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Assessment and Remediation of Contaminated Sediments (ARCS) Program

Assessment Guidance Document

Abstract

This document provides guidance on procedures for assessing the nature and extent of sediment contamination as applied to areas in the Great Lakes region. The document was prepared by the Toxicity/Chemistry Work Group as part of the Assessment and Remediation of Contaminated Sediments (ARCS) Program, administered by the U.S. Environmental Protection Agency's (USEPA) Great Lakes National Program Office (GLNPO), in Chicago, Illinois.

Assessment of sediment contamination is intended to determine whether chemical concentrations in the sediments are sufficient to cause adverse effects on either aquatic organisms or organisms higher in the food chain, including humans. One of the main goals of the Toxicity/Chemistry Work Group was the selection of scientifically sound methods for assessing sediment quality. The selected sediment assessment methods were then applied in demonstration studies at several of the Great Lakes Areas of Concern (AOCs).

The sediment assessment methods described in this document include an integration of physical, chemical, and biological information. Decisions regarding the possible need for sediment remediation could therefore be made on the basis of a preponderance of evidence.

The chapters of this guidance document focus on various topics related to the assessment of contaminated sediments. Included is guidance on the necessary elements of a quality assurance and quality control (QA/QC) program, considerations for the conduct of field surveys, screening-level analyses (i.e., relatively rapid, low-cost tests to focus subsequent comprehensive analyses on the more contaminated sediments), chemical analyses, toxicity tests for assessing biological impacts, assessments of benthic invertebrate community structure, surveys of fish tumors and abnormalities, and data presentation and interpretation techniques. In addition to descriptions of the available options within each chapter, recommendations are made to guide the selection of appropriate sediment assessment methods, using the experience gained by the Toxicity/Chemistry Work Group to illustrate key issues. It is intended that the guidance on appropriate sediment assessment methods provided herein may be applied to other Great Lakes AOCs as they undergo investigation by Great Lakes Remedial Action Plan (RAP) personnel at the Federal, State, and local levels.

This report should be cited as follows:

U.S. Environmental Protection Agency. 1994. "ARCS Assessment Guidance Document." EPA-905-B94-002. Great Lakes National Program Office, Chicago, IL.

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Table Of Contents 

• ACKNOWLEDGMENTS
• ABSTRACT
• LIST OF FIGURES
• LIST OF TABLES
• ACRONYMS AND ABBREVIATIONS

1. INTRODUCTION
   • BACKGROUND
   • OVERVIEW OF SEDIMENT ASSESSMENT METHODS
   • OVERVIEW OF THE ASSESSMENT GUIDANCE DOCUMENT
2. QUALITY ASSURANCE AND QUALITY CONTROL
   • QUALITY ASSURANCE PROGRAM
   • DEVELOPMENT OF DATA QUALITY OBJECTIVES AND MEASUREMENT QUALITY OBJECTIVES
     • Data Quality Objectives
     • Measurement Quality Objectives
   • QUALITY ASSURANCE AND QUALITY CONTROL SAMPLES
     • Replicate Samples
     • Blank Samples
     • Reference Materials
     • Matrix Spikes
     • Surrogate Spikes
     • Initial Instrument Calibration Standards
     • Ongoing Calibration Check Samples
     • Control Charts
   • PREPARATION OF QUALITY ASSURANCE PLANS
   • DEVELOPMENT OF A LABORATORY AUDIT PROGRAM
     • Evaluation Samples
     • Laboratory Performance and System Audits
   • DATABASE REQUIREMENTS AND DATA VERIFICATION/VALIDATION METHODS
   • CONCLUSIONS
   
   
3. SEDIMENT SAMPLING SURVEYS
   • SEDIMENT SAMPLING VESSEL
     • Sampling Vessel Used in the ARCS Program
   • FIELD POSITIONING METHODS
     • Advantages and Disadvantages of Available Positioning Systems
     • Field Positioning System Used in the ARCS Program
   • SEDIMENT SAMPLING PROCEDURES
     • Grab Samplers
     • Sediment Corers
     • Sediment Samplers and Procedures Used in the ARCS Program
     • Conclusions
   • FIELD PROCESSING OF SEDIMENT SAMPLES FOR PHYSICAL AND CHEMICAL ANALYSES
   • FIELD PROCESSING OF SEDIMENT SAMPLES FOR BENTHIC COMMUNITY ANALYSES
   • FIELD PROCESSING OF SEDIMENT SAMPLES FOR TOXICITY TESTING
   • SEDIMENT CHARACTERIZATION BY REMOTE SENSING
     • Acoustic Subbottom Profiling
     • Electrical Resistivity (Conductivity) Profiling
     • Conclusions
     
