Metals in The Hydro Cycle

wim.salomons@home.
nl
W. Salomons U. Forstner
Metals in
the Hydrocycle
With 149 Figures
Springer-Verlag
Berlin Heidelberg New York Tokyo 1984
wim.salomons@home.nl
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
_ _ _ _ _ Sedimentation
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 10 13 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
Introduction 3
Environment
Concent rat ion (mg I"
10-4 10-3 10-2 10-1 10 10 2 103 104 105
Rivers
Estuaries - surface
-bottom
Shelves -surfaca
-middle
-bottom
Oceans - surface
-middle
-bottom
Fig. 3. Particulate concentrations in the hydrological cycle. (Kranck, 1980)
Natural Anthropogenic
LITHOSPHERE
ROCKS
11000.000.0001
o Fluxes 103 to/Jahr

D Reservoir 10 3 to
Fig. 4. Present-day and pre-historical cadmium fluxes. (Brunner and Baccini, 1981)
natural processes of weathering and erosion and volcanic activity. However, with
the large-scale extraction of ore from the earth's crust, it is necessary to take into
account the great influence man has on metal cycles. This is especially the case for
metals found in the atmosphere. Historically the rate of emission of trace metals
to the atmosphere has been low due to their low volatility. However, with the ad-
vent of high-temperature processe's like smelting and fossil fuel combustion, the
rate of emission for some trace metals has substantially increased. This shift from
natural control to anthropogenic control represents a significant perturbation of
metal cycles.
As an example of this influence the pre-industrialised and present-day cycle of
cadmium are presented in Fig. 4.
For cadmium most fluxes exceed the natural ones. Fluxes to the atmosphere
are more than 5 times the natural flux. Most of this cadmium is deposited on the
continents and influences terrestrial ecosystems.
4 Introduction
The influence of man on trace metal cycling is not restricted to the increase of
fluxes. Deforestation, construction of deep harbours and man-made reservoirs af-
fect the rate of transport of particulate trace metals. The acidification of continen-
tal waters and soils, the introduction of complexing agents (e.g., NTA) in natural
systems as well as the eutrophication all affect trace metal behaviour and cause per-
turbations on the natural pathways from rivers to the oceans.
In this book we will give an account of the presently available knowledge on
the movement qf trace metals along the hydrological cycle, emphasizing the pro-
cesses. In order to do so, the book.is divided in two parts. The first part (Chaps. 2
and 3) gives an overview on new developments on speciation, adsorption/desorp-
tion and diagenesis of trace metals; aspects which are common to all parts of the
cycle. In the second part (the main theme of the book), the individual parts of the
hydrological cycle, atmosphere, continental waters, estuaries and oceans, are dis-
cussed.
2 Interactions with Ligands, Particulate Matter
and Organisms
2.1 Introduction
A rough description of the occurrence and behaviour of trace metals in aquatic and
terrestrial systems is presented in Fig. 5. In the aquatic environment four abiotic
reservoirs are distinguished: the suspended matter, the sediments, the surface
waters and the pore waters. These four reservoirs strongly interact with each other.
Between the suspended matter and the metals in solution, adsorption/desorption
and (co-)precipitation processes take place. The suspended matter and the de-
posited sediments are interlinked through sedimentation and erosion processes.
Processes taking place after deposition (diagenesis) provide the interstitial waters
with sometimes high concentrations of trace metals, which through processes such
as diffusion, consolidation and bioturbation are able to influence the metal concen-
trations in the surface waters.
All four reservoirs as well as the groundwater and the soil in the terrestrial en-
vironment influence metal uptake by biota. The determination of the bio-available
fraction in each of the abiotic reservoirs is presently one of the major study areas
in metal research. Bio-availability as well as the interactions between the abiotic
AnUAT I C
STUDIES
Fig. 5. Schematic presentation of metal reservoirs and their interactions in aquatic and terrestrial sys-
tems
reservoirs is determined by the speciation of the trace metals, speciation being de-
fined as "the determination of the individual physico-chemical forms of the ele-
ment which together make up its total concentration" (Florence, 1982).
In this chapter a review on speciation and bio-availability of trace metals in
aquatic systems will be given. Terrestrial systems are discussed in Chaps 4.6.1 and
5.2.4.
2.2 Metal Ions in Aquatic Systems
The behaviour of trace metals in aquatic systems is highly complex due to the large
number of possible interactions with ill-defined dissolved and particulate com-
ponents and non-equilibrium conditions. Direct precipitation of metal compounds
may take place when external factors change. These precipitation barriers com-
monly arise because of changes in pH, in oxidation potential, or in concentrations
of precipitating substances. Causes for precipitation include interactions of water
with solids, mixing with other water, and loss or addition of gases (Rose et aI.,
1979). Major types are (see Perel'man, 1967, as cited by Rose et aI., 1979):
(a) oxidation type (iron- and manganese-oxides or native sulfur precipitated by
oxidation of reducing solutions and usually caused by water emergence at the sur-
face or a flow of reducing water out of a swamp);
(b) reducing type (U, V, Cu, Se and Ag precipitated as metals or lower-valency
oxides by reduction of oxidizing water and usually caused by an encounter with
organic matter or a mixing with reducing waters or gases);
(c) reducing sulfide type (Fe, Cu, Ag, Zn, Pb, Hg, Ni, Co, As and Mo are pre-
cipitated as sulfides by reduction of oxidizing sulfate waters, usually by the action
of sulfate-reducing bacteria) (U, V and Se may also be precipitated and the causes
are the same as for the reducing type, but they require the presence of dissolved
sulfate);
(d) sulfate-carbonate type (Ba, Sr and Ca precipitated by increased sulfate or
carbonate as a result of the mixing of waters, the oxidation of sulfide, or passage
into carbonate rock);
(e) alkaline type (Ca, Mg, Sr, Mn, Fe, Cu, Zn, Pb, Cd and other elements pre-
cipitated by increased pH, usually caused by the interaction of acid waters with car-
bonates or silicate rocks, or its mixing with alkaline waters);
(t) adsorptive type (adsorption or coprecipitation of ions on accumulations of
Fe-Mn-oxides, clays, and organic materials) (the cations of transition metals and
those with high valence tend to be more strongly adsorbed than anions and low-
valency cations).
If relevant stability constants are known, the equilibrium concentration of a
dissolved metal, its inorganic speciation and its stable solid compounds can be cal-
culated. The solubility curves for cadmium and zinc in Fig. 6, taking into account
the range of carbonate content normally encountered in inland waters (10- 3 to
10- 2 mole dissolved CO 2 per litre), show a minimum at pH values of9.3. Assum-
ing pH values to be 7 to 8 in normal river waters (under oxidizing conditions) it
Metal Ions in Aquatic Systems 7
1.2
0 \ 1._. 1O-.Jeco2
1.0
0..,
~O
I I
~\
,\\1
10-2 Mole C02 0.8
-1
, f'\ 0.6
r
-2 \
Zn 2 +
\
\
\
~\ line 0.4 I
I
't \~ ~ ~
I
I
'- \ 0.2 I
e
-4 :z:
.!E'
\\ ~\. '., C
:z:1 I
." .,
U -5 0.0 N Ol~
III \,\ -I:z:
.2
., ' ~ \ ~:O
-6 -0.2 1-
CadmiUm~ ',:,\ \
/I
I C
IN
" 1'..\ -0.4
-7
" " ....... ~ , l
..... " ... __ .... I
I
-8 -0.6
a
' ...... _/
~' Eh
b
-9 (V)
4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 pH 2 4 6 8 10 12 14
pH ~
Fig.6a,b. Solubilities of zinc and cadmium as a function of pH (Fig. a) and fields of stability of solids
and dissolved zinc species in the system Zn + CO 2 + S + H 2 0 at 25°C and I atm (fig. b) in water
(from Hem, 1972). (a) Total dissolved carbon dioxide species, 10- 3 and 10- 2 mole/I, resp.; ionic
strength of 0.0; Log C in moles Zn or Cd/I. (b) Dissolved zinc activity, IO- s mole/I; dissolved carbon
dioxide and sulfur species, 10- 3 mole/I
has been calculated that between 100 and 1000 ~g/I zinc (and 5 to 100 ~g/I cad-
mium) may be present in the dissolved state. In the system, Zn + S + CO 2 + H 2 0,
where the zinc concentration is 10- 5 molar (together with 10- 3 moles of dissolved
CO 2 and sulfur), three solid phases are possible: the sulfide, carbonate and hydrox-
ide of zinc. In aerated water, zinc carbonate is the stable phase if the pH fall below
8.3; above a pH of8.3 a precipitation of zinc hydroxide occurs.
The solution of this type of chemical equilibrium calculation is usually accom-
plished by the use of readily-accessible computer programmes (see Nordstrom et
aI., 1979). Also the calculation ofthe dissolved speciation of trace metals is readily
accomplished. An example of recent calculations on the dissolved speciation of
trace metals in seawater and in surface waters is given in Table I.
Modelling of aquatic systems is still hampered by the absence of good data
bases to validate the models used. Only in the last few years has it been possible
to overcome the technical problems associated with the sampling and analysis of
trace metals at the ppb or sub-ppb levels. At present, geochemical modelling is ex-
tremely valuable in predicting trends under changing conditions and is at present
one of the objects that mathematical modelling can achieve quite well. However,
it should be understood that any model is only as good as the equilibrium constants
used (or parameters used for kinetic submodels) as well as the preconceived ideas
the modellers have in their particular description of the system.
Table 1. A Calculated speciation of metals in model seawater at pH 8.2. B Calculated speciation of

metals in model freshwater at pH 6.0. C Calculated speciation of metals in model freshwater at pH 9.0
(Tumer et aI., 1981)
Cation Free OH F Cl 80 4 C0 3
A Model seawater pH 8.2

Cd 2 + 3 * * 97 * *
Co2 + 58 I * 30 5 6
Cr 3 + * 100 * * * *
Cu+ * 100
2
Cu + 9 8 3 79
*
Hg2+ * * * 100 * *
Mn2+ 58 * * 37 4 1
Pb2+ 3 9 * 47 1 41
46 12 35 4 3
B Model freshwater pH 6.0
Cd2+ 96 * * 2 2 *
Co 2 + 98 * * * 2 *
Cr 3 + * 95 * * 1
Cu+ 95 5
Cu2+ 93 1 * * 2 4
Hg2+ * 8 * 92 * *
Mn 2 + 98 * * * 2 *
Pb2+ 86 2 * 4 7
Zn 2 + 98 * * * 2 *
C Model freshwater pH 9.0
Cd 2 + 47 4 * 47
Co 2 + 20 7 * * * 73
Cu+ 95 5
Cu 2 + * 3 * * * 96
Hg2+ * 100 * * * *
Mn2+ 62 I * * 35
Pb2+ * 5 * * * 95
Zn2+ 6 78 * * * 16
* = Indicates calculated abundance < 1%

-=Indicates ligand not considered
An example of a modelling approach for the prediction of dissolved copper

levels in a river in which dump leachate from copper containing waste ore was dis-
charged is shown in Fig. 7. The leachate is acidic due to the oxidation of pyrite and
contains high concentration of dissolved copper. In the river system the natural
alkalinity of the riverwater causes a neutralization of the dump leachate and a pre-
cipitation of copper. The neutralization and the precipitation were simulated in the
laboratory by mixing riverwater and dump leachate in various proportions. The
results of these experiments are compared in Fig. 7 with a number of calculations.
In the experiment riverwater and dump leachate were mixed in various propor-
tions and the pH and resulting copper concentration measured. In one calculation
equilibrium with atmospheric CO 2 was allowed for, and in the other, it was as-
sumed that the mixing and travel time in the river did not allow equilibrium with
Metal Ions in Aquatic Systems 9
10 Cu. mg/I
6 5 pH 4
I i i
A
,ICurJHIz~1
---,------------------_.
C.JOH~CO,
*
• log KcuO= -19.9
Equilibrium with
B I"SO:' -:\l----::::::::::::
I'---CU-10-H~'-.• .,. ::::
.. log KcuO= -19.9
No equilibrium with PC0 2 atmosphere c EcuillO• • • •~C~.,~IO~~~~:::::::::
• log Kcuo =-20.35
* Experimental curve A. K . value DI CuO 1. 19.9
10-2'---'--'--'--............-'--'--'--'--'--'--' pH 8 . K. va luf! of CuD 1 - 19.9 [no !:quilibrium with atmosphere)
5.6 6.0 6.4 6.8. 7.2 7.6 8.0 C . K. y,i!lue of CoO I . 20.35
Fig.7. Experimentally determined relationship between pH and copper concentrations and the results
of three model calculations using the Charon geochemical model
the atmosphere over the river stretch considered. The calculation in which equilib-
rium with CO 2 was allowed for gave the best agreement between observed and cal-
culated values; however, inserting a different K-value of CuO gives a better agree-
ment. Also the solid phases controlling the solubility in this rather simple system,
depend to a large extent on the K-values used and on equilibrium with the atmo-
sphere (see insert in Fig. 7). This example shows the complexity in the geochemical
modelling of even a simple system.
Geochemical modelling may also be used to evaluate the need for additional
parameters to be measured as was shown by Jenne et al. (1980) in their study of
the behaviour of cadmium in drainage waters from a mining area in the USA. It
was found that the disagreement between observed and calculated cadmium con-
centrations was not due to thermodynamic data of octavite (CdC0 3 ) but rather
that the incorporation of sulfide levels at a fractional milligram per liter level was
sufficient to find an agreement between the results of the geochemical model and
the experimental results. Similarly Jenne (1981) concluded that to reliably evaluate
solubility equilibria of metal sulfides and phosphates in water contaminated by oil
shale leachates, that the detection limits for sulfide and phosphate need to be at
least as low as 0.005 mg/l and 0.01 mg/l respectively.
The greatest limitations in computing aqueous speciation in natural waters are
the absence of appropriate methods to address the complexation of metals by or-
ganic ligands and the disequilibrium between redox couples (Jenne, 1981). Addi-
tional limitations include the lack of sufficient thermodynamic and kinetic data
and the lack of competence of the available geochemical models. The most urgently
needed data for geochemical modelling include (Jenne, 1981):
- analytical techniques of separating dissolved organic compounds in classes,

quick determination of stability constants which are independent of hydrolysis,
other complexation, and ionic strength effects;
- improved methods for the analytical valence speciation and/or information on
estimating the redox potential of one couple from another redox couple;
- increased competence of state-of-the-art geochemical models, and
- critical evaluation of selected thermodynamic and kinetic data and collection of
additional thermodynamic data on certain complexes.
2.3 Speciation of Dissolved Metals
The various methods to determine the speciation of trace metals in solution can
be divided in four broad categories:
- Chemical equilibrium models.
With the readily available chemical equilibrium models it is possible to calculate,
once the species in solution have been identified and the relevant equilibrium
constants are known, the equilibrium distribution of trace metals over the vari-
ous organic and inorganic complexes taken into account by the model.
- Physical separation methods.
Using physical separation methods, like filtration, it is possible to classify the
species according to size.
'0 IS SOL VE O' 0.4 51' 'PARTICULATE'

AOSORBEO STRUCTURAL STRUCTURAL
METAL FORM FREE COMPLEX ED COLLOIDAL ON
PARTICLES (ORGANIC) (INORGANIC
SPECIATION -------I -a1fec¥ve --1

