The Handbook
of Environmental Chemistry
Editor-in-Chief: O. Hutzinger
Volume 5 Water Pollution
Part N
Advisory Board:
D. Barceló · P. Fabian · H. Fiedler · H. Frank · J. P. Giesy · R. A. Hites
T. A. Kassim · M. A. K. Khalil · D. Mackay · A. H. Neilson
J. Paasivirta · H. Parlar · S. H. Safe · P. J. Wangersky
The Handbook of Environmental Chemistry
Recently Published and Forthcoming Volumes
Environmental Specimen Banking
Volume Editors: S. A. Wise and P. P. R. Becker
Vol. 3/S, 2006
Polymers: Chances and Risks
Volume Editors: P. Eyerer, M. Weller
and C. Hübner
Vol. 3/V, 2006
Marine Organic Matter: Biomarkers,
Isotopes and DNA
Volume Editor: J. K. Volkman
Vol. 2/N, 2005
Environmental Photochemistry Part II
Volume Editors: P. Boule, D. Bahnemann
and P. Robertson
Vol. 2/M, 2005
The Rhine
Volume Editor: T. P. Knepper
Vol. 5/L, 03.2006
Air Quality in Airplane Cabins
and Similar Enclosed Spaces
Volume Editor: M. B. Hocking
Vol. 4/H, 2005
Persistent Organic Pollutants
in the Great Lakes
Volume Editor: R. A. Hites
Vol. 5/N, 2006
Environmental Effects
of Marine Finfish Aquaculture
Volume Editor: B. T. Hargrave
Vol. 5/M, 2005
Antifouling Paint Biocides
Volume Editor: I. Konstantinou
Vol. 5/O, 2006
The Mediterranean Sea
Volume Editor: A. Saliot
Vol. 5/K, 2005
Estuaries
Volume Editor: P. J. Wangersky
Vol. 5/H, 2006
The Caspian Sea Environment
Volume Editors: A. Kostianoy and A. Kosarev
Vol. 5/P, 2005
Environmental Impact Assessment of Recycled
Wastes on Surface and Ground Waters
Engineering Modeling and Sustainability
Volume Editor: T. A. Kassim
Vol. 5/F (3 Vols.), 2005
Oxidants and Antioxidant Defense Systems
Volume Editor: T. Grune
Vol. 2/O, 2005
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Persistent Organic Pollutants
in the Great Lakes
Volume Editor:
Ronald A. Hites
With contributions by
J. E. Baker · T. F. Bidleman · D. L. Carlson · K. Coady
S. J. Eisenreich · J. P. Giesy · P. A. Helm · R. A. Hites
K. C. Hornbuckle · L. M. Jantunen · P. D. Jones · K. Kannan
S. A. Mabury · J. W. Martin · D. C. G. Muir · J. L. Newsted
R. J. Norstrom · J. H. Offenberg · J. Ridal · M. F. Simcik
J. Struger · D. L. Swackhamer
123
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Environmental chemistry is a rather young and interdisciplinary field of science. Its aim is a complete
description of the environment and of transformations occurring on a local or global scale. Environmental chemistry also gives an account of the impact of man’s activities on the natural environment by
describing observed changes.
The Handbook of Environmental Chemistry provides the compilation of today’s knowledge. Contributions are written by leading experts with practical experience in their fields. The Handbook will grow
with the increase in our scientific understanding and should provide a valuable source not only for
scientists, but also for environmental managers and decision-makers.
The Handbook of Environmental Chemistry is published in a series of five volumes:
Volume 1: The Natural Environment and the Biogeochemical Cycles
Volume 2: Reactions and Processes
Volume 3: Anthropogenic Compounds
Volume 4: Air Pollution
Volume 5: Water Pollution
The series Volume 1 The Natural Environment and the Biogeochemical Cycles describes the natural
environment and gives an account of the global cycles for elements and classes of natural compounds.
The series Volume 2 Reactions and Processes is an account of physical transport, and chemical and
biological transformations of chemicals in the environment.
The series Volume 3 Anthropogenic Compounds describes synthetic compounds, and compound
classes as well as elements and naturally occurring chemical entities which are mobilized by man’s
activities.
The series Volume 4 Air Pollution and Volume 5 Water Pollution deal with the description of civilization’s
effects on the atmosphere and hydrosphere.
Within the individual series articles do not appear in a predetermined sequence. Instead, we invite
contributors as our knowledge matures enough to warrant a handbook article.
Suggestions for new topics from the scientific community to members of the Advisory Board or to the
Publisher are very welcome.
