Pesticides in Stream Sediment and Aquatic Biota Distribution, Trends, And Governing Factors - Chapter 1 pps

Characteristics of Studies Reviewed2.1 General Design Features 3.1.1 Aggregate Detection Frequencies of Pesticides Bias From Selection of Target Analytes Comparison of Bed Sediment and A

Distribution, Trends, And Governing Factors

Pesticides in Stream Sediment and Aquatic Biota

Lisa H Nowell, U.S Geological Survey, Sacramento, California Paul D Capel, U.S Geological Survey, Minneapolis, Minnesota Peter D Dileanis, U.S Geological Survey, Sacramento, California

Distribution, Trends, And Governing Factors

Pesticides in Stream Sediment and Aquatic Biota

Volume Four of the Series Pesticides in the Hydrologic System

Robert J Gilliom, Series Editor U.S Geological Survey National Water Quality Assessment Program

INTRODUCTION TO THE SERIES

Pesticides in the Hydrologic System is a series of comprehensive reviews and analyses of

our current knowledge and understanding of pesticides in the water resources of the United States and of the principal factors that influence contamination and transport The series is presented according to major components of the hydrologic system—the atmosphere, surface water, bed sediments and aquatic organisms, and ground water Each volume:

• summarizes previous review efforts;

• presents a comprehensive tabulation, review, and analysis of studies that have

measured pesticides and their transformation products in the environment;

• maps locations of studies reviewed, with cross references to original publications;

• analyzes national and regional patterns of pesticide occurrence in relation to such factors as the use of pesticides and their chemical characteristics;

• summarizes processes that govern the sources, transport, and fate of pesticides in each component of the hydrologic system;

• synthesizes findings from studies reviewed to address key questions about pesticides

in the hydrologic system, such as:

How do agricultural and urban areas compare?

What are the effects of agricultural management practices?

What is the influence of climate and other natural factors?

How do the chemical and physical properties of a pesticide influence its behavior

in the hydrologic system?

How have past study designs and methods affected our present understanding? Are water-quality criteria for human health or aquatic life being exceeded?

Are long-term trends evident in pesticide concentrations in the hydrologic system? This series is unique in its focus on review and interpretation of reported direct measurements of pesticides in the environment Each volume characterizes hundreds of studies conducted during the past four decades Detailed summary tables include such features as spatial and temporal domain studied, target analytes, detection limits, and compounds detected for each study reviewed.

Pesticides in the Hydrologic System is designed for use by a wide range of readers in the

environmental sciences The analysis of national and regional patterns of pesticide occurrence, and their relation to use and other factors that influence pesticides in the hydrologic system, provides a synthesis of current knowledge for scientists, engineers, managers, and policy makers

at all levels of government, in industry and agriculture, and in other organizations The interpretive analyses and summaries are designed to facilitate comparisons of past findings to current and future findings Data of a specific nature can be located for any particular area of the country For educational needs, teachers and students can readily identify example data sets that meet their requirements Through its focus on the United States, the series covers a large portion

of the global database on pesticides in the hydrologic system and international readers will find

much that applies to other areas of the world Overall, the goal of the series is to provide readers from a broad range of backgrounds in the environmental sciences with a synthesis of the factual data and interpretive findings on pesticides in the hydrologic system.

The series has been developed as part of the National Water Quality Assessment Program

of the U.S Geological Survey, Department of Interior Assessment of pesticides in the nation’s water resources is one of the top priorities for the Program, which began in 1991 This comprehensive national review of existing information serves as the basis for design and interpretation of studies of pesticides in major hydrologic systems of the United States now being conducted as part of the National Water Quality Assessment.

Series Editor Robert J Gilliom

U S Geological Survey

Residues of pesticides, especially the organochlorine pesticides, in bed sediment and aquatic biota have been an environmental concern since the 1960s Because of their toxicity and persistence, the majority of organochlorine pesticides (including DDT) were banned in the United States during the 1970s Yet, more than 20 years later, residues of DDT and other organochlorine pesticides continue to be detected in air, rain, soil, surface water, bed sediment, and aquatic and terrestrial biota throughout the world Moreover, recent research suggests that low levels of some organochlorine pesticides have the potential to affect the development, reproduction, and behavior

of fish and wildlife, and possibly of humans as well

The primary goal of this book is to assess the current understanding of the occurrence and behavior of pesticides in bed sediment and aquatic biota—the two compartments of the hydro- logic system in which organochlorine pesticides are likely to reach their highest levels This book has two objectives Much of the book concerns organochlorine pesticides—evaluation of their environmental fate, their distribution throughout United States rivers and streams, the extent to which residues have declined since most of these pesticides were banned, and the potential biological significance of the remaining residues This coverage is a natural consequence of the historical importance of these compounds and their tendency to accumulate in sediment and biota.

A second objective of this book—and an important one, despite there being relatively little mation on this topic in the existing literature—is an assessment of the potential for currently used pesticides to accumulate in bed sediment and aquatic biota of hydrologic systems

infor-Previous reviews of pesticides in bed sediment or aquatic biota provide fairly thorough treatment of the occurrence, distribution, and trends of many organochlorine pesticides in the Great Lakes region and in coastal and estuarine areas of the United States However, existing reviews do not provide the same perspective for bed sediment and aquatic biota in United States rivers and streams To accomplish this, we have compiled the results of most published studies that measured pesticides in bed sediment or aquatic biota, or both, in rivers and streams in the United States These studies include monitoring studies, which range from local to national in scale, as well as field experiments designed to assess the environmental fate of pesticides in hydrologic systems The initial literature search covered reports published up to 1993, but many articles and reports published after 1993 were included as they became available For all the studies reviewed, concise summaries of study sites, target analytes, and results are provided in a series of tables (at the back of the book)

There were good technical arguments for combining the review of pesticides in sediment and aquatic biota into a single book, despite the large volume of literature in each of these two areas Because of their physical and chemical properties, the same chemicals tend to accumulate

in both media Also, a number of studies measured pesticides in both media at the same time, so that separating these media into two separate books would require duplication of effort for both the authors and the readers.

