% for the T/C and RA/M workgroups.
Hopefully, 100 percent of the stations/sites can be sampled but inclement weather conditions are
expected to hinder or limit (in the case of ice) the sampling program. A completeness of 100% is
expected for the E/T workgroup sampling effort.
5.3.1.4 Comparability
Comparability for field sampling will be maintained by having one laboratory (LLRS) collect all
the samples (master and reconnaissance station) for the T/C workgroup using USEPA approved
methods. Bottom sediment mapping efforts will maintain comparability by having only a single
laboratory perform all the profiling for the whole ARCS program. Within the RA/M workgroup,
sample collection will also be performed using USEPA approved equipment and methods that are
similar, if not identical, between the two AOCs to be characterized, thereby maintaining comparability
of the sampling techniques. E/T workgroup sample collection will follow standard USACE dredging
practices or practices being utilized at the Sheboygan Harbor or Ashtabula River Superfund sites.
For the three ARCS program primary AOCs, the collected bulk sample will be homogenized and
distributed to all participating laboratories from ERL-D.
5.3.2 Laboratory Analysis
The analysis phase of the ARCS program measurements allows the most quantitative
evaluation of data quality. The following sections will discuss the five basic quality assurance
objectives as well as detectability.
5.3.2.1 Detectability
The data users have determined specific levels of instrument detection for the parameters
being analyzed. The MDLs for these instrument determined parameters and their appropriate
reporting units are listed in Table 5. The MDLs listed in Table 5 are broken down by the media in
which the analysis is going to be performed. These media include sediment, fish tissue, elutriates,
and water (which includes pore water and water column samples). It should be noted that not all
parameters are to be analyzed in all media. MDLs are only presented for those medium in which
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analyses are to occur and are known at this time. Method detection limits for the ARCS program
are defined as 3 times the standard deviation of the measured concentration of 15 or more blanks
or low-level standards whose concentrations are within a factor of 10 of the ARCS required IDL.
MDLs should be determined prior to any analysis of routine samples and should be determined for
each instrument used for the element(s) or compound(s) quantification.
It should be noted that for the detection limits of organic contaminants associated with the
mini-mass balance/synoptic surveys performed by the RA/M workgroup, that the MDLs may have
to be lowered in order to obtain 90% or more of the samples having detectable contaminant levels.
A lesser number of samples with quantifiable contaminant concentrations could severely restrict the
modelers efforts.
5.3.2.2 Precision and Accuracy
The MQOs for precision and accuracy of the physical, inorganic, and organic analyses are
provided in Table 5. Accuracy will be assessed through the use of CRMs, SRMs, or other standards
and are generally defined as a known value ± an acceptance range. Precision is assessed through
the use of replicate samples and generally determining the %RSD or RPD, whichever is appropriate,
among the replicates. Exceptions to these generalizations are presented in the tables. It should
be noted that precision of the water quality parameters used in conjunction with bioassays and fish
bioaccumulation studies is the only quality assurance objective required in the ARCS program,
excluding the need for proper initial calibration of the instrument, probe, titrator, etc.
The MQOs for precision and accuracy for the bioassays and fish bioaccumulation studies are
presented in Table 6. Accuracy will be assessed through the use of the reference sediment,
reference toxicant, and long-term monitoring of the coefficients of variance among reference toxicant
use for a given bioassay. Precision will be measured by determining the %RSD among the replicates
performed for each of the tests.
5.3.2.3 Representativeness
The integrity of the sediment, water, fish tissue, and elutriate samples is to be maintained
during sample analysis activities. Homogenization of the samples prior to shipment to the analytical
laboratories as well as a second homogenization of the received sample at the laboratory will help
ensure that a uniform stock of sample is available from which aliquot selection for analysis can be
made. Homogenization of bulk samples will be performed in cement mixers for a fixed amount of
time with homogeneity being determined visually by obtaining a sample with consistent color,
texture, and water content throughout the entire sample. At the analytical laboratory, the sample
homogenization will be performed via stirring, by hand or mechanically, until visual homogeneity in
terms of color, texture, and water content are obtained. Once the sample is deemed to be
homogeneous at the analytical laboratory, aliquots will be taken of solid phase samples randomly
by the insertion of the sampler (spatula, spoon, knife, etc.) and collecting the sample.
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5.3.2.4 Completeness
The completeness objective for all inorganic and organic parameters analyzed is set at 90
percent or better. The completeness objective for the bioassay and fish bioaccumulation studies
is set at 80 percent or better. It is possible to attain 100 percent completeness if a sufficient
quantity cf each sample is available to complete all analyses and reanalyses that may be necessary.
Completeness for the fish tumor and abnormality studies is set at 100 percent determination and
quantification of the fish collected from the field.
5.3.2.5 Comparability
Analytical data from the ARCS program is expected to be comparable among the laboratories
involved through the use of standardized, documented, accepted USEPA methods or their equivalents
and through the use of common reporting units. Comparability of the analytical results will also be
assessed through the replication of some analytical procedures and bioassays on the "same"
sediment sample by different analytical laboratories.
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Section 6
Quality Assurance Implementation
6.1 Control of Data Quality
The following subsections describe the methods used to control the quality of data produced
during the various data collection phases and to ensure that the MQOs described in section 5 are
being met.
6.1.1 Field Sampling and Characterization
Control of data quality in the sampling phase of the ARCS program is primarily a responsibility
of the various sampling crews. A field audit (to be discussed in section 6.1.3.3.1) will be performed
by the EMSL-LV and LESAT QA staff to help control the quality of the field sampling and
characterization program. The following sections will discuss the QA implementation for the field
sampling program as they relate to the quality assurance objectives.
ft /. /. / Precision and Accuracy
In order to ensure the precision of the field sampling and characterization program for the
reconnaissance stations, duplicate core samples will be collected and described during each
sampling day in each AOC. If marked differences are noted, both cores should be discarded, two
new cores should be obtained after slightly moving the boat so that the recoring will not be from
the exact same location. A field audit (to be discussed in section 6.1.3.3.1) will also be performed
by the EMSL-LV and LESAT QA staff to help control the accuracy and precision of the field sampling
and characterization program.
