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Information contained herein does not necessarily reflect the policy or views of the Society of Environmental Toxicology and Chemistry SETAC.. The book is the product of efforts initiated

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Coordinating Editor of SETAC Books

Joseph W Gorsuch Gorsuch Environmental Management Services, Inc.

Webster, New York, USA

Based on the SETAC North America Workshop onMercury Monitoring and Assessment

14 -17 September 2003Pensacola, Florida, USA

Edited byReed Harris • David P Krabbenhoft Robert Mason • Michael W Murray Robin Reash • Tamara Saltman

Indicators of Change

Ecosystem

Mercury Contamination

CRC Press is an imprint of the Taylor & Francis Group, an informa business

Boca Raton London New York 8892_C000.fm Page iii Monday, January 29, 2007 11:33 AM

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Published in collaboration with the Society of Environmental Toxicology and Chemistry (SETAC)

1010 North 12th Avenue, Pensacola, Florida 32501 Telephone: (850) 469-1500 ; Fax: (850) 469-9778; Email: setac@setac.org Web site: www.setac.org

ISBN-10: 1-880611-86-4 (SETAC Press) ISBN-13: 978-1-58488-661-7 (SETAC Press)

© 2007 by the Society of Environmental Toxicology and Chemistry (SETAC) SETAC Press is an imprint of the Society of Environmental Toxicology and Chemistry.

No claim to original U.S Government works Printed in the United States of America on acid-free paper

10 9 8 7 6 5 4 3 2 1 International Standard Book Number-10: 0-8493-8892-9 (Hardcover) International Standard Book Number-13: 978-0-8493-8892-7 (Hardcover) This book contains information obtained from authentic and highly regarded sources Reprinted material is quoted with permission, and sources are indicated A wide variety of references are listed Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use Information contained herein does not necessarily reflect the policy or views of the Society of Environmental Toxicology and Chemistry (SETAC) Mention of commercial or noncommercial products and services does not imply endorsement or affiliation by the author or SETAC.

The content of this publication does not necessarily reflect the position or policy of the U.S government or sponsoring organizations and an official endorsement should not be inferred.

No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any informa- tion storage or retrieval system, without written permission from the publishers.

For permission to photocopy or use material electronically from this work, please access www.copyright.com (http:// www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC) 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for

identification and explanation without intent to infringe.

Library of Congress Cataloging-in-Publication Data

Ecosystem responses to mercury contamination : indicators of change / edited by Reed Harris … [et al.].

p cm.

Includes bibliographical references (p ).

ISBN 0-8493-8892-9 (alk paper)

1 Mercury Environmental aspects 2 Environmental indicators 3 Environmental monitoring I

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SETAC Publications

Books published by the Society of Environmental Toxicology and Chemistry(SETAC) provide in-depth reviews and critical appraisals on scientific subjectsrelevant to understanding the impacts of chemicals and technology on the envi-ronment The books explore topics reviewed and recommended by thePublications Advisory Council and approved by the SETAC North America,Latin America, or Asia/Pacific Board of Directors; the SETAC Europe Council;

or the SETAC World Council for their importance, timeliness, and contribution

to multidisciplinary approaches to solving environmental problems The sity and breadth of subjects covered in the series reflect the wide range of disci-plines encompassed by environmental toxicology, environmental chemistry, andhazard and risk assessment, and life-cycle assessment SETAC books attempt topresent the reader with authoritative coverage of the literature, as well as para-digms, methodologies, and controversies; research needs; and new develop-ments specific to the featured topics The books are generally peer reviewed forSETAC by acknowledged experts

diver-SETAC publications, which include Technical Issue Papers (TIPs), workshop

summaries, newsletter (SETAC Globe), and journals (Environmental Toxicology and Chemistry and Integrated Environmental Assessment and Management), are

useful to environmental scientists in research, research management, chemicalmanufacturing and regulation, risk assessment, and education, as well as to stu-dents considering or preparing for careers in these areas The publications pro-vide information for keeping abreast of recent developments in familiar subjectareas and for rapid introduction to principles and approaches in new subjectareas

SETAC recognizes and thanks the past coordinating editors of SETAC books:Andrew Green, International Zinc Association

Durham, North Carolina, USAC.G Ingersoll, Columbia Environmental Research Center

US Geological Survey, Columbia, Missouri, USAT.W La Point, Institute of Applied Sciences

University of North Texas, Denton, Texas, USAB.T Walton, US Environmental Protection AgencyResearch Triangle Park, North Carolina, USAC.H Ward, Department of Environmental Sciences and EngineeringRice University, Houston, Texas, USA