Library of Congress Control Number: 2005938926
ISSN 1433-6863
ISBN-10 3-540-29168-7 Springer Berlin Heidelberg New York
ISBN-13 978-3-540-29168-8 Springer Berlin Heidelberg New York
DOI 10.1007/b13133
This work is subject to copyright. All rights are reserved, whether the whole or part of the material
is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of
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Editor-in-Chief
Prof. em. Dr. Otto Hutzinger
Universität Bayreuth
c/o Bad Ischl Office
Grenzweg 22
5351 Aigen-Vogelhub, Austria
Volume Editor
Prof. Ronald A. Hites
Indiana University
School of Public
and Environmental Affairs
1315 East Tenth Street
Bloomington, IN 47405, USA
Advisory Board
Prof. Dr. D. Barceló
Prof. Dr. J. P. Giesy
Dept. of Environmental Chemistry
IIQAB-CSIC
JordiGirona, 18–26
08034 Barcelona, Spain
Department of Zoology
Michigan State University
East Lansing, MI 48824-1115, USA
Prof. Dr. R. A. Hites
Prof. Dr. P. Fabian
Lehrstuhl für Bioklimatologie
und Immissionsforschung
der Universität München
Hohenbachernstraße 22
85354 Freising-Weihenstephan, Germany
Dr. H. Fiedler
Scientific Affairs Office
UNEP Chemicals
11–13, chemin des Anémones
1219 Châteleine (GE), Switzerland
hfi
Prof. Dr. H. Frank
Lehrstuhl für Umwelttechnik
und Ökotoxikologie
Universität Bayreuth
Postfach 10 12 51
95440 Bayreuth, Germany
Indiana University
School of Public
and Environmental Affairs
Bloomington, IN 47405, USA
Dr. T. A. Kassim
Department of Civil
and Environmental Engineering
College of Science and Engineering
Seattle University
901 12th Avenue
Seattle, WA 98122-1090, USA
Prof. Dr. M. A. K. Khalil
Department of Physics
Portland State University
Science Building II, Room 410
P.O. Box 751
Portland, OR 97207-0751, USA
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VI
Prof. Dr. D. Mackay
Prof. Dr. Dr. H. Parlar
Department of Chemical Engineering
and Applied Chemistry
University of Toronto
Toronto, ON, M5S 1A4, Canada
Institut für Lebensmitteltechnologie
und Analytische Chemie
Technische Universität München
85350 Freising-Weihenstephan, Germany
Prof. Dr. A. H. Neilson
Prof. Dr. S. H. Safe
Swedish Environmental Research Institute
P.O. Box 21060
10031 Stockholm, Sweden
Department of Veterinary
Physiology and Pharmacology
College of Veterinary Medicine
Texas A & M University
College Station, TX 77843-4466, USA
Prof. Dr. J. Paasivirta
Department of Chemistry
University of Jyväskylä
Survontie 9
P.O. Box 35
40351 Jyväskylä, Finland
Prof. P. J. Wangersky
University of Victoria
Centre for Earth and Ocean Research
P.O. Box 1700
Victoria, BC, V8W 3P6, Canada
wangers@telus. net
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Preface
Environmental Chemistry is a relatively young science. Interest in this subject,
however, is growing very rapidly and, although no agreement has been reached
as yet about the exact content and limits of this interdisciplinary discipline,
there appears to be increasing interest in seeing environmental topics which
are based on chemistry embodied in this subject. One of the first objectives
of Environmental Chemistry must be the study of the environment and of
natural chemical processes which occur in the environment. A major purpose
of this series on Environmental Chemistry, therefore, is to present a reasonably
uniform view of various aspects of the chemistry of the environment and
chemical reactions occurring in the environment.
The industrial activities of man have given a new dimension to Environmental Chemistry. We have now synthesized and described over five million
chemical compounds and chemical industry produces about hundred and fifty
million tons of synthetic chemicals annually. We ship billions of tons of oil per
year and through mining operations and other geophysical modifications, large
quantities of inorganic and organic materials are released from their natural
deposits. Cities and metropolitan areas of up to 15 million inhabitants produce
large quantities of waste in relatively small and confined areas. Much of the
chemical products and waste products of modern society are released into
the environment either during production, storage, transport, use or ultimate
disposal. These released materials participate in natural cycles and reactions
and frequently lead to interference and disturbance of natural systems.
Environmental Chemistry is concerned with reactions in the environment.
It is about distribution and equilibria between environmental compartments.
It is about reactions, pathways, thermodynamics and kinetics. An important
purpose of this Handbook, is to aid understanding of the basic distribution
and chemical reaction processes which occur in the environment.