For the RA/M workgroup sampling program, in association with the mini-mass
balance/synoptic surveys, a series of "dry" sampling runs will be performed by the sampling crews
prior to collection of ARCS program samples to ensure the working conditions of the collection
equipment as well as to familiarize the samplers with the proper operation of the equipment and
the needs of the ARCS program. Duplicate samples of the river water, particulate, and CSOs will
be collected in the field at a rate of one duplicate per sampling day per AOC during the synoptic
surveys to help assess the imprecision error component. Further, a field audit will be performed by
the EMSL-LV and LESAT QA staff to ensure that the sampling protocols and QC program is being
followed as stated in the laboratory submitted QAPj'Ps.
6.1.1.2 Representativeness
Representativeness of the field sampling and characterization program will be maintained by
the collection of samples throughout the entire AOC for the T/C and RA/M workgroups and at the
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locations identified by the workgroup members during their initial meetings. During the sampling
program, sediments with a wide range in characteristics and contaminant levels will be collected
to represent several different contamination scenarios in the Great Lakes basin. For the E/T
workgroup, representativeness of the sediments in the AOC is not a major concern in their field
sampling program (see section 4.1.3 for more detail). The E/T workgroup sampling crew is only
responsible for the collection of bulk samples that have been grossly contaminated (i.e., high
contaminant concentrations).
6.1.1.3 Completeness
Sampling protocols specify that the sampling of 90 percent or more of the designated master
stations. Reconnaissance station surveys will collect as many samples as is permitted financially
per AOC (approximately 200 samples or 60 cores). If a sampling site is inaccessible, the reason
for excluding the site must be formally documented by the sampling crew and reported to the
workgroup chair, workgroup members, and GLNPO.
6.1.1.4 Comparability
The consistent use of standardized sampling methods and specified protocols for the
sampling phase provides field data that are comparable to data collected at all AOCs for all three
workgroups. Comparability is further maintained by using a single laboratory to collect all master
and reconnaissance stations for the T/C workgroup.
6.1.2 Laboratory Analysis
Laboratories participating in the analysis of samples in the ARCS program were selected
primarily on the laboratory's capacity to provide the services required and ability to produce data
of known and high quality (i.e., their expertise in the given areas of analysis). At the request of the
workgroup chair or GLNPO staff, pre-award audit samples will be created by EMSL-LV and LESAT
to provide an examination of the analytical capabilities of a given laboratory. The results of these
analyses will be rated according to the pre-award audit scoring evaluation sheets provided in
Appendix A. Further discussion of the pre-award audit program is presented in section 6.1.3.
6.1.2.1 Detectability
The analytical laboratories will be required to make repeated determinations of the IDLs prior
to sample analysis. The IDLs serve as an estimate of the lowest concentration of an analyte that
an instrument can reliably detect. In addition, the laboratories must satisfy the MDLs, outlined
previously in Table 5 for physical, inorganic, and organic analyses, in which the acceptance criteria
is that the MDLs > IDLs. The laboratories are also required to demonstrate with control charts that
the analytical system is under control at all times during analysis. If deficiencies are identified, the
laboratory QA officer should be notified immediately and prepare a written report to be submitted
to the ARCS QA officer, workgroup chair, and GLNPO staff stating the reasons for the failure to
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meet the criteria and proposing a new MDL that can be obtained at the laboratory for ARCS QA
approval.
6.1.2.2 Precision and Accuracy
Upon the satisfactory completion of the QA requirements by the analytical laboratory, a data
package for each AOC is submitted to the ARCS QA officer and GLNPO database manager for
evaluation. The data are evaluated and then validated in accordance with the precision and
accuracy MQOs for the various QC samples. Precision for each type of assessment sample must
meet the objectives outlined previously in the MQO tables of section 5. Reanalysis may be
requested for certain parameters or batches on the basis of imprecise or inaccurate results from
the assessment samples, if sample holding times have not been exceeded.
6.1.2.3 Representativeness
Upon receipt of each analytical sample from either the field or laboratory responsible for the
homogenization and distribution of the collected bulk samples, the PI or sample custodian is
required to re-homogenize the sample, where appropriate, to ensure the representativeness of
aliquots used during the analyses. All samples not in use are to be stored at 4 ± 2° C or frozen at -
20 ± 5° C, whichever is appropriate for the given sample type, in the dark at the analytical
laboratory. Temperatures should be monitored daily and recorded in a bound logbook. If the
temperature limits are exceeded, documented corrective actions should be taken to maintain the
integrity of the stored samples. Notification of the laboratory QA officer should be done immediately
upon identification of any problem.
6.1.2.4 Completeness
The completeness objectives for the physical and chemistry analyses has been set at 90
percent while a completeness of 80 percent is acceptable for the bioassay and fish bioaccumulation
studies for the ARCS program. A level of 100 percent completeness may be obtained if sufficient
sample is available to complete all routine analyses and reanalyses, where necessary.
Completeness for the fish tumor and abnormality surveys has been set at 100% for both qualitative
and quantitative analyses of the fish collected from the field investigations.
6.1.2.5 Comparability
Comparability will be maintained through the use of standard documented USEPA
methodologies for parameter determinations. If a USEPA method is not available, the method
selected should be clearly documented by reference, preferably, with some other form of standard
methodologies such as ASTM or by providing a written SOP in the submitted QAPjP. Non-USEPA
methods should meet with approval from the ARCS QA officer prior to use in the ARCS program.
The QA/QC procedures specified for the analytical laboratories allow for the determination of
measurement uncertainty so that the results can be compared among laboratories directly through
the replication of some test procedures on the "same" samples by different laboratories or indirectly
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through the overall assessment of laboratory performance on a given QC sample type (i.e.. reagent
blank, replicates, etc.) on a parameter and project basis.
6.1.3 ARCS Audit Program
The ARCS audit program can be divided into three primary sections, namely, the production
and grading of audit samples, the conducting of performance audits, and the performance of on-site
system audits. Each of these portions of the audit program will be discussed in the following
sections.
6.1.3.1 Audit Samples
Upon the request of the GLNPO staff, workgroup chairs, or the laboratories, audit samples
containing the analytes of interest will be prepared by the QA staff at EMSL-LV and LESAT. Audit
samples will be prepared and analyzed in the same manner as routine samples with the appropriate
QA/QC measures being applied as specified in this document and the individual laboratory QAPjPs.
