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571 Pages·1996·16.933 MB·English
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Global and Regional Mercury Cycles: Sources, Fluxes and Mass Balances NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and Physical Sciences Kluwer Academic Publishers D Behavioural and Social Sciences Dordrecht, Boston and London E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change PARTNERSHIP SUB·SERIES 1. Disarmament Technologies Kluwer Academic Publishers 2. Environment Springer-Verlag I Kluwer Academic Publishers 3. High Technology Kluwer Academic Publishers 4. Science and Technology Policy Kluwer Academic Publishers 5. Computer Networking Kluwer Academic Publishers The Partnership Sub-Series incorporates activities undertaken in collaboration with NA TO's Cooperation Partners, the countries of the CIS and Central and Eastern Europe, in Priority Areas of concern to those countries. NATo-PCo-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 50000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galllei, 1-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (©WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO POO, Overijse, Belgium. Series 2: Environment - Vol. 21 Global and Regional Mercury Cycles: Sources, Fluxes and Mass Balances edited by Willy 8aeyens Department of Analytical Chemistry, Vrije Universiteit Brussel, Belgium Ralf Ebinghaus GKSS Forschungszentrum Geesthacht, Germany and Oleg Vasiliev Institute for Water and Environmental Problems, Barnaul Siberian Branch, Russian Academy of Sciences, Russia Kluwer Academic Publishers Dordrecht / Boston / London Published in cooperation with NATO Scientific Affairs Division Proceedings of the NATO Advanced Research Workshop on Regional and Global Mercury Cycles: Sources, Fluxes and Mass Balances Novosibirsk, Russia July 10-14, 1995 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN-13: 978-94-010-7295-3 e-ISBN-13: 978-94-009-1780-4 001: 10.1007/978-94-009-1780-4 Published by Kluwer Academic Publishers, P.O. Box 17,3300 AA Dordrecht, The Netherlands. Kluwer Academic Publishers incorporates the publishing programmes of D. Reidel, Martinus Nijhoff, Dr W. Junk and MTP Press. Sold and distributed in the U.S.A. and Canada by Kluwer Academic Publishers, 101 Philip Drive, Norwell, MA 02061, U.S.A. In all other countries, sold and distributed by Kluwer Academic Publishers Group, P.O. Box 322, 3300 AH Dordrecht, The Netherlands. Printed on acid-free paper All Rights Reserved © 1996 Kluwer Academic Publishers and copyright holders as specified on appro priate pages within Softcover reprint of the hardcover 1 st edition 1996 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. TABLE OF CONTENTS Preface ...................................................... ix Foreword .................................................... xi List of Participants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. xv List of Contributors ............................................ xxi PART 1. ANALYTICAL ASPECTS ON THE DETERMINATION OF MERCURY 1.1. Mercury Analysis and Speciation in Environmental Samples M. Horvat . .............................................. 1 PART 2. MERCURY FLUXES AND BUDGETS 2.1. Global Regional and Local Mercury Budgets 2.1.1. Trends in Atmospheric Mercury Concentrations over the Atlantic Ocean and at the Wank Summit, and the Resulting Constraints on the Budget of Atmospheric Mercury F. Slemr ............................................... 33 2.1.2. The Global Mercury Cycle: Oceanic and Anthropogenic Aspects W.F. Fitzgerald and R. Mason . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . .. 85 2.1.3. Estimation of Atmospheric Input and Evasion Fluxes of Mercury to and from the Great Lakes W.H. Schroeder . ......................................... 109 2.1.4. A Regional Mercury Budget for Siberia and the Role of the Region in Global Cycling of the Metal S.A. Sukhenko and O.F. Vasiliev .............................. 123 2.1.5. Emission and Local Deposition Estimates of Atmospheric Mercury in North-Western and Central Europe R. Ebinghaus and O. Kriiger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135 2.2. Emission Inventories and Regional Transport Models for Mercury 2.2.1. Emission Inventories of Atmospheric Mercury from Anthropogenic Sources J.M. Pacyna ............................................ 161 2.2.2. Inventory of North American Hg Emissions to the Atmosphere D.B. Porcella, P. Chu and M.A. Allan .......................... 179 2.2.3. Numerical Modeling of Regional Transport, Chemical Transformations and Deposition Fluxes of Airborne Mercury Species G. Petersen, J. Munthe and R. Bloxam .......................... 191 2.2.4. A Model of the Chemical Transformation of Mercury and its Long-Range Atmospheric Transport M. Galperin, M. Sofiev and E. Mantseva ........................ 219 vi 2.3. Mercury Cycling in the Oceans 2.3.1. Mercury Fluxes at the Ocean Margins D. Cossa, M. Coquery, C. Gobeil and J.-M. Martin . ................ 229 2.3.2. Sources, Sinks and Biogeochemical Cycling of Mercury in the Ocean R.P. Mason and W.F. Fitzgerald .............................. 249 2.4. Mercury in Lakes, Rivers and Estuaries 2.4.1. Mercury in the Katun River Basin: A Case Study of a Naturally Polluted System O.F. Vasiliev, T.S. Papina, S.S. Eyrikh and S.A. Sukhenko ............ 273 2.4.2. Particulate, Dissolved and Methylmercury Budgets for the ScheIdt Estuary (Belgium and the Netherlands) W. Baeyens and M. Leermakers ............................... 