Laws regulating toxic substances in various countries are designed to assess
and control risk of chemicals to man and his environment. Science can contribute in two areas to this assessment; firstly in the area of toxicology and secondly in the area of chemical exposure. The available concentration (“environmental exposure concentration”) depends on the fate of chemical compounds
in the environment and thus their distribution and reaction behaviour in the
environment. One very important contribution of Environmental Chemistry to
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X
Preface
the above mentioned toxic substances laws is to develop laboratory test methods, or mathematical correlations and models that predict the environmental
fate of new chemical compounds. The third purpose of this Handbook is to help
in the basic understanding and development of such test methods and models.
The last explicit purpose of the Handbook is to present, in concise form, the
most important properties relating to environmental chemistry and hazard
assessment for the most important series of chemical compounds.
At the moment three volumes of the Handbook are planned. Volume 1 deals
with the natural environment and the biogeochemical cycles therein, including some background information such as energetics and ecology. Volume 2
is concerned with reactions and processes in the environment and deals with
physical factors such as transport and adsorption, and chemical, photochemical and biochemical reactions in the environment, as well as some aspects
of pharmacokinetics and metabolism within organisms. Volume 3 deals with
anthropogenic compounds, their chemical backgrounds, production methods
and information about their use, their environmental behaviour, analytical
methodology and some important aspects of their toxic effects. The material
for volume 1, 2 and 3 was each more than could easily be fitted into a single volume, and for this reason, as well as for the purpose of rapid publication of available manuscripts, all three volumes were divided in the parts A and B. Part A of
all three volumes is now being published and the second part of each of these
volumes should appear about six months thereafter. Publisher and editor hope
to keep materials of the volumes one to three up to date and to extend coverage
in the subject areas by publishing further parts in the future. Plans also exist for
volumes dealing with different subject matter such as analysis, chemical technology and toxicology, and readers are encouraged to offer suggestions and
advice as to future editions of “The Handbook of Environmental Chemistry”.
Most chapters in the Handbook are written to a fairly advanced level and
should be of interest to the graduate student and practising scientist. I also hope
that the subject matter treated will be of interest to people outside chemistry
and to scientists in industry as well as government and regulatory bodies. It
would be very satisfying for me to see the books used as a basis for developing
graduate courses in Environmental Chemistry.
Due to the breadth of the subject matter, it was not easy to edit this Handbook. Specialists had to be found in quite different areas of science who were
willing to contribute a chapter within the prescribed schedule. It is with great
satisfaction that I thank all 52 authors from 8 countries for their understanding
and for devoting their time to this effort. Special thanks are due to Dr. F. Boschke
of Springer for his advice and discussions throughout all stages of preparation
of the Handbook. Mrs. A. Heinrich of Springer has significantly contributed to
the technical development of the book through her conscientious and efficient
work. Finally I like to thank my family, students and colleagues for being so patient with me during several critical phases of preparation for the Handbook,
and to some colleagues and the secretaries for technical help.
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Preface
XI
I consider it a privilege to see my chosen subject grow. My interest in Environmental Chemistry dates back to my early college days in Vienna. I received
significant impulses during my postdoctoral period at the University of California and my interest slowly developed during my time with the National
Research Council of Canada, before I could devote my full time of Environmental Chemistry, here in Amsterdam. I hope this Handbook may help deepen
the interest of other scientists in this subject.
Amsterdam, May 1980
O. Hutzinger
Twenty-one years have now passed since the appearance of the first volumes
of the Handbook. Although the basic concept has remained the same changes
and adjustments were necessary.
Some years ago publishers and editors agreed to expand the Handbook by
two new open-end volume series: Air Pollution and Water Pollution. These
broad topics could not be fitted easily into the headings of the first three
volumes. All five volume series are integrated through the choice of topics and
by a system of cross referencing.
The outline of the Handbook is thus as follows:
1.
2.
3.
4.
5.
The Natural Environment and the Biochemical Cycles,
Reaction and Processes,
Anthropogenic Compounds,
Air Pollution,
Water Pollution.
Rapid developments in Environmental Chemistry and the increasing breadth
of the subject matter covered made it necessary to establish volume-editors.
Each subject is now supervised by specialists in their respective fields.
A recent development is the accessibility of all new volumes of the Handbook
from 1990 onwards, available via the Springer Homepage springeronline.com
or springerlink.com.
During the last 5 to 10 years there was a growing tendency to include subject
matters of societal relevance into a broad view of Environmental Chemistry.
Topics include LCA (Life Cycle Analysis), Environmental Management, Sustainable Development and others. Whilst these topics are of great importance
for the development and acceptance of Environmental Chemistry Publishers
and Editors have decided to keep the Handbook essentially a source of information on “hard sciences”.
With books in press and in preparation we have now well over 40 volumes
available. Authors, volume-editors and editor-in-chief are rewarded by the
broad acceptance of the “Handbook” in the scientific community.