Results from the analyses will be graded with an 80 percent representing the minimum passing
grade. Audit sample scoring evaluation sheets will be provided in Appendix A. The audit sample
scoring evaluation system will be designed to be flexible such that when multiple media and/or
mixed chemistry classes (i.e., inorganic and organic) are to be performed, no single medium or
chemistry class will dominate the grading scheme. For example, if a laboratory is performing metals
analyses in water samples as well as PCBs, PAHs, and pesticides quantification in both sediment
and water columns, each class of compounds or medium will be equally weighted in the developed
grading scheme.
Audit sample types can be divided into two categories, namely, pre-award and routine audit
samples. Pre-award audit samples will be used to assess a laboratory's capability to perform the
analyses it will be running on the routine samples. Pre-award audit samples may be either single
analyte (i.e., conductivity) or analyte group (i.e., PCBs) or may be composite samples containing
several classes of compound (i.e., a mixture of PCBs, pesticides, and PAHs in one ampule). Single
analyte or analyte group samples will be used to test quantification efficiency while the composite
audit samples will check extraction/cleanup efficiencies in addition to the quantification capabilities
of the laboratory.
Routine audit samples are similar to the pre-award audit sample but will only be prepared as
composited samples, where appropriate. Routine audit samples will undergo extraction, cleanup,
and quantification during the analysis of routine sample batches. Grading of the routine audit
samples will be based solely upon the accuracy of the results following the criteria established for
reference materials in section 5.2.4.
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6.1.3.2 Performance Audits
Performance audits for the ARCS program should involve the inspection of the facilities,
discussion of methodologies to be used and QA/QC limits that are applicable with the laboratory
technician, and preliminary data review to assess the success/failure of the laboratory's QA
program. These audits should be performed by the laboratory QA officer or designee. Upon
completion of the audit, a written report should be prepared, maintained- on file, and submitted to
GLNPO, the workgroup chair, and ARCS QA officer. The report should identify any deficiencies
noted, the corrective actions undertaken, and the results of the reanalysis, if conducted.
Performance audits should be conducted a minimum of once during the ARCS program preferably
at the beginning or near the beginning of the analyses so that any problems can be controlled and
corrected early in the program.
A series of performance audits will be performed by GLNPO personnel to ensure the proper
functioning of the ARCS QA and database management programs established at EMSL-LV and
LESAT. These audits will check the progress of the initial establishment QA program, provide
overviews of the operational, established ARCS QA program, provide reviews and status of the
ARCS program from the QA point of view (i.e., audit sample results, QAPjP preparation, quality of
submitted data, etc.), as well as examine and review the QA/QC validation procedures for the
submitted databases (to be discussed in section 6) at LESAT. These audits will be performed
annually or more frequently as deemed necessary by the GLNPO staff or members of the AIC.'
6.1.3.3 System Audits
A major factor in controlling data quality is the independent on-site system audit, which
ensures that all of the program participants are adhering to the protocols in a consistent manner.
The system audit team will ideally consist of three external scientists, two from the QA staff at
EMSL-LV and LESAT and one from the GLNPO. Members of the audit teams will be selected to
provide the expertise in the given subject area (i.e., for the major analyses to be performed at the
laboratory) and in the field of QA. The on-site field and laboratory audits will be described in the
following text.
6.1.3.3.1 Field System Audits
At least one field system audit will be scheduled for the sampling of the reconnaissance
stations to be conducted by the LLRS laboratory for the T/C workgroup and during the collection of
samples for the mini-mass balance/synoptic survey conducted by the RA/M workgroup. The audit
team will observe the coring procedures, data recording, bottom profiling, and location determination
as well as sample collection, handling, preservation, and storage techniques for several days within
a selected AOC. Informal checks on the characterization of the cores will be made on sediment
characteristics such as texture, layer thickness and boundary determinations, color, and odor. These
checks will be performed by the audit team and compared to the results obtained from the sampling
crew. If discrepancies are noted, discussions will be held immediately to resolve the problem while
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the core is still intact. Upon completion of each sampling day, the audit team will discuss any
deficiencies that might influence the integrity of the samples with the sampling crew. A final oral
summary of the findings and concerns of the audit team will be presented upon completion of the
audit with a subsequent written report being submitted to GLNPO, the laboratory, and workgroup
chair. Unfortunately due to the relative lateness of the establishment of the formal ARCS QA
program, no field system audits will be performed during master station sampling by LLRS for the
T/C workgroup nor during the collection of the bulk samples by the USAGE for the E/T workgroup.
6.1.3.3.2 Laboratory System Audits
Each analytical laboratory generating data for the ARCS program can expect at least one on-
site system audit. The audits will generally consist of a laboratory tour, data review, and
discussions about the concerns identified by the audit team during both the laboratory tour and
during data review. During the laboratory tour, the following general elements will be examined or
performed:
analytical instrumentation,
discussions with laboratory technicians to ensure their working knowledge of the program,
organism culturing facilities and test areas,
sample preparation and storage areas,
sample tracking and documentation, and
SOPs and logbooks.
These audits will preferably performed approximately one-third of the way through the sample
analyses. An evaluation report will be prepared for the audit and submitted to GLNPO with copies
being sent to the laboratory and appropriate workgroup chair or chairs (if work is to be performed
for multiple workgroups). The laboratory may respond to the audit report in a written manner and/or
may request an additional audit to show that all the deficiencies have been eliminated. No system
audits will be scheduled for laboratories that produce single or limited (< 5 parameters)
measurement data.
6.2 Data Validation/Verification
The intent of this section is to give a brief overview of the various mechanisms that may be
used in defining and implementing the data validation/verification procedures and the corrective
actions that may be taken if the MQOs are not satisfied.
6.2.1 Data Validation
Data validation for the ARCS program will be those analyses or checks that are performed by
EMSL-LV and LESAT QA staff on the submitted data to assess the degree of success that a
laboratory obtained in meeting the MQOs specified for their project. Data validation will be
performed on both the field sampling and characterization data as well as the analytical laboratory
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data. Each of these two data types and their validation procedures will be discussed in the
following sections.
6.2.1.1 Field Sampling and Characterization Data
Validation of the field sampling and characterization data will be the primary responsibility of
the field sampling crews. Field data submitted to EMSL-LV and LESAT should include, at a
minimum, the following items:
sampling dates,
site location (latitude and longitude),
sample identification codes/numbers (see section 4.1.1),
sample preparation, labeling, and shipping,
number and type of samples collected including field duplicates, trip blanks, etc.,
sample preservation and storage conditions,
chain-of-custody/shipping forms, and
a listing, with explanation, of any departures or problems encountered during sampling that
deviate from the written and approved sampling QAPjP.
