Table Of ContentW. Salomons U. Forstner
Metals in
the Hydrocycle
With 149 Figures
Springer-Verlag
Berlin Heidelberg New York Tokyo 1984
Dr. WIM SALOMONS
Delft Hydraulics Laboratory
Institute for Soil Fertility
P.O. Box 30003
NL-97S0 RA Haren (Gr)
The Netherlands
Professor Dr. ULRICH FORSTNER
Arbeitsbereich Umweltschutztechnik
Technische Universitat Hamburg-Harburg
Harburger SchloJ3straJ3e 20
Postfach 901403
0-2100 Hamburg 90
Fed. Rep. of Germany
ISBN-13: 978-3-642-69327-4 e-1SBN-13: 978-3-642-69325-0
DOT: 10.1007/978-3-642-69325-0
Library of Congress Cataloging in Publication Data. Salomons, W. (Willem), 1945-. Metals in
the hydrocycle. Includes index. I. Water chemistry. 2. Geochemistry. 3. Metals. I. Forstner,
Ulrich. II. Title. GB855.S241983 551.9 83-20049
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Preface
Metals in the hydrological cycle represent a very broad subject
covering all parts of the geological cycle. The present version
of this book, therefore, would not have been possible without
the comments and suggestions for improvement on draft ver
sions of the various chapters by a large number of colleagues.
We wish to express our gratitude to:
P.A. Cawse (AERE, UK), J.N. Galloway (University of
Virginia, USA) and S.E. Lindberg (Oak Ridge National Labo
ratory, USA) for reviewing the chapter on atmospheric trace
metals.
G. Batley (CSIRO, Australia) and B.T. Hart (Chisholm In
stitute of Technology, Australia) for reviewing the chapter on
speciation of dissolved metals.
E.K. Duursma (Delta Institute, The Netherlands), J.M.
Bewers and P.H. Yeats (Bedford Institute of Oceanography,
Canada) and D. Eisma (Netherlands Institute for Sea Re
search, the Netherlands) for reviewing the chapter on estuaries.
P. Baccini (EAWAG, Switzerland) and W. Davison (Fresh
water Biological Association, UK) for reviewing the chapter on
lakes.
E.T. Degens (University of Hamburg, W-Germany) for re
viewing the chapter on the oceans, and J.P. Al (Public Works
Department, The Netherlands) for reviewing most of the indi
vidual chapters.
Without the collaboration of these colleagues this book
would not have been possible in its present form.
We want to thank E. Allersma (Delft Hydraulics Labora
tory, The Netherlands) for writing the chapter on sediment
physics, E. Steinnes for his contribution on atmospheric pollu
tion in Norway and G.Glass (EPA, USA) for the suggestion
"Hydrocycle. "
Finally, we are grateful to Mrs. S. van Dijk and A. Schreur
for typing most of the manuscript, D. Godfrey and Mrs. M.
Recke who corrected part of the book and Mrs. Little-Gadow
who prepared table 11 (non-marine sediments).
W.SALOMONS
U.FORSTNER
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . .
2 Interactions with Ligands, Particulate Matter and Organisms
2.1 Introduction . . . . . . . . 5
2.2 Metal Ions in Aquatic Systems 6
2.3 Speciation of Dissolved Metals 10
2.3.1 Physical Separation 11
2.3.2 ASV-Labile Species 13
2.3.3 Ion-Exchange Methods. 15
2.3.4 Speciation Schemes 15
2.4 Interaction with Ligands. . . 18
2.5 Interaction with Particulate Matter 24
2.5.1 Sorption Processes. . . . . 25
2.5.2 Mechanisms. . . . . . . . 25
2.5.3 Sorption on Metal Oxides and Organic Substances 28
2.5.4 Sorption of Metal-Organic Complexes 33
2.5.5 Interactions in Natural Systems 36
2.6 Solid Speciation . . . . . . . . 44
2.7 Metal Interaction with Organisms. . 50
2.7.1 Metal Uptake by Organisms. . 50
2.7.2 Solid Speciation and Bioavailability 55
2.7.3 Transformation of Metal by Organisms. 58
3 Sediments and the Transport of Metals
3.1 Introduction . . . . . . 63
3.2 Composition of Sediments 63
3.3 Transport of Sediments . 65
3.4 Distribution and Deposition 67
3.5 Grain Size Effects. . . . . 69
3.6 Anthropogenic Influences on Metal Concentrations in
Sediments . . . . . . . . . . . 76
3.6.1 Background Concentrations. . . . . . 76
3.6.2 Sediment Core Studies . . . . . . . . 78