1 - - - - -- - -
J~_'~h __ J
equilibrium models I 1pure pbases
MOOELLING
--------.1 1______ - -
size fractionation
- - -
UV photolysis
OPERATIONAL ASV .... ith ch!'!!.i£I!.!.P~!!!L8.!'E.~nl ____
MEASUREMENT
Chelex
-------, I
-----------------~------
extraction procedures
- J - - - - - -
DIRECT ISE I
LECTROCHEMICAl A§,V-=-=-=J ------ -------,
MEASUREMENT exhaustive ele~troIY.!lis_ .~_ _ ____ J
BIOLOGICAL
UPTAKE
phyto
plankton
_______________ l_______ ~-------,
paJticle feeders I
- - - - " --- -- - .J
Fig. 8. Classification of metal compounds according to size and methods to determine the distribution
of the trace metals species in natural waters. (Redrawn after Turner and Whitfield, 1980).
Physical Separation 11
- Chemical methods.
With the chemical methods the metals are classified according to their interac-
tion with substances like chelating agents or by their behaviour at the mercury
electrode during voltammetric measurements.
- Direct chemical methods.
Few methods exist for a positive identification of metal species in solution, ex-
ceptions are the organo-metal species, for which several elegant methods have
been designed (Chau and Wong, 1983).
In most cases the three methods are combined into speciation schemes. Fur-
thermore biological assays have been developed to determine the influence of metal
species on organisms. Figure 8 gives a summary ofthe various methods in use.
2.3.1 Physical Separation
Size fractionation alone is potentially a useful technique for speciation since the
bio-available fraction is generally associated with the smaller size categories (Bat-
ley, 1983) and several methods exist to fractionate metals in surface waters with
physical techniques.
The most common method to speciate metals in surface waters is filtration
through a 0.45 11m nominal pore size filter. In this way a distinction is made be-
tween "dissolved or soluble" and particulate metals. Two filters are generally in
use:
- cellulose membrane filters
- polycarbonate filters
The cellulose filters are depth filters with a thickness of about 150 11m, an ir-
regularly shaped pore structure and interconnecting pore parts. Particles may be
trapped within the membrane structure. Furthermore, they represent a consider-
able surface area for adsorption.
The pore size to filter thickness ratio is smaller for polycarbonate membrane
filters, which are more like screen filters. They consist of films with a thickness of
about 10 m in which the required holes are etched. Due to their structure they offer
far less area for adsorption. A disadvantage is the fact that they are more prone
to clogging and often require vigorous stirring of the solution (breaking up oflarg-
er particles). A review of manufacture and use of these filters has been given by
Strathmann (1981).
Both vacuum and pressure filtration is applied; however, with the latter method
phytoplankton cells may be ruptured. These ruptured cells contribute to the solu-
ble organics, nutrients and metals in the filtrate (Florence and Batley, 1980). In
waters with a high turbidity the results may be effected by the clogging of the pores,
and in extreme cases the water is filtered through the filter cake instead of the mem-
brane filter.
It should be stressed that all experimentally determined results on the fraction-
ation of extremely low levels of trace metals are subject to contamination from the
materials used and to adsorption during the filtration steps or during storage of
the water sample. Care should be taken to carry out the procedure as soon as pos-
sible after sampling, because during storage, changes in pH, temperature and mi-
crobial degradations may take place, all affecting the distribution of metals over
the various phases (Benes and Steinnes, 1974; Smith, 1976; Florence and Batley,
1980; Piotrowicz et al., 1983).
A further size fractionation of the "dissolved fraction" passing through a
0.45 11m urn filter is possible with variety of techniques (Table 2). In using a com-
bination of ultra-membrane filters and polycarbonate membrane filters a range
from 1 nm to 12 11m can be covered (Hoffmann et al., 1981; v.d. Meentet al., 1982).
Some results of a sequential size fractionation of surface waters is shown in Fig.9.
Table 2. Physical methods for the size fractionation of "dissolved" compounds in natural waters
Method Range References
Filtration 0.015-12 ~lm Van den Meent et al. (1982)

Ultra-filtration 1- 15 nm Benes and Steinnes (1974), Giesy and Briese
MW (molecular weight) (1977), Smith (1976), Guy and Chakrabarti
500--300.000 (1976), Benes et al. (1976), Buftle et al. (1978),
Hoffmann et al. (1981)
Dialysis 1-15 nm Benes and Steinnes (1974, 1976), Benes et al.
(1976), Guy and Chakrabarti (1976), Benes
(1980)
Centrifugation and Depends on g-force and Lammers (1967), Benes and Steinnes (1975)
ultra-centrifugation specific gravity
Ion-exclusion Betz (1979), Gjessing (1965), Steinberg (1980),
chromatography Tuschall and Brezonik (1980)
CARBON IRON
4 2
en 70%
.g
<.J
Q
Q 2
..
.....
15%
0
COPPER
_ 1.0 _ 0.4
~
5-
=
<..>D.5 ~Ol
0:
0
LEAO CAOMIUM
OA 0.4
Fig. 9. The distribution of iron, cop-

per, manganese, cadmium, lead, and
O~~~~~~~~ organic carbon over size fractions in
cl0 10.2525 .100 1100 110 10.2525 . 100 1100 the Minnesota river (Eisenreich et
Fraction (1000MW) al.,1979)
ASV-Labile Species 13
In Minnesota and Mississippi river waters, the metals were found to be mainly
associated with the intermediate molecular weight fractions between 1000 and
10,000, in these fractions no detectible free or labile bound metals were found as
defined by ASV (Anodic Stripping Voltammetry), indicating that the complexes
belong to the very moderately labile or slowly labile fraction as defined by Figura
and McDuffie (1980). To obtain more information on the metals in the filtrates,
organic carbon determinations are carried out (Giesy and Briese, 1977; Hoffmann
et ai., 1981) or the organic matter composition is characterised with advanced tech-
niques like pyrolisis mass spectrometry (v.d. Meent et ai., 1982).
Sequential filtration by nUcleopore filters is also a convenient method to frac-
tionate aerosol samples (Heidam, 1981).
Dialysis methods have been used quite extensively by Benes and co-workers
(Benes and Steinnes, 1974; 1976; Benes et ai., 1976; Benes, 1980). A dialysis bag
is placed in the solution to be analysed. Only ionic species and small complexes pass
through the membrane. After equilibrium has been reached the contents of the bag
can be analysed with a variety of techniques to access the ionic fraction (and small
complexes) of metals in the sample. However, recent evidence suggests that not all
small ionic species [e.g. Cuz(OH)z] pass through (Truitt and Weber, 1981). Recent-
ly this method has been used in the field in combination with an active biological
monitoring programme (using the bivalve Dreissena polymorpha) to determine the
bio-available species of metals (Del Castilho et ai., 1983).
The disadvantage of this technique is its long equilibration time. However, this
drawback has been overcome by using a combination of dialysis and ion- exchange
techniques (Hart and Davies, 1977). The solution from the dialysis bag is continu-
ously passed through an ion exchange column in a closed loop system. In this way
an optimum concentration gradient is obtained over the dialysis membrane, speed-
ing up the separation.
Less often used methods include centrifugation (Lammers, 1967; Benes and
Steinnes, 1975) and ion exclusion chromatography (Gjessing, 1965; Betz, 1979;
Steinberg, 1980) and reverse-phase liquid chromatography (Lee, 1981; Mills and
Quinn, 1981).
2.3.2 ASV -Labile Species
Voltammetric techniques are the most common to obtain information on the spe-
ciation of trace metals in solution. The analysis is performed in a cell which con-
tains a mercury drop or film electrode. A voltage is applied to the mercury elec-
trode more negative than is necessary to reduce the metal ion in solution. The
metals move toward the electrode and are reduced, with the formation of an amal-
gam at the electrode. In this way metals are concentrated in the mercury electrode.
The amount of metal removed from the solution by this concentration step is about
0.25 % of the total content (Barendrecht, 1967). After this concentration step, the
voltage is reversed and a gradually increasing voltage is applied to the electrode.
As the voltage approaches the oxidation potential of one of the metals present, the
ions of the metal pass into the solution and the current increases. The potential at
which metals pass into the solution is characteristic for each metal and the current
is proportional to the concentrations in the original solution. Metals which can be

analysed by this method (e.g. which are reducible at the mercury electrode) include
the environmentally important Cu, Pb, Cd, Zn, Sn, Cr, Co, Mn and Ni. More de-
tailed information on the ASV-method and related polarographic techniques can
be found in several textbooks (Brainina, 1974; Bond, 1980).
The processes occurring at the electrode are important, since they determine the
species of the metal which is actually measured (Davison, 1978). The concentration
measured with ASV corresponds to the electroreducible species, the aquo ion and
those metal complexes which are in sufficiently labile equilibrium during the time
scale of the measurement. This time scale can be associated with a diffusion time
in the layer surrounding the electrode, which is in the order of ms. The fraction
measured by ASV was termed "very labile fraction" in the speciation scheme of
Figura and McDuffie (1980). This fraction includes the aquo metal ion and com-
plexes like the lead-glycine complex. Complexes like CdNTA, however, are rela-
tively non-labile to the ASV -method.
To detect all simple ionic species in solution buffering to a pH of 5 is recom-
mended (Batley, 1983); at higher pH values ionic species like hydroxy carbonates
of lead and cadmium are electrochemically inactive, whereas at lower pH values
organic complexes may dissociate and metals adsorbed on colloidal material may
be released.
ELECTROCHEMICALL Y ACTIVE ELECTROCHEMICALL Y INACTIVE
LABILE NON - LABILE
ORGANIC COMPLEXES ----+---..,.·ORGANIC COMPLEXES
lower pH
Adsorption
Adsorption
METAL IONS :::;~;:::====t====>~
_ PARTICULATE
MATTER
Desorption
'lower pH ,
I
I Flocculation
I
INORGANIC
COMPLEXES ----~------3.~
I COLLOIDS
I
Fig.tO. Interrelationships between various metal species in water and their relationship to electro-
analytical methods. (Redrawn after Whitfield, 1975)
Speciation Schemes 15
By chemical treatment of the solution, e.g. lowering of the pH and destruction

of the organic matter, electrochemically inactive species may be transformed into
electrochemically active species (see Fig. 10).
The direct analysis of surface waters (at a predetermined pH) gives an oper-
ationally defined metal fraction. However, in a number of studies it has been pos-
sible to relate this ASV -labile fraction with biological uptake by organisms (Young
et aI., 1979; Crecelius et aI., 1981).
2.3.3 Ion-Exchange Methods
In the ion-exchange method, the water sample is brought into contact with an ion-
exchange medium either in a batch technique or by passing the sample through a
column packed with the ion-exchange medium. Chelex is probably the most used.
When Chelex is added to the water sample it competes with the ligands for com-
plexation of the trace metals. The fraction of the metals not removed by the Chelex
resin is called the "bound fraction" and the fraction taken up by the resin, the "ex-
changeable" fraction (Hart and Davies, 1977; 1981a; 1981b). Calculation showed
that only if the formation constant between the metal and the ligand in solution
is in the order of 13 or 14 can it compete effectively with the resin. Therefore all
ligands with formation constants (log K) less than about II are stripped off their
metals. Those substances which keep the metals bound to them are probably non-
ion-exchangeable fractions, which exist as colloids and inorganic forms (Hart and
Davies, 1981a).
Figura and McDuffie (1979; 1980) used a kinetic approach for the separation
of metal species by Chelex resins by using a short equilibration time of about 7 s
by passing the water sample over a small column followed by a long equilibration
time with the batch technique (72 h). The CdNTA complex which is non-labile
with the ASV -method is now retained on the Chelex column. The fraction retained
by the column is termed the "moderately labile" fraction, the amount retained by
the batch technique the "slowly labile" fraction. The fraction not retained by the
column and by the batch technique is termed the "inert" fraction and is likely to
be similar to the bound fraction as defined by Hart and Davies (1977; 1981a;
1981 b). A range of ion-exchange materials was evaluated by Florence (1982) to
find a simple procedure to determine aquatic toxicity of trace metals. However, an
unequivocal recommendation could not be made, and should await algal toxicity
tests in progress.
2.3.4 Speciation Schemes
Several of the individual methods discussed in the foregoing section can be brought
into speciation schemes to differentiate between forms of metals.
The first and still most comprehensive scheme was used by Batley and co-work-
ers (Batley and Florence, 1976; Batley and Gardner, 1978). The scheme divided the
sample in fractions passing in 0.45 J.1m um filter and separating the particulate
metals from the "dissolved" metals. The "dissolved" metal fraction is measured
Sample
Filter
O,40flm Nucleopore
1 Acidify 1 Acidify 1 Add Chelex 1 Dialyse

2 Digest 2 Digest 2 Elute 2 Elute Chelex
3 Analyse 3 Analyse 3 Analyse 3 Analyse
Fig.H. The analytical speciation scheme developed by Hart and Davies (1981 a)
Fe Cd Cu Pb Zn
1400
=
....
5- 1000 50 Parti c" late
Meta l Mp
""
Bound Metal
~ 600 30 Mb
<.J
Ion Exchangeable
10
Metal Mi.
200
Oialysabl e
Motal Md
Fig. 12. The Hart and Davies scheme applied to freshwater (F) and estuarine waters (E) from the Yarra
River (Australia). (Hart and Davies, 1981a)
with ASV making a distinction possible between ASV-labile and non-AS V-labile
fraction (called the "bound fraction"). The "dissolved" fraction is also passed
through a chelating resin column, before and after removing the organic matter
with UV -radiation. With this scheme they were able to identify seven classes of
compounds. The scheme is laborious (analysis time for one sample about 1 day),
which precludes its application to routine analysis, and the scheme is possibly more
complex than is needed for biological availability studies (Batley, 1983).
The Hart and Davies scheme (Hart and Davies, 1977a; 1977b; 1981a; 1981b) is
much simpler, it defines filtrable, exchangeable and dialysable metal fractions
(Fig. II):
The amount of exchangeable metal is determined in a batch procedure with
Chelex and the dialysable fraction is obtained with the combined ion-exchange-
dialysis technique discussed in Chap. 2.3.3. This method has been applied to lakes
and estuaries and some results are shown in Fig. 12.
Speciation Schemes 17
DIGEST, EVAP.
TOTAL TM'S
+ ASV
TOT. SOLUBLE TM'S
CHELEX COLUMN
CHELEX BATCH
13 DAYS)
DIGEST,
EVAP.
+ASV
'INERT'
Cd Cu
~
--------------------i-
_---------1
------------------
Susqbl~ann.
1
I 1 _
St. Lawrence
----...I-L.£..<..y.7?<~W7_7'S~'7"iI
_
Hudson
1-.
~ ________ ~~~~~~wu
Zn Pb
t========j-----~---~:~~:::
_---- -----------1 ~
~~ 1 _ Hudson
B ASVor very labile traction ~ Slowly labile traction
CD Very + moderately labile tractions • Inert traction
Fig. 13. The kinetic speciation scheme developed by Figura and McDuffie (1979; 1980) with results for
a number of river waters
A kinetic fractionation scheme has been developed by Figura and McDuffie