     
4. SCREENING-LEVEL ANALYSES
   • SUMMARY OF SCREENING-LEVEL METHODS
     • Total PAHs by Fluorometry
     • Total PCBs, Chlorinated Pesticides, and Other Organic Chemicals by Enzyme Immunoassay
     • Total Petroleum Hydrocarbons by Infrared Spectroscopy
     • Semivolatile Organic Compounds by Thin-Layer Chromatography
     • Metals by X-ray Fluorescence
     • Rapid Toxicity Tests
   • INDICATOR ANALYSES
     • Results for Core Samples Analyzed During the ARCS Program
     • Correlation Between Indicator and Comprehensive Analyses
   • CONCLUSIONS
   
   
5. CHEMICAL ANALYSES
   • METHOD SELECTION (GENERAL OVERVIEW)
   • CONVENTIONAL VARIABLES
     • Sediments
     • Tissues
     • Conclusions
   • ORGANIC COMPOUNDS
     • Nonchlorinated Semivolatile Organic Compounds
     • PCBs and Chlorinated Pesticides
     • PCDDs and PCDFs
   • ORGANOMETALLIC COMPOUNDS
     • Methylmercury
     • Butyltin Compounds
   • METALS
     • Sediments
     • Tissues
     • Elutriate and Pore Water
   • CONCLUSIONS
   
   
6. EVALUATION OF SEDIMENT TOXICITY
   • OVERVIEW
   • INTRODUCTION
   • EXPERIMENTAL DESIGN
   • METHODS FOR SAMPLE COLLECTION AND EXPOSURE
     • Sediment Manipulation and Characterization: The Importance of Maintaining Sediment Integrity
     • General Exposure Procedures for Sediment Toxicity Tests
     • Quality Control and Quality Assurance for Sediment Toxicity Tests
   • DATA ANALYSIS
   • EVALUATION OF SEDIMENT TOXICITY TESTS IN THE ARCS PROGRAM
     • Toxicity Test Methods
     • Data Analysis Approach
     • Sensitivity
     • Discriminatory Ability
     • Combined Sensitivity and Discriminatory Abilities
     • Similarities in Measured Endpoint Responses
     • Correlations Between Toxicity Test Endpoint Responses
     • Comparisons of Acute and Chronic Toxicity Testing with Whole Sediments
   • EVALUATION OF TOP-RANKED TOXICITY TESTS
   • CONCLUSIONS AND RECOMMENDATIONS
     • Criteria for Selection of Individual Toxicity Tests
     • Recommended Toxicity Tests
     
     
7. ASSESSMENT OF BENTHIC INVERTEBRATE COMMUNITY STRUCTURE
   • INTRODUCTION
   • EXPERIMENTAL DESIGN
   • METHODS FOR SAMPLE COLLECTION
     • Grab Samplers
     • Artificial Substrate Samplers
   • DATA ANALYSIS
   • THE ARCS APPROACH
     • Site Description
     • Methods
     • Quality Assurance and Quality Control for Benthic Invertebrate Community Analysis
     • Statistical Analysis
   • SUMMARY AND RECOMMENDATIONS FOR FUTURE STUDIES
   
   
8. FISH TUMORS AND ABNORMALITIES
   • INTRODUCTION
   • ROLE OF FISH TUMOR SURVEYS IN ASSESSING SEDIMENT CONTAMINATION
   • USE OF FISH TUMOR SURVEYS TO INFER CAUSE-AND-EFFECT LINKAGES
   • HISTOPATHOLOGY AS A SENSITIVE ASSESSMENT TOOL
   • METHODS AND MATERIALS
     • Fish Collection
     • Fish Processing
     • Evaluation of Tissue Samples
     • Quality Assurance and Quality Control
   • THE ASHTABULA RIVER AOC TUMOR SURVEY
     • External Abnormalities
     • Histological Findings
     • Biological Correlations
     • Contaminant Correlations
   • DISCUSSION
     • Limitations of Results
     • Recommendations
     
