Table Of ContentGlobal and Regional Mercury Cycles:
Sources, Fluxes and Mass Balances
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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
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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.