285 2.4.3. Mercury Distribution and Fluxes in Lake Baikal M. Leermakers, C. Meuleman and W. Baeyens .................... 303 2.4.4. The Elbe River: A Special Example for a European River Contaminated Heavily with Mercury R.-D. Wilken and D. Wallschliiger ............................. 317 2.4.5. Mass Balance Studies of Mercury and Methyl Mercury in Small Temperate/Boreal Lakes of the Northern Hemisphere C.J. Watras, K.A Morrison and R.c. Back . ... -................... 329 2.5. Hg in Terrestrial Systems 2.5.1. Forests and the Global Biogeochemical Cycle of Mercury S.E. Lindberg ........................................... 359 2.5.2. Terrestrial Mercury and Methylmercury Budgets for Scandinavia A. Iveifeldt, J. Munthe and H. Hultberg ......................... 381 2.5.3. The Role of Organic Matter in Mercury Cycle G.M. Varshal, N.S. Buachidze, T.K. Velyukhanova and D.N. Chkhetia .... 403 PART 3. NATURAL AND INDUSTRIAL SOURCES OF MERCURY 3.1. Eastern Europe and Siberia 3.1.1. Mercury Contamination of the Environment due to Gold Mining in Zabaikalye T.G. Laperdina, M. V. Melnikova and T.E. Khvostova ................ 415 3.1.2. Industrial Mercury Sources in Siberia M.A. Yagolnitser, V.M. Sokolov, A.D. Rabtsev, A.A Obolenskii, N.A Ozerova, S.Ya. Dvurechenskaya and S.A. Sukhenko .............. 429 3.1.3. Mercury Speciation in Mineral Matter as an Indicator of Sources of Contamination V.L. Tauson, V.F. Gelety and V.I. Men'Shikov ..................... 441 3.1.4. Natural Mercury Sources in the Environment: Contribution of Siberia AA Obolenskiy .......................................... 453 3.1.5. Mercury in Geological Systems N.A. Ozerova ............................................ 463 vii 3.1.6. Mercury in Soils of the Southern West Siberia G.N. Anoshin, I.N. Malikova and S.1. Kovalev ..................... 475 3.1.7. Case Studies on Mercury Related Environmental Problems in Hungary U. Fiigedi, A. Moyzes, L. 6dor and E. Vetii-Akos .................. 491 3.1.8. Mercury in the Environment of the Central Part of the Balkan Peninsula S. Karamata, N. Ozerova, S. Jankovic, A. Chemova and P. Zivkovic ..... 499 3.2. Tropical Regions 3.2.1. SCOPE Project: Evaluation of the Role and Distribution of Mercury on Ecosystems with Special Emphasis on Tropical Regions C. Ramel ............................................... 505 3.2.2. Lessons and Questions from Studies on Mercury in the Amazon Region A. Jemelov ............................................. 515 PART 4. CONCLUSIONS OF THE WORKING GROUP DISCUSSIONS 4.1. Working Group Report on Atmospheric Mercury ................... 523 4.2. Working Group Report on Oceanic Mercury Cycling ................ 531 4.3. Working Group Report on Terrestrial Mercury Cycling .............. 543 4.4. Working Group Report on Inland Waters ........................ 547 Subject Index ................................................ 553 PREFACE Among the toxic trace metals, mercury is one of the most hazardous environmental pollutants and is therefore a substance of first priority in ecotoxicology. In addition, high levels of mercury in air, drinking water or in food can cause serious health problems and even be dangerous for life. For example fish especially tend to concentrate mercury in their tissues and analyses have shown that this mercury is almost entirely in the form of methylmercury. Hence, issues of great importance are the identification of the main mercury sources in the environment, the evaluation of their relative magnitudes and the recognition of the processes governing the mercury migration in the environment. The comprehension of these issues can be achieved only through the multidisciplinary collaboration of scientists and experts from a large number of countries. The NATO Advanced Research Workshop on "Regional and Global Mercury Cycles: Sources, Fluxes and Mass Balances" was intended as an important step forward to reach this goal. In the past, scientists in the east or the west were not aware of each others results, could not benefit from the progress made in the adverse area and made erroneous estimates of natural and industrial sources and fluxes in that adverse area. The idea to hold this meeting in Novosibirsk was offered by the Chairman of the Siberian Branch of the Russian Academy of Sciences, Prof. V. Koptuyg, in connection with the SCOPE project "Evaluation of the Role and Distribution of Mercury on Ecosystems". The motor behind the organization of the Workshop in Novosibirsk was Dr. S. Sukhenko from the Institute of Water and Environmental Problems of Barnaul, Siberia. Unfortunately he could not finish this task because a tragic event decided otherwise. At the meeting the organizers expressed their wish to dedicate the Workshop and the book to the memorial of Dr. S. Sukhenko. The Directors and the Organizing Committee of the NATO Advanced Research Workshop ENVIR.ARW 941402 also wish to acknowledge and thank NATO, as well as the scientists and secretarial personnel of the Russian Academy of Sciences, Siberian Branch, of GKSS, Geesthacht-Hamburg, and of VUB, Brussels, for their support and assistance to the organization of the Workshop and the editing of the book. Willy Baeyens, Prof. Dr. IX Foreword In the summer of 1995, under NATO sponsorship, approximately 50 scientists from NATO and Cooperation Partner Countries lived and worked together for one week in Akademgorodok - Novosibirsk, the Siberian Branch of the Russian Academy of Sciences to establish the state of the art on regional and