Data generated for specific analytical parameters in the field, such as pH, dissolved oxygen, light
transmissivity, temperature, etc., will undergo the same procedures for data validation as analytical
laboratory-generated data that are presented in the next section - section 6.2.1.2.
At EMSL-LV and LESAT, who will act as an intermediate database repository, field data will
be examined for consistency, relative accuracy, and completeness of the submitted data and
completeness (as defined for the data quality objectives) for the ARCS sampling program. For this
discussion, consistency will be defined as the use of the same descriptive terms, reporting units,
and station coordinates (i.e., latitude and longitude) throughout the field database. Relative
accuracy will be defined as consistency within the reported measurements. For example, the
latitudes and longitudes of all sampling sites within a given AOC will be checked to ensure that they
are within several minutes of each other and not several degrees. Additional checks on the
completeness of the data will be performed by the ODES database management system (to be
discussed in section 9) which has been selected as the final database repository. If deficiencies
exist in the field data, the laboratories will be contacted and expected to provide the missing or
erroneous data.
6.2.1.2 Analytical Laboratory Data
Validation of the analytical laboratory data will be one of the primary responsibilities of the
QA staff at EMSL-LV and LESAT. All data will be reviewed for the following items:
completeness of the submitted dataset in terms of missing data,
completeness of the submitted data in terms of the completeness quality assurance
objective,
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formal submission of the data as indicated by signatures of the PI and laboratory QA
officer,
logbooks, in particular to determine holding time violations,
raw data including sample weights, extract volumes, dilution or concentration factors,
instrument readings (e.g., chromatograms, quantification reports, etc.), and dates of
analysis, where appropriate,
proper frequency of use and successful completion of the established MQOs for QC
samples including spikes, replicates, blanks, accuracy standards, reference toxicants, and
reference sediments on a dated per batch basis,
MDLs and their determinative data and dates of determination,
calibration data on a per instrument per analyte basis with associated calibration plot and
successful completion of acceptance criterion,
QA reports of in-house performance audits and other reports as mandated in the
submitted QAPjPs, and
a discrepancy report indicating at what point during the laboratory operations the formal
ARCS QA program was initiated and providing a discussion of the QA program at the
laboratory prior to the institution of the ARCS overall QA program.
Data validation will be determined manually by members of the QA staff. If time permits and
dependent upon similarity of submitted datasets and QA/QC requirements, a computerized checking
system will be developed.
If deficiencies are identified, a data flagging system will be developed at EMSL-LV and LESAT.
The data validation flagging system will clearly indicate the type of deficiency (i.e., failure to meet
MQOs of QC samples, sample collection problems, etc.), the degree of the deficiency (high or low),
and identify miscellaneous problems, such as missing data values. Further, data comparisons will
be made among the laboratories that have analyzed the same sediment sample for the parameters.
Discrepancy flags for inter-laboratory comparisons will also be developed and applied to the
appropriate datasets. A final QA summary for the entire dataset on a per laboratory basis will be
created by the ARCS QA officer for incorporation into the final ODES database. The final QA report
to be submitted to GLNPO by EMSL-LV and LESAT will contain a complete accounting of all QA/QC
violations in the ARCS program.
6.2.2 Data Verification
Data verification will be performed by the ODES system. ODES is designed to perform checks
on the appropriateness of submitted data ranges, formats, and codings prior to the uploading of
the data into the final repository. If discrepancies are identified, the EMSL-LV and LESAT QA staff
will take steps to correct the problem(s) which may include data checking, data entry, or contacting
the appropriate laboratory for the missing information. A more complete discussion of the data
verification process is presented in section 9.
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Section 7
Data Quality Assessment and Reporting
This QAMP has defined the MQOs (see section 5) and described the implementation of the
QA program for the ARCS program (see section 6). This section describes the statistical
assessment procedures that will be applied to the data and the general assessment of the data
quality accomplishments. QA reports to management will also be discussed.
7.1 Statistical Design
7.1.1 Assessment of Detectability
The assessment of detection limits is accomplished on a parameter basis at two different
levels, namely, compliance with ARCS specified MDLs and calculation of actual IDLs. The final
results will be grouped in tabular form to allow comparisons among the values for any parameter
of interest.
7.1.2 Assessment of Precision
A statistical evaluation procedure that has been applied to other USEPA funded large scale
programs will be applied to the data in order to assess possible uncertainty stemming from
confounded data collection imprecision. An additive model will be used, where an observed value
of any characteristic is considered as the sum of the "true" or accepted value plus an error term.
This model assumes that data uncertainty is directly related to the error variance (Miah and Moore,
1988).
The error variance is dependent upon the "true" value of the sediment characteristics of
interest. Because of the wide range of analyte concentrations for the sediments, it is necessary to
separate the concentration range into segments of error variance that serve as estimates of data
measurement uncertainty. The ARCS program statistical approach, therefore, requires that the entire
analytical concentration range be partitioned into several intervals not necessarily of equal length.
An assumption is made that the error variance within each interval is independent of, and changes
with, "true" analyte concentration.
Within this framework, the error variance is represented by a step function (Rudin, 1974) where
each step value is the error variance for a specific defined interval. A pooled estimate of the error
variance is obtained by taking a weighted average of the individual step values, using the
corresponding degrees of freedom as the weighting characteristic.
A fundamental difficulty of this approach is assessing the effect of the error variances on the
routine sample data. A measure of this effect, delta, is estimated by averaging the step values of
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the error standard deviation using the proportion of routine samples in each interval as the
weighting characteristic. Since data collection is a multi-phase process and uncertainty accumulates
in the data with each progressive phase, the cumulative uncertainty is estimated with the delta
values using the QC data.
7.1.3 Assessment of Accuracy
The assessment of accuracy will be based on the ongoing calibration check samples and the
use of CRMs, SRMs, or standards for the inorganic and organic analyses while for the bioassays
and fish bioaccumulation studies, the assessment of accuracy will rely upon the use of reference
toxicants and the reference sediment. The recoveries of matrix and surrogate spikes for the
inorganic and organic analyses can also be used in the assessment of accuracy although the error
component involved in these samples is confounded by the interactions of the matrix with the spiked
element or compound and hence, the extraction efficiency of the analytical methodology. Accuracy
for most parameters in the ARCS program is based upon the known concentration of the material
plus or minus an acceptance range around that known value.