This book was made possible by the National Water Quality Assessment Program of the U.S Geological Survey The authors wish to express their thanks and appreciation for the suggestions, reviews, and assistance provided by many individuals in the development of this book We are indebted to Steven Larson (U.S Geological Survey) for his assistance in conducting bibliographic searches, for providing references and other materials, and for valuable discussions.

We also wish to thank Loreen Kleinschmidt (Toxicology Documentation Center at the University

of California, Davis) for her support in conducting literature searches, obtaining references, and assisting in many other ways during the research and writing phase of this book Thanks also go

to William Fitzpatrick and Joyce Calipto (formerly undergraduates at the University of California, Davis) for obtaining many references and entering them in a bibliographic database, to Jean Lucas (U.S Geological Survey) for providing copies of references and other materials, and Gail Thelin (U.S Geological Survey) for Geographic Information System support To the many individuals, too numerous to mention by name, who sent us copies of their papers and reports, or provided lists of references, we are very grateful We also wish to thank several individuals who assisted us in obtaining electronic data: Larry Shelton and Kathy Shay (U.S Geological Survey data), Thomas O’Connor (National Oceanic and Atmospheric Administration data), and Peter Lowe and L Rod DeWeese (U.S Fish and Wildlife Service data) Thanks also go to Robert Gilliom, Jack Barbash, and Michael Majewski (U.S Geological Survey) for helpful discussions

of various topics covered in this book Special thanks are due to Steven Goodbred (U.S Geological Survey) for his technical review of portions of the book, helpful discussions of various topics, providing references on endocrine disruption, and assistance in summarizing some of the monitoring studies reviewed in this book We are indebted to Herman Feltz (U.S Geological Survey) and Gregory Foster (George Mason University) for providing timely, thorough, and helpful reviews of the manuscript Their excellent suggestions greatly improved the quality of this book We also wish to thank the authors and publishers who gave permission to reproduce various figures or tables from their publications

Several employees of the data, cartography, and publications sections of the U.S Geological Survey contributed to the production of this work We are indebted to Naomi Nakagaki and Thomas Haltom for producing the maps presented in this book Our grateful thanks go to Susan Davis, Yvonne Gobert, and Glenn Schwegmann for their considerable efforts in the preparation and editing of text, tables, illustrations, and references, and in producing a high-quality camera- ready work Finally, we are indebted to our technical editor, Thomas Sklarsky, for his thorough, painstaking work in editing the manuscript, and his masterful job of organizing the production of the finished, camera-ready work

Lisa H Nowell Paul D Capel Peter D Dileanis

EDITOR’S NOTE

This work was prepared by the U.S Geological Survey (USGS) Although it has been edited for commercial publication, some of the style and usage incorporated is based on the USGS’s

publication guidelines (i.e., Suggestions to Authors, 7th edition, 1991) For example, references

with more than two authors are cited in the text as “Smith and others (19xx),” rather than “Smith,

et al (19xx),” and some common-use compound modifiers are hyphenated For units of measure, the international system of units is used for most based and derived units except for the reporting

of pesticide use, which is commonly expressed in English units (e.g., pound[s] active ingredient), and the concentration, usually expressed in the metric equivalent (e.g., micrograms per liter) In addition to the standard use of italics, identification of new terms when first used, or of technical terms when first defined, are also denoted by italic type.

Every attempt has been made to design figures and tables as “stand-alone,” without the need for repeated cross reference to the text for interpretation of illustrations or tabular data Some ex- ceptions have been made, however, because of the complexity or breadth of the figure or table As

an aid in comparison, the same shading patterns are shown in the Explanation of all pesticide usage maps, though each pattern may not necessarily apply to every map In some cases, a figure

is shown just before its mention in the text to avoid continuity with unrelated figures or to promote effective layout The U.S Department of Agriculture’s 10 farm production regions (Figure 3.13 and Section 3.3) are capitalized to denote proper names of specific geographical areas.

Some of the longer tables are located at the end of the chapter or in the appendixes to maintain less disruption of text In Tables 2.1–2.3 (Appendixes A, B, and C), the analyte names are reported as in the original reference, and so, multiple common names for the same pesticide (e.g., DCPA and dacthal) occur in these tables In Table 2.2, geographic and personal names are spelled in the same way as in the original reference In addition to the complete spelling of a name, its abbreviation may have been used in the large tables (e.g., California and Calif.; River and R.) when necessary to economize cell space

As an organizational aid to the author and reader, chapter headings, figures, and tables are identified in chapter-numbered sequence The list of abbreviations and acronyms in the front of the book do not include chemical names, which are listed in Appendix D, or symbols and functions in mathematical equations, which are defined when used Rather than creating new abbreviations for common terms, some of the abbreviations listed have multiple representations

(e.g., “na” for not applicable and not analyzed), though the abbreviations are defined more

precisely when used.

With the exception of the index, this work was edited, illustrated, and produced as ready copy by the USGS’s Pesticide National Synthesis publications team, Sacramento, California.