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Preface xiii

Acknowledgments xv

About the Editors xvii

Chapter 1 Introduction 1

Reed Harris, David Krabbenhoft, Robert Mason, Michael W Murray, Robin Reash, and Tamara Saltman 1.1 Mercury Emissions and Deposition 3

1.2 Mercury Concentration Trends in Fish 4

1.3 Book Objectives 7

1.3.1 Establishing Baseline Conditions and Temporal Trends 8

1.3.2 Establishing Cause-Effect Relationships 9

1.3.3 Sampling Strategy 9

1.3.4 Monitoring Data and Modeling 9

References 10

Chapter 2 Airsheds and Watersheds 13

Charles T Driscoll, Michael Abbott, Russell Bullock, John Jansen, Dennis Leonard, Steven Lindberg, John Munthe, Nicola Pirrone, and Mark Nilles Abstract 13

2.1 Introduction 14

2.1.1 Objective 17

2.1.2 Limitations 18

2.1.2.1 Emissions of Mercury 18

2.1.2.2 Detection of Trends 18

2.1.3 Attribution of Causality 20

2.1.4 Overall Criteria for Selecting Monitoring Sites, Global and Regional Influence 20

2.2 Airsheds 22

2.2.1 Introduction 22

2.2.2 The Chemistry of Atmospheric Mercury 25

2.2.2.1 Dry Deposition to Terrestrial and Aquatic Receptors 25

2.2.2.2 Wet Scavenging by Precipitation Events 25

2.2.2.3 Atmospheric Residence Time 26

2.2.3 Measurements and Analytical Methods 26

2.2.4 Modeling and the Need for Co-location/Intensive Sites 27

2.2.5 Existing Atmospheric Mercury Monitoring Networks 27

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2.2.6 Air Quality Mercury Intensive Sites 32

2.2.7 Total Ecosystem Deposition 33

2.2.7.1 Snow Surveys 35

2.3 Watersheds 35

2.3.1 Introduction 35

2.3.2 Intensive Watershed Monitoring 38

2.3.3 Soil Surveys 41

2.3.3.1 Forest Floor Surveys 41

2.3.3.2 Surface Water Surveys 41

References 41

Chapter 3 Monitoring and Evaluating Trends in Sediment and Water Indicators 47

David Krabbenhoft, Daniel Engstrom, Cynthia Gilmour, Reed Harris, James Hurley, and Robert Mason Abstract 47

3.1 Introduction 48

3.1.1 Objectives 50

3.2 Sediment and Water Indicators 50

3.2.1 Criteria for Selecting Sediment and Water Indicators 50

3.3 Recommended Indicators 52

3.3.1 Sediment-Based Indicators 55

3.3.1.1 Total Hg Concentration in Sediment 55

3.3.1.2 MeHg Concentration in Sediment 57

3.3.1.3 Percent MeHg in Sediment 63

3.3.1.4 Instantaneous Methylation Rate 64

3.3.1.5 Sediment Hg Accumulation Rates in Dated Cores 65

3.3.2 Water-Based Indicators 69

3.3.2.1 Total Hg in Water 70

3.3.2.2 MeHg in Water 75

3.4 Monitoring Strategy 78

3.5 Ancillary Data 80

3.6 Anticipated Response Times 81

Acknowledgments 82

References 82

Chapter 4 Monitoring and Evaluating Trends in Methylmercury Accumulation in Aquatic Biota 87

James G Wiener, R.A Bodaly, Steven S Brown, Marc Lucotte, Michael C Newman, Donald B Porcella, Robin J Reash, and Edward B Swain Abstract 87

4.1 Introduction 88

4.2 Objectives 89

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4.3 Aquatic Biological Indicators 90

4.3.1 Criteria to Select Indicators 90

4.3.2 Candidate Aquatic Biological Indicators 91

4.3.2.1 Fish 92

4.3.2.2 Benthic Invertebrates 95

4.3.2.3 Zooplankton 97

4.3.2.4 Phytoplankton 98

4.3.2.5 Periphyton 99

4.3.3 Recommended Aquatic Biological Indicators 100

4.4 Monitoring and Trend Analysis 104

4.5 Ancillary Data 107

4.6 Interpretation of Trend-Monitoring Data 108

4.6.1 Sources of Variation and Potential Confounding Factors 108

4.6.2 Steps to Constrain Confounding Factors and Enhance Interpretation 110

Acknowledgments 113

References 113

Chapter 5 Wildlife Indicators 123

Marti F Wolfe, Thomas Atkeson, William Bowerman, Joanna Burger, David C Evers, Michael W Murray, and Edward Zillioux Abstract 123