7.1.4 Assessment of Representativeness
The sampling aspect of representativeness is assessed by comparing the individual site
locations and AOC coverage with the locations and expected coverage DQOs.
Representativeness of the measurement quality samples is assessed by comparing the
concentration ranges of data from the field duplicates, where collected, to the overall concentration
range of the routine sample data. This is accomplished through the application of critical values
determined by the Kolmogorov-Smirnov test (Conover, 1980) which assesses the ability of the
duplicate samples to track the distribution of the routine sample concentrations.
Representativeness of the homogenization and subsampling procedures at the analytical
laboratories may be assessed using precision estimates for the analytical replicate samples.
7.1.5 Assessment of Completeness
Field sampling completeness is assessed by comparing the actual number of stations
collected to the number requested during the design phase of the ARCS program. Completeness
of the sample preparation and analytical phases are easily calculated using data from the verified
database by calculating the number of analyses passing the QA requirements divided by the number
of analyses performed at a given laboratory.
7.1.6 Assessment of Comparability
Comparability is perhaps the most difficult of the data quality attributes to assess, primarily
because of the many different aspects of comparison that are involved. Following completion of
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the ARCS program, a comparison will be made among the laboratories that will focus on method
differences, QC sample results, laboratory effects, and other QA features of the program. Summary
statistics will be used to collate individual values into pooled groups that enable the data users to
discern trends of interest within the overall ARCS program.
7.2 Quality Assurance Reports to Management
The Pis or QA staffs at each participating laboratory are required to produce at least one
written report to document their ARCS program QA activities as well as several oral laboratory
updates at the all-hands meetings to be planned throughout the duration of the ARCS program. The
general contents of these reports are presented in the following sections.
7.2.1 Status Reporting
Communications among the various participants in the ARCS program should be maintained
through conference calls, site visits, release of preliminary draft data, and all-hands and workgroup
meetings. These activities provide all participants with the current status of operations and allow
prompt discussion and resolution of issues related to the research plan, methodologies, or QA
implementation.
7.2.2 Formal Reporting
In addition to the laboratory submitted QAPjPs, the Pis and laboratory QA officers will be
required to produce a final written summary of the QA activities and results from their laboratory.
This report should accompany the submission of the laboratory QA approved dataset. Other
periodic QA reports will be submitted to the ARCS QA officer, workgroup chairs, and GLNPO staff
as specified in the laboratory's QAPjP.
In addition to this QAMP, the QA staff at EMSL-LV and LESAT will produce a final QA report
which will summarize all aspects of the overall ARCS QA program as related to the entries in the
final database. The QA staff will also produce a documented sample/data tracking system such
that hardcopy and electronic forms of the database can be easily located, identified, and collated
for use and distribution by the staff at GLNPO.
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Section 8
Quality Assurance/Quality Control of Historical Databases
8.1 Objectives
In order to assess the environmental impacts resulting from the implementation of remedial
alternatives, the RA/M workgroup will perform hazard evaluations of exposures to, and impacts
resulting from, contact with contaminated sediments and media containing sediment contaminants
incurred by all receptors of concern under the "no action" and other remedial alternatives. The
hazard evaluation objectives will draw upon the development and integration of predictive tools to
describe future hazards and risks. The development and validation of the hazard evaluation models
will proceed in two phases. Phase I will focus on developing modeling tools using existing historic
information while Phase II will validate and calibrate approaches developed in Phase I using current
synoptic information about the areas obtained during the intensive mini-mass balance studies.
To accomplish Phase I modeling goals, historical datasets will be collected from published
reports and utilized in the model development process. One concern that has been expressed by
the RA/M workgroup is that the "quality of the chemistry data to be used in the model construction
is unknown. Therefore, a QA/QC evaluation scale for the historical data will be developed by EMSL-
LV and LESAT.
The following section will address how the QA/QC evaluation scale will be developed and its
intended use in the assessment of the historical data. It should be noted that evaluation scales
will only be produced for inorganic and organic chemistry analyses. No evaluation scales will be
developed for bioassays, fish bioaccumulation studies, benthic community structures, or fish tumor
and abnormality studies.
8.2 Evaluation Scale
The initial phase in the creation of the QA/QC evaluation scale will be to perform an extensive
literature search to determine all the possible forms of QA/QC samples that might be applied to
inorganic and organic chemistry analyses. Upon completion of the literature search, a second list
will be generated for those additional QA/QC practices, not identified through the use of QA/QC
samples, that can influence or be used to check the quality of the data. This list will include items
such as frequency of QA/QC sample use, exceeded sample holding times, and instrument calibration
problems.
The various components will be placed into five general categories, namely, accuracy,
precision, spike recovery, blanks, and miscellaneous. These five areas encompass the major areas
of concern in a good quality assurance program. Each of the components will then receive a
ranking as to its perceived importance in the assurance of high quality data. As a general rule,
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higher or maximum values will be assigned to the components of the QA/QC evaluation scale that
are essential in a good QA/QC program. Lesser values will be credited to various additional
samples that may have been used in the QA/QC design of a given laboratory to assess different
system error components.
Contaminants will be grouped into broad categories that cover similar types of elements or
compounds. These categories will include: acid volatile sulfides, metals, organometals, polynuclear
aromatic hydrocarbons, polychlorinated biphenyls, chlorinated pesticides, chlorinated benzenes,
chlorinated naphthalenes, chlorinated dioxins and furan congeners, volatile chlorinated compounds,
and miscellaneous analyses (such as particle-size analysis and total organic carbon content). A
further subdivision of these broad categories will be performed by analytical matrix (e.g., fish tissue,
water column, elutriate, sediment, etc.). Additional or different categories may be used depending
upon the grouping of the contaminants in the received datasets.
Upon completion of the assignment of the individual variable values, an acceptance level will
be determined for each of the five general categories. The acceptance levels will have a two-fold
purpose, namely, (1) to provide a basis for determining the acceptability of the overall dataset or
parameter group (such as metals, acid volatile sulfides, etc.), and (2) to provide the data user with
the potential to evaluate the dataset further if qualifying flags (to be discussed) are present.