Characteristics of Studies Reviewed

2.1 General Design Features

3.1.1 Aggregate Detection Frequencies of Pesticides

Bias From Selection of Target Analytes Comparison of Bed Sediment and Aquatic Biota

3.1.2 Pesticide Occurrence in Major National Monitoring Programs

The FDA’s National Monitoring Program for Food and Feed The Bureau of Commercial Fisheries–USEPA’s National Pesticide Monitoring Program

The FWS’s National Contaminant Biomonitoring Program The USGS–USEPA’s Pesticide Monitoring Network The NOAA’s National Status and Trends Program The USEPA’s National Study of Chemical Residues in Fish

3.1.3 Comparisons of Major National Programs

3.2 National Pesticide Use

3.2.1 Agricultural Use

3.2.2 Nonagricultural Uses

Home and Garden Industrial, Commercial, and Government Buildings and Land Subterranean Termite Control

Forestry

3.2.3 Trends and Conclusions

3.3 Geographic Distribution in Relation to Use

3.3.1 Historically Used Organochlorine Insecticides

Bed Sediment Aldrin and Dieldrin Total DDT

Aquatic Biota Aldrin and Dieldrin Chlordane

Total DDT Heptachlor and Heptachlor Epoxide Mirex

Toxaphene

3.3.2 Currently Used Pesticides

Bed Sediment Aquatic Biota Dicofol, Lindane, and Methoxychlor Endosulfan

Chlorpyrifos Dacthal Trifluralin Other Currently Used Pesticides

3.4 Long-Term Trends

3.4.1 Historically Used Organochlorine Insecticides

Bed Sediment Aquatic Biota Aldrin and Dieldrin Chlordane

Total DDT Endrin

α-HCH Heptachlor and Heptachlor Epoxide Hexachlorobenzene

Toxaphene

3.4.2 Currently Used Pesticides

Bed Sediment Aquatic Biota Lindane Methoxychlor Dacthal Pentachloroanisole

4.1.2 Sources to Bed Sediment

The Water Column Aquatic Biota Ground Water

4.1.3 Sources to Aquatic Biota

The Water Column Bed Sediment

4.2 Behavior and Fate of Pesticides in Bed Sediment

4.2.3 Transformation Processes

Hydrolysis Oxidation and Reduction Photochemical Reactions Biotransformation

4.3 Behavior and Fate of Pesticides in Aquatic Biota

4.3.1 Phase-Transfer Processes

Passive Diffusion Sorption and Desorption Elimination

Tissue Decomposition

4.3.2 Transport Processes

Consumption by Predators Migration or Downstream Movement Reproduction

4.3.3 Biotransformation Processes

Oxidation Reduction Hydrolysis Conjugation

CHAPTER 5

Analysis of Key Topics—Sources, Behavior, and Transport

5.1 Effect of Land Use on Pesticide Contamination

5.1.1 Agriculture

5.1.2 Forestry

5.1.3 Urban Areas and Industry

5.1.4 Remote or Undeveloped Areas

5.2 Pesticide Uptake and Accumulation by Aquatic Biota

5.2.1 Bioaccumulation Terminology and Simple Models

5.2.2 Biomagnification

5.2.3 Equilibrium Partitioning Theory

5.2.4 Evidence from Laboratory and Field Studies

Evidence of Biomagnification in the Field Effect of Trophic Level on Contaminant Concentrations Bioaccumulation Factors

Field Modeling Testing Predictions of Equilibrium Partitioning Theory Correlation Between Bioconcentration Factor and Chemical Properties

Fish/Sediment Concentration Ratios Effect of Trophic Level on Fugacity Lipid Normalization

5.2.5 Converging Theories of Bioaccumulation

Uptake Processes Partitioning From Water Uptake of Sediment-Sorbed Chemicals Dietary Uptake and Biomagnification Factors Affecting Route of Uptake Elimination Processes

Biological Factors that Affect Bioaccumulation Body Length, Body Weight, and Age

Lipid Content Gill Ventilation Volume and Other Gill Characteristics Blood Flow

Metabolism Growth Rate Reproductive State Species

Tissue Sex

Other Biological Factors Interaction Among Biological Factors Chemical Characteristics that Affect Bioaccumulation Molecular Size, Shape, and Structure

Solubility Chemical Stability

Environmental Conditions that Affect Bioaccumulation Temperature

pH and Salinity Dissolved Organic Matter and Particulate Concentrations Oxygen Concentration

Other Environmental Conditions Bioaccumulation Models

Steady-State or Equilibrium Partitioning Models Compartment-Based Kinetic Models

Physiologically Based Kinetic Models Effect of Environmental and Physiological Conditions

5.3 Seasonal Changes in Pesticide Residues

5.3.1 Pesticide Use

Agricultural Sources Industrial Sources

5.3.2 Weather-Driven and Streamflow-Related Events

Irrigation Precipitation and Storm Events Winter or Spring Snowmelt and Runoff Reservoir Water Release

Water Inflow to Estuaries

5.3.3 Agricultural Management Practices

5.3.4 Environmental Conditions

Ambient Water Concentrations Temperature

Salinity Turbidity Vegetative or Snow Cover Spring Turnover

5.3.5 Seasonal Biological Factors

Reproductive Cycle Lipid Content Enzyme Activity Population Shifts Feeding Activity, Growth Rate, Food Source, and Habitat Migration

5.3.6 Summary

Bed Sediment Aquatic Biota

5.4 Physical and Chemical Properties of Pesticides in Sediment and

Aquatic Biota

5.4.1 Properties that Control Accumulation in Sediment and Aquatic Biota

Hydrophobicity Persistence

5.4.2 Chemodynamic Relations

Water Solubility and Soil Half-Life

n-Octanol-Water Partition Coefficient and Soil Half-Life

5.4.3 Predictions from Chemodynamic Relations

5.5 Composition of Total DDT as an Indicator of DDT Sources and

Period of Use

5.5.1 Possible Sources of DDT Residues in the Environment

5.5.2 Environmental Fate of DDT

5.5.3 The DDT/Total DDT Ratio as an Indicator of

Time in the Environment Case Study: Salinas River and Blanco Drain Case Study: California Soil Monitoring Survey Conclusions