(1979; 1980). Individual parts of this scheme have already been discussed. An ASV-
measurement ("very labile fraction") is carried out after filtration over a 0.45 11m
filter. The filtered sample is passed through a short chromatographic column filled
with Chelex. The contact time is about 7 s. The fraction retained by the column
is called the "very moderately labile fraction". The eluate from the column is
brought in contact with Chelex in a batch procedure for 3 days. The fraction re-
tained is called the "slowly labile" fraction and the fraction remaining in solution
the "inert fraction". In this way trace metal complexes are differentiated according
to their kinetic behaviour. A scheme of this fractionation method, together with
some results are given in Fig. 13.
The scheme is simple and this operational approach could be useful for bio-
availability studies (Batley, 1983).
A size fractionation scheme of Hoffmann et al. (1981) consists of a centrifu-
gation step followed by filtration through 0.45 ~m filter followed by ultra- filtra-
tion over filters with nominal molecular weight cut-offs of lOS, 2.5 x 10\ 104 , and
10 3 • In the filtrate complexing capacity of organic matter as well as the total or-
ganic matter content were determined. Some results of this scheme have already
been presented in figure 9. The Harrison-Laxen scheme (Harrison and Laxen,
1981) consists of a size fractionation with nucleopore filters from 0.12 ~m to
0.0015 ~m. Apart from total filtrable metals, ASV-labile metals before and after
destruction of the organic matter are determined in the filtrates of the 1 ~m and
0.08 ~m filters. Chelex labile metals are determined additionally in the 1 ~m fil-
trate. Harrison and Laxen also carried out experiments with ultra-filters; however
these proved to be prone to adsorption and were not incorporated in the final
scheme. For most freshwaters studied the UV-radiation technique for destroying
the organic matter was not feasible, inorganic brown deposits were formed and a
pH increase was observed. Hasle and Abdullah (1981) combined ultra-filtration
followed by the determination oflabile, acid-soluble and total metals with ASV for
coastal seawaters.
Radiotracers were used by Amdurer et al. (1982) to study the behaviour of
metals in large marine microcosms. Their speciation scheme consists of filtration
through 0.45 ~m filters followed by sequential filtration with ultra-filters followed
by weight cutoff of 10 5 , 104 and 10 3 • Additionally the filtrate from the 0.45 ~m fil-
ters was passed through an activated charcoal column followed by passage through
a Chelex column. The fraction retained by charcoal represents some combination
of organically complexed and colloidal metals, plus dissolved inorganic species.
The species in the effiuent are obviously very unreactive towards most adsorbing
surfaces and complexing agents since they passed through a very strong adsorbent
(charcoal) and chelating agent (Chelex).
2.4 Interaction with Ligands
Most natural waters have a certain capacity to reduce the toxicity of added metals,
which has been attributed to the presence of ligands in the waters complexing the
added metal ions and making them less bio-available for organisms. Furthermore
the adsorption of metal ions to particulates in waters is influenced by the presence
ofligands (see Chap. 2.5).
The complexation of added ionic metals to natural waters is generally referred
to as the complexing capacity of the water (Hart, 1981; Neubecker and Allen,
1983).
The determination of chemical forms of organic matter in surface waters is
quite demanding, but is of little value in providing information as to possible in-
Interaction with Ligands 19
teractions of these species with inputs of heavy metals (Florence and Batley, 1980).
Therefore operationally defined methods are used to determine the response of sur-
face waters to the addition of ionic metal species.
When trace metals are added to a natural water sample, the metal ions are dis-
tributed over the various complexing ligands present. When equilibrium has been
reached the total metal concentration is given by (Hart, 1981):
[M]= [Mn+]+ [MI] + [ML] . (1)
Where: [Mn+] is the concentration of the free metal ion; [MI] is the total concen-
tration of the inorganic complexes, [ML] is the total concentration of the inorganic
complexes.
The metal-organic complex will be in equilibrium with the free ion:
L- *K[Mn+] [L t]
(2)
M - 1+*K[Mn+]
Where L t is the total concentration of ligand capable of binding M and is equal

to L + ML; L is the concentration of the free ligand; *K is the conditional equilib-
rium constant for the reaction:
Mn++L=ML
* _ [ML]
(3)
K- [Mn+] [L]
Generally L t is referred to as the metal complexing capacity. To calculate the con-

centration of the metal ion in complexing form it is necessary to determine the
value of the conditional equilibrium constant *K. This is not the true thermodyna-
mic equilibrium constant since it only holds for certain conditions of pH and ionic
strength.
The various methods to determine the complexing capacity and the *K value
all consist of titration of the surface water sample with a suitable metal ion. Typical
curves which can be obtained in this way are shown in Fig. 14.
At first most of the added metal is complexed by the ligands present in the water
and only a small increase in uncomplexed copper is obtained; this increase is deter-
mined by the K-value. When all the ligands are complexed, the response of the free
metal increases in proportion to the amount of added metal.
Equation (3) can be rearranged into the form:
(4)
which shows that plotting [Me]/[Me] versus [Me] should result in straight line, with
a slope ofL t -1 and intercept (*K·L t)-1.
The data can also be plotted in a second slightly different way if the concept
of binding capacity is introduced (e.g. the total amount of binding sites available
for complexing the added metal ion per unit weight). Then:
Lt=BC·OM (5)
Be is the total amount of binding sites per unit weight of the complexing material.
OM is the concentration ofthe complexing material.
3000
• Rhine
KdX1D BMol·l Complex;ng capac;ly 0.25" M
.IJsselmeer 2.0
K.D.7.1oBMol·l Complox;ng copac;ly 0.53" M •
2000 1.5
'-
'"
3-1.0
=
1000 ~
.!!
:0;
.!! 0.5
>
III
C
ow.~~~~ ______ ~ ______ ~
o 20 40 60 1.1 1.2 1.3 14 15 t6

Cu ("gil) Complexing capacity
Fig. 14. Typical curves obtained for the titration of river Rhine and the IJ sseImeer and the relationship
between ASV -labile copper and the complexing capacity
Substitution of equation 5 in 4 gives a Langmuir adsorption isotherm:
x= [ML] =(BC. *K. [Mn+])j(l +*K[Mn+]) (6)

OM
which can be rearranged into:
[Men+]X= l/BC· *K+Mn+ IBC. (7)
Plotting of [Men +(X] against Men + results in a straight line whose slope and inter-
cept are BC - 1 and (BC*K] - 1 respectively. Equation 6 requires the amount of
complexing material in the sample as an additional parameter. This type of ap-
proach is often used for determining the com pie xing capacity and *K values of iso-
lated humic substances from natural waters (Mantoura and Riley, 1975; Guy and
Guy and Chakrabarti, 1976; Mantoura et aI., 1978; Klotz, 1982) or fractionated
suspended matter (v.d. Meent et aI., 1982). It should be stressed that data on com-
plexing capacity alone are not sufficient for interpretation of the response of sur-
face waters to added ionic metal. Different waters may have the same complexing
capacity, however if the *K-values show large differences, the amount of added
metal which remains in the ionic form shows large differences.
A method to determine the complexing capacity of natural waters should have
the following characteristics (Hart, 1981):
- selectivity for the metal ion added
- capacity to measure the metal, or a related quantity at very low concentrations
around 10 - 8 M
- capacity to provide information on both metal binding ligand concentrations
and conditional formation constants
- not require the addition of other reagents that may disturb the equilibrium or
bind the added metal
not require preconcentration that may disturb the natural equilibrium

and finally the method should be relatively rapid.
The equilibrium of the added metal to the ligands in solution may take a con-
siderable amount of time (Benes and Steines, 1974; Batley and Florence, 1976).
Few detailed studies have been carried out with respect to the time-dependency of
the measurement. Allen et al. (1978) found an initial rapid binding of the trace
metals (minutes) followed by a much slower (24 h) binding of a small extra
amount. Based on these studies it can be concluded that most complexing-capacity
studies which are carried out within 10 min to 2 h may underestimate the total
complexing capacity by as much as 20% (Hart, 1981).
One of the most common methods used to determine the complexing capacity
is anodic stripping voltammetric (see Table 3 for references). However, as dis-
cussed in Chap. 2.3.2 this method determines the electrochemically active species,
Table 3. Summary of methods to determine the complexing capacity of natural waters. (Based on
Hart, 1981 and Neubecker and Allen, 1983, with some new additions of recent literature)
Method Description References
Voltammetric The solution is titrated with copper, Chau et al. (1974), Ernst et al. (1975),
methods and the response "ASV -labile" metal Smith (1976), Shuman and Wood-
is measured ward (1977), Duinker and Kramer
(1977), Hanck and Dillard (1977),
Sugai and Healy (1978), Shuman and
Cromer (1979), Baccini and Suter
(1979), Bhat et al. (1981), Hart and
Davies (1981), Blustein and Shaw
(1981), Tuschall and Brezonik (1981)
Ion exchange Metal ions are added to the natural Baccini and Suter (1979), Van den Berg
methods water sample which contains a certain and Kramer (1979a, 1979b),
amount of an ion-exchange medium Figura and McDuffie (1979),
(Mn0 2 , Dowex, Chelex). Metal left Crosser and Allen (1977)
in solution is measured with suitable
technique
Ion selective The solution is titrated with copper Buffle et al. (1977, 1980), Buffle (1980),
electrodes or cadmium ions, and the metal ion Giesy et al. (1978), Giesy (1980),
is measured with the ISE Sunda and Hanson (1979),
van den Meent et al. 1982), Giesy and
Briese (1980), McCrady and Chap-
man (1979), Bhat et al. (1981)
Biological Decrease in photosynthetic activity of Giichteretal. (1978), Davey etal. (1973),
methods plankton upon addition of metal Srna et al. (1980)
Growth suppression of bacteria upon Gillespie and Vaccaro (1978,1981)
addition of metal
Uptake of 3H-labelled amino acids Sunda and Ferguson (1982i)
by bacteria
Dialysis methods Copper ions are added to the surface Guy and Chakrabarti (1976), Truitt and
water sample and the uncomplexed Weber (1981)
and complexed metal is separated by
dialysis
which includes both the free aquo metal ions, certain inorganic complexes (depend-
ing on pH) and organic complexes with small K values. Adsorption of organic mat-
ter at the electrode can depress the current signal for a given added metal concen-
tration resulting in an effect similar to that produced by binding ligands in solu-
tion. This can give rise to errors although the effect is only usually observed with
excessively high organic concentrations.
Ion-selective electrodes (both cadmium and copper) have been used quite often.
Although it is the only method which can measure the free ionic form, its main
drawback is low sensitivity. Natural waters have to be concentrated to obtain suf-
ficient ligand concentration to obtain a break in the curve. Large spikes have to
be added; in this way, strongly complexing ligands at low concentrations may be
overlooked. Apart from these two methods, which rely more or less on direct mea-
surement of metal species, there exist a number of techniques, which use an addi-
tional step to separate the uncomplexed from the complexed metal ions. In the
dialysis method (Table 3) the surface water is titrated with copper similar to the
preceding methods; however, in the solution is placed a dialysis bag, which allows
the free movement of small metal complexes. After equilibration the contents of
the bag are analysed. As has been mentioned above, a considerable drawback of
the technique is the rather long equilibration time needed.
An ion-exchange method for the determination of complexing capacity and of
conditional equilibrium constants has been proposed by v.d. Berg and Kramer
(1979a; 1979b). In the solution to be titrated a suspension of Mn0 2 is present. Add-
ed metal ions distribute themselves over the ion-exchange medium, the ligands and
part remains as the free metal ion. The total metal (Me+ MeL) in solution can be
determined after removing the Mn0 2 from suspension by filtration. In order to
evaluate the formulae properly, it is necessary to determine the free aquo ion.
This can be done by measuring the amount of adsorbed metal on the MnO z
suspension and relating it to an experimentally determined adsorption curve in ab-
sence ofligands. From the adsorption curve and the measured adsorbed metal con-
centration, the free metal concentration can be determined and plots of [Me]/[MeL]
versus Me can be constructed to determine Lt and K in a way similar to that as
described in the preceding section. In the calculation it is assumed that no adsorp-
tion of metal-ligand complexes take place. However, this type of adsorption cannot
be excluded (see Chap. 2.5.4.).
A number of studies have provided evidence that the free metal ion is the toxic
metal species for organisms (Sunda and Guillard, 1976; Gillespie and Vaccaro,
1978). This fact is the basis for bio-assay techniques to determine the complexing
capacity and in some cases also the equilibrium constants. The growth rate of an
organism (or other metabolic parameters) is measured as a function of added metal
ions. The first metal added will be complexed by the ligands present, and only a
small metabolic effect on the organism is the result. However, after all ligands are
complexed with metals, the added metal will remain in the ionic form and affect
the organisms.
Davey et al. (1973) used a marine diatom as the test organism. Seawater and
seawater to which EDT A and histidine as complexing agents were added were ti-
trated with copper and the growth depression of the diatom was measured. Gille-
spie and Vaccaro (1978) used bacteria cultures isolated from the Saanich Inlet in
100
Fig. 15. Depression in the uptake
of 14C labelled glucose by bacteria :;
'x
in water from the Sargasso Sea 0 x
II:
and Nantucket Sound as a func- ~
z 0
\
tion of added copper. (Redrawn 0
80
U
after Gillespie and Vaccaro, 1978)
I"
~
Z
0 I x NANTUCKET
t= 60
cC SOUND.
....
i I x
in
t/)
cC 40
\SA~GASSO
! "
x", x
w o
t/)
0
'x-
U
:::I SEA
....
"...
U
I
...
20
0
1-
1
1
0, - - - - -
00 4 8 12 16 20
ADDED COPPER (u9L- 1 )
British Columbia in a similar way. In the latter investigation the uptake of 14C la-
belled glucose was used as a metabolic parameter. Some results for the Sargasso
Sea and the Nantucket Sound are presented in Fig. IS.
The midpoint of the segment showing maximum change for each of the curves
was interpreted as the copper saturation point (Davey et ai, 1973), which is related
to the complexing capacity. Ultra-violet radiation, which destroys the organic mat-
ter, removed most of the complexing capacity present in the waters studied.
Gachter et al. (1978) studied Lake Alpnach in Switzerland and used native
phytoplankton as test organisms. The water was spiked with 14C labelled sodium
bicarbonate and the primary production was measured as a function of added cop-
per. Sma et al. (1980) compared the ASV-method for the determination of the
complexing capacity with a biological method employing a diatom. The biological
complexing capacity was defined as the differences in the amount of copper needed
to produce a 50% reduction in growth (EC so value) between filtered and ultra-fil-
tered water. A correlation coefficient of 0.993 was observed between the titration
method and the biological assay. The uptake of3H labelled amino acid by bacteria
in seawater from high- and low-productivity areas was used by Sunda and Fer-
guson (1982). The bio-assays indicated higher complexation of added copper in
high productivity coastal samples. The conditional stability constants obtained
were high and varied between 9 and II (log K).
A short summary of data on complexing capacity an K-values for natural
waters are presented in Table 4. (Part of the organic matter responsible for the
complexing capacity of natural waters originates from exudates of organisms,
which subject is treated in Chap. 2.7.3). Large variations in complexing capacity
of natural waters are observed. Although high dissolved organic matter contents
will in general cause a high complexing capacity, the ratio of complexing capacity
per mg of dissolved organic carbon (DOC) shows large variations. These large
Table 4. Complexing capacity and conditional equilibrium constants for selected surface waters
Water Complexing Conditional Method and References

capacity equilibrium
llMjI constant (log K)
Lake water:
Chapel Hill 31 S.2 (pH=7) ASV-titration. Shuman and Woodward
(1977)
Black Lake 126 4.8 (pH=6.S) ASV-titration. Shuman and Woodward
(1977)
Lake Alpnach 0.03-0.07 10.1-10.7 (pH=8.1) Bioassay with algae (Giichter et aI., 1978)
Lake Ontario 0.33 9.S (pH = 8.4) Ion exchange methods (V d Berg and
Kramer, 1979)
Melimex experiment 2.4 11.0 (pH = 8.8) ASV-titration (Baccini and Suter, 1979)
River water:
Magela Creek 0.07-0.46 7.5--8.S (pH=6.0) ASV-titration. Hart and Davies (1981)
Mississippi River 0.88-1.08 9.9-10.7 (pH =8.1) ASV-titration. Hoffmann et al. (1981)
Seawater:
Gulf of Mexico O.OOS-O.1S 9-11 (pH=8.1) Bio-assay with bacteria. Sunda and
Ferguson (1982)
variations apparently reflect the differences in molecular structure of the organic