Evaluations of the datasets will be presented to the RA/M workgroup members as the point
sum by analyte groupings plus any qualifying flags that might be appropriate. Qualifying flags will
be associated with each of the point sums. The flags will be used to indicate some form of
deficiency in the dataset such as a failure to meet the project's MQOs for the analyzed QA/QC
samples, holding time violations, major methodology differences between that of the ARCS program
and that used during the actual sample analyses, or any other factor that could adversely affect the
quality of the generated data. Further, the flags will indicate the direction of the deficiency identified
in the dataset (i.e., above or below the established MQOs of the original project).
It is intended that the final evaluations will not preclude the use of any data in question in the
development of the model. Any and all data may be used at the discretion of the data user. These
ratings will be simple indicators to inform the data user of the quality of data that is being
incorporated into their model's development.
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Section 9
Data Management System
9.1 Ocean Data Evaluation System (ODES)
The Ocean Data Evaluation System (ODES) is a mainframe computerized system that is in
production at NCC on the IBM 3090 system. ODES was designed to support the decision making
processes associated with marine/water monitoring programs. Since ODES was originally designed
for saltwater systems, some modification of data fields will need to be made to adapt the system
for the fresh water environment analyzed in the ARCS program.
ODES is comprised of three separate components: the ODES database, ODES reporting and
graphical tools, and ODES menu system. Through the ODES menu system a user may access
information stored in the ODES database and use the ODES tools to produce analytical reports.
The ODES database will combine source input information with river, harbor, and bay environmental
information including biological data, sediment pollutant data, and water quality as well as
physical/chemical and oceanographic data.
At this time, ODES can accommodate many different kinds of environmental data. These
categories that are appropriate for the ARCS program including the following:
Benthic infauna,
Bioaccumulation,
Fish pathology,
Water quality,
Sediment grain size,
Sediment pollutants, and
Bioassays.
During the data review process at LESAT, any missing data file types will be reported to GLNPO.
The GLNPO database manager will then make contact with Tetra Tech, Inc., of Bellevue, Washington
or American Management Systems, Inc. of Arlington, Virginia, for the creation of new modules or
modification of existing modules to allow for .the entry of all ARCS data into the final ODES-based
data repository.
9.2 Overview of the Databases
There are two types of data collected for the ARCS project, the field sampling data and the
analytical laboratory data which includes the QA/QC data. Each type of data has its own
requirements and components which will be discussed in the following sections.
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9.2.1 Field Sampling Data
The field sampling data is information about the sample and sampling area. Data concerning
the sampling area would include the river/bay/harbor sampled, type of station (master or
reconnaissance), latitude and longitude of each site, map location and identifiers, meteorological
conditions, river stage, flow velocity, and flow direction. Data concerning the sample would contain
the following information: sampling equipment used, sample weight/volume collected, sample
number, type of sample (sediment, water column, particulate, CSO, etc.), depositional horizon/layer
characteristics, such color, texture, and odor, as well as the time and date of collection, agency, and
sampling crew identification.
9.2.2 Analytical Laboratory Data
The analytical laboratory data is the physical, chemical, and biological analyses performed on
the samples. Data will generally include the type of test, parameter to be analyzed, routine
analytical results on each sample, QC results, and calibration information, where appropriate. Data
for a particular sample will include the following: sample number, extraction procedure, reporting
units, sample dry weight (moisture content), laboratory applied flags, and the associated results
from spikes, replicates, accuracy standards, ongoing calibration check samples, control, reagent
blanks, reference toxicants, and reference sediments, where applicable.
9.3 Database Processing, Validation, and Verification
All data, after QC checks, will be stored in the ARCS ODES database. The ARCS database
will hold all information that is submitted to the ODES system. The database will contain both field
and analytical laboratory data. Upon receipt of the data, computer processing will begin at LESAT.
It should be noted that data can be received in any computer-readable format from the analytical
laboratories. Generally, the processing of received databases will proceed in the following manner:
1) incorporation of received data into SAS,
2) conversion of incorporated data to a SAS shell database,
3) validation of the database,
4) addition of the QA/QC report by LESAT,
5) conversion of SAS dataset to ODES readable database (ASCII format),
6) submission of database for uploading and checking into ODES,
7) verification of the database by checking for validity of format, codes, and data ranges by
ODES, and
8) uploading of the verified data into the final mainframe repository.
The ODES system is highly dependant on the use of coded information to represent internal
data fields. Three different general classes of codes, excluding header and sample identifier codes,
will be used in the ODES system, namely, chemical codes, taxonomic codes, and miscellaneous
codes which include data qualifiers (e.g., the data represents the mean, blank corrected, or below
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the MDL), bioassay types, material analyzed (sediment, tissue, water), sampling gear type,
meteorological conditions, and chemical analysis methods. Use of these codes allows for the rapid,
rigorously formatted, systematic entry of data into ODES as well as limiting the required storage
space for any given dataset.
Data entered into the ODES format is stored as a series of records that are specifically
combined by ODES into a final data file. Each file converted to the ODES format is composed of
a series of general record types which are as follows:
Survey header record which includes report information common to the entire dataset (e.g.,
investigator's name, survey dates),
Station header record which includes information about the station where the sample was
collected (e.g., location, water depth),
Sample record which includes information about each samples (e.g., depth of core, gear
used to collect sample),
Station environment record which is used to record information about the environmental
conditions at the station where the sample was collected (e.g., temperature),
Data record which reports information on pollutant concentrations found in each of the
samples,
Header record of QA/QC samples for reporting blanks, spikes, and other QA/QC samples
referred to within the dataset,
Species abundance data record used in benthic community structure determinations to
report species abundance counts,
Biomass data record which reports biomass for each species or higher level taxa group,
and
Bioassay conditions record which includes information on type of bioassay conducted and
the physical conditions under which tests were conducted (e.g., photoperiod, static or flow-
through conditions).
Bioassay data record for reporting Microtox luminescence results, bioassay survival
percentages, number of offspring produced (for reproductive bioassay endpoints), larval
abnormalities, dry weight of animal (for growth endpoints of Pimephales promelas). length
and growth of roots, fronds, and shoots, enzyme activity, LC50 values, EC50 values, and
substrate cover.