5.5.4 The DDT/Total DDT Ratio as an Indicator of DDD Use

5.5.5 The o,p ′-DDX/Total DDT Ratio as an Indicator of Industrial Origin or

Time in the Hydrologic System

CHAPTER 6

Analysis of Key Topics—Environmental Significance

6.1 Effects of Pesticide Contaminants on Aquatic Organisms and

Fish-Eating Wildlife

6.1.1 Toxicity to Organisms in the Water Column

USEPA’s Water-Quality Criteria for Protection of Aquatic Organism

Pesticides in Whole Fish—Analysis of Potential Fish Toxicity Fish Kills Attributed to Pesticides

Fish Diseases Associated with Chemical Residues

6.1.2 Toxicity to Benthic Organisms

Approaches to Assessing Sediment Quality Sediment Background Approach

Equilibrium Partitioning Approach Biological Effects Correlation Approach Sediment Toxicity Approach

Definitions of Sediment Quality Guidelines Sediment Background Levels (Lakes Huron and Superior) USEPA’s Sediment Quality Criteria

USEPA’s Sediment Quality Advisory Levels Apparent Effects Thresholds

Effects Range Values for Aquatic Sediment Florida’s Probable Effect Levels and Threshold Effect Levels Canada’s Interim Sediment Quality Guidelines

USEPA’s Procedure for Classifying Sites by Probability of Adverse Effects

Modified Procedure for Classifying Studies by Probability of Adverse Effects

Pesticides in Bed Sediment—Comparison with Background Levels Pesticides in Bed Sediment—Analysis of Potential Adverse Effects

on Benthic Organisms Aldrin and Dieldrin Chlordane

DDT and Metabolites Other Pesticides Summary and Conclusions

6.1.3 Toxicity to Wildlife

Guidelines for Pesticides in Whole Fish NAS/NAE’s Guidelines for Protection of Fish-Eating Wildlife New York’s Fish Flesh Criteria for Piscivorous Wildlife Pesticides in Whole Fish—Analysis of Potential Adverse Effects on Fish-Eating Wildlife

Aldrin and Dieldrin Chlordane

DDT and Metabolites Toxaphene

Other Pesticides Summary

6.1.4 Other Toxicity Concerns

Effects of Chemical Mixtures Potential Endocrine-Disrupting Effects of Pesticides

6.1.5 Summary

6.2 Effects of Pesticide Contaminants in Aquatic Biota onHuman Health

6.2.1 Human Exposure to Pesticides

Pesticide Residues in Human Tissues Breast Milk

Adipose Tissue Blood

Other Human Tissues Summary and Conclusions Sources of Human Exposure to Pesticides Dietary Intake of Pesticides

6.2.2 Potential Toxicity to Humans

Organochlorine Insecticides Organophosphate Insecticides Carbamate Insecticides Pyrethroid Insecticides Herbicides

Fungicides

6.2.3 Standards and Guidelines for Pesticides in Edible Fish and Shellfish

USEPA’s Tolerances FDA’s Action Levels

USEPA’s Guidance for Use in Fish Advisories

6.2.4 Pesticides in Edible Fish and Shellfish—Analysis of Potential

Adverse Effects on Human Health Aldrin and Dieldrin

Total Chlordane Total DDT Other Pesticides

6.2.5 Other Toxicity-Related Issues

Effect of Fish Preparation and Cooking on Pesticide Residues Relative Cancer Risks

Exposure to Multiple Contaminants Potential Endocrine-Disrupting Effects of Pesticides

6.2.6 Summary

CHAPTER 7

Summary and Conclusions

Appendix A

Table 2.1 Pesticides in bed sediment and aquatic biota from rivers and

estuaries in the United States: National and multistate monitoring studies

LIST OF FIGURES

1.1 Pesticide movement in the hydrologic cycle

2.1 Site locations for major national programs that sampled bed sediment

2.2 Site locations for major national programs that sampled aquatic biota

2.3 Geographic distribution of state and local monitoring studies that were

reviewed These studies are listed in Table 2.2

2.4 Geographic distribution of process and matrix distribution studies that were

reviewed These studies are listed in Table 2.3

2.5 Distribution of study effort by decade of sampling and by pesticide class Duration (total study years) of study effort was calculated from all the monitoring studies listed

3.2 Pesticides detected in aquatic biota, shown by the percentage of sites with detectable residues at one or more sites at any time for individual pesticide analytes Data are combined for whole fish, fish muscle, and shellfish from all the monitoring studies listed in Tables 2.1 and 2.2

3.3 Pesticide occurrence in major national programs that sampled bed sediment

or aquatic biota during the 1970s

3.4 Pesticide occurrence in major national programs that sampled bed sediment

or aquatic biota during the 1980s

3.5 Estimated total use of conventional pesticides, showing agricultural and

nonagricultural use, in the United States from 1964 to 1995

3.6 Estimated annual use of conventional pesticides in the United States by

market sector from 1979 to 1995

3.7 Estimated annual herbicide use in the United States by market sector

3.10 Estimated use of conventional pesticides in the United States in 1995,

by market sector and pesticide type

3.11 Pesticide use on national forest land, 1977–1993

3.12 The relation between aggregate site detection frequency and 1966 national

agricultural use, shown for organochlorine insecticides and transformation products detected in sediment and aquatic biota The percentage of sites with detectable levels

is for all monitoring studies (listed in Tables 2.1 and 2.2)