3.6.3 Quantification of Environmental Impact 79
VIII Contents
3.7 Early Diagenesis of Trace Metal Compounds in Sediments 85
3.7.1 Sampling of Interstitial Waters . . . . 85
3.7.2 Diagenetic Environments . . . . . . . 86
3.7.3 Diagenetic Mobilization of Trace Metals 92
4 Metals in the Atmosphere
4.1 Introduction . . . . . . . . . . . . . . . . . . . 99
4.2 Natural and Anthropogenic Emissions of Trace Metals 100
4.3 Atmospheric Particles . . . . . . . . . . . .. 103
4.4 Deposition of Atmospheric Particles. . . . . .. 109
4.5 Metal Concentrations in Urban, Rural and Remote
Atmospheres . . . . . . . . . . . . . . . . 113
4.6 Environmental Impact of Airborne Trace Metals 116
4.6.1 Terrestrial Ecosystems . '. . . . . . . . 117
4.6.2 The Arctic and Antarctic Aerosol . . . . 124
4.6.2.1 Concentrations in Arctic and Antarctic
Areas . . . . . . . . . . 125
4.6.2.2 Seasonal Changes . . . . . . . . .. 126
4.6.2.3 Origin of the Arctic Aerosol . . . .. 128
4.6.3 Metals in the Oceanic Aerosol: Continental or
Ocean Derived? . . . . . . . . . . . . 131
4.6.3.1 Formation of the Oceanic Aerosol.. 131
4.6.3.2 Sea Surface Microlayer . . . . .. 133
4.6.3.3 Composition of the Oceanic Aerosol. 134
5 Metals in Continental Waters
5.1 Introduction . . . . . . . . . . . . 138
5.2 Metals in Rocks and Soils . . . . . . 140
5.2.1 Igneous and Metamorphic Rocks 141
5.2.2 Weathering and Element Migration 144
5.2.3 Chemistry of Sedimentary Rocks. . 148
5.2.4 Metals in Soils . . . . . . . . . 150
5.2.4.1 Soil Constituents and Metal Binding. 151
5.2.4.2 Trace Metal Concentrations in Soils 152
5.2.4.3 Metal Transfer from Soil to Plants 153
5.2.4.4 Problems with River-borne Metal
Pollutants on Agricultural Soils . . 155
5.2.4.5 Land Disposal of Metal-Contaminated
Waste Materials. . . 158
5.3 Metals in Rivers . . . . . . . . 159
5.3.1 Trace Metals in River Water 159
Contents IX
5.3.2 Dissolved and Solid Transport. 161
5.3.2.1 Geographical Variability 161
5.3.2.2 Seasonal Variability . . 163
5.3.3 Metals in River Sediment . . . 164
5.3.3.1 Factors Affecting Compositions. 164
5.3.3.2 Variability of Data . . 165
5.3.3.3 Influence of Grain Size. . . 166
5.3.3.4 Metal Forms. . . . . . . 167
5.3.4 Impact of Metals in River Systems. 170
5.3.4.1 Distribution of Metal Pollutants. 170
5.3.4.2 Historical Evolution. . . . . . 172
5.3.4.3 Metal Budgets and Local Inputs 174
5.3.5 Complexing Agents in River Systems. 176
5.4 Metals in Lakes. . . . . . . . . . . . . . 179
5.4.1 Introduction. . . . . . . . . . . . . 179
5.4.2 Accumulative Phases in Lake Sediments. 182
5.4.3 Trace Metal Fluxes as Reflected in the Sediments 185
5.4.4 Metals Cycling in Lakes. . . . . 189
5.4.5 Metals Cycling in Stratified Lakes 198
5.4.6 Atmospheric Inputs in Lakes . . 203
6 Metals in Estuaries and Coastal Environments
6.1 Introduction . . . . . . . . . . . . . . 212
6.2 Estuarine Circulation . . . . . . . . . . 213
6.3 Conservative and Non-Conservative Behaviour 216
6.4 Behaviour of Particulate Trace Metals During Estuarine
Mixing. . . . . . . . . . . . . . . . . . 217
6.5 Iron and Manganese. . . . . . . . . . . . . . . . 220
6.6 Trace Metals in Estuaries: Field Investigations . . . . 223
6.7 Trace Metals in Estuaries: Laboratory Investigations and
Simulations. . . . . . . . . . . . . . . . . 233
6.8 Environmental Impact Studies . . . . . . . . 240
6.8.1 United States Estuaries and Coastal Areas. 241
6.8.2 Mediterranean Sea. . . . . . . . . . 245
6.8.3 Western Europe . . . . . . . . . . . 246
6.8.4 Environmental Impact of Metals in Biota 250
6.9 Estuaries as Sinks for Trace Metals? . . . . 254
7 Metals in the Ocean
7.1 Introduction . . . 258
7.2 Vertical and Horizontal Distribution of Trace Metals 261
7.3 Particulates and Metal Behaviour. . . . . . . . . 266
x
Contents
7.4 Composition of Oceanic Sediments 269
7.4.1 Marine Sedimentary Facies . 269
7.4.2 Metal Concentrations. . . . 272
7.4.3 Metal Enrichment in Deep-Sea Sediments . 275