global mercury cycles: sources, fluxes and mass balances; to evaluate what data we have and what data we need for international inventory of anthropogenic as well as natural mercury emissions and to assess their scales and impact; to consider which transformation and migration processes have to be included in future mercury transport models; to discuss the results of some case studies in connection with geographical and geological particularities of corresponding territories and industrial activities, in a context of global and regional fluxes and mass balances; to make an evaluation of existing models for mercury biogeochemical cycles and mass balances including the methods for their conception and calculation. Novosibirsk was selected as the place to host the workshop since Siberia with its vast territory and variety of natural zones is a region of great interest with regard to global and regional mercury balances. Siberia contains many areas with large mercuriferous belts, and mercury deposits. They are the main natural sources from which, due to degassing and weathering, mercury is emitted to the atmosphere and released to the waters. And vice versa, huge boreal forests and vast areas of tundra and wetlands (bogs) are believed to be efficient sinks of atmospheric mercury. These processes may playa significant role in global mercury cycling. In several industrialized regions of Siberia a diversity of factories are using mercury in their industrial and technological processes, giving rise to its emissions. Numerous power plants burning a substantial amount of coal for energy and heat production, and local metal melters are also essential contributors to mercury emissions to the atmosphere. From the early 1800s, Siberia is an important area of gold mining based on mercury use and this' activity continues up to now. The themes that were focused on were analytical methods, atmospheric mercury, oceanic mercury, Hg in terrestrial systems and inland waters. The method adopted in the workshop was to first present a state of the art of all validated information on the topics, assess what data shall be available in the near future and finally what information is currently missing as well as propositions for future research. The results of the major discussions of the ARW are encapsulated in the papers of this book which comprises both invited keynote addresses, short papers related to specific sources or processes and working group summaries. All papers were reviewed regarding content and editing and taking into account that a major aim of the workshop was to obtain a large database about the natural sources of mercury and their roles, and to consider all types of mercury transformation and migration processes in NATO, COP and xi xu third world countries. The papers are grouped under headings representing the main themes of the workshop. A number of the main conclusions of the workshop are highlighted below: • On the analytical level, techniques for the speciation of mercury in biological and environmental samples were well established, but this is not the case for extreme low concentrations such as in water and in air. Quality assurance programs (QNQC protocols, field intercomparison studies, training of personnel) should be integrated in each Hg project in order to compare data on regional and global scales. • Anthropogenic Hg emission inventories for Northern America and Europe have been established and revised but adequate data from other major producers and users of Hg containing fuels and products is missing. Hemispheric and global models should be made which include the most relevant atmospheric mercury chemistry, deposition processes, soil and vegetation reactions such as methylation, re-emission and runoff and physico-chemical processes of the marine environment. Local scale models are needed to assess the near source deposited Hg and its distribution. • Significant gaps remain in our knowledge on mercury inputs to the oceans. Current data on mercury in rivers is not representative of the world's rivers and data on Hg in oceanic precipitation is sparse. The current understanding of the accumulation of methylmercury in the marine food chain is limited. Dimethylmercury has been found in deep ocean waters, but it is not clear what organisms are involved. Methylmercury fluxes to and from the ocean need to be established. • Concerning the terrestrial Hg cycle both new data and modeling show that dry deposition of Hg is the dominant input to forests and that emission and re-emission may be important. Reliable methylmercury data are available for the different terrestrial compartments and the waters draining these systems. A compilation of existing data from a geological database with spatial resolution of mercury sources across the globe is required. Degassing rates of different geological source types, e.g. geothermal areas, active faults and background areas as well as their seasonal variations should be measured. • In inland waters the mercury methylation process has been shown to be particularly rapid in low oxygen zones, low pH and high humic matter content and dependent on the season. Several Siberian lakes, however, exposed to important local Hg contamination show very low levels in fish. These types of lakes (high pH, low DOC) have not yet been investigated intensively and the methylationldemethylation processes in relation to the speciation of in-flowing mercury need to be investigated.

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