matter and its ability to complex added metals. The differences in complexing ca-
pacity are also reflected in the conditional equilibrium constants measured, differ-
ences of 5 orders of magnitude are observed. The low values in the order 10 5 are
similar to the ones measured for isolated humic acids from water and soils. How-
ever, the high values cannot be explained by carboxylate ligands (predominant in
humics) alone. Compounds of proteinaceous material are probably responsible for
the high com pie xing constants observed (Hoffmann et aI., 1981; Baccini and Suter
1979; Tuschall and Brezonik, 1980). In a number of studies two sites for complex-
ation of metals with different K-values have been found (Gachter et aI., 1978; Bac-
cini and Suter, 1979; Hart and Davies, 1981; Sunda and Ferguson, 1983).
2.5 Interaction with Particulate Matter
Interactions between particulates and metals play an important role in the regula-
tion of dissolved metal concentrations (the most bio-available). Moreover adsorp-
tion is the first step in the ultimate removal of trace metals from the hydrological
cycle; the ultimate sink being the oceanic sediments. Changing environmental pa-
rameters like pH (acid rain), chlorinity (in estuaries) or the discharge of complexing
agents (NT A) all affect adsorption/desorption processes.
To understand the fate of trace metals in the hydrological cycle and to predict
the consequences of human changes an understanding of the interaction of trace
metals with the particulates is essential.
Mechanisms 25
Although much excellent research has been carried out on the physico-chemical
principles of trace metal adsorption on model substrates, the applicability of the
results to the "real world" is still hampered by our lack of knowledge on the surface
properties of aquatic particulates. However, recently a number of studies have
been conducted on model substrates and sediments, which are relevant to processes
in the hydrological cycle. The more relevant studies will be discussed. In depth in-
formation of the theoretical background can be found, for example, in the book
publications of Stumm and Morgan (1981) and Anderson and Rubin (1981).
2.5.1 Sorption Processes
The forms of sorption most commonly encountered in connection with solute

transport in soil and sediment are adsorption, chemisorption and ion exchange;
there should be no difference between "sorption" and "coprecipitation" (Jenne,
1976; Laxen and Sholkovitz, 1981). For example, experiments on cadmium ad-
sorption/coprecipitation with amorphous iron oxyhydrate have clearly shown that
the removal efficiency is essentially identical whether the iron is precipitated before
the trace metal is added (adsorption) or afterwards (co precipitation) (Benjamin et
aI.,1982).
Physical adsorption on the external surface of a particulate is based on Van der
Waals forces of the relatively weak ion-dipole or dipole-dipole interactions. Addi-
tional reactions can occur with physical sorption on the particle's inner surface or
in pores. Representative solid substances include iron oxides, aluminium hydrox-
ides, clay minerals and organic matter and molecular sieves (Lieser, 1975).
Chemical adsorption is characterized by the formation of chemical associations
between ions or molecules from solution and the surface particles.
Sorption based on ion exchange is a chemical process in which negative or posi-
tive charges in the mineral lattice (such as in clay minerals) are compensated for
by ions possessing opposite charges, which, more or less hydrated in the inner
layers, are exchangeable by ions from the solution.
2.5.2 Mechanisms
Various theories have been proposed to describe and interpret the adsorption of
metal ions on solid surfaces. With respect to the interactions with hydrous oxides
Stumm et aI. (1976; 1980) have summarized the following mechanisms:
(1) the Gouy-Chapman-Stern-Graham model which accounts for specific and
electrostatic adsorption;
(2) the adsorption-hydrolysis model which postulates that the adsorption ofhy-
drolyzable metal ions is directly related to the presence of hydrolyzed species;
(3) the ion-solvent interaction model which considers coulombic, solvation
and specific chemical energy interactions as the ion approaches the interface, and
which implies that a lowering of the ionic charge of the metal species (such as by
hydrolysis) decreases the ion-solvent interaction (which represents a barrier to
close approach of multiply-charged ions to the surface);
(4) the ion exchange model according to which cations, upon adsorption on the
hydrous oxide surface groups (= Me-OH), replace protons;
(5) the surface complex formation model in which the hydrous oxide surface
groups (= Me-OH, or = Me-OH-HO) are treated similarly to the amphoteric
functional groups in polyelectrolytes as complex forming species.
While the "physical" -approach theories (1), (2) and (3) interprete the adsorp-
tion in terms of a combination of electrostatic interactions between ions and the
surface charge and ion-solvent interactions, the chemical-approach theories (4)
and (5) involving reactions of adsorbable species with chemical entities on the solid
surface - are now favoured by most researchers 1 (Hohl and Stumm, 1976;
Schindler et aI., 1976; Davis and Leckie, 1978; Davis et aI., 1978; Davis and Leckie,
1979; Westall and Hohl, 1980; Bourg, 1982).
Although model calculations of the adsorption of Cu(II) and Pb(II) on quartz
by Vuceta and Morgan (1979) suggest that both concepts can be used to explain
experimental data, there seems to be a justification for the preference of the chemi-
cal approach for two reasons (Bourg, 1982): (a) Some cations are adsorbed at pH-
values for which surfaces are positively charged (e.g. Pb on y-AI 2 0 3 ), and (b) the
tendency of ligands to form surface complexes with a given hydrous metal oxide
is similar to that of the solution complexation with the corresponding metal. A
summary of major coordination phenomena at oxide-water interfaces is given in
Fig. 16 (after Schindler, 1981).
These oxide surfaces can act as weak acids or bases in solution , undergoing
protonation in response to changes in solution pH (Stumm et aI., 1970; Benjamin
et aI., 1982):
SO-+H+=SOH (1)
SOH+H+ =SOH! (2)
(where SOH represents a single protonated surface oxide site). And, in addition,
the surface can enter into "complexation" reactions with other ions in solution, by
which protons are released to solution when an uncomplexed metal adsorbs:
(3)
This type of alteration in surface charge resulting from chemical reactions is fre-
quently referred to as "specific adsorption" (for details see Stumm and Morgan,
1981). Whereas the phenomenon was initially understood in terms of competition
for surface sites with protons and other cations, this model is now extended to the
adsorption of complexes of metals (Bourg, 1979).
Inspection of reaction (3) allows one to predict the effects on adsorption by
changing pH or adsorbent concentration (Benjamin and Leckie, 1981): Increasing
1 In a controversial discussion on the article "Ultimate Removal Mechanisms of Elements from the
Ocean" by Li (I 98 I) it has been proposed by Whitfield and Turner (I 982) that their electronegativity
model involving physical parameters such as ionic potential (z/r) and ionisation potential (Whitfield
and Turner, 1979; Turner et aI., 1980) could fully explain seawater composition without the compli-
cations associated with a mechanistic study of surface complex reactions, which - according to the
reply of Li (1982) - should be preferred as the consistent explanation to the observed partition of
elements between the solid and liquid phases in the ocean
Mechanisms 27
Fig. 16. Coordination phenomena at ox- HI+)H ~ 1_)

ide-water interface (Schindler, 1981; in '0 . . _ 0 _ 0
f;1~I'Jlnnnt~f;'ift~lntm
Anderson/Rubin: Adsorption of inor-
ganics at solid/liquid interfaces; Ann
Arbor Science Pub!., p. 6) (a)
(a) Acid-base reactions of surface hy-
droxyl groups ,-<-1 0 - H + M'+
~ "f-
(b) Deprotonated surface hydroxy Is co-
ordinate with dissolved metal ions. (b) r~~i;,i
Several species may be formed si-
multaneously.
.;~-O-H + Ml+
~
(c) Surface hydroxyls are replaced by ~~-O-H
W~~~~~
dissolved ligands. n'W~'~S '-f
(d) A dissolved metal ion coordinates

~)'
with both deprotonated surface hy- ~- O-H
droxyls and dissolved ligands. (c) ~ + HPO~
(e) A dissolved multidentate ligand -<)(-O-H
,.,.- .,
coordinates with both X and the dis-
solved metal ion M. --.-,
(d) ;:;';* - O- H + M' + + L
If:)~ ': :;': '.
(e) ~'~-O- H + L + M
'+
' ~AA~· 1
X: Si. Ti. AI. Fe etc .
SOH drives the reaction to the right, increasing adsorption; similarly increasing pH
increases adsorption of cations.
This behaviour - the fraction of metal adsorbed increases with increasing solid
concentration at fixed total metal concentration and constant pH - is directly anal-
ogous to the titration of a metal cation with a dissolved complexing ligand (Ben-
jamin and Leckie, 1980).
Results of Cd adsorption experiments in which metal partition between solid
and solution phases are varied over wide ranges of pH and concentrations of iron
oxide adsorbents are given in Fig. 17 (Benjamin and Leckie, 1981)
It has been stressed by Benjamin et aI. (1982) that since the location of the pH-
adsorption-"edge" depends on adsorbent concentration, a statement such as "cad-
mium adsorbs onto iron oxide at pH 7" is meaningless unless the concentration of
adsorbent (and adsorbate) is known.
In a general sense, a sorptive-desorptive reaction between solution and solid
phases can be a kinetic one (in which the relative amount of solute in the solution
and in the solid matrix changes with time), or it can be an equilibrium situation
in which the above mentioned relationship is attained rapidly and thereafter re-
mains constant. In the few cases where kinetics were investigated, surface reactions
were found not to be single step reactions (Chen et aI., 1973; Anderson, 1981). Ex-
periments by Benjamin and Leckie (1981) showed a rapid and almost complete
metal uptake lasting no more than one hour, followed by a second, slower uptake
process perhaps lasting days, or possibly months; the first effect was thought to be
true adsorption, and the second to be slow adsorbate diffusion into the solid sub-
strate.
PERCENT Cd ADSORBED
100
80
/
5 X 107 M CdT
60 10.1 M
2S"C
Fe(OH b
40
c 1.3 X 10- 2
o 3.9 X 10- 3
x 1.3 X 10- 3
20
A 6.5 X 10- 4
+ 1.3 X 10-4
.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

pH
Fig. 17. Fractional adsorption (adsorption edges) of cadmium on amorphous Fe(OHh as a adsorbate
concentration (Fe-T) and pH. (Benjamin and Leckie, 1981)
Since surface complex formation constants have been determined, such as for
the oxide/water interface (Davis and Leckie, 1979), humic substances (Perdue,
1979), and metal-multiligand systems (MacCarthy and Smith, 1979), models can
be devised to evaluate the competition between sites of soluble ligands and those
of surfaces of metal ions (Morel et al., 1973; Lu and Chen, 1977; Jenne, 1979). The
surface formation constants show the same trend in stability as the corresponding
solute complex formation constants (e.g., Stumm et al., 1980).
2.5.3 Sorption on Metal Oxides and Organic Substances
Typically adsorption of metals increases from near nil to near 100% as pH in-
creases through a critical range 1-2 units wide (Benjamin et al., 1982, see Fig. 17).
This means that a small shift in pH in surface water, as may occur in lakes, causes
a sharp increase or decrease in dissolved metal levels (Chap. 5.4.6).
The onset of the adsorption is characteristic for each metal. An adsorption edge
situated at a lower pH means a metal more competetive with H + and thus a larger
surface complex formation constant (data of Bourg, 1983, indicate that among the
various natural substrates montmorillonite is an exception as up to 80% of the sur-
face sites originate from charge deficiences caused by lattice isomorphous substi-
tutions and thus are not pH-dependent). Adsorption experiments performed by
Leckie et al. (1980) with cadmium, zinc, copper, lead, silver, arsenic and chromium
onto amorphous iron oxyhydroxide, y-alumina and a-Si0 2 as a function of adsor-
bent and adsorbate concentrations, solution composition, and pH (Fig. 19 and 20)
show that the pH of adsorption increases in the order Pb < Cu < Zn < Cd < Ag and
in the order SeO 4 < CrO 4 < Se0 3 < AsO 4 under otherwise identical conditions.
Sorption on Metal Oxides and Organic Substances 29
100
-----.-
Fig.18a, b. Metal adsorption on
organic surfaces (bacteria). (Af-
ter Nelson et aI., 19SI). Fig. ISa
gives the speciation-distribution
80 r-
diagram for cadmium, Fig.ISb
is the same for copper, both as a C
function of pH •u C~.
!
....
..'"
0-
c0 60 r-
.
.
E
.
is 40r-
.!!
•u
0-
t/)
-.~
~
20f-
CdCI-
CdS0 4 : ~CdC03
a 0
6.5 7.0 7.5 8.0
pH
100
/"
CUBactey·~
c
•u
!0-
r:
80
60
.
.!!
"S •
I •
..
Q 20
.!!
•u
0-
•
t/)
cu(0;7
10
•
CuC03 (aq)
b 0
6.0 7.0 8.0 9.0
pH
This means that under normal conditions in surface water (and at same concen-
trations of adsorbates and adsorbents) lead and copper are more strongly bound
to these surfaces than zinc and cadmium.
The hydrogen ion concentration, or pH, is probably the single most important
factor influencing metal adsorption also on organic surfaces. Experiments per-
formed by Nelson et al. (1981), however, indicate that the effect of pH on the ad-
sorption of copper and cadmium by bacteria contrasts with the pH adsorption
"edges" for these metals on inorganic surfaces. Whereas on oxide surfaces heavy
metal adsorption increases from near zero to near 100% over a narrow pH range
of about two units (see Fig. 17), the highly attenuated pH adsorption "edge" for
bacteria in Fig. 18 may represent the greater range over which protonation of sur-
PERCENT METAL ADSORBED