Bayreuth, July 2001
Otto Hutzinger
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Contents
Persistent Organic Pollutants in the Great Lakes: An Overview
R. A. Hites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
Polychlorinated Biphenyls in the Great Lakes
K. C. Hornbuckle · D. L. Carlson · D. L. Swackhamer · J. E. Baker
S. J. Eisenreich . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
Polychlorinated Dibenzo-p-dioxins
and Dibenzofurans in the Great Lakes
R. J. Norstrom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
Pesticides in the Great Lakes
K. Kannan · J. Ridal · J. Struger . . . . . . . . . . . . . . . . . . . . . . . 151
Toxaphene in the Great Lakes
D. C. G. Muir · D. L. Swackhamer · T. F. Bidleman · L. M. Jantunen . . . . 201
Polychlorinated Naphthalenes in the Great Lakes
P. A. Helm · K. Kannan · T. F. Bidleman . . . . . . . . . . . . . . . . . . 269
Polycyclic Aromatic Hydrocarbons in the Great Lakes
M. F. Simcik · J. H. Offenberg . . . . . . . . . . . . . . . . . . . . . . . . 309
Brominated Flame Retardants in the Great Lakes
R. A. Hites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Perfluorinated Compounds in the Great Lakes
J. P. Giesy · S. A. Mabury · J. W. Martin · K. Kannan · P. D. Jones
J. L. Newsted · K. Coady . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
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Foreword
I grew up in Detroit, Michigan. One day when I was a little boy my grandparents
took me to a park on the shore of what I was told was the Detroit River.
I remember being amazed to see very large ships passing by. It wasnt long
before I learned that the Detroit River was part of the Laurentian Great Lakes
system and that these big ships moved among all five of the lakes. In our social
studies class (which was mostly a class in maps), I learned that the land I was
seeing across the Detroit River was a foreign country called Canada and that
the United States-Canadian international border ran through four of the Great
Lakes. We also learned that the Great Lakes were closely tied to the cultural
heritage of both countries and that the lakes had served as a highway leading
to the exploration, settlement, and eventual industrialization of this region of
North America.
The Great Lakes are big – the total area of the Great Lakes’ drainage basin is
∼ 40% larger than France – and the Great Lakes contain the largest reservoir of
fresh, surface water on earth; only the polar ice caps contain more fresh water.
The lakes are an especially valuable natural resource to the United States,
to Canada, and to the world. A brief study of a map shows that the Great
Lakes basin is highly populated in the south and includes such major cities
as Chicago, Illinois; Detroit, Michigan; Cleveland, Ohio; and Toronto, Ontario.
Large concentrations of industry and agriculture are also located in the Great
Lakes region. All of this anthropogenic activity has had its environmental costs.
Agricultural runoff, urban waste, industrial discharge, landfill leachate, and
atmospheric deposition all contribute to the pollution of the lakes.
In the late 1960s, growing public concern about the deteriorating environmental quality of the Great Lakes stimulated research on the inputs and
behavior of pollutants in the lakes. Governments in both the United States
and Canada responded to the concern by regulating pollutant discharges and
initiating research on the sources, fates, and effects of pollutants in the lakes.
These efforts were formalized in the first Great Lakes Water Quality Agreement
between Canada and the United States in 1972.
Because of this increased attention, major reductions were made in pollutant inputs, and by the 1970s some results were clear. Oil slicks disappeared;
dissolved oxygen levels improved; odor problems were eliminated; beaches
reopened; and algal mats disappeared. Buoyed by these successes, attention
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XVI
Foreword
shifted to persistent toxic contaminants in the 1980s, as reflected in the 1987
Amended Great Lakes Water Quality Agreement.
The book you are holding brings together what is known about the major classes of these persistent organic pollutants in the Great Lakes. Each
chapter reviews our knowledge of the extent of contamination of the various parts of the Great Lakes ecosystem (air, water, sediment, fishes, birds,
etc.), what is known about the trends over time of this contamination, and
knowledge about the mechanisms by which these pollutants are mobilized
in the lakes. Detailed information is presented on polychlorinated biphenyls
(PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins), pesticides, toxaphene, polychlorinated naphthalenes (PCNs), polycyclic aromatic
hydrocarbons (PAHs), brominated flame retardants (including polybrominated biphenyls and diphenyl ethers), and perfluoroalkyl acids (PFAs). As my
wife points out, I have not done much; I have simply asked my friends and colleagues to write chapters and added my name to the book’s cover. While this is
an oversimplification of an editor’s job, she is not too far from the mark. Thus,
I want to sincerely thank the authors of the various chapters for their more or
less prompt attention to researching and writing each chapter. Without these
authors, there would be no book and no cover to bear my name. We all hope
that you, the reader, will find this book to be a useful resource for research,
decision making, and teaching.