3.13 The U.S Department of Agriculture’s farm production regions

3.14 The geographic distribution of total dieldrin in bed sediment of major United States rivers (1972–1982) from USGS–USEPA’s Pesticide Monitoring Network,

shown in relation to 1966 agricultural use of aldrin plus dieldrin by

farm production region

3.15 The geographic distribution of total DDT in bed sediment of major United States rivers (1972–1982) from USGS–USEPA’s Pesticide Monitoring Network, shown in relation to 1966 agricultural use of DDT plus DDD by farm production region

3.16 The geographic distribution of total DDT in sediment at coastal and

estuarine sites (1984–1989) from NOAA’s National Status and Trends Program, shown in relation to 1966 agricultural use of DDT plus DDD by

farm production region

3.17 The geographic distribution of total DDT in sediment at coastal and

estuarine sites (1984–1989) from NOAA’s National Status and Trends Program, shown in relation to 1990 population density

3.18 The geographic distribution of dieldrin in whole freshwater fish (1976–1979)

from FWS’s National Contaminant Biomonitoring Program, shown in

relation to 1966 agricultural use of aldrin plus dieldrin by

farm production region

3.19 The geographic distribution of dieldrin in whole freshwater fish (1986)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1966 agricultural use of aldrin plus dieldrin by farm production region

3.20 The geographic distribution of dieldrin in whole freshwater fish (1976–1979)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1987 corn production

3.21 The geographic distribution of dieldrin in whole freshwater fish (FWS’s

National Contaminant Biomonitoring Program) and in estuarine mollusks

(NOAA’s National Status and Trends Program) in 1986, shown in relation to

1966 agricultural use of aldrin plus dieldrin by farm production region

3.22 The geographic distribution of total chlordane in whole freshwater fish

(1976–1979) from FWS’s National Contaminant Biomonitoring Program,

shown in relation to 1966 agricultural use of chlordane by

farm production region

3.23 The geographic distribution of total chlordane in whole freshwater fish

(1986) from FWS’s National Contaminant Biomonitoring Program, shown in

relation to 1966 agricultural use of chlordane by farm production region

3.24 The geographic distribution of total chlordane in whole freshwater fish

(FWS’s National Contaminant Biomonitoring Program) and in estuarine

mollusks (NOAA’s National Status and Trends Program) in 1986, shown in

relation to 1966 agricultural use of chlordane by farm production region

3.25 The geographic distribution of total DDT in whole freshwater fish (1976–1979)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1966 agricultural use of DDT plus DDD by farm production region

3.26 The geographic distribution of total DDT in whole freshwater fish (1986)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1966 agricultural use of DDT plus DDD by farm production region

3.27 The geographic distribution of total DDT in whole freshwater fish (FWS’s

National Contaminant Biomonitoring Program) and in estuarine mollusks

(NOAA’s National Status and Trends Program) in 1986, shown in relation to agricultural use of DDT plus DDD in 1966 by farm production region

3.28 The geographic distribution of toxaphene in whole freshwater fish (1976–1979) from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1966 agricultural use of toxaphene by farm production region

3.29 The geographic distribution of toxaphene in whole freshwater fish (1986)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1966 agricultural use of toxaphene by farm production region

3.30 The geographic distribution of toxaphene in whole freshwater fish (1972–1974) from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1987 cotton production

3.31 The geographic distribution of toxaphene in whole freshwater fish (1976–1979) from FWS’s National Contaminant Biomonitoring Program, shown in relation

to 1987 cotton production

3.32 The geographic distribution of toxaphene in whole freshwater fish

(1980–1981) from FWS’s National Contaminant Biomonitoring Program,

shown in relation to 1987 cotton production

3.33 The geographic distribution of toxaphene in whole freshwater fish (1984) from FWS’s National Contaminant Biomonitoring Program, shown in relation to 1987 cotton production

3.34 The geographic distribution of toxaphene in whole freshwater fish (1986)

from FWS’s National Contaminant Biomonitoring Program, shown in relation

3.38 The geographic distribution of chlorpyrifos in fish (1986–1987) from USEPA’s National Study for Chemical Residues in Fish, shown in relation to 1988

agricultural use of chlorpyrifos by farm production region

3.39 The geographic distribution of trifluralin in fish (1986–1987) from USEPA’s National Study for Chemical Residues in Fish, shown in relation to 1988

agricultural use of trifluralin by farm production region

3.40 Temporal trends in dieldrin concentrations in whole fish sampled by the

FWS’s National Contaminant Biomonitoring Program from 1969 to 1986

3.41 Temporal trends in total chlordane concentrations in whole fish sampled

by the FWS’s National Contaminant Biomonitoring Program

from 1976 to 1986

3.42 Temporal trends in total chlordane concentrations in mussels

(Mytilus californianus) at seven estuarine and coastal sites sampled by

the California Mussel Watch from 1979 to 1988

3.43 Temporal trends in total DDT concentrations in whole fish sampled by the

FWS’s National Contaminant Biomonitoring Program from 1969 to 1986

3.44 Temporal trends in toxaphene concentrations in whole fish sampled by the

FWS’s National Contaminant Biomonitoring Program from 1972 to 1986

4.1 Metabolic fate of 14C-labeled aldrin in organisms of a model ecosystem

4.2 The major biotransformation pathways of dieldrin in bluegills

4.3 The major biotransformation pathways of DDT in fish

4.4 The biotransformation pathways of the organophosphate insecticide

fenitrothion in fish

4.5 The biotransformation pathways of the N-methylcarbamate insecticide

carbaryl in fish

5.1 Concentration frequency plot for DDD in bed sediment from agricultural,

urban, and undeveloped areas in southern Florida (1968–1972)

5.2 Concentration frequency plot for dieldrin in bed sediment from agricultural, urban, and undeveloped areas in southern Florida (1968–1972)