100
a
80
60
40
-3
am.- Fe(OH)3 (1x10 M)
0
100
80
b
60
40
20
100
80 C
60
40
20 c>- Si0 2 ( 30 9/1 )
0
4.5 5.0 5.5 9.0 9.5
pH
Fig.19a-i:. Fractional adsorption of metals on various oxide substrates (Fig. 19a: amorphous Fe(OHh;
Fig. 19b: y-AI 2 0 3 ; Fig. 19c: a-Si0 2 ) and effects of adsorbate concentrations (after data from Leckie et
a!., 1980)
face (and, to a much lesser extent, probably intercellular) functional groups occurs
(Nelson et aI., 1981). The adsorption maximum of copper in the vicinity of pH 8
(Fig. 18) appears to be unique to the biological system; copper speciation above
pH 7 is strongly influenced by formation of the soluble Cu(OH)z (aq.) complex
which becomes the dominant soluble species above neutral pH values. The data
Sorption on Metal Oxides and Organic Substances 31
given by Nelson et al. (1981) suggest that the equilibrium distribution of metals be-
tween bacterial solids and solutes is mediated primarily by physicalchemical
factors and is not influenced greatly by active biological transport processes.
A decrease in dissolved metal concentrations normally inplies a shift of the ad-
sorption edge to lower pH-values; i.e., at normal pH-conditions smaller concen-
trations of a certain metal are more thightly bound to the solid matter (at same ad-
sorbent concentration) than higher contents; these changes of the adsorption edge,
however, may be strongly different for the individual metals and solid substrates
[compare Fig.19a and b for different zinc concentrations with amorphous
Fe(OHh and different cadmium concentrations with y-Al203]. Copper sorption
onto a-Si0 2 was unique among all systems studied by Leckie et al. (1980) in that
increasing CUT increases fractional adsorption (Fig. 19c); such a relationship is ex-
pected if copper precipitates in bulk solution or on the a-Si0 2 surface or if the ad-
sorbing species are polynuclear.
Competitive adsorption has also been studied by Leckie et al. (1980) to get in-
formation about the distribution and energy of different groups of surface sites.
The result for adsorption of Cd on amorphous Fe(OHh in the presence of much
greater concentrations of Zn, Cu, or Pb (Fig. 20a) indicates that Cu contents have
a much smaller effect than that expected and that the predicted adsorption edge
is at a pH even higher than that for 5·10- 5 M Cd in the absence of competition.
PERCENT CADMIUM
100
100
a C
80 80
60
40
20
am.- Fa(OH)3 (1x1 0-3M)
0
6.5 7.0 7.5 8.0 8.5
pH
100
b
80
60
40
Fig.20a.;:. Fractional adsorption of cadmium on
oxide surfaces (Fig. 20a and 20e: amorphous
20
Fe(OHh; b: y-A1 2 0 3) and the effect of compet-
ing inorganic ions. (a and b after data from Leckie
OL-__ ~ __ ~ ____ ~ __ ~ ____J -_ _ ~
et aI., 1980; c after Benjamin and Leckie, 1982)
This supports that oxide surfaces consist of discrete groups of sites and site ener-
gies; the preferred adsorption sites for Cd, Zn, Cu, and Pb are apparently distinct
from one another on amorphous Fe(OHh On y-Al z0 3 (Fig.20b) Cu and Pb do
not bind to the same high-energy sites - often less than 0.1 percent of the total num-
ber of surface sites available for trace element adsorption (according to estimate
of the authors) - as Cd, but Zn does. The latter findings suggest that there are great
differences in the site-specificity for individual metals on these surfaces.
Ligands which form dissolved complexes with metal ions can either increase or
decrease metal adsorption. Figure 20c (from Benjamin and Leckie, 1982) indicates
that chloride and sulfate (and ammonia) generally decrease fractional adsorption
of cadmium at a given pH. The decrease is consistent with the hypothesis that the
complexed metal absorbs somewhat less strongly than the uncomplexed metal
(Benjamin and Leckie, 1981). On the other hand, cadmium thiosulfate complexes
adsorb in a qualitatively different manner and, on oxides with sufficiently positive
surface charge, they can adsorb more strongly than free aquo cadmium (see Chap.
2.5.4.3).
The effect of ionic strength which - as in solution chemistry - can affect the sur-
face constants (Bourg, 1983) has practical implications for the metal sorption at
changing salinities, e.g. in the estuarine mixing zone (see Chap. 6). In a study per-
formed by O'Connor and Kester (1975) on the adsorption of copper and cobalt
from fresh and marine systems it was found that MgZ + interferes with adsorption,
presumably by competing with the trace metals for the surface sites. Similar indi-
cations have been presented in more recent studies by Gupta and Harrison (1981)
and Millward and Moore (1981) both suggesting that the major cations, calcium
and magnesium, are co-adsorbed with heavy metals and compete with these species
for adsorption sites increasingly with increasing salinity. An alternative explana-
tion for the reduced adsorption of heavy metals at higher salinities is the formation
of chlorocomplexes competing with adsorption. Experiments performed by
Salomons (1980) indicate a significant decrease of Cd-adsorption by chlorinity in-
crease. Recent data of Bourg (1983) show that the Cl-complexation and the Ca2+
(and MgZ +) competition are felt more strongly by Zn than by Cu because, for Cu,
surface constants are greater and the chi oro complex constants are smaller. In real
estuarine systems the effects of coagulation have to be considered for the evalua-
tion of solution/solid interactions of metals. Experimental data of Sholkovitz and
Copland (1981) indicate that removal of river-borne substances by coagulation
with Ca2+ at seawater concentrations ranges from large (Fe-80%, humic acid-
60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Co, Mn-3%) and
it is suggested that destabilization of colloids is the most effective mechanism dur-
ing these interactions.
Apart from competition between surfaces and ligands in solution, the various
phases in the sediment also compete for adsorption and complexation of the trace
metals (see Chap. 2.5.5). Oakley et al. (1981) studied, in model systems, the com-
petition between bentonite clay, iron and manganese hydroxides and humic acids
for sorption of trace metals in seawater. The conditional equilibrium adsorption
constants determined for Cu were much higher than those for Cd for all solid
phases. The affinity for humic acid relative to the other phases was high for Cu and
low for Cd. Based on the laboratory results, the model predicted that the clay frac-
Sorption of Metal-Orjanic Complexes 33
tion is a major sink for Cu and Cd for the geochemical phases used (Oakley et ai.,
1981).
2.5.4 Sorption of Metal-Organic Complexes
As it has been discussed in Chap. 2.5.2 and in Fig. 16 (processes "d" and "e") the
interactions of metal-organic complexes with solid surfaces can easily be described
by electrostatic forces between charged entities. The surface charge of particulates
in natural waters, which may arise from chemical reactions at the surface, by lattice
imperfections at the solid surface (or by isomorphous replacements within the lat-
tice), and by adsorption of surfactant ions (Stumm and Morgan, 1981) is strongly
pH-dependent. Fig. 21 gives examples of surface charge data for suspended and
colloidal solids in natural waters; these simplified curves are based on results by
different investigators whose experimental procedures are not comparable and
may depend upon variables other than pH. However, the curves indicate charac-
teristic trends that at low pH a positively charged surface prevails; at high pH, a
negatively charged surface is formed, and at some intermediate pH (the isoelectric
point) the net surface charge will be zero. Qualitatively it can be assumed that
under normal pH-conditions of surface waters, silica, clay minerals, feldspars and
b-Mn0 2 are negatively charged and may exhibit a stronger affinity for positively
charged metal ions than do, for example, amorphous iron oxyhydrates or alumina.
This may be the major reason for observations, that in Fe/Mn concretions minor
transition metal cations, such as copper, cobalt, nickel, and zinc are associated with
the manganese phase, whereas elements with aqueous anionic charge such as silica,
phosphate and arsenic are related to the iron lamina (Jones and Bowser, 1978).
The various ways in which adsorption of the metal is affected when metal ions
bind to dissolved ligands to form soluble complexes,has been demonstrated by
Davis and Leckie (1978) and is schematically represented in Fig. 22 (from Benjamin
et ai., 1982).
Complexation may reduce the tendency of the metal ion to sorb, as apparently
is the case when cadmium ions form complexes with chloride or sulfate (Fig. 20).
Alternatively, if the ligand is an anion that adsorbs strongly at low pH, the ligand
may bind to the surface at low pH and "take the metal along with it", as this is
N
0.2
E
....
()
w 0.1
"<
a:
J:
() 0
w
~ -0.1
LL
a:
::)
(J) -0.2
0 2 4 6 8 10 pH 12
Fig 21. Effect of pH on surface charge of inorganic particles (Stumm and Morgan, 1981, P 613)
Ii
Fig. 22. Schematic representation of the
Me
reactions leading to enhanced adsorption of a
metal at low pH in the presence of a complex-
ing ligand (from Benjamin and Leckie, 1982)
· Me
L19 <111.--- LigMe(aq)
Lig JJ
Low pH metal - ligand - surface interactions
Tf
Me
LigMe LigMe(aq)
Lig J,J
High pH metal . ligand . surface interactions
lDD
E
~80
Q)
'0
E
..360
c
.2
C. Fig. 23. Adsorption of various
:;40
...,
III complexes on y-AI 2 0 3 . Concen-
<I: tration of copper, ligands, so-
2D lids, and ionic strength are 10 - 4
M, 10 - 3 M, I g/Iiter, and 0.025
0 M, respectively (Elliott and Hu-
2 4 11 ang, 1979)
pH
the case, for example, for the effect of cyanide on nickel adsorption on (J(-FeOOH,
which is significantly increased at lower pH-values (Benjamin et ai., 1982).
Data of Elliott and Huang (1979; 1981) have shown that adsorption of many
organic metal complexes on oxide surfaces is primarily electrostatic in nature; that
is, binding of a negatively charged species to a positively charged surface. Fig. 23
depicts the adsorption of complexes of Cu(II) with glycine, aspartic acid and ni-
trilotriacetic acid on y-AI 2 0 3 . The most adsorbable species was the divalent
Cu(Asp h-entity, which experiences a greater Coulombic attraction for the positive
alumina surface than the somewhat less adsorbed CuNT A-univalent anion. Fi-
Sorption of Metal-Organic Complexes 35
100r-r---..---...-----r---:;--:.......-::p_....=::::::::=r-----.-----,
1:10
pH
Fig. 24. The effect of ligand:metal ratio in copper(IJ) removal (adsorption and/or precipitation). Con-
centrations of copper, 1'-Al Z0 3 and ionic strength are 10- 4 M, g/Iiter, and 0.025 M, respectively. Ligand
(NT A) concentration is variable. The dashed line represents the typical removal pattern of Cu(IJ) alone
due mainly to precipitation (Elliott and Huang, 1979)
nally, the copper-glycinate complexes exhibited the smallest preference for the y-
AI 2 0 3 surface (Elliott and Huang, 1979).
The effect of ligand to metal ratio is shown in Fig. 24 for the Cu-NTA-AI 2 0 3
system (Elliott and Huang, 1979). When Cu 2 + is in excess to NTA, hydrolysis al-
ters the picture of "Cu-only" to some extent; considering the curves, however, for
which NT A:Cu > 1.0, it is clear that an increase in ligand concentration results in
a decrease in Cu(II) adsorption at normal surface water conditions. Conceptually,
this effect can be visualized as a competition for surface sites between the CuNT A -
complex and the free NTA ligand. The HNTA 2 - competes apparently for avail-
able surface sites and hinders CuNTA - adsorption, the effect being most pro-
nounced in the pH region most conductive to "free" NT A uptake (Huang and El-
liott, 1979).
The reduced adsorption of metals in the presence of strong organic chelators,
which has considerable environmental significance with respect to the already per-
formed or planned replacement of detergent phosphates by NT A or EDT A (Chap.
5.3.5), has been demonstrated, among others, by Huang and Bowers (1980) and
by Theis and Richter (1980)in experimental systems, the latter using iron oxide as
solid substrate.
It should be noted, however, that part of these interactions cannot be explained
by simple electrostatic effects. In addition to these mechanisms, the functional
groups of an adsorbed ligand may serve as "new adsorption sites" for trace metals
at the surface or may simply stabilize adjacent surface sites. The "new adsorption
site" may be more reactive than an isolated oxide surface site, and in this sense the
presence of an adsorbing complexing ligand in an oxide suspension can change the
chemical microenvironment at the surface (Davis and Leckie, 1978). Initial efforts
have ~een made to introduce a semiquantitative model for metal-ligand-surface in-

teractions during adsorption which considers complexed species to be either
"metal-like" or "ligand-like", depending on whether adsorption of the complex in-
creases or decreases with increasing pH, respectively (Benjamin and Leckie, 1981).
The data thus far obtained suggest that organic-metal interactions play an im-
portant role in the initial distribution of a trace metal between the solid and the
soluble phase, either through competition or enhanced adsorption of organic-
metal species or through films or organic matter on sedimentary particles. Sub-
sequent diagenetic effects (aging of metastable phases, decay of organic matter, dis-
solution of minerals), however, causes a redistribution of trace metals (see
Chap. 3).
2.5.5 Interactions in Natural Systems
The solid phases interacting with dissolved constituents in natural waters consist
of a variety of components including clay minerals, carbonates, quartz, feldspar
and organic solids. These components are usually coated with hydrous manganese
and iron oxides, and by organic substances.
Iroti and manganese oxyhydrates can be present in X-ray amorphous, micro-
crystalline and in more "aged" crystalline forms both as coatings or as discrete
phases. Fe/Mn oxyhydrates are present in all parts of the hydrogical cycle. Alloch-
thonous particles in river systems already contain (aged) Fe/Mn oxides, addition-
ally they are formed in stratified lakes, estuaries, and at the sediment/water inter-
face. A further site, particularly for the deposition of Mn-oxide, is the surface of
carbonate minerals where there is a microzone of higher pH (Lee, 1975). It is main-
ly the differentiation under changing redox conditions which determines the rela-
tive accumulation of trace metals in Fe/Mn concretions in both marine and fresh-
waters.
Organic surfaces for metal sorption could arise in three possible ways (Hart,
1982): (i) from organisms such as bacteria and algae; (ii) by the breakdown of
plant and animal material and by the condensation of lower-molecular-weight or-
ganics (this material would characteristically have a high molecular weight and
would possess many of the properties of polyelectrolytes and colloidal materials);
and (iii) by lower-molecular-weight organic matter being sorbed onto clay or
metal oxide substrates (Davis, 1980; Davis and Gloor, 1981; Tipping, 1981). Al-
though the difference between these three surface types is not well understood, with
respect to trace metal uptake, there is a general agreement that at least one major
binding mechanism involves salicylic entities; other stronger binding entities (such
as peptides) may also be present in some systems (Hart, 1981). Data given by Hunt-
er (1980) and Tipping (1981) suggest that at least part of the organics adsorbed on-
to the particulate matter in natural waters has carboxylic and phenolic functional
groups available for binding with trace metals. The bulk of soluble organic matter
has characteristics similar to those offulvic acid (Saar and Weber, 1982); the hy-
drogen ion concentration determines which forms of the fulvic acid and metal ions
are prevalent. The trace metal adsorption capacity of organic matter is generally
between that for metal oxides and clays (Guy and Charkrabarti, 1976). Data from
Interactions in Natural Systems 37
reducing sediment show that all of the Zn, almost all of the Cu and a major part
of the Fe, Ni, and Co, but only small portions of the Mn are bound to humic type
material (Nissenbaum and Swaine, 1976). Organic-rich sediments from Lake On-
tario include nearly all the Cu, about 5-10% of the Pb, Cr, and Ni, and less than
5% of the Co, Cd and Zn in humic and fulvic matter; the metal contents of humic
acids at the sediment-water interface exceeded those at lower depths, suggesting
that the bulk of the metal burden is acquired in the water column or at the interface
(N riagu and Coker, 1980). Kerndorf and Schnitzer (1980) did not find correlations
between the affinities of trace metals to sorb on humic acid and their atomic
weights, atomic numbers, valencies and crystal and hydrated ionic radii.
The effect of organic substances from filtered lake water corresponds well to
the sorption characteristics for salicylic and phthalic acids on Al 2 0 3 -surfaces
(Davis, 1980). Sorption experiments on river sediments, which had been treated
with hydrogen peroxide (to partially eliminate organic matter) showed a significant
decrease of the sorption capacity for copper, zinc, cadmium and lead (Tad a and
Suzuki, 1982). Studies on the bonding of radionuclides on different organic sub-
strates (Clayton et aI., 1982) indicate both an increase and decrease of the sorption
characteristics - depending from ligands and concentrations of the organic com-
pounds. Investigations of Baccini et al. (1982) on the effect of organic matter in
the lacustrine environment revealed, that the deposition of organic substances on
solid surfaces usually coincides with a decrease of the sorption of heavy metals on
these substrates. An even more differentiated picture has recently been given by
Laxen (1983) in his experiments on the adsorption of Pb, Cd, Cu, and Ni onto hy-
drous iron oxides under realistic conditions: Uptake is slightly greater during co-
precipitation than adsorption, suggesting that adsorption sites are blocked as the
precipitate forms and ages (maximum 24 h). Soluble humic substances enhance
Cd, Pb, and Ni adsorption but retain Cu in solution. This behaviour is consistent
with the formation of soluble copper-humic complexes, which the enhancement of
adsorption for the other metals corresponds to the adsorption of humics ( < 10%
of total humics; Tipping, 1981), which is rapidly increasing over the range of
0-0.5 mg/I, approaching saturation above this value.
Sorption/desorption experiments on natural sediments have been performed by
many researchers, in a more or less empirical, qualitative way. Only recently, ef-
forts have been made to investigate the mechanisms and factors controlling the in-
teractions between dissolved and solid metal species in natural systems. An ex-
ample is the work of Lion et al. (1982) on trace-metal adsorption characteristics
of estuarine particulate matter, which includes a thorough examination of the con-
tributions of Fe/Mn-oxide and organic surface coatings, by adsorption ex-
periments onto the residual phases after several steps of sequential extraction (see
Chap. 2.6.). These initial studies of metal adsorption onto relatively unaltered es-
tuarine particulate surfaces were undertaken to evaluate adsorption kinetics, ex-
perimental precision, the effect of adsorbate/adsorbent concentration ratio and re-
versibility of adsorption equilibria.
The latter aspect is particularly interesting in this context, since it was demon-
strated that reversibility of the sorption processes was strongly different in natural
mixtures of solid substrates from the experience on well-characterized solid sur-
faces. Fig. 25 a,b, give the results of two separate experiments with lead and cad-
100 adjust pH to 5.0