Bloomington, Indiana, August 2005
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Ronald A. Hites
Hdb Env Chem Vol. 5, Part N (2006): 1–12
DOI 10.1007/698_5_038
© Springer-Verlag Berlin Heidelberg 2005
Published online: 23 November 2005
Persistent Organic Pollutants in the Great Lakes:
An Overview
Ronald A. Hites
School of Public and Environmental Affairs, Indiana University, Bloomington, IN 47405,
USA
1
Introduction: The Great Lakes . . . . . . . . . . . . . . . . . . . . . . . . .
2
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
Overview of Chapters . . . . . . .
Polychlorinated Biphenyls . . . .
Dioxins . . . . . . . . . . . . . . .
Pesticides . . . . . . . . . . . . . .
Toxaphene . . . . . . . . . . . . .
Polychlorinated Naphthalenes . .
Polycyclic Aromatic Hydrocarbons
Brominated Flame Retardants . .
Perfluorinated Compounds . . . .
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11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
Abstract This chapter presents background information on the Great Lakes and summarizes the content of each chapter of this book.
1
Introduction: The Great Lakes [1]
The Laurentian Great Lakes (not to be confused with the Great Lakes in
Africa) are located near the middle of the North American continent. There
are five Great Lakes, and they are called Lakes Superior, Michigan, Huron,
Erie, and Ontario; see Fig. 1. Lake St. Clair is, strictly speaking, not one of the
Great Lakes, but it is part of the connection between Lakes Huron and Erie.
The United States-Canadian international border runs through four of the
lakes, and collectively the Great Lakes are closely tied to the cultural heritage
of both the United States and Canada. Early on, the lakes were the highway
that led to the exploration, settlement, and eventual industrialization of this
region of North America. The lakes have provided a thriving commercial fishery (now largely vanished) and water for drinking, transportation, power,
industry, and recreation.
The Great Lakes are big; see Table 1. From the westernmost corner of Lake
Superior to the easternmost shore of Lake Ontario, these lakes cover a distance of > 1200 km. The total water area of the lakes is 244 000 km2 —an area
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2
R.A. Hites
Fig. 1 Map of the Great Lakes showing the major geographic features (from [1])
about the size of Great Britain. The total area of the Great Lakes’ drainage
basin is 766 000 km2 —an area much larger than the combined areas of Germany and Italy and ∼ 40% larger than France. In this drainage basin, the
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183
563
257
147
406
12 100
82 100
128 000
210 000
39
4380
191
425 500
181 600
607 100
10 057 000
176
494
190
85
282
4920
57 800
118 000
176 000
33
2630
99
10 057 000
Michigan
176
332
245
59
229
3540
59 600
134 000
194 000
31
6160
22
1 503 000
1 191 000
2 694 000
Huron
173
388
92
19
64
484
25 700
78 000
104 000
25
1400
2.6
10 018 000
1 665 000
11 683 000
Erie
74
311
85
86
244
1640
19 000
64 000
83 000
23
1150
6
2 704 000
5 447 000
8 151 000
Ontario
24 707 000
8 484 000
33 191 000
22 700
244 000
522 000
766 000
32
17 000 d
Total
a Measured at low water height. b Land drainage area for Lake Huron includes the St. Marys River; Lake Erie includes the St. Clair-Detroit
system; and Lake Ontario includes the Niagara River. c Including islands. d These totals are greater than the sum of the shoreline lengths for
the lakes because they include the connecting channels (excluding the St. Lawrence River).
Elevation a (in meters)
Length (in km)
Breadth (in km)
Average depth a (in meters)
Maximum depth a (in meters)
Volume a (in km3 )
Water area (in km2 )
Land drainage area b (in km2 )
Total area (in km2 )
% Water relative to total area
Shoreline length c (in km)
Retention time (years)
Population: U.S. (1990)
Canada (1991)
Totals
Superior
Table 1 Physical features and population of the Great Lakes (from [1])
Persistent Organic Pollutants in the Great Lakes: An Overview
3
4
R.A. Hites
lakes themselves cover about 32% of this area. The lakes contain 22 700 km3
(or 2.27 × 1016 L) of freshwater, much of which is still pure enough to be consumed with minimal treatment. The Great Lakes contain the largest reservoir
of fresh, surface water on earth—about 18% of the world’s supply; only the
polar ice caps contain more fresh water.