5.3 The logarithm of the bioconcentration factor (log BCF) for 10 chlorobenzenes measured in rainbow trout as a function of exposure time (days)

5.4 Correlations between the logarithm of the bioconcentration factor (log BCF)

and the logarithm of the n-octanol-water partition coefficient (log Kow)

5.5 The relation between the logarithm of the bioconcentration factor (log BCF) in

mosquitofish (Gambusia affinis) and the logarithm of the n-octanol-water

partition coefficient (log Kow) for various organic chemicals in laboratory

model ecosystem studies

5.6 The relation between the logarithm of the bioconcentration factor

(log BCF) in mosquitofish (Gambusia affinis) and the logarithm of the

water solubility (log S, µg/L) for various organic chemicals in laboratory

model ecosystem studies

5.7 The gill uptake efficiency and 24-hour gill transport measured using an in vivo fish

(rainbow trout) model in relation to the logarithm of the n-octanol-water partition coefficient (log Kow) for 15 organic chemicals

5.8 The ratio of (fugacity in animal)/(fugacity in water) for PCBs in deep-water

fish of Lake Michigan

5.9 The ratio of (fugacity in animal)/(fugacity in water) for four pesticides in

four fish species from Coralville Reservoir in Iowa

5.10 The logarithm of the fugacity of organochlorine compounds in various

media from the Lake Ontario region

5.11 The ratio of (fugacity in animal)/(fugacity in water) for Lake Ontario rainbow

trout in relation to the logarithm of the n-octanol-water partition coefficient

(log Kow) for 15 organochlorine compounds

5.12 The relation between the logarithm of the bioconcentration factor (log BCF)

and the logarithm of the n-octanol-water partition coefficient (log Kow) for the following compounds: polychlorinated dibenzofurans, polychlorinated

dibenzo-p-dioxins, polybrominated biphenyls, polychlorinated naphthalenes,

polychlorinated anisoles, polybrominated benzenes, polychlorinated biphenyls, and polychlorinated benzenes

5.13 The relation between the logarithm of the biomagnification factor (log BMF)

and the logarithm of the n-octanol-water partition coefficient (log Kow)

for the following compounds: polychlorinated dibenzo-p-dioxins,

polychlorinated biphenyls, and mirex

5.14 The relation between the logarithm of the uptake rate coefficient (log k1)

and the logarithm of the n-octanol-water partition coefficient (log Kow) for the following compounds: polychlorinated dibenzofurans, polychlorinated

dibenzo-p-dioxins, polybrominated biphenyls, polychlorinated naphthalenes,

polychlorinated anisoles, polybrominated benzenes, polychlorinated biphenyls, and polychlorinated benzenes

5.15 The relation between the logarithm of the elimination rate coefficient (log k2)

and the logarithm of the n-octanol-water partition coefficient (log Kow) for the following compounds: polychlorinated dibenzofurans, polychlorinated

dibenzo-p-dioxins, polybrominated biphenyls, polychlorinated naphthalenes,

polychlorinated anisoles, polybrominated benzenes, polychlorinated biphenyls, polychlorinated benzenes, and mirex

5.16 The relation between the logarithm of the overall elimination rate constant

(log kT) in the guppy, and the logarithm of the n-octanol-water partition coefficient (log Kow), for selected halogenated compounds

5.17 The relation between percentage of fat in dorsal muscle tissue and total body length for channel catfish from the Des Moines River

5.18 The relation between percentage of fat in dorsal muscle tissue and age for

channel catfish from the Des Moines River

5.19 The relation between dieldrin concentration in dorsal muscle tissue and

total body length for channel catfish from the Des Moines River

5.20 The relation between dieldrin concentration in dorsal muscle tissue and age

for channel catfish from the Des Moines River

5.21 The relation between 14C-DDT concentration in mosquitofish and

fish body weight

5.22 The relation between the logarithm of the uptake rate constant (log k1)

in the guppy, and the logarithm of the n-octanol-water partition coefficient

(log Kow), for selected halogenated compounds

5.23 The relation between the logarithm of the transport rate and the logarithm of

the n-octanol-water partition coefficient (log Kow) when pore transport is not negligible

5.24 Conceptual diagram of the proposed mechanism of organic chemical

biomagnification in fish, illustrating the increase of the chemical fugacity

in the gastrointestinal tract caused by food digestion and absorption

5.25 Schematic representation of a physiologically based pharmacokinetic model

for a chemical absorbed through the gill and metabolized in the liver

5.26 Seasonal variations in total DDT concentrations in estuarine oysters

(Crassostrea virginica) from three catchment basins in relation to

DDT use in 1985

5.27 PCB concentrations in zooplankton and in water as a function of time in

large outdoor model ecosystems in Sweden during 1983–1984

5.28 Bioconcentration factors for p,p ′-DDT in whole yearling rainbow trout

exposed to p,p ′-DDT in solution at ambient water temperatures of 5°, 10°,

and 15 °C, as a function of exposure time

5.29 Relation between the logarithm of the bioaccumulation factor (log BAF) for

phytoplankton from Green Bay, Lake Michigan, and the logarithm of the

n-octanol-water partition coefficient (log Kow) for various contaminants,

during winter and summer

5.30 The relation between the logarithm of soil half-life (days) and the logarithm of the

water solubility (log S) for pesticides analyzed in sediment and aquatic biota

by the monitoring studies reviewed

5.31 The relation between the logarithm of soil half-life (days) and the logarithm

of the water solubility (log S) for pesticides analyzed in sediment and

aquatic biota by the monitoring studies reviewed, compared with pesticides

that were rarely analyzed in these media

5.32 The relation between the logarithm of soil half-life (days) and the logarithm

of the n-octanol-water partition coefficient (log Kow) for pesticides detected in