adjust pH to 5.5 100
15 nin (24 IY or
90 90 168 hr 2641Y
Q Q
W w B
IrI 80 A IrI 80
II: II:
0 0
en en
Q Q 70 adsorption curve
« «
.a for Pb with 24 hr
'0 60 CL 60 equilibration
0
....z ....z
w 50
w 50 0
0 II:
W
II: 40
w
CL 40
CL
30 30
equilibration
20 20
4 5 6 7 8 9 10 2 3 4 5 6 7 8
pH pH
Fig. 25A,B. Kinetics of desorption from unaltered salt marsh sediment A Cadmium, B lead. (From Lion
et aI., 1982)
mium on sediment samples from the oxidized surface layer of mudflats in the South
San Francisco Bay estuary (Lion et ai., 1982). Reaction systems were equilibrated
for 24 h at the appropriate pH for approximately 90% metal adsorption as deter-
mined by prior experiments; the pH was then lowered to that appropriate for 20%
to measure reversibility of sorption reaction. The results indicate slow release of
adsorbed Cd within a time frame of 96 h, whereas Pb was substantially non-labile
over the 264-h duration of the experiment.
In addition to these differences in the reversibilities between the sorption of
metals on mono-mineralic oxidic surfaces and natural sediments there is a
characteristic decrease of the slope of the adsorption edge for the natural solid
compared to the well-characterized surfaces, e.g. of amorphous iron oxyhydrate
(Lion et ai., 1982, see also Reid and McDuffie, 1981; Huang et ai., 1977).
Experimental data of Bourg (1982; 1983) indicate that the sorption edge of sed-
iments can vary considerably; the sediment of the Gironde Estuary, for example,
is characterized by a pH/ZPC (pH for which the overall surface charge is equal to
zero) of 4.84 which is similar to the charge conditions of kaolinite, whereas the
Rhone sediment exhibits a pH/ZPC of 9.42, more or less resembling to the mono-
mineralic sorbents such as y-A1203 and montmorillonite. These differences should
imply different sorption/desorption behaviour at changing salinities, e.g. in es-
tuaries. When the surface is positively charged (pH < pH/ZPC) increasing salinity
promoted desorption; when pH > pH/ZPC adsorption is expected under these con-
ditions.
The removal of trace metals from the sea-water into the sediment has found
much interest since the earlier days of marine geochemistry. The phenomenon of
"scavenging" or adsorption onto solid surfaces is frequently invoked by marine
chemists as an important control on the distribution of chemical elements in sea-
water, since the strong undersaturation with respect to most of the trace metal hy-
droxides and carbonates excludes precipitation of inorganic compounds as an ex-
-12
-4 Acetic Acid
-8 \r
0
0- 4
•
2 4
~
0
•
2
•
2 8
~
~
III
4 III
.2 .2
12
8
16
12
20
o -4 -8 -12 -16 -20 -2 -4 -6 -8 -10
log*K, SOLN
Fig.26. A comparison of the equilibrium constants defining metal/marine particle interactions. (After
Balistrieri et a!., 1981)
planation (Goldberg, 1954; Krauskopf, 1956; Schindler, 1967). However, sorption

models which have been developed from pure solids and which can explain these
processes to some extent (Schindler, 1975) are somewhat unsatisfactory, since one
cannot expect that these discrete phases contribute much to the real particulate
matter in the marine environment. It has been stressed by Balistrieri et al. (1981)
that particles immersed in natural seawater rapidly lose the surface charge charac-
teristics they exhibit in pure solutions and acquire weakly electronegative proper-
ties consistent with the formation of a macromolecular organic film (Neihof and
Loeb, 1974; Loeb and Neihof, 1977; Hunter and Liss, 1977). In a comparison of
the surface properties of marine particulate matter with model oxides and organic
compounds Balistrieri et al. (1981) have shown that pure oxides are not suitable
as model substances for marine particulate matter and the use of metal oxides (Fig.
26a) will significantly underestimate the complexing ability of the sinking particu-
late matter in seawater; on the other hand, as is indicated in Fig. 26b, the range of
equilibrium constants for marine particles falls within the range of constants that
describe metal interactions with model organic compounds, and it is, therefore,
suggested that metal interactions with marine particles in the deep ocean are con-
trolled by organic compounds that coat the surface of the particles.
Two additional studies are discussed here to demonstrate the large irriversible
nature of metal sorption on natural solids:
With respect to the behaviour of trace metals at the freshwater/seawater inter-
face an experimental design given by Salomons (1980) showed typical effects for
the earliest stages of diagenesis. Desorption was studied by adding cadmium and
zinc to suspended matter in riverwater. After adsorbing periods of 1, 3, 8, 24 and
60 days, NaCI was added to the suspension to increase the chloride concentration
to 19%0 (approx. seawater composition). After an adsorption period of only one
Table 5. Percentage of cadmium and zinc not released from river suspended matter after treatment with
NaCl-solution (Salomons, 1980)
Adsorption time
1 day 3 days 8 days 24 days 60 days
Cadmium 24 30 33 37 40
Zinc 60 67 70 74 88
Table 6. Release of elements which had been adsorbed for 7 months on Mediterranean sediments
(from Duursma, 1976, after Ros Vicent et al., 1976)
Leaching agent Percentage leached"
Mn Fe Co Cu Zn Sr Ru Ag Cd Cs Ce Pb
Acetic acid/ammonium 50 0 33 0 4-33 100 10 0 100 2 50 50

acetate pH 5.4
Acetic acid pH 2.3 100 75 tOO 30 10-80 100 25 0 100 30 90 50
" Values exclude the element concentrations originally present
day, 24% of the adsorbed cadmium and 60% of the adsorbed zinc remains bound
to the sediment (Table 5); after 60 days 40% of the cadmium and 88% of the zinc
bound to the sediment is not released after NaCI treatment. Apparently, the ad-
sorbed zinc and cadmium become more strongly bound to the sediment with in-
crease in time.
In an experiment performed by Ros Vicent et al. (1976) where elements were
adsorbed for more than 7 months by Mediterranean sediment, different leaching
rates were determined for the individual elements after treatment with acetic acid/
ammonium acetate (pH 5.4) and acetic acid (pH 2.3). Table 6 shows that among
the elements Mn, Fe, Co, Cu, Zn, Sr, Ru, Ag, Cd, Cs, Ce and Pb, strontium and
cadmium were extracted totally with the weak leaching agent, while iron, copper,
silver - and to a large extent also cesium, ruthenium, zinc and cobalt - remained
solidly bound on the sediment. This means that Sr and Cd are adsorbed only in
exchangeable positions without any immobilization into fixed inter-crystalline po-
sitions even after prolonged periods of contact (Duursma, 1976). Leaching with
unbuffered acetic acid significantly increased the rate of mobilization for iron
(75%), cobalt (67%), zinc (up to 47%), cerium (40%), copper and cesium (approx.
30%), compared to the buffered acetic acid extract (Table 6).
A comparison of the bonding intensity of stable metal nuclides and their in-
stable counterparts - the latter supplied from radioactive emission of nuclear
power and processing plants - in sediments from the lower Rhone River indicate
typical differences in element behaviour as a result of the different history of these
nuclides (Fig. 27a, b). The extractability of both cesium (stable Cs and Cs-137) and
manganese (stable Mn and Mn-54) isotopes were studied with a leaching sequence
including ammonium acetate (exchangeable cations), hydroxylamine hy-
Cs Mn
100 --.....-=....
80
60 60 ,,
,,
,,
,
,,
,
40 40 '
a:stable Cs
a:stable Mn i;\\""",
20 b:Cs-134 20 b: Mn- 54
c: Cs-137
'lIo..-- ___ .... _____*b
o ~.--~--~--~--~~ o .~~--~--~--~--~
OR AC HY OX HP NA OR AC HY OX HP NA
Fig. 27. Comparison of chemical extractability of artificial and stable isotopes (a: stable Cs and Cs-\37;
b: stable Mn and Mn-54) from a sediment sample of the Rhone River (river km 268; Barrage Valla-
brcques)
drochloride (easily reducible phases), oxalate buffer solution (moderately reducible

fraction), hydrogen peroxide extractant (organic/sulfidic phases) and nitric acid
(part of the residual fraction, e.g. silicate phases). The curves in Fig. 27 indicate the
decrease of concentration/activity after each extraction step compared to the orig-
inal sediment (= 100%). It is clear that the difference in the leachability ofCs-com-
pounds mainly occurs within the residual fraction, whereas the major difference be-
tween the stable Mn-isotopes and Mn-54 can be seen in the reducible sediment
fractions. One of the implications of these data is that under reducing conditions
there should be a more intensive release of the radioactive manganese nuclides
compared to their stable counterparts, i.e. the "availability" of the geologically
younger Mn-nuclide for short-term chemical interaction and biological uptake is
much higher than for the stable, "geochemical" Mn-isotopes (Schoer and Forstner,
in prep.)
A detailed characterization of trace-metal surface-phase association and par-
ticulate adsorptive behaviour was performed by Lion et a!. (1982), studying the ad-
sorption of cadmium and lead on leaching residuals of the San Francisco Bay
sediment mentioned above. Using the Tessier et a!. (1979) extraction sequence for
an operationally defined distinction of major metal phases (see Chap. 2.6) it was
found that substantial fractions of total extractable Cd and Cu (50% and 65%, re-
spectively) were found to be associated with organic phases while approx. 70% of
total extractable Pb was removed during the extraction of Fe/Mn oxides. The re-
sults of the adsorption experiments given in Fig. 28a and Fig. 28b (from Lion et
a!., 1982) show that the adsorption edge for Cd shifted dramatically to lower frac-
tional adsorption across the pH range after the organic extraction step, while the
edge for Pb shifted to lower fractional adsorption after extraction of carbonate
100
Sediment B = 1.0 9/1 o Oft.~ 't) Fig. 28.8 Cadmium adsorption on-
90 O~ to sequentially extracted estuarine
CdT = 10-7 M
80 qj? salt marsh sediment B. b. Lead
I~l
1=0.6 (NaN03) adsorption onto sequentially ex-
....Is
t;";r
T=250C
'tI
70 tracted estuarine salt marsh sedi-
.
'tI
C
60
ment B. (From Lion et aI., 1982)
iii 50
Ii
:IE
..
I) 'It
40
C
0
ai
IL
30
Sediment Treatment
20 x Unaltered
v v v MgCI2 Extracted
10 .,/ 0 NaOAc & NH20H-HCI Ext.
/! 0 0 0 H 2 0 2 Extracted
0
a 3 4 5 6 7 8 9 10
pH
100
Sediment B=0.25 gIl
90
Pb T =10-6 M
80 1=0.6 (NaN03)
..
'tI
70
T=250C
.
~
'tI
C
60
!:IE 50
..ai
C 40
30
IL Sediment Treatment
20 x Unaltered
v MgCI2 Extracted
10 o NaOAc & NH20H-HCI Exl
o H~2 Extracted
0
b 3 4 5 6 7 8 9 10
pH
plus Fe-Mn components. Despite several inconsistencies involved in the chemical

extraction procedures, which will be discussed in the next chapter, the results of
the study performed by Lion et al. (1982) suggest that "the role of sediment com-
ponents may be evaluated from the perspective of competitive adsorption phenom-
ena and that sediment adsorption characteristics and extractant-determined com-
ponent-metal associations yield consistent information on the binding of metals".
It has been shown in the previous paragraphs that particulates playa most im-
portant role in the distribution of trace metals between the dissolved and solid
phases because they offer sites for adsorption. The interactions are complicated be-
cause the various sedimentary surfaces and the inorganic and organic ligands in so-
lution all compete for complexation of the metals (Fig. 29). The results of the vari-
ous investigations are summarized in Fig. 29:
1. The speciation of the metals in solution may enhance adsorption if the ligands
themselves are adsorbed onto mineral surfaces, or the speciation may prevent
adsorption if the complexing ligands form strong complexes (with metals) which
are not adsorbed onto mineral surfaces.
I
IRON
INORGANIC LIGANDS
MANGANESE
HIGH MOLECULAR WEIGHT LOW MOLECULAR WEIGHT
~ ORGANICS ORGANIC LIGANDS 5"
" !!.
1 f
I" i
i
•
i
::I
I
n
0:
ca
i
I"
1
I
~
i
i
n coatings
~.L- ______ ______
sorption
~.
Sorplion
~~L-_ _ _ _ _ _ _
Sorpllon Sorption
z-.____~l~
! SUSPENDED MATTER
!I
n (particulate metal speciation)
-•
o3 T
I
i
•
Sedimentation
Resuspenslon
Fig.29. Summary of major processes and mechanisms in the interactions between dissolved and solid
metals species in surface waters
2. The speciation of the solid phases, particularly with respect to the nature of their
surfaces, determines the extent ofthe sorption, although mineral particles them-
selves are able to adsorb trace metals. The particles are often covered with hy-
drous iron and manganese oxides and/or organic films which have a great abil-
ity to remove trace metals from solutions. The nature of these coatings is still
subject to discussions; for a complete understanding of the metal behaviour in
aquatic systems more studies are needed.
3. Aging effects and other diagenetic processes taking place after deposition cause
a redistribution of trace metals over the various components of the sediments;
the available data suggest that these processes cause a stronger binding to the
sedimentary particles. However, for a better understanding more research is
needed on these kinetic changes and redistributions.
4. Sediments indirectly influence the speciation of dissolved metals because they

are a substrate for biogeochemical transformations which result in the forma-
tion of methyl-ated species of some trace metals. Additionally, diagenetic
changes cause an enrichment of dissolved organic matter (DOM) in the intersti-
tial waters. The DOM undoubtedly influences the speciation of the interstitial
trace metals and, after a subsequent release of the DOM to overlying waters (by
bioturbation, compaction and erosion), it also influences the speciation of
metals there.
2.6 Solid Speciation
Of the various processes, products, and substrates of metal enrichment in aquatic