     
9. DATA PRESENTATION AND INTERPRETATION
   • SEDIMENT QUALITY DESCRIPTION AND MAPPING
     • Preparing Base Maps
     • Data Set Mapping
   • SEDIMENT CLASSIFICATION METHODS
     • Whole Sediment Toxicity Testing
     • Spiked Sediment Toxicity Testing
     • Interstitial Water Toxicity Identification Evaluation
     • Equilibrium Partitioning
     • Tissue Residues
     • Benthic Macroinvertebrate Community Structure
     • Sediment Quality Triad
     • Apparent Effects Threshold
     • National Status and Trends Program Effects-Based Approach
     • Use of the Sediment Classification Approaches
   • NUMERICAL RANKING OF HAZARDOUS SEDIMENTS TO PRIORITIZE SITES FOR REMEDIAL ACTION
     • Ranking Sites Based on Toxicity Estimated from Chemistry Data
     • Ranking Sites Based on Toxicity as Measured by Laboratory Toxicity Tests
     • Ranking Sites Based on Toxicity as Measured by Benthic Community Structure
     • Final Ranking
   • CONCLUSIONS AND RECOMMENDATIONS
   
   
10. CONCLUSIONS


11. REFERENCES

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List of Figures

• Figure 1-1. Buffalo River Area of Concern, New York
• Figure 1-2. Indiana Harbor Area of Concern, Indiana
• Figure 1-3. Saginaw River Area of Concern, Michigan
• Figure 2-1. Steps in the data quality objectives process
• Figure 3-1. R/V Mudpuppy
• Figure 3-2. Example sample numbering system used in the ARCS Program
• Figure 3-3. Diagram of acoustic subbottom profiling
• Figure 7-1. Artificial substrate samplers used to collect aquatic invertebrates in the ARCS Program
• Figure 7-2. Total concentration of simultaneously extracted metals (Cd, Cr, Cu, Ni, Pb, Zn) vs. mean total invertebrate abundance at three priority AOCs
• Figure 7-3. Total PAH concentration vs. mean total invertebrate abundance at three priority AOCs
• Figure 7-4. Total PCB concentration vs. mean total invertebrate abundance at three priority AOCs
• Figure 7-5. Composition of the invertebrate taxa collected using an artificial substrate sampler and a Ponar grab sampler at the Buffalo River AOC
• Figure 7-6. Composition of the invertebrate taxa collected using an artificial substrate sampler and a Ponar grab sampler at the Indiana Harbor AOC
• Figure 7-7. Composition of the invertebrate taxa collected using an artificial substrate sampler and a Ponar grab sampler at the Saginaw River AOC
• Figure 9-1. Examples of single-value point maps
• Figure 9-2. Example use of icons to plot the value of a single parameter
• Figure 9-3. Example use of icons to plot the values of multiple parameters
• Figure 9-4. Example use of icons to plot both quantitative (copper concentrations) and qualitative (sediment type) parameters
• Figure 9-5. Examples of different contouring algorithms applied to the same data set
• Figure 9-6. Example of a pseudo 3-dimensional surface model generated from a 2-dimensional contour map
• Figure 9-7. Example of a 2-dimensional contour map "draped" over a pseudo 3-dimensional surface model
• Figure 9-8. Use of triaxial graphs to plot sediment quality triad data