The data records also will contain information about specific data and flags. There are
separate variables for QC measures, such as spike recoveries and CRMs usage and acceptance
ranges. Other variables will specify a series of codes which are used to identify the samples in
ODES. These variables include the source code, series code, year, and scan code. The source code
is a two character code that will indicate the location of the sampling survey, e.g., BR = Buffalo
River. The series code is to help separate different media analyzed from the same sample or
sampling site. Series codes will be as follows:
P = Pore water,
E - Elutriate,
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W = Water.
T = Tissue,
S = Sediment,
R = Particulates, and
O = Oil.
Scan codes will be applied to the data to indicate the time or year by quarter or month in which the
sampling event occurred.
Each data record has an internal structure that is specific to the file type and level. Data are
stored in fields of these records. Each field is designed to accommodate a particular kind of data,
and the order of these fields, the spacing between them, and the format of their contents are
carefully defined to allow unambiguous and error-free data entry. Each record in the database will
represent one chemical analyzed per sample set. It should be noted that not all records are
applicable to all analyses (e.g., the species abundance record is not applicable to sediment pollutant
data files). The ODES system automatically selects which are appropriate to the type of data being
entered into the system.
Verification of the data will take place before the data are added to the final ARCS database.
After the data have been converted to the ODES format, the data will be visually checked to insure
no errors occurred during the processing of the data. Further, a flagged data file will be created
by ODES, reviewed, and appropriate changes made to the database. The ODES system will verify
that all codes, ranges of data, and formats are appropriate and allowed in ODES. Upon completion
of all the data validation/verification checks, the database will be uploaded onto the mainframe
computer system and will thus become available to all investigators and the general public.
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References
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References
Adams, W.J., R.A. Kimerle, and R.G. Mosher. 1985. Aquatic safety assessment of chemicals sorbed
to sediments. In R.D. Cardwell, R. Purdy, and R.C. Bahner (eds.), Aquatic toxicology and
hazard assessment. Seventh Symposium, ASTM SIP 854. Amer. Soc. Testing and Materials,
Philadelphia, Pennsylvania, pp. 429-453.
Ambrose, R.B., T. Wool, J. Connolly, and R. Schanz. 1988. WASP4, a hydrodynamic and water quality
model - model theory, user's guide, and programmer's guide. EPA/600/3-87/039. U.S.
Environmental Research Laboratory, Athens, Georgia.
American Public Health Association. 1985. Standard methods for the examination of water and
wastewater. 16th ed. American Public Health Association, Washington, D.C.
American Society of Testing and Materials. 1989. New standard guide for conducting solid phase
sediment toxicity tests with freshwater invertebrates. Amer. Soc. Testing and Materials,
Philadelphia, Pennsylvania. 55 pp.
American Society of Testing and Materials. 1987. Annual book of ASTM standards, water, and
environmental technology. Vol. 11.01 and 11.02. Amer. Soc. Testing and Materials, Philadelphia,
Pennsylvania.
Bloom, N. 1989. Determination of picogram levels of methylmercury by aqueous phase ethylation,
followed by cryogenic gas chromatography with cold vapour atomic fluorescence detection .
Can. J. Fish. Aquatic Sci. 46:1131-1140.
Code of Federal Regulations. 1987. Protection of Environment. Title 40. Part 268, Appendix I.
p. 692-707.
Conover, W.J. 1980. Practical nonparametric statistics. 2nd edition. J. Wiley and Sons, New York.
493 pp.
Costle, D.M. 1979a. EPA quality assurance policy statement. Administrator's memorandum, 5-30-79.
U.S. Environmental Protection Agency, Washington, D.C.
Costle, D.M. 1979b. Quality assurance requirements for all EPA extramural projects involving
environmental measurements. Administrator's Policy Statement, 6-14-79. U.S. Environmental
Protection Agency, Washington, D.C.
Cutter, G.A., and T.J. Oatts. 1987. Determination of dissolved sulfide and sedimentary sulfur
speciation using gas chromatography-photoionization detection. Anal. Chem. 59:717-721.
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Folch, J.. M. Lees, and G.H. Sloane Stanley. 1957. A simple method for the isolation and purification
of total lipids from animal tissues. J. Biol. Chem. 226:497-509.
Great Lakes National Program Office. 1989. Green Bay/Fox River mass balance study.
EPA-905/8-89/001. U.S. Environmental Protection Agency, Great Lakes National Program Office,
Chicago, Illinois.
Krahn, M.M., C.A. Wigren, R.W. Pearce, LK. Moore, R.G. Bogar, W.D. MacLeod, Jr., S. Chan, and D.W.
Brown. 1988. New HPLC cleanup and revised extraction procedures for organic contaminants.
Standard Analytical Procedures of the NOAA National Analytical Facility. NOAA National
Analytical Facility, Environ. Conserv. Div., Northwest and Alaska Fish. Center, National Marine
Fisheries Serv., Seattle, Washington.
Miah, M.J., and J.M. Moore. 1988. Parameter design in chemometry. In Chemometrics and intelligent
laboratory systems. 3(1988)31-37. Elsevier Science Publishers, Amsterdam, The Netherlands.
National Oceanographic and Atmospheric Administration. 1985. Standard analytical procedures of
the NOAA Analytical Facility, 1985-1986. NOAA Technical Memo. NMFS F/NWC-92.
New York State Department of Environmental Conservation. 1989. Buffalo River remedial action plan.
New York State Department of Environmental Conservation, Albany, New York.
Nielson, K.K., and R.W. Sanders. 1983. Multielement analysis of unweighed biological and geological
samples using backscatter and fundamental parameters. Adv. X-ray Anal. 26:385-390.
Plumb, R.H., Jr. 1981. Procedures for handling and chemical analysis of sediment and water samples.
Technical report EPA/CE-81-1. Prepared by Great Lakes Laboratory, State University College
at Buffalo, Buffalo, N.Y., for the U.S. Environmental Protection Agency/Corps of Engineers
technical committee on criteria for dredged and fill material. U.S. Army Engineer Waterways
Experiment Station, CE, Vicksburg, Mississippi.
Rhoades, J.D. 1982. Soluble Salts. In A.L. Page et'al. (ed.) Methods of soil analysis. Part 2.
Agronomy 9:167-179. Amer. Soc. Agronomy, Inc., Madison, Wisconsin.