sediment and aquatic biota by the monitoring studies reviewed

5.33 The relation between the logarithm of soil half-life (days) and the logarithm

of the n-octanol-water partition coefficient (log Kow) for pesticides analyzed in

sediment and aquatic biota by the monitoring studies reviewed, compared with

pesticides that were rarely analyzed in these media

6.1 Cumulative frequency distribution of the maximum concentrations of dieldrin in

sediment reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.2 Cumulative frequency distribution of the maximum concentrations of total chlordane

in sediment reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.3 Cumulative frequency distribution of the maximum concentrations of p,p ′-DDE in

sediment reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.4 Cumulative frequency distribution of the maximum concentrations of total DDT in

sediment reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.5 Cumulative frequency distribution of the maximum concentrations of diazinon

in sediment reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994)

6.6 Percentage of all monitoring studies (published 1960–1994) in probability

of adverse effects categories

6.7 Percentage of recently published (1984–1994) monitoring studies in

probability of adverse effects categories

6.8 Cumulative frequency distribution of the maximum concentrations of dieldrin

in whole fish reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.9 Cumulative frequency distribution of the maximum concentrations of total chlordane

in whole fish reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.10 Cumulative frequency distribution of the maximum concentrations of total DDT in

whole fish reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.11 Cumulative frequency distribution of the maximum concentrations of toxaphene in

whole fish reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.12 Egg mortality in double-crested cormorants from 12 colonies in the Great Lakes

and one reference colony (Manitoba, Canada) as a function of the concentration of

H4IIE bioassay-derived TCDD equivalents

6.13 Cumulative frequency distribution of the maximum concentrations of dieldrin

in fish muscle reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.14 Cumulative frequency distribution of the maximum concentrations of chlordane

in fish muscle reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

6.15 Cumulative frequency distribution of the maximum concentrations of total DDT

in fish muscle reported by the monitoring studies reviewed, shown for all studies

(published during 1960–1994) and recently published (1984–1994) studies

LIST OF TABLES

Note: Pages out of sequence indicate that some tables have been placed at the end of the book 1.1 Summary of review articles and books on pesticides in bed sediment and aquatic biota

in the United States or on processes governing sorption and bioaccumulation

2.1 Pesticides in bed sediment and aquatic biota from rivers and estuaries in the

United States: National and multistate monitoring studies

2.2 Pesticides in bed sediment and aquatic biota from rivers in the

United States: State and local monitoring studies

2.3 Pesticides in bed sediment and aquatic biota from rivers in the

United States: Process and matrix distribution studies

2.4 General study characteristics condensed from Tables 2.1, 2.2, and 2.3

3.1 Total number of sites and samples, and corresponding aggregate detection

frequencies (in percent) of pesticides in bed sediment from United States rivers,

calculated by combining data from the monitoring studies in

Tables 2.1 and 2.2

3.2 Total number of sites and samples, and corresponding aggregate detection

frequencies (in percent) of pesticides in aquatic biota from United States rivers,

calculated by combining data from the monitoring studies in

Tables 2.1 and 2.2

3.3 Total number of sites and corresponding aggregate detection frequencies (in percent)

of pesticides in whole fish, fish muscle, and mollusk samples from United States

rivers, calculated by combining data from the monitoring studies in

Tables 2.1 and 2.2

3.4 Design features of major national programs that measured pesticide residues

in bed sediment or aquatic biota

3.5 Estimated pesticide use in agricultural, home and garden, and industry

settings in the United States, and detections in ground water, surface water, rain,

air, sediment, and aquatic biota

3.6 Analysis of pesticides in bed sediment and analysis of pesticides in

aquatic biota

3.7 Selected physical and chemical properties of pesticide analytes that were targeted in bed sediment and aquatic biota studies

3.8 Aldrin plus dieldrin use on corn and toxaphene use on cotton, 1964–1976

3.9 Trends in residues of DDT and metabolites in aquatic biota: Median residues from

several national surveys

4.1 Phase I biotransformation reactions of pesticides in fish

4.2 Phase II biotransformation (conjugation) reactions of pesticides in fish

5.1 Residues of total DDT in samples from the Carmans River Estuary,

Long Island, New York

5.2 Biota–sediment accumulation factors measured in some laboratory and

field studies

5.3 The relative importance of dietary sources to bioaccumulation of various

chemicals in studies reviewed in Macek and others (1979)

5.4 Time required by biota to eliminate 50 percent of the body burden (t1/2, in days) during depuration in uncontaminated flowing water

5.5 Factors reported in the literature to affect contaminant accumulation

by aquatic biota

5.6 Pesticides predicted to be potential contaminants in bed sediment and aquatic biota on the basis of hydrophobicity and persistence, with estimated pesticide use, the percentage of total samples with detectable concentrations, and the

total number of samples

6.1 Acute aquatic toxicity of pesticides detected in aquatic biota

6.2 Potential chronic toxicity to aquatic biota in studies that monitored pesticides

6.5 Effects range–low (ERL) and effects range–median (ERM) values

for dieldrin and the 14 concentrations, arranged in ascending order, that were used

to determine these values

6.6 Selected results of studies that monitored pesticides in bed sediment

6.7 Percentage of studies in probability of adverse effects classes, Tiers 1, 2, and 3,

for pesticides in bed sediment

6.8 Standards and guidelines for pesticides in aquatic biota

6.9 Selected results of studies that monitored pesticides in whole fish and the

percentage of those studies that exceeded guidelines for the protection of

fish-eating wildlife

6.10 Inhibitor concentrations necessary for 50 percent inhibition of [3H]17β-estradiol binding to aER by environmental chemicals