5.1 Introduction 124

5.1.1 Objectives 124

5.2 Issues of Concern 127

5.2.1 Geographical and Habitat Differences 127

5.2.2 Methodological Issues 130

5.3 Host Factors 131

5.3.1 Bioavailability 132

5.3.2 Toxicokinetics and Toxicodynamics 132

5.4 Types of Bioindicators 133

5.4.1 Indicators of Exposure 133

5.4.2 Indicators of Effect 133

5.5 Candidate Bioindicator Species 134

5.5.1 Mammals 134

5.5.1.1 Mink (Mustela vison) 134

5.5.1.2 River Otter (Lontra canadensis) 134

5.5.1.3 Raccoon (Procyon lotor) 135

5.5.1.4 Bats 135

5.5.1.5 Marine Mammals 136

5.5.2 Birds 137

5.5.2.1 Bald Eagle (Haliaeetus leucocephalus) 137

5.5.2.2 Osprey (Pandion haliaetus) 137

5.5.2.3 Common Loon (Gavia immer) 138

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5.5.2.4 Common Merganser (Mergus merganser) 138

5.5.2.5 Seabirds 139

5.5.2.6 Insectivorous Birds 141

5.5.3 Reptiles and Amphibians 142

5.5.3.1 Reptiles 142

5.5.3.2 Amphibians 143

5.5.4 Other Potential Indicators 146

5.5.4.1 Albatrosses 146

5.5.4.2 Hawks 146

5.5.5 Identification of Indicators through Development of Water Quality Criteria for Wildlife 146

5.6 Tissue and Other Samples 147

5.6.1 Hair 147

5.6.2 Feathers 148

5.6.3 Eggs 149

5.6.4 Organs 149

5.6.4.1 Blood 149

5.6.4.2 Brain 149

5.6.4.3 Liver 150

5.6.4.4 Muscle 150

5.6.4.5 Kidney 151

5.7 Physiological, Cellular, and Molecular Biomarkers 151

5.7.1 What Is in the Pipeline? Future and Promising Biomarkers 152

5.8 Elements of a Biomonitoring Framework 158

5.8.1 Monitoring Design Considerations 158

5.8.2 Trend Detection: The Florida Everglades Case Study 161

5.8.2.1 Retrospective Studies 162

5.8.2.2 Prospective Studies 162

5.8.3 Recommended Wildlife Indicators 163

Acknowledgments 165

References 166

Chapter 6 An Integrated Framework for Ecological Mercury Assessments 191

Tamara Saltman, Reed Harris, Michael W Murray, and Rob Reash 6.1 Introduction 191

6.2 Recurring Themes 192

6.2.1 Design of the Monitoring Network 193

6.2.1.1 Criteria for Selection of Indicators 195

6.2.2 Considerations for Sampling 196

6.2.2.1 Sampling Scale 199

6.2.2.2 Sampling Location 201

6.2.2.3 Sampling Frequency 202

6.2.2.4 Overall Duration of Sampling 202

6.2.3 Monitoring for Trends and Monitoring for Causality 203

6.2.4 Integration of Monitoring with Modeling Capabilities 203

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6.3 Complexities/Confounding Factors 205 6.4 Recommendations 205 References 206

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This book proposes a framework for a national-scale program to monitor changes

in mercury concentrations in the environment following the reduction of atmosphericmercury emissions The book is the product of efforts initiated at a workshop held

in Pensacola, Florida, in September 2003, involving more than 30 experts in thefields of atmospheric mercury transport and deposition, mercury cycling in terrestrialand aquatic ecosystems, and mercury bioaccumulation in aquatic food webs andwildlife Participants represented government agencies, industry groups, universities,and nonprofit organizations

In many parts of North America, mercury concentrations in fish are high enough

to cause concern for people and wildlife that eat fish As a result, fish consumptionadvisories are common, and several states and the U.S federal government havepassed rules to reduce mercury emissions in the United States A carefully designedmonitoring program is needed to establish trends in mercury concentrations in theenvironment and to identify the influence of changes in mercury emissions on thesetrends The charges assigned to the workshop participants included 1) the develop-ment of a set of indicators to determine whether mercury concentrations in air, land,water, and biota are changing systematically with time; 2) guidance regarding amonitoring strategy to assess these trends; and 3) guidance regarding additionalmonitoring needed to determine whether observed changes in mercury concentra-tions are related to reductions in mercury emissions The resulting frameworkdescribed in this book reflects the consensus of the workshop participants thatmonitoring trends in mercury concentrations at a national scale is difficult butachievable, and monitoring should be started sooner rather than later