The Great Lakes basin is highly populated in the south and includes such
major cities as Chicago, Illinois; Detroit, Michigan; Cleveland, Ohio; and
Toronto, Ontario. More than 10% of the United States’ population and more
than 25% of the Canadian population live in the Great Lakes basin. Large concentrations of industry are located in the Great Lakes region; for example,
the U.S. and Canadian automobile industry is located there. Agriculture is
also an important part of the Great Lakes basin’s economy; ∼ 25% of Canadian and ∼ 7% of United States agricultural production is in the Great Lakes
basin. Of course, all of this activity is not without its environmental costs.
Agricultural runoff, urban waste, industrial discharge, and landfill leachate all
contribute to the pollution of the lakes. In addition, the large surface area and
slow flushing rates of the lakes makes them vulnerable to the deposition of
contaminants from the atmosphere.
Because of the sheer magnitude of the Great Lakes’ watershed size, physical characteristics, such as climate and soils, vary across the basin. In the
north, the climate is relatively cold, and the terrain is dominated by granite
bedrock called the Canadian (or Laurentian) Shield, which consists of Precambrian rocks under a generally thin layer of acidic soils. Conifers dominate
the northern forests. In the southern areas of the Great Lakes basin, the climate is warmer, and the soils are deeper with layers of clay, silt, sand, and
gravel, which were deposited by glaciers. In the southern basin, the lands can
be readily used for agriculture. In several places in the basin, the original
landscape has been replaced by sprawling urban development.
The lakes have very different depths, and thus they have very different
properties and responses to environmental insult. The depth profile of the
lakes is shown in Fig. 2.
Lake Superior is by far the largest, deepest, and coldest of the five lakes.
This lake has a water retention time of almost 200 years. There is little agriculture in Lake Superior’s basin (largely because of the poor soils and cold
climate); instead most of the basin is forested. The sparse human population
around Lake Superior results in relatively little pollution entering the lake as
a result of local human activity, but because of its large surface area and its
small drainage area, large amounts of pollutants are delivered by deposition
from the atmosphere.
Lake Michigan is the second largest of the lakes, and it is the only lake
entirely within the United States. The northern part of Lake Michigan is in
the colder and less developed upper Great Lakes region, and this region is
sparsely populated, except for the Fox River Valley, which drains into Green
Bay. In fact, this bay has been contaminated by wastes from a large concen-
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Persistent Organic Pollutants in the Great Lakes: An Overview
5
Fig. 2 Diagram indicating the relative depths (in meters below the lake surface) and surface elevations (in meters above sea level) of the five Great Lakes measured along the
long axis of each lake. The vertical exaggeration is 2000 : 1. The inter-lake lock and river
systems are numbered. From [1]
tration of pulp and paper mills in this part of Wisconsin. The Southern Lake
Michigan basin is among the most urbanized areas in the Great Lakes system,
being the home of the greater Milwaukee, Chicago, and Gary metropolitan
areas. About 12 million people live in this region.
Lake Huron (including Georgian Bay) is the third largest of the lakes.
The human impacts in the Lake Huron basin are relatively minor, consisting mostly of recreational uses. For example, many Canadians have cottages
on the shallow, sandy beaches of Lake Huron or along the rocky shores of
Georgian Bay. On the United States side of the lake, the Saginaw River basin
is farmed and contains the Flint, Saginaw, and Bay City metropolitan areas.
Saginaw Bay has also received industrial waste from the chemical industry
centered in Midland, Michigan.
Lake Erie is the smallest and shallowest of the lakes, and it has been
heavily impacted by urbanization and agriculture. Lake Erie receives runoff
from agricultural areas in southwestern Ontario, northern Ohio, and southern Michigan. In addition, there are numerous metropolitan areas located in
the Lake Erie basin; these include Cleveland, Ohio, and Buffalo, New York.
The average depth of Lake Erie is only 19 meters, and as a result, it warms
rapidly in the spring and summer, and it frequently freezes over in winter.
Lake Erie also has the shortest water residence time of the lakes (2.6 years),
and thus, the condition of this lake can change rapidly.
Lake Ontario is much deeper than its upstream neighbor, having an average depth of 86 meters and a water residence time of ∼ 6 years. Major Canadian urban industrial centers, such as Hamilton and Toronto, Ontario, are
located on its shore. The southern (U.S.) shore of Lake Ontario is less urbanized and is not intensively farmed, except for a narrow band along the
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R.A. Hites
lake itself. Lake Ontario has also received contaminants from the chemical
industry operating along the Niagara River in New York.
In the late 1960s, growing public concern about the deterioration of environmental quality of the Great Lakes stimulated research on the inputs and
behavior of pollutants in the lakes. Governments in both the United States
and Canada responded to the concern by regulating pollutant discharges and
initiating research on the sources, fates, and effects of pollutants in the lakes.