7.4.3.1 Diagenetic Metal Enrichment-Manganese
Nodules . . . . . . . . . . . .. 276
7.4.3.2 Metal Enrichment from Hydrothermal
Inputs. . . . . . . . . . . . .. 281
7.5 Cycling of Trace Metals Between Continents and Oceans 284
8 Summary and Qutlook 287
References. . 291
Subject Index 333
1 Introduction
Trace metals have been transported along the hydrological cycle since the first oc
currence of water on the planet earth. Water providing the medium for weathering
of the continents as well the medium for transport (together with the atmosphere)
of trace metals.
Figure 1 gives a schematic presentation of the movement of trace metals along
the hydrological cycle. The outer ring represents the particulate transport, the in
ner ring the movement of soluble trace metals and the interactions with the particu
lates. Finally, the center represents the atmosphere and its influence on all parts
of the hydrological cycle.
Along the pathway from continents to the oceans, the trace metals are subject
to a large number of processes. During transport environmental changes effect the
distribution over the dissolved and particulate phases. The accumulation in the lat
ter causes a retention in the transport to the oceans, which under normal circum
stances (transport in solution) takes only days to weeks. Particulate trace metals
may permanently accumulate in lakes or in river systems. However, this does not
mean that those metals are removed from the system. Sediments act as a reservoir
and changing environmental conditions may cause a remobilization of the accumu
lated metals.
Fig. I. Movement of trace metals
in the hydrological cycle
2 Introduction
Advective velocity (cm/sec)
10.8 10.4
Tropo.spheric _
winds
Surface water ____
currents
Particles. dr0.Ps _____
settling in air
Particles
settling in water---
Ground
- - - -water flow
Evaporation.
- upwelling in oceans
Ocean floor
- spreading
_____S edimentation
oceans and lakes
(m/y)
Fig.2. Characteristic velocities associated with major transport processes in the hydrological cycle.
(Lerman, 1979)
Important processes are taking place at the interface river/ocean and in the con
tinental shelf. In these areas an accumulation of natural and anthropogenic trace
metals takes place. In addition. estuaries and shelf areas are areas in which har
bours and industrial centers are located. By nature harbours and estuaries are ef
ficient sediment traps, a feature which interferes with human activities. Huge quan
tities of (contaminated) sediments have to be removed from the world's navigation
channels and are dumped either on land or in the ocean. In this way they end up
in places, which they never would reach by natural processes.
Once the riverine (or atmospheric) trace metals have entered the oceans, they
take part in the intricate biogeochemical processes and cycling in the world oceans.
Ultimately, they become incorporated in the oceanic sediments, where they will
spend several millions of years before taking part in the next hydrological cycle.
Each part of the hydrological cycle has its own time scales for the movement
of metals in it (Fig. 2).
From the rates of sedimentation on the ocean floor to the velocity of particles
in the atmosphere differences of 1013 are found. Also the residence time of trace
metals in the various reservoirs varies from days (rivers, atmosphere) to several
thousands of years (oceans).
Another highly variable factor is the particulate concentrations. High concen
trations are found in rivers and in estuaries, whereas the concentrations in the
oceans are extremely low (Fig. 3).
Due to variations in time scales, biological activity and particulate concen
trations, the processes are seldom taking place under equilibrium conditions; kinet
ics play an important role.
Trace metals are introduced directly in each compartment (Fig. I) and are
transported from one compartment to another. Sources for trace metals are the