solids, three major types can be distinguished.
- A rise in pH and oxygen content promotes the formation of metal hydroxides,
carbonates and other metal precipitates. Hydrous Fe and Mn oxides constitute
significant "sinks" for heavy metals through the effects of sorption/ coprecipita-
tion;
- in waters rich in organic matter, minerals may be solubilized by the combined
processes of complexation and reduction (Theis and Singer, 1974); reincorpor-
ation of metals into the sediment involves the mechanisms of adsorption, floc-
culation, polymerization, and precipitation (Jonasson, 1977);
metals are transported and deposited as major, minor, or trace constituents in
the detrital minerals derived from rocks and soils, in organic residues, and in sol-
id waste material.
The relative importance of these mechanisms and substrates with respect to the
accumulation of trace metals in aquatic particulate matter can be estimated as fol-
lows in Table 7.
Table 7. Estimation of the relative importance of mechanisms and substrates in metal accumulation
Detrital Reactive Trace metal Iron and Calcium

minerals, organic precipitates, manganese carbonate,
organic matter e.g., oxides oxy- non-apatite
residues carbonates hydroxides phosphates
Incorporation in inert positions, e.g., XX X

lattice-bound in crystals
Adsorption = physical sorption C X X
Chemical sorption and CC XX X XXX XX
co precipitation
Precipitation of discrete minerals XXX
Complexation/flocculation/ CC XXX CC C
aggregation
C, CC: Effective via coatings on other substrates
Solid Speciation 45
It should be noted that the various organic and inorganic phases are interre-
lated: clay minerals, carbonates, and other suspended materials form nucleation
centers for the deposition of Fe and Mn hydroxides as well as for organic coatings;
in systems rich in reactive organic matter the otherwise very important role of Fe
and Mn oxides as direct sorbants of metal ions is either overshadowed by competi-
tion from the more effective associations with humic acids or organo-clays (Jonas-
son, 1977), or is obscured by coating of organic matter (see Chap. 2.5.3).
Only part of the metal associations present may take part in short-term geo-
chemical processes and/or are bioavailable. From a look at Table 7 one would ex-
pect that mobilization and further release to the water phase and/or biological up-
take mainly occurs from the non-residual fractions, which, however, will behave
quite different under certain environmental conditions and according to their dif-
ferent stabilities. For the differentiation of the relative bonding strength of metals
in different phases, sequential extraction procedures have been developed which-
in combination with direct experiments on organisms - could also enable the es-
timation of the potential metal transfer from polluted particulate matter to biota.
However, whereas the determination of the relative binding strength seems to pose
basically operational problems the correlation with the biological parameters
(Chap. 2.7) is not yet satisfactory. Before discussing the relations between chemi-
cal phases of solid substrates and biological uptake an overview on the distribution
of trace metals in "detrital", "lattice-bound" or "residual" fractions will be given.
Problems related to soil fertility quite early led to the development of leaching
techniques to estimate the availability of trace metals in soils for plants (Jackson,
1958). Most of the earlier studies do not consider the various sinks for trace metals
in soils; some exceptions are studies on the speciation of copper by Shuman (1979)
and McLaren and Crawford (1973).
In the sediment-petrographic field, interest was focussed initially on differ-
entiating between authigenic and detrital phases using single step leaching tech-
niques. By chemical leaching with EDTA, dilute hydrochloric acid and acetic acid,
the distribution of elements in detrital igneous minerals and authigenic phases in
pelagic sediments could be estimated (Goldberg and Arrhenius, 1958). Further
progress was achieved by the introduction of a combined acid-reducing agent of
1 M hydroxylamine hydrochloric acid and 25% (v/v) acetic acid by Chester and
Hughes (1967) for the separation offerromanganese minerals, carbonate minerals
and adsorbed trace metals ("non-lithogenous fraction") from marine sediments.
Recent developments in solid phase differentiations were mainly promoted by
environmental studies, both in soil science and in water research. For the estima-
tion of the relative bonding strength of metals in different phases, extraction pro-
cedures have been applied, both as single leaching steps and combined in sequential
extraction schemes (Pickering, 1981; Salomons and combined in sequential extrac-
tion schemes (Pickering, 1981; Salomons and Forstner, 1980).
Methods for single leaching steps are given in Table 8.
In determining the amount of exchangeable metal ions, an extractant is used
which contains cations more strongly bound to the exchange positions as com-
pared with the metal; common extractants in use are BaCI 2 , MgCl 2 and NH 4 0Ac.
The ion-exchangeable fraction of trace metals is still ill-defined, as is indicated by
significant metal releases in replicate experiments (Salomons and Forstner, 1980).
Table 8. Methods for the extraction of metals from major chemical phases in sediments (examples).
(After Salomons and Forstner, 1980)
Adsorption and cation exchange

BaCl 2 -triethanolamine pH 8.1 Jackson (1958)
MgCl 2 Gibbs (1973)
Ammonium acetate, pH 7 Engler ct al. (1974)
Carbonate phases
CO 2 -treatment of suspension Patchineelam (1975)
Acidic cation exchanger Deurer et al. (1978)
NaOAc/HOAc-buffer (pH 5) Tessier et al. (1979)
Reducible phases (in approximate order ot release of iron)
Acidified hydroxylamine (+0.01 M HN0 3 ) Chao (1972)
Ammonium oxalate buffer Schwertmann (1964)
Hydroxylamine-acetic acid Chester and Hughes (1967)
Dithionite-citrate buffer Holmgren (1967)
Organic fraction (inc. sulfides)
H 2 0 2 -NH 4 0Ac (PH 2.5) Engler ct al. (1974)
H 2 0 2 -HN0 3 Gupta and Chen (1975)
Organic solvents Cooper and Harris (1974)
0.1 M NaOH/H 2 S0 4 Volkov and Fomina (1974)
To release metal ions weakly bound to specific inorganic sites (e.g. on carbon-
ates) extraction with 0.4 M HOAc, HOAc/NaOAc (pH 5), or complexing agents
(of moderate ligand strength) has been recommended (Pickering, 1981). A single
extraction method for the determination of trace metals associated with carbonates
makes use of an acidic ion-exchanger (Deurer et aI., 1978).
Dissolution of the amorphous (or "poorly ordered") inorganic phases can be
promoted by reducing the iron and manganese to lower valency states, e.g. through
reactions with hydroxylamine, oxalate or dithionite ions. Oxalate treatment did
not appear to attack crystalline material, but it has been shown that the degree of
interaction varies with illumination (Schwertmann, 1964; Eaton, 1977; Pickering,
1981). For routine investigations an extraction with 0.3 M HCl can be recom-
mended because this procedure requires fewer manipulations (Malo, 1977).
The metal fraction associated with organic matter has been extracted through
oxidation of this component with NaOCI or H 2 0 2 , by dissolving the sediment us-
ing Na4 P 2 0 7 , through proton displacement (with 0.5 M HCl) or by chemical com-
petition (e.g. using 0.05 N EDTA); the apparent ability of both EDTA and HCl
to release metal ions associated with both organic and oxide phases has led to these
being used as extractants for the evaluation of the total nondetrital fraction (Pick-
ering, 1981). For the dissolution of detrital or lattice-bound components a com-
bination of acids has generally been used. Nitric acid promotes destruction of or-
ganic matter, but when used alone or in conjuction with HCl or HCI0 4 , the pro-
cedure does not completely dissolve some types of silicate minerals.
A schematic representation of the ability of different extractant solutions to re-
lease metal ions from particulate matter is given in Fig. 30 (Pickering, 1981).
This diagram implies - dashed segments indicate areas of uncertainty - that ex-
traction procedures may only crudely differentiate between the different forms of
Solid Speciation 47
RETENTION MODE
EXTRACTANT
Ion Surface Precipitated Co.ppted. Co.ordinated Occluded Lattice
TYPE Exchange adsorption (CIIJ, S,OH) amorphous to organics (crystalline component
hydrous
Sites
oxides) ~~rJ:sjS (mineral)
MgCI2
Electrolyte -------
--- .....
HOAc HOAc/OAc-
--
Acetic Acid --------
(buffer)
(reducing)
HOAc +
-NH20H -------- ------
Oxalic Acid
(buffer)
HOx + NH40X
--- L!Q~~~I!~l_
dil. Acid
0.4 m
---- r-------- f----------
HCI
r--------~
--
(cold)
HCI + HN03; HN03 + HCI04
Acid (hot) -------
Mixtures HCI + HN03 + HF
---
II-HF)
Chelating
Agents
EDTA, DTPA
---------- ----
~1!?!!z -------- ---
-----
r-!!-~-~~ ±!!!~~~~L ---
~S202. ~trat'!........:!:. _HCDj
(alk.ppte)
Basic ------- ~H-----~
Solns. NaF
----
Fusion Na2CD3
(+ Acid leach)
Fig. 30. Schematic representation of the ability of different extractant solutions to release metal ions re-
tained in different modes or associated with specific soil fractions. Dashed segments indicate areas of
uncertainty. From Pickering (1981), in CRC Critical Reviews in Analytical Chemistry, Nov. 1981, pp.
233-266
selected species in sedimentary material. In particular, despite of clear advantages

of a differentiated analysis over investigations of total sediment, it should be clearly
pointed out that the various extraction steps are not as selective as sometimes
stated. Several problems are chosen for illustration of this point (Salomons and
F (mtner, 1980; Forstner and Calmano, 1982):
1. labile metal phases could be transformed during sample preparation, which
can occur especially for samples from reducing environments (see discussion
by Jenne et aI., 1980);
2, processes of reeadsorption and precipitation have to be considered (see dis-
cussion by Rendell et aI., 1980);
3. reactions are influenced by the duration of the experiment and by the ratio of
solid matter to volume of extractant. Some of the extractants are more specific
than others, such as shown by repeated experiments (Heath and Dymond,
1977). A too high solid content, together with an increased buffer capacity may
cause the system to overload; such an effect is reflected, for example, by chang-
ing pH-values in time dependent tests (Pfeiffer et aI., 1982);
4. there are major objections to the use ofbariumchloridejtriethanolamine (Jack-
son, 1958; the latter compound is used to raise the pH to 8.1) or mag-
nesiumchloride (Gibbs, 1973) for the determination of exchangeable trace
metals; there are chelating effects of the organic agent and the formation of
soluble metal-chloro-complexes. The neutral ammonium acetate solution (1
molar) seems to offer an acceptable compromise for the estimation of ion-ex-
changeable trace metal contents (Salomons and Forstner, 1980);
5. basic metal oxides may be formed during initial high pH conditions, for ex-
ample, for humic extraction with sodium hydroxide or sodium pyrophosphate
(Burton, 1978);
6. difficulties occur with all carbonate extractions: reprecipitation under oxygen-
ated conditions following CO 2 treatment, adsorption of organic compounds
on exchanger resin, pH effects on labile oxyhydrates. However, the major ad-
vantage of this step lies in the reduction of the buffer capacity of the sample
before applying the following leaching steps (Forstner et aI., 1981);
7. problems in the acid reducing steps are encountered particularly with the uti-
lization of the dithionite/citrate extraction (Tessier et aI., 1979): contamination
by metals in the reagent, clogging of the burner during atomic absorption anal-
ysis, decomposition of the extractant and formation of sulfides (most of them
being highly insoluble);
8. treatment with hydrogen peroxide affects both labile as well as relatively stable
bound metal components (Engler, 1980);
9. treatment with organic solvents are poorly suited for routine applications
(Salomons and Forstner, 1980); and
10. the differentiation of organic and sulfidic metal associations, e.g. in the peroxi-
de fraction, is not as yet possible (Calvert and Batchelor, 1978).
In connection with the problems arising from the disposal of contaminated

dredge material, sequential extraction procedures have been developed, which in-
clude the successive leaching of metals from interstitial waters, and from ion ex-
changeable, easily reducible, organic and residual sediment fractions (Engler et aI.,
1974; Gupta and Chen, 1975; Gambrell et aI., 1976). Based on our experience and
an evaluation of the relevant literature, we have suggested a standard extraction
procedure consisting of three steps for the differentiations of the three major
groups of phases mentioned in the introduction to this Chapter (Salomons and
Forstner, 1980):
- extraction with acidified hydroxylamine hydrochloride at pH 2 (including the
extraction of exchangeable cations and of carbonate-bound metals);
- extraction with acidified hydrogen peroxide, followed by an extraction with am-
monium acetate to remove any readsorbed metal ions;
- total analysis (HF/HC10 4 ) of the residue remaining after the first two ex-
tractions.
This scheme, including an additional step for exchangeable cations was used for
the study of sediments from 18 different river systems (see Chap. 5.3). In extension
of this sequence and using the experience of the work from Tessier et aI. (1979) a
six-stage chemical leaching process was developed for the assessment of the en-
vironmental compability of dredged materials that avoids some inadequacies of
earlier experiments (Forstner et aI., 1981; Forstner and Calmano, 1982):
Step I: Exchangeable cations - 1 M ammonium acetate, pH 7, solid/solution ratio
1:20, 2 hrs shaking time;
Step 2: Carbonate fraction - 1 M sodium acetate buffer, pH 5 (Tessier et aI., 1979);
1:20, 5 hrs shaking at 20°C;
Solid Speciation 49
Step 3: Easily reducible phases (Mn oxide, partly amorphous Fe-oxyhydrates) -