These efforts were formalized in the first Great Lakes Water Quality Agreement between Canada and the U.S. in 1972.
Because of this increased attention, major reductions were made in pollutant inputs, and by the 1970s, some results were clear. Floating debris
and oil slicks disappeared; dissolved oxygen levels improved; odor problems
were eliminated; beaches reopened; and algal mats disappeared. Attention
shifted to persistent toxic contaminants in the 1980s, as reflected in the 1987
Amended Great Lakes Water Quality Agreement. Given that some of these
toxic substances accumulate as they move through the food chain, top predators such as lake trout, fish-eating birds (such as cormorants, ospreys, and
herring gulls), and people can receive relatively high doses of these contaminants.
This book brings together what is known about the major classes of these
persistent organic pollutants (the so-called POPs). Each chapter reviews our
knowledge of the extent of contamination of the various parts of the Great
Lakes ecosystem (air, water, sediment, fishes, birds, etc.), what is known about
the trends over time of this contamination, and information about the mechanisms by which these compounds are mobilized in the lakes. The following
section presents abstracts of the contents of each chapter.
2
Overview of Chapters
2.1
Polychlorinated Biphenyls
Polychlorinated biphenyls (PCBs) were widely used in the Great Lakes region
primarily as additives to oils and industrial fluids, such as dielectric fluids
in transformers. PCBs are persistent, bioaccumulative, and toxic to animals
and humans. The compounds were first reported in the Great Lakes natural environment in the late 1960s. At that time, PCB production and use was
near the maximum level in North America. Since then, inputs of PCBs to
the Great Lakes have peaked and declined: Sediment profiles and analyses
of archived fish indicate that PCB concentrations have decreased markedly
in the decades following their phase-out in the 1970s. Unfortunately, PCB
concentrations in some fish species remain too high for unrestricted safe
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Persistent Organic Pollutants in the Great Lakes: An Overview
7
consumption. PCB concentrations remain high in fish because of their persistence, tendency to bioaccumulate, and the continuing input of the compounds
from uncontrolled sources. PCBs are highly bioaccumulative, and many studies have shown that the complex food webs of the Great Lakes contribute to
the focusing of PCBs in fish and fish-eating animals. PCB concentrations in
the open waters are in the range of 100–300 pg/L and are near equilibrium
with the regional atmosphere. PCBs are hydrophobic yet are found in the dissolved phase of the water column and in the gas phase in the atmosphere,
and they continue to enter the Great Lakes environment. The atmosphere,
especially near urban-industrial areas, is the major source to the open waters of the lakes. Other sources include contaminated tributaries and in-lake
recycling of contaminated sediments. Until these remaining sources are controlled or contained, unsafe levels of PCBs will be found in the Great Lakes
environment for decades to come.
2.2
Dioxins
Good information exists on the occurrence, geographical distribution, and
temporal trends of dioxins in Great Lakes’ air, water, sediments, fish, seabirds,
and people. Dioxin congener patterns and concentrations in sediment indicate that atmospheric input dominated in Lake Superior, southern Lake
Michigan, and Lake Erie. Inputs from the Saginaw River to Lake Huron
and from the Fox River to upper Lake Michigan added some dioxin loading to these lakes above atmospheric deposition. Lake Ontario was heavily
impacted by the input of dioxins, particularly 2,3,7,8-tetrachlorodibenzop-dioxin, from the Niagara River. Sediment core and bio-monitoring data
revealed that dioxin contamination peaked in most lakes in the late 1960s to
early 1970s, followed by rapid, order of magnitude declines in the mid to late
1970s. The downward trend stalled in some lakes in the 1980s, but seems to
have continued after the late 1990s, probably in response to various remediation efforts and reductions in dioxin emissions to the atmosphere. During
the height of contamination, effects attributed in whole or in part to dioxin
contamination included reproductive failure in lake trout and herring gulls
in Lake Ontario. Aryl hydrocarbon receptor-mediated sub-lethal effects may
still be occurring in seabirds and fish, but much of this is thought to be due
to dioxin-like PCBs rather than dioxins.
2.3
Pesticides
Spatial distributions and temporal trends of pesticides in sediment, water,
and fish indicate good progress in the reduction of persistent organochlorine pesticides in the Great Lakes Basin. Concentrations of many of the
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R.A. Hites
organochlorine pesticides have decreased significantly in Great Lakes wildlife,
subsequent to restriction of these compounds’ usage in the Great Lakes
basin in the 1970s and the 1980s. Nevertheless, concentrations of several
organochlorine pesticides in the Great Lakes are currently either not declining or are declining only slowly. The current concentrations of several
organochlorine pesticides seem to be at a steady state, such that the amount
lost to the sediments and exported either to the atmosphere or flowing out
through the St. Lawrence River is balanced by input from rivers and the
atmosphere. Thus, further reductions in the input of organochlorine pesticides and the continued recovery of wildlife populations are dependent, in
part, on the control of new inputs.