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List of Tables

• Table 2-1. Examples of the measurement quality objectives for inorganic and organic chemistry analyses of sediment used by the ARCS Program
• Table 3-1. Comparison of positioning systems
• Table 3-2. Advantages and disadvantages of various sediment samplers
• Table 3-3. Recommended sample sizes, containers, preservation techniques, and holding times
• Table 4-1. Indicator analysis descriptions and citations
• Table 4-2. Mean values for selected indicator variables in core samples
• Table 4-3. Comparison between predicted and measured Microtoxreg. EC50 values
• Table 5-1. Approximate costs for chemical analyses
• Table 6-1. Rating of selection criteria for selected whole sediment toxicity test organisms
• Table 6-2. Sediment toxicity tests evaluated in the ARCS Program
• Table 6-3. Advantages, disadvantages, and routine uses of sediment phases in laboratory toxicity tests
• Table 6-4. Ranking of toxicity test endpoints by sensitivity over four AOC surveys
• Table 6-5. Ranking of toxicity test endpoints by discriminatory ability over four AOC surveys
• Table 6-6. Combined ranking of ARCS toxicity tests: sensitivity + discriminatory ability
• Table 6-7. Factor analysis of ARCS sediment toxicity test data
• Table 6-8. Toxicity test endpoints with the highest average r² and lowest average P values
• Table 6-9. Percentage of significant correlations between benthic and nonbenthic endpoint responses
• Table 6-10. Optimal toxicity test battery groupings
• Table 6-11. Toxicity test selection approach
• Table 6-12. Example of selection of toxicity tests based on study objectives
• Table 7-1. Percent contribution of major taxa to the total number of taxa collected in grab samples from the Buffalo River in October 1989
• Table 7-2. Percent contribution of major taxa to the total number of taxa collected in grab samples from the Indiana Harbor in August 1989
• Table 7-3. Percent contribution of major taxa to the total number of taxa collected in grab samples from the Saginaw River in December 1989
• Table 7-4. Percent contribution of major taxa to the total number of taxa collected in grab samples from the Saginaw River in June 1990
• Table 7-5. Mean abundance (number/m²) of oligochaetes collected in grab samples from the Buffalo River in October 1989
• Table 7-6. Mean abundance (number/m²) of oligochaetes collected in grab samples from Indiana Harbor in August 1989
• Table 7-7. Mean abundance (number/m²) of oligochaetes collected in grab samples from the Saginaw River in December 1989
• Table 7-8. Mean abundance (number/m²) of oligochaetes collected in grab samples from the Saginaw River in June 1990
• Table 7-9. Mean abundance (number/m²) of chironomids collected in grab samples from the Buffalo River in October 1989
• Table 7-10. Mean abundance (number/m²) of chironomids collected in grab samples from the Saginaw River in December 1989
• Table 7-11. Mean abundance (number/m²) of chironomids collected in grab samples from the Saginaw River in June 1990
• Table 7-12. Mean abundance (number/m²) of molluscs collected in grab samples from the Buffalo River in October 1989
• Table 7-13. Mean abundance (number/m²) of molluscs collected in grab samples from the Saginaw River in December 1989
• Table 7-14. Mean abundance (number/m²) of molluscs collected in grab samples from the Saginaw River in June 1990
• Table 7-15. Comparison of absolute and relative abundances of oligochaetes and chironomids for each Area of Concern
• Table 7-16. Prevalences of larval chironomid mouthpart deformities from Buffalo River, Indiana Harbor, and Saginaw River AOCs
• Table 7-17. Percentage of total variance of benthic invertebrate abundance estimates partitioned among various sources
• Table 8-1. Selected mean concentrations of polynuclear aromatic hydrocarbons in sediments and the prevalence of liver tumors in brown bullheads from the Black, Cuyahoga, Ashtabula, and Huron rivers
• Table 9-1. Possible conclusions resulting from use of the sediment quality triad approach
• Table 10-1. ARCS Toxicity/Chemistry Work Group

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Acknowledgements

This report was prepared by the Toxicity/Chemistry Work Group as part of the Assessment and Remediation of Contaminated Sediments (ARCS) Program administered by U.S. Environmental Protection Agency's (USEPA) Great Lakes National Program Office (GLNPO) in Chicago, Illinois. Editing of individual chapters was performed by Mr. Rick Fox of GLNPO and PTI Environmental Services. Dr. Philippe Ross of The Citadel, Charleston, South Carolina, and Mr. Rick Fox served as chairmen of the Toxicity/Chemistry Work Group. Mr. David Cowgill and Dr. Marc Tuchman of GLNPO served as the ARCS Program managers.

Contributors to this report included:

Chapter 1.
Rick Fox, USEPA, GLNPO, Chicago, Illinois
Peter Landrum, National Oceanic and Atmospheric Administration, Ann Arbor, Michigan
Lawrence McCrone, PTI Environmental Services, Bellevue, Washington

Chapter 2.
Brian Schumacher, USEPA, Environmental Monitoring Systems Laboratory, Las Vegas, Nevada
Rick Fox, USEPA, GLNPO, Chicago, Illinois
J.C. Filkins, USEPA, Environmental Research Laboratory, Large Lakes Research Station, Grosse Ile, Michigan
Bob Barrick, PTI Environmental Services, Bellevue, Washington

Chapter 3.
V.E. Smith and S.G. Rood, AScI Corporation, Dearborn, Michigan

Chapter 4.
J.E. Rathbun, L.L. Huellmantel, M. Tracy, and K.A. Ahlgren, AScI Corporation, Dearborn, Michigan