Rudin, W. 1974. Real and complex analysis. McGraw-Hill Publishers, New York. 22 pp.
Stanley, T.W., and S.S. Verner. 1985. The U.S. Environmental Protection Agency's Quality Assurance
Program. In Quality assurance for environmental measurements. ASTM STP 867. Amer. Soc.
Testing and Materials, Philadelphia, Pennsylvania, pp. 12-19.
Strickland, J.D.H., and T.R. Parsons. 1972. A practical handbook for sea water analysis. 2nd ed. Fish.
Res. Bd. Can. Bull. 167. pp. 310.
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Taylor, J.K. 1987. Quality assurance of chemical measurements. Lewis Publishers, Chelsea. Michigan.
328 pp.
U.S. Environmental Protection Agency. 1990. Sample preparation procedure for spectrochemical
analyses of total recoverable elements in biological tissues. In Methods for chemical analysis
of water and wastes. 2nd ed. EPA-600/4-79-020. Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio.
U.S. Environmental Protection Agency. 1989. Short-term methods for estimating the chronic toxicity
of effluents and receiving waters to freshwater organism. EPA 600/4-89-001. Environmental
Monitoring Systems Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio.
U.S. Environmental Protection Agency. 1986. Test methods for evaluating solid waste. SW-846. U.S.
Environmental Protection Agency, Washington, D.C.
U.S. Environmental Protection Agency. 1985. Methods for measuring the acute toxicity of effluents
to aquatic organisms. EPA 600/4-85-013. Environmental Monitoring Systems Laboratory, U.S.
Environmental Protection Agency, Cincinnati, Ohio.
U.S. Environmental Protection Agency. 1983. Methods for chemical analysis of water and wastes.
EPA-600/4-79-020. Environmental Monitoring and Support Laboratory, U.S. Environmental
Protection Agency, Cincinnati, Ohio.
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Appendix A
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Appendix A
Analytical Laboratory Pre-Award Evaluation Scoring Sheet
This appendix presents an example of the pre-award audit sample evaluation scoring sheet.
This particular scoring system has been developed for analyses that will be performed at SUC-B in
which numerous parameters in both inorganic and organic classes are to be quantified. The
resultant score must be greater than or equal to 80 percent for the laboratory to be allowed to
perform analyses on routine samples in the ARCS program.
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PRE-AWARD SCORING SHEET FOR ARCS PROJECT
LABORATORY:
LABORATORY DIRECTOR:
Quantitation of Inorganics:
Quantitation & Identification of Organics:
Quality Control for Inorganics:
Quality Control for Organics:
Miscellaneous:
TOTAL SCORE: (maximum total points = 1388)
PERCENTAGE: %
NOTE: A minimum "passing" score is 80%.
Scored by:
Brian A. Schumacher, Ph.D.
ARCS Quality Assurance Officer
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PART I. QUANTITATION OF INORGANICS
Parameter Points
Pb (water) 5
Fe (water) 5
Cu (water) 5
Pb (soil) 5
Fe (soil) 5
Cu (soil) 5
Pts Awarded
(Samples)
1
2
I
Total
Score
I
(Parameter
I
(Conductivity
I
I
(Hardness
i
1
(Alkalinity
|
Points
3
3
3
Pts Awarded
(Samples)
1
I
Total
Score
Parameter Points
TOC 5
Pts Awarded
(Samples)
1
2
Total
Score
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PART II. QUANTITATION AND IDENTIFICATION OF ORGANICS
Parameter
Points
5
a-chlordane
y-chlordane
Dieldrin
| DDT (total)
I
PCB 1016
PCB 1221
| PCB 1248
PCB identification 10
| (a) anthracene" 5
(b)fluorantheneb
(k)fluorantheneb
| (a)pyreneb
I
jchrysene
5
5
5
5
5
5
Pts Awarded |
(Samples! | Total
Score
1
I 2
N/A
N/A"
I
= N/A = not applicable.
= benzo compounds (i.e. benzo(a)anthracene).
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PART III. QUALITY CONTROL FOR INORGANICS
Sample Type Pts"
Reagent Blanks
All < IDL 9
One or more > IDL 0
Certified Reference Material
All CRMs within ± 20% 15
One or more CRMs out 0
Matrix Spikes
All within 100 ± 15%
recovery 20
One out of criteria 10
Two or more out of
criteria 0
On-Going Calibration Check
All within 10% 30
One or more outside
10% limit 0
Precision of Replicates
All %RSD < 20% 15
One %RSD > 20% 8
Two or more
%RSDs > 20% 0
Instrument Detection Limits
All IDLs < ARCS IDL 30
One IDL > ARCS IDL 15
Two or more out of
criteria 0
SUBTOTALS
Points Awarded
Metals" | Metals0
N/A
Cond.
N/Ad
N/A
Hard. (Alkal.
N/A
N/A
TOC
Total
Score
- potential points awarded per category.
b - metals in water.
0 - metals in soils used to represent particulates.
d - N/A = not applicable.
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PART IV. QUALITY CONTROL FOR ORGANICS
WATER SAMPLES
Sample Type Points*
Reagent Blanks
All < IDL 16
One or more > IDL 0
Certified Reference Material
All CRMs within ± 20% 22
One or more CRMs out 0
Matrix Spikes
All within 100 ± 30%
recovery 27
One out of criteria 17
Two or more out of
criteria 0
Points Awarded
Pest.
Surrogate Spikes
All within 100 ± 30%
recovery 27
One out of criteria 17
Two or more out of
criteria 0
On-Going Calibration Check
All within 10% 37
One or more outside 10% 0
Precision of Replicates
All %RSD < 20% 22
One %RSD > 20% 15
Two or more %RSDs > 20% 0
Instrument Detection Limits
Determination and Level 37
Improper or too hiah 0
SUBTOTALS
PCBs
PAHs
k Total |
Score |
I
I
I
I
* - potential points awarded per category.
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PARTV. MISCELLANEOUS
This section is for miscellaneous checks such as frequency of use of QC samples,
concentration levels in spikes, adherence to protocols, proper reporting units, etc.
Individual comments will be listed in this section as they pertain to a given deficiency.
All points will be negative in this section.
Pts. Reasons
*'U.S. GOVERNMENT PRINTING OFFICE: 1994 - 550-001/80352
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