The frequency of detection of current-use pesticides in the Great Lakes
generally increased in the order Superior < Huron and Georgian Bay < Ontario < Erie. The highest concentrations among current-use pesticides were
measured for atrazine, metolachlor, 2,4-D, and diazinon in the western basin
of Lake Erie, because of the close proximity to areas where these pesticides are
applied in both agricultural and urban settings. Future monitoring activities
should focus on the major pesticides that are in current use. At present, programs are in place to analyze for about half of the pesticides used. Additive
and synergistic effects of pesticide mixtures must be examined more closely,
since existing guidelines have been developed for individual pesticides only.
2.4
Toxaphene
Toxaphene is a major persistent organic contaminant in air, water, and fish in
the Great Lakes. The story of toxaphene in the Great Lakes, like that of most
other persistent organochlorine compounds, has only become clear after the
ban on the use of this pesticide in the mid-1980s. The spatial and temporal
trends of toxaphene in the Great Lakes are now reasonably well documented.
Highest concentrations in fish and lake water are found in Lake Superior.
Concentrations of toxaphene declined in lake trout from Lakes Michigan,
Huron, and Ontario during the 1990s (half-lives of 5–8 years) but not in Lake
Superior. Recent measurements suggest no declines from the mid-1990s to
2000 in all four lakes. Modeling has demonstrated that the colder temperatures and low sedimentation rates in Lake Superior, and to some extent in
Lake Michigan, conspire to maintain high toxaphene concentrations in the
water column. Sediment core profiles from Lakes Michigan, Ontario, and Superior all show declining inputs in the past 10–20 years, mirroring reduced
emissions following toxaphene deregistration in the United States in 1986.
Atmospheric transport of toxaphene from agricultural soils in the southern
United States continues and modeling results suggest that 70% of the atmospheric inputs to the Great Lakes are due to long range atmospheric transport
and deposition from outside of the basin itself. Some degradation is apparent
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Persistent Organic Pollutants in the Great Lakes: An Overview
9
in the Lake Superior food web based on non-racemic enantiomer fractions
for selected chlorobornanes, but for most congeners this process is slow and
does not result in negative food web biomagnification in Lake Superior. High
proportions of hexa- and heptachlorobornanes have been found in some lake
sediments and tributary waters, indicating that slow degradation, mainly via
dechlorination, is proceeding within the Great Lakes basin.
Toxaphene concentrations probably did not reach levels that would, by
themselves, cause effects on salmonid reproduction, survival, or growth in
the Great Lakes. The levels and effects of toxaphene in fish-eating birds and
mammals (such as mink) in the Great Lakes have never been thoroughly
investigated; however, it seems likely that exposure levels for birds and mammals would have been lower than for PCBs. In some Great Lakes jurisdictions,
concerns remain about human exposure to toxaphene via consumption of
Lake Superior lake trout. Given the long half-lives in fish and water, elevated
toxaphene is likely to remain a contaminant issue in the Great Lakes until the
middle of the 21st century.
2.5
Polychlorinated Naphthalenes
Polychlorinated naphthalenes (PCNs) have entered the Great Lakes through
the production and use of Halowax technical mixtures, as trace contaminants in Aroclor PCB mixtures, and through industrial processes such as
chlor-alkali production and waste incineration. Air concentrations of PCNs
were highest in urban areas, and congener profiles indicate that evaporative
emissions relating to past uses are the dominant sources, but combustion
processes also contribute. Sediment measurements indicate that the highest
PCN concentrations are in the Detroit River, and congener profiles indicate
Halowax contamination from past inputs. Fish from this area had the highest reported concentrations in the Great Lakes region, followed by lake trout
from Lake Ontario. Estimates of dioxin toxic equivalents of PCNs indicate
their contributions are as important as the dioxin-like PCBs in some aquatic
species, and more important in air and sediments. No time trend information
for PCNs in the Great Lakes exists, and further spatial assessment, and toxic
equivalent comparisons of PCNs, dioxins, and PCBs in additional fish species
should be undertaken.
2.6
Polycyclic Aromatic Hydrocarbons
Polycyclic aromatic hydrocarbons (PAHs) are produced during the incomplete combustion of organic material. PAHs can also be produced through
natural, non-combustion processes, and they may be present in uncombusted
petroleum. Uncombusted petroleum can be a direct source to the waters of
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