Chapter 5.
Eric Crecelius, Brenda Lasorsa, Lisa Lefkovitz, Battelle, Pacific Northwest Division, Marine Sciences Laboratory, Sequim, Washington
Peter Landrum, National Oceanic and Atmospheric Administration, Ann Arbor, Michigan
Bob Barrick, PTI Environmental Services, Bellevue, Washington

Chapter 6.
G. Allen Burton, Jr., Wright State University, Dayton, Ohio
Christopher G. Ingersoll, National Biological Survey, Columbia, Missouri

Chapter 7.
Timothy Canfield, National Biological Survey, Columbia, Missouri
Thomas La Point, Clemson University, Clemson, South Carolina
Michael Swift, University of Minnesota, Monticello, Minnesota

Chapter 8.
Mary Ellen Mueller, National Biological Survey, Washington, DC
Michael Mac, National Biological Survey, Office of Research Support, Washington, DC

Chapter 9.
S.G. Rood and V.E. Smith, AScI Corporation, Dearborn, Michigan
J.C. Filkins, USEPA, Environmental Research Laboratory, Large Lakes and Rivers Research Branch, Grosse Ile, Michigan
Mark L. Wildhaber and C.J. Schmitt, National Biological Survey, Columbia, Missouri

Chapter 10.
Lawrence McCrone, PTI Environmental Services, Bellevue, Washington

This report was edited and produced by PTI Environmental Services for Battelle Ocean Sciences under USEPA Contract No. 68-C2-0134.

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Acronyms and Abbreviations

AET - apparent effects threshold ANOVA - analysis of variance AOC - Area of Concern ARCS - Assessment and Remediation of Contaminated Sediments ASTM - American Society for Testing and Materials AVS - acid-volatile sulfide AWQC - ambient water quality criteria CAB - cellulose acetate butyrate the Corps - U.S. Army Corps of Engineers CRM - certified reference material CVAA - cold vapor atomic absorption CVAF - cold vapor atomic fluorescence DBC - dibutylchlorendate DCB - decachlorobiphenyl DGPS - differential global positioning system DQO - data quality objective ECD - electron capture detection ER-L - effects range-low ER-M - effects range-median FID - flame ionization detection GC/MS - gas chromatography/mass spectrometry GFAA - graphite furnace atomic absorption spectroscopy GIS - geographic information system GLNPO - Great Lakes National Program Office GMP - geologic modeling program GPC - gel permeation chromatography GPS - global positioning system HPLC - high-pressure liquid chromatography HRMS - high-resolution mass spectrometry HSI - hepatosomatic index ICP/AES - inductively coupled plasma-atomic emission spectroscopy ICP/MS - inductively coupled plasma-mass spectrometry IDL - instrument detection limit IUPAC - International Union of Pure and Applied Chemistry ICP/AES - inductively coupled plasma-atomic emission spectroscopy ICP/MS - inductively coupled plasma-mass spectrometry IDL - instrument detection limit IUPAC - International Union of Pure and Applied Chemistry

LaMP - Lakewide Management Plan LLRS - Large Lakes Research Station LOQ - limit of quantification MDL - method detection limit MQO - measurement quality objective NFCRC - National Fisheries Contaminant Research Center NOAA - National Oceanic and Atmospheric Administration NOEL - no-observed-effect-level OCN - octachloronaphthalene %RSD - percent relative standard deviation PAH - polynuclear aromatic hydrocarbon PCA - principal component analysis PCB - polychlorinated biphenyl PCDD - polychlorinated dibenzo-p-dioxin PCDF - polychlorinated dibenzofuran PEL - probable effects level QA/QC - quality assurance and quality control QAMP - quality assurance management plan QAPP - quality assurance project plan RAP - Remedial Action Plan (for Great Lakes AOCs) RPD - relative percent difference RRF - relative response factor SIM - selected ion monitoring SQV - sediment quality value SRM - standard reference material TBT - tributyltin TCDD - 2,3,7,8-tetrachlorodibenzo-p-dioxin TCMX - tetrachloro-m-xylene TDL - target detection limit TEL - threshold effects level TIE - toxicity identification evaluation TLC - thin-layer chromatography TOC - total organic carbon TPH - total petroleum hydrocarbon U.S. NIST - U.S. National Institute of Standards Technology USEPA - U.S. Environmental Protection Agency USGS - U.S. Geological Survey XRF - x-ray fluorescence

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