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The authors and editors of this book wish to acknowledge the U.S EnvironmentalProtection Agency and the Electric Power Research Institute, who sponsored aSociety of Environmental Toxicology and Chemistry (SETAC) workshop in Sep-tember 2003 in Pensacola, Florida More than 30 international experts gathered todiscuss and propose a framework for a national mercury monitoring program toevaluate the effectiveness of mercury emissions controls on mercury concentrations

in the environment This book and a companion journal publication (Mason et al.2005) are the products of the workshop and subsequent efforts

We also wish to thank the Society of Environmental Toxicology and Chemistry(SETAC), as well as Greg Schiefer, in particular, who did an excellent job inproviding the venue and organizational expertise for this project

Each of the contributions in this book has been peer-reviewed The opinionsexpressed in this book are those of the participants and may not reflect those of any

of their agencies, the funding agencies, or SETAC

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About the Editors

Reed Harris is a principal engineer with TetraTech Inc and has more than 25 years of experience

in the environmental engineering field Since

1988, he has focused on studying the behavior ofmercury in the environment He has developed andapplied simulation models of mercury cycling andbioaccumulation in lakes, reservoirs, and the Flor-ida Everglades Reed is currently managing awhole ecosystem mercury addition experimentknown as the Mercury Experiment to AssessAtmospheric Loadings in Canada and the UnitedStates (METAALICUS) in Ontario, Canada, that

is examining the relationship between atmosphericmercury deposition and fish mercury concentrations

David Krabbenhoft, PhD, is a research

scientist with the U.S Geological Survey

He has general research interests in the

geochemistry and hydrogeology of

aquatic ecosystems Krabbenhoft began

working on environmental mercury

cycling, transformations, and fluxes in

aquatic ecosystems with the Mercury in

Temperate Lakes project in 1988; since

then, the topic has consumed his

profes-sional life In 1994, he established the

USGS Mercury Research Laboratory,

which includes a team of multidisciplinary

mercury investigators The laboratory is

a state-of-the-art analytical facility strictly

dedicated to the analysis of mercury, with low-level speciation In 1995, he initiatedthe multi-agency Aquatic Cycling of Mercury in the Everglades (ACME) project.More recently, Dave has been a Primary Investigator on the internationally conductedMETAALICUS project, which is a novel effort to examine the ecosystem-levelresponse to loading an entire watershed with mercury The Wisconsin Mercury ResearchTeam is currently active on projects from Alaska to Florida, and from California toNew England Since 1990, he has authored or co-authored more than 50 papers onmercury in the environment In 2006, Krabbenhoft served as the co-host for the 8thInternational Conference on Mercury as a Global Pollutant in Madison, Wisconsin

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Robert P Mason, PhD, is a professor

in the Department of Marine Sciences atthe University of Connecticut Prior tothis recent appointment (from Septem-ber 2005), he was at the ChesapeakeBiological Laboratory, part of the Uni-versity of Maryland’s Center of Environ-mental Science, for 11 years Prior tothis, he received his PhD from the Uni-versity of Connecticut in 1991, and com-pleted a postdoctoral program at theRalph Parsons Laboratory at MIT He has been working on various aspects ofmercury biogeochemical cycling and bioaccumulation for the past 15 years and haspublished more than 70 papers, including numerous book chapters, on mercury inthe ocean, atmosphere, and in terrestrial ecosystems He has graduated 11 MS andPhD students during his career His work has been widely cited and has been used

to develop global mercury models and as the basis for setting local, regional, andnational mercury regulations

Michael W Murray, PhD, has been staff

sci-entist with the Great Lakes office of the National

Wildlife Federation since 1997 His work has

included scientific and policy research on a

number of diverse issues involving toxic

chem-icals and water quality, including mercury

sources, fate and transport, ecological and

human health effects, and control options;

assessments of water quality criteria and total

maximum daily load plans; and assessment of

fish consumption advisory development and

communication protocols Murray received MS

and PhD degrees in water chemistry from the

University of Wisconsin–Madison, where his

research addressed several aspects of the

envi-ronmental chemistry of polychlorinated

biphe-nyls He has authored or co-authored 6 peer-reviewed publications as well as ous reports, and has served on a number of conference planning and technicalcommittees, including the SETAC North America Technical Committee He is also

numer-an adjunct lecturer in Environmental Health Sciences at the University of Michignumer-an’sSchool of Public Health

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