6.11 Dieldrin residues in human adipose tissue, 1963–1976

6.12 Frequency of pesticides and metabolites detected in urine from persons

12–74 years old, United States, 1976–1980

6.13 Percentage of samples that contained the most frequently detected pesticides, and the number of pesticides detected, in the FDA Total Diet Study from

1978 to 1991

6.14 Pesticide intake (µg/kg body weight/d) in total diet analyses for three

age–sex groups in 1991 and corresponding FAO–WHO acceptable daily intake and USEPA reference dose values

6.15 Mammalian toxicity characteristics of pesticide analytes that were detected

in aquatic biota in the monitoring studies reviewed

6.16 Mechanisms of action of several different herbicide classes

6.17 Selected results of studies that monitored pesticides in fish muscle and percentage of those studies that exceeded standards and guidelines for the protection of human health

6.18 Selected results of studies that monitored pesticides in shellfish and

percentage of those studies that exceeded standards for the protection of human health

6.19 Estimated cancer risks from breathing urban air and consuming various foods and water, including Lake Michigan fish and Niagara River water

6.20 Interactive effects reported in the literature for pesticides

found in aquatic biota

CONVERSION FACTORS

cubic meter (m3) 35.31 cubic foot (ft3)

square kilometer (km2) 0.3861 square mile (mi2)

square meter (m2) 10.76 square foot (ft2)

cubic foot (ft3) 0.02832 cubic meter (m3)

square foot (ft2) 0.09290 square meter (m2) square mile (mi2) 2.5900 square kilometer (km2)

atmosphere (atm) 1.01325 ×105 pascal (Pa)

pascal (Pa) 9.869 ×10-6 atmosphere (atm) pascal (Pa) 1.4507 ×10-4 pounds per square inch (psi) pounds per square inch (psi) 6.8947 ×103 pascal (Pa)

Temperature is given in degrees Celsius ( °C), which can be converted to degrees Fahrenheit ( °F) by the following equation:

°F = 1.8(°C) + 32

ABBREVIATIONS AND ACRONYMS

Note: Clarification or additional information is provided in parentheses Abbreviations for chemical compounds are included in Appendix E.

Government, Private Agencies, and Legislation

BofCF, Bureau of Commercial Fisheries

CDFA, California Department of Food and Agriculture

CSWRCB, California State Water Resources Control Board

FAO–WHO, Food and Agriculture Organization (United Nations)–World Health Organization FDA, Food and Drug Administration

FFDCA, Federal Food Drug and Cosmetic Act

FIFRA, Federal Insecticide, Fungicide, and Rodenticide Act

FQPA, Food Quality Protection Act

FWS, Fish and Wildlife Service

NAS/NAE, National Academy of Sciences and National Academy of Engineering

NOAA, National Oceanic and Atmospheric Administration

NYDH, New York Department of Health

RCRA, Resource Conservation and Recovery Act

U.S., United States

USDA, U.S Department of Agriculture

USEPA, U.S Environmental Protection Agency

USGS, U.S Geological Survey

Monitoring Programs and Surveys

BEST, Biomonitoring of Environmental Status and Trends

NASQAN, National Stream Quality Accounting Network

NAWQA, National Water Quality Assessment (Program)

NCBP, National Contaminant Biomonitoring Program

NMPFF, National Monitoring Program for Food and Feed

NS&T, National Status and Trends (Program)

NSCRF, National Study of Chemical Residues in Fish

NYSDEC, New York State Department of Conservation

NUPAS, National Urban Pesticide Applicator Survey

NURP, Nationwide Urban Runoff Program

PMN, Pesticide Monitoring Network

TSMP, Toxic Substances Monitoring Program (California)

Miscellaneous Abbreviations and Acronyms

A, air

AB, aquatic biota

ADP, adenosine diphosphate

aER, alligator estrogen receptor

AET, apparent effects threshold

AET-H, apparent effects threshold–high

AET-L, apparent effects threshold–low

AGRICOLA, a bibliographic database of the National Agricultural Library (USDA)

AL, action level

ATP, adenosine triphosphate

BAF, bioaccumulation factor

BCF, bioconcentration factor

BMF, biomagnification factor

BSAF, biota–sediment accumulation factor

Bt, Bacillus thuringiensis var Kurstaki

C, Celsius, channel

CGM, geometric mean concentration

CH, high concentration (one standard deviation above the mean)

Cmax, the maximum concentration reported in a study

COA, co-occurrence analysis

CP, chlorophenoxy (chlorophenol)

CPG, Compliance Policy Guide (FDA)

DL, detection limit

DOM, dissolved organic matter

E2/11KT ratio, ratio of 17β estradiol to 11-ketotestosterone

Ea, activation energy

EC50, median effective concentration

EDL, elevated data level

EH, redox potential

EP, equilibrium partitioning, extraction procedure

ERL, effects range–low

ERM, effects range–medium

F, f test statistic in analysis of variance

f, fugacity

FCL, Four County Landfill

FCV, final chronic value

foc, fraction of organic carbon (of a particle)

FTC, fish tissue concentration

FY, fiscal year

GC/MS, gas chromatography with mass spectrometric detection

GIT, gastrointestinal tract

GW, ground water

i, insufficient guidelines to determine a Tier 1–2 boundary value ISQG, interim sediment quality guideline (Canadian)

KD, solid-water distribution coefficient

kgoc, kilograms of organic carbon in sediment

Koc, organic carbon normalized sediment-water distribution coefficient

Kow, n-octanol-water partition coefficient

L, lower screening value

LC, Lincoln City

LC50, median lethal concentration

LD50, median lethal dose

MIA, Miami International Airport