0.1 M NH 2 0H·HCl +0.01 M HN0 3 , pH 2 (Chao, 1972), dilution 1:100,12 hrs
shaking;
Step 4: Moderately reducible phases (e.g., amorphous and poorly crystallized Fe
oxyhydroxides) -0.2 M ammonium oxalate+0.2 M oxalic acid, pH 3 (Schwert-
mann, 1964), dilution 1: 100,24 hrs shaking time;
Step 5: Organic fraction, inc. sulfides - 30% H 2 0 2 + HN0 3 , pH 2, 85°C, extract-
ed with 1 M ammonium acetate, dilution 1: 100,24 hrs shaking;
Step 6: Residual fraction (e.g. detrital silicates, crystalline Fe-oxides) - conc.
HN0 3 , 120°C, dilution 1: 100.
This scheme has been applied, apart from the major studies on river sediments
and dredged materials, to demonstrate the relative mobility of particle-associated
trace metals in sewage material, in sediments affected by acid rain (Reuther et a!.,
1981; 1982; see Chap. 5.4.6), in sand filter column experiments (Forstner et aI.,
1979), and - with modifications - for the speciation of reducible metal compounds
in pelagic sediments (Forstner and Stoffers, 1981; Pfeiffer et aI., 1982). Some of the
results of these and similar studies of other authors can be summarized as follows:
1. There is still a good deal of controversy in the question, if the peroxide step
should be used after reduction of oxide phases or before. Data from M.L. Jack-
son (1956; cited by Jenne and Luoma, 1977) indicate that under mildly acidic
conditions, hydrogen peroxide effectively solubilizes manganese oxides and
their occluded elements (see also Jenne, 1968). It seems, that the organically
bound portion of most metals in the earlier studies has been overestimated (En-
gler et aI., 1974; Gupta and Chen, 1975). In any case, pH-controls of the extracts
after treatment are the prerequisite to obtain comparable results.
2. For studies on marine pelagic sediments (see Chap. 7.4) the oxalate buffer is
most suited for determining the facies type and for the estimation of relative
amounts of authigenic and detrital components due to the low rate of metal re-
lease in duplicate experiments. The acidified hydroxylamine hydrochloride
buffer can be of advantage for the investigation of processes involved in diage-
netic remobilization and enrichment of metals in Fe/Mn concretions as it indi-
cates the relative availability of the metals in the easily reducible fractions of
micro nodules and sediments (Callender and Bowser, 1980).
3. With the exception of cadmium and manganese, the amount of heavy metals in
exchangeable positions is usually very low. The most important enrichment
phases in sediments are apparently the easily (Cd, Zn, Mn) and moderately (Fe,
Pb, Cu, Cr) reducible components, e.g. Fe/Mn oxyhydroxides. Data from sew-
age materials - using the same extraction sequence - indicate significantly
higher percentages of metals in the peroxide fraction (organic and sulfidic
phases) than was found for the sediments (Forstner and Calmano, 1982).
4. Comparison of 10 techniques for metal and substrate extractions among the
sediments of 19 estuaries from south and west England by Luoma and Bryan
(1981) indicate that substrate characterization is best accomplished by Fe and
Mn extractions with acid ammonium oxalate or 1 N HCI, and humic substances
extraction with 0.1 NaOH or 1 N ammonia. Statistical relationships indicate
that the extractable phase for Fe is more important than total Fe in binding Ag,
Cd, Cu, Pb and Zn in oxidized sediments, and the operationally defined humic
substance fraction of organic material is highly important in binding Ag
and Cu.
S. In a comparative study on the specificity of different leaching steps in the
"Tessier"-scheme on single mineral phases it was shown by Rapin and Forstner
(1983) that the carbonate extraction (Ca-, Mn-, Cd-, and Pb-carbonates) by
sodium acetate buffer was particularly "selective", followed by the acidified hy-
droxylamine hydrochloride agent for the mobilization of reducible Mn, Ni, Fe,
Cu, and Zn species from deep-sea Fe/Mn-nodules, whereas treatment of
goethite, hematite, vivianite, and various clay minerals produced controversial
data for the individual metal examples. Another result of this study was the
finding that iron and sulfur are more easily extracted from anoxic freshwater
sediments than from reduced marine deposits, probably due to the less stable
mackinawite-type minerals compared to the marine pyrite formations.
6. For all metal examples a clear decrease of the residual component is shown with
increasing overall metal concentrations. These data suggest that the surplus of
metal contaminants introduced into the aquatic system from man's activities
usually exists in relatively unstable chemical forms and should, therefore, be
more accessible for short- and middle-term geochemical processes - including
biological uptake - than the detrital, predominantly natural metal compounds.
7. With regard to the various influencing factors affecting the chemical as-
sociations of trace elements in less contaminated as well as in polluted sedi-
ments, investigations on sedimentary core profiles seem to be particularly use-
ful. Apart from the characteristic developments in the chronological sequences,
there is a major advantage in comparing samples when they have been treated
according to the same extraction procedures and analytic methods. This also
pertains to filter column experiments, as long as the filling material can be con-
sidered homogeneous with respect to grain size and chemical composition
(Forstner et aI., 1982).
2.7 Metal Interaction with Organisms
2.7.1 Metal Uptake by Organisms
There are two types of processes which influence the metal concentrations in or-
ganisms. These are:
- the metal concentrations in the abiotic reservoirs,
- the biochemical processes occurring inside the organisms.
Processes of the first type will be discussed in the main part of this book, the
second are outside the scope of this book. Several successful studies are being car-
ried out on the biochemistry of metals in organisms, especially with regard to bi-
valves (George, 1980; Fowler, 1981). In this chapter we will focus on methods to
determine the bioavailability in the four abiotic reservoirs. Bioavailability is de-
Metal Uptake by Organisms 51
Metal forms in the Uptake mechanisms

growth medium
Ions or inorganic/organic Easily available ------I.~ Passive/active bonding
compounds in solution to the cell walls/
surfaces, translocation
Exchangeable ions in Available
inside cell/body
organic or inorganic
exchange complexes
(e.g. humic materials
and clay particles)
..
•
Complexes or chelates
Less available
with organic materials
Ingestion as "fooer,
..
Precipitated insoluble Available only after
passage throughout
compounds and altered chemical
digestive system,
coprecipitate on solids conditions
absorption and
.
Incorporated in solid Available only incorporation into
biological materials after decomposition tissues/organs
Incorporated in the
Available only
crystalline structures
after weathering
of primary and/or
secondary minerals
Metat~p_o_O_I______________ Excretion 01 metallormS~4

both in the liquid
_____A_q_u_a_t_i_C......OI rganisms
and solid forms
Excretion of complexants
...
Leaching and decay
Feed_back mechanisms
Fig.31. Availability of metal forms for biological uptake (After Baudo 1982, reproduced with per-
mission of the author)
fined as that fraction of the total metal concentration in each of the abiotic re-
servoirs which is taken up by organisms (Fig. 5). The different forms of metals in
the growth medium and their effects on the uptake of metals in organisms are
schematically summarized in Fig.31 (from Baudo, 1982). It has been stressed by
Baudo (1982) that the last three forms pertain to the "consumer" organisms alone,
whereas the first three are equally shared with the "producers". The particulate
form of the element can assume an important role in the uptake processes, at least
for some kinds of organisms, such as filter feeders and deposit feeders. Conversely,
the biota may interact in a number of ways with its surrounding medium, modify-
ing the pseudo-equilibria among chemical species in the water-solid phases. The
bioavailability of trace metals in solution depends on their speciation.
Sunda and Gillespie (1979) studied the response of a marine bacterium to add-
ed copper and the influence of complexing agents like NT A, humic acids as well
as salinity. The response of the bacterium, as measured by the uptake ofC-141a-
belled glucose did not depend on the total copper concentration but depended on
Fig. 32. Three-dimensional

plot of survival of grass
shrimp Palaemonetes pugio,
exposed to four different
salinities and five different
cadmium concentrations for
96 h. (Engel and Fowler,
1979)
I-
28
Z
W
(J
II:
W
D.
..J
<I:
>
120
100 NTA .-.
Salinity _---_ - "4=----
....... -,-
>
II:
:::l
80
,I(-
.-
_,I ·,
III
I- 60
z Fig. 33. The percent survival of the grass
w 40
•
_.
0 shrimp Palaemonetes pugio as a function of
II: I
w 20 I the ionic cadmium concentration. (The data
-,/
Q.
0 for salinity and NTA were replotted from

6.0 7.0 Sunda, Engel and Thuotte, 1978)
P (Cd 2 +)
the cupric ion activity. A relationship was derived between the inhibition of glucose
uptake and cupric ion activity. Growth rate inhibition of the estuarine diatom
Thalassiosirampseudona was also related to the cupric ion activity and not the total
copper concentration (Sunda and Guillard, 1976). In a study of the influence of
copper on growth of 11 species of marine phytoplankton (Gavis et aI., 1981) it was
observed that the pCu response curves are very similar to published curves for ti-
tration of negative surface charge of polymer molecules and bacteria. They sug-
gested that the cupric ion acts as a toxic agent by binding to the cell surface, de-
creasing negative surface charge and perhaps as a result altering transport systems
in cell membranes.
Allen et al. (1980) studied the influence of zinc and complexing agents on algal
growth and found a good correlation with the free zinc ion, the latter being calcu-
lated with a chemical equilibrium model. The influence of chlorinity and total cad-
mium concentration on survival of the grass shrimp Palaemonetes pugio is shown
in Fig. 32 (Engel and Fowler, 1979).
With an increase in chlorinity, the concentration of the free cadmium and the
toxicity of cadmium to the grass shrimp both decreased. In another experiment
Metal Uptake by Organisms 53
NT A replaced chloride complexing agents. If the percent survival obtained from

both experiments is plotted against the ionic cadmium concentration (calculated
with a chemical equilibrium model) nearly identical curves are obtained proving,
that free ionic cadmium is the toxic agent (Fig. 33).
The results of a study on copper uptake by Daphnia magnia (Andrew et aI.,
1977) have been treated with factor analysis and multiple regression analysis to de-
termine the relative toxicities of the copper species (Magnuson et aI., 1979). The
results yielded tentative conclusions that the carbonate copper complexes are not
toxic, the anionic hydroxy copper complexes contribute 15~ 18% to the toxicity of
copper and the free copper and/or the neutral and/or cationic hydroxy complexes
are responsible for 60~70% of the toxicity. However, in some cases the complex-
ation of trace metals may enhance their uptake. In a study on the influence of che-
lating agents on the uptake of cadmium by Mytilus edilus (George and Coombs,
1977) it was observed that prior complexation of cadmium with either EDT A, hu-
mic and alginic acids or pectin doubles both the rate of accumulation and the final
tissue concentrations. Apparently the metal is not transported across the cell mem-
brane barriers as a simple ionic species but must be first complexed to ligands either
in the cell membranes or in some form of carrier. But the final tissue distribution
of cadmium was unaffected by the differences in the complex used. Thus inside the
cell the metal must be trapped by ligands which prevent their back diffusion. The
proposed mechanisms for the transport of metals across cell membranes is shown
in Fig. 34.
Also natural complexing agents present in the water are able to detoxify metals
added to surface waters, in fact one of the methods for assessing the complexing
capacity of natural waters is based on bio-assays (Chap. 2.4). Although it is now
well established that the free metal ion (and some alkylated species, see Chap. 2.7.3)
have the greatest bioavailability compared with other complexes present in surface
waters, their direct measurement is difficult if not impossible with presently avail-
able techniques. With the ion selective electrode it is possible for certain elements
to directly measure the free ionic species. However, this method is limited by its
sensitivity. Therefore indirect methods have to be used, to relate the free ionic spe-
cies to an operationally defined parameter. Several methods are in use and all are
based on the methods for speciation of trace metals discussed in the preceding sec-
tions.
Although sediments are able to detoxify surface waters by adsorption/precip-
itation processes, causing a decrease in the dissolved metal concentrations, part of
the metals in the sediments is bioavailable. However, to assess the bioavailability
of metals in sediments is difficult due to the complexity of the system:
~ metals may be taken up from the ingested particles or from the pore waters,
~ is the uptake mediated by the food (e.g. bacteria) which accumulate metals from
the sediment and/or pore waters?
~ are the processes in the gut important or the binding of the metals to the sedi-
ments (Luoma and Bryan, 1978)?
The fact that particulate bound metals are available for organisms has been
proven by a number of elegant experiments conducted for the development of a
3.0 0 Macoma Balthica

,.
13 Scrobicularia Plana
2.5 0 Sediments - synthesis
+
Ikinetic
M + L2 trap . ML2
2.0
f
~ MLI
III
"- ~
III
::L
1.5 ~ ~
;..-: ~
Fig. 34. Within the cytoplasm a second ligand
~~
1.0 ::::
~
r v: :': L-2 traps the metal and controls the sub-
sequent accumulation there , To explain this
~ ;-:
~ ~ ~ :' effect a hierarchy of binding strength of the li-
0.5 ;..-: ~ ;;: gands must be assumed, which are ever-in-
v: '
V creasing during these processes (Simkiss et aI.,
I ~ ;..-: ~ ;; 1982)
0.0
;..-:
.... h V. h ~ ::
Kats Waarde Bath
Ellewoutsdijk
Fig. 35. Metals concentrations in M acoma Baltica exposed to the same concentrations of metal in sur-
face waters (Eastern Scheidt, The Netherlands) but in a different sedimentary environment. Ash-free
dry weight. (Marquenie, 1983)
bioassay technique for sediments by Marquenie (1983). Experimental animals were

put into natural sediments which were contaminated to different extents, the con-
tainers with sediment and organisms were then placed in natural waters. In this
way the organisms (Macoma baltica and Scrobicularia plana) were exposed to the
same contaminant concentrations in the surface waters but to a different sedimen-
tary environment. Concentrations of metals in the experimental animals reflect the
metal concentrations in the sediments (Fig. 35).
It might be concluded that contaminated sediments form potential environ-
mental risks for the organisms they harbor and their predators. Although major
pathways by which metals enter the organisms (ingested particles, food or pore
waters) were not determined in this study, other studies indicate the relative impor-
tance of pore waters (Prosi, 1981).
In an experimental design of Luoma and Jenne (1976) where specimens of de-
posit-feeding clam Macoma balthica kept in "sediment" and in dialysis bags (sep-
arated from sediment) were compared, no detectable uptake of Cd-109 occurred
through ingestion of either labelled organic detritus or particulate hydrous iron ox-
ide which has been coated with organic material. Detectable uptake of Cd-l 09 was
observed when clams were exposed to either hydrous-iron oxide particulates which
lacked the organic coating or San Francisco Bay sediment labelled with the nu-
clide. These data illustrate that large pools of non-crystalline Cd (and probably of
other trace metals) in natural sediments (e.g., at least some forms of the organically
Solid Speciation and Bioavailability 55
complexed metal) may be unavailable to deposit feeding organisms. Although in

most cases high concentrations of metals in organisms are detrimental, Gibbs et
ai. (1981) reported high concentrations of copper (in excess of 600 Jlg/g) in some
polycheates which made them unpalatable for predators. In fact these high concen-
trations of copper may be regarded as a chemical defence system.
Very little information is available on the simultaneous effects of a mixture of
trace metals on organisms. Wong et ai. (1978) tested a mixture of metals whose in-
dividual concentrations fulfilled the recommended levels for the Great Lakes Wa-
ter Quality Objectives. The mixture of metals proved to be very toxic to freshwater
algae in lake water and culture medium. Similar observations have been reported
by Hongve et ai. (1980). They also tested the influence of NT A on individual metal
toxicity and on a solution in which metals were simultaneously present. The metal
mixture becomes more toxic with the presence of NTA, whereas for most individ-
ual metals (except mercury) the toxicity was reduced. These studies show the need
for more studies on synergistic effects. Setting of water quality objectives based on
experiments with single metals may not adequately protect aquatic organisms
(Wong et aI., 1978).
2.7.2 Solid Speciation and Bioavailability
Estimation on the remobilization of metals under changing environmental con-

ditions and on the potential uptake by biota are two major objectives of species
differentiations on particle-bound trace metals. The geochemical processes affect-
ing the mobilization of trace metals from sediments and the application of speci-
ation schemes will be discussed in the various chapters dealing with individual
parts of the hydrological cycle. In this section the use of speciation methods to de-
termine bioavailability of metals in sediments is discussed.
The availability of trace elements to organisms may be influenced by factors
such as (1) the physiological and ecological characteristics of the organisms, (2)
the form of dissolved trace elements, as well as the chemical and physical charac-
teristics of water, and (3) the form of trace elements in solids (Jenne and Luoma,
1977). With respect to factor (1) the characteristics of "biomagnification" and
"detoxification" for metals depend from many influences such as the ecological sit-
uation of an organism (e.g., choice offood, choice of macro- and microhabitat, and
extent and periodicity of activity), the digestive physiology of the organism or parts
of it, and effect of other chemical constituents (stimulation or competitive inhibi-
tion of uptake) both at the environmental interface of an organism or within tis-
sues; in particular the differences among individuals in the formation of binding
agents for metals may offer a partial explanation for the range of element concen-
trations in organs exposed to toxic doses of trace elements (Jenne and Luoma,
1977).
The bioavailability (and toxicity) of dissolved trace elements (factor 2) is af-
fected by speciation among the free hydrated (aquo) forms and among the various
organic and inorganic complexes of the various valence states (2.7.1). It has been
shown in Chap. 2.3 that the analytical determination of different solute forms of
trace elements in natural waters and soil solutions is still largely in the semiquanti-
tative stage.
While organic complexation usually reduces the bioavailability of solute forms
of trace elements (see Chap. 2.7.1), there are indications that increased trace-ele-
ment uptake through complexation may occur resulting from a decrease in rate and
extent of trace-element sorption by sediments, solubilization of solid forms of trace
elements in soils and sediments, a valence reduction and/or stabilization of the re-
duced valence state or vice versa and formation of physiologically active complexes
(Jenne and Luoma, 1977).
With respect to solid speciation (factor 3) much work has been done on the rela-
tion between chemical leachability and plant uptake of metals. Highly significant
dependencies have been evidenced for extractants such as 0.05 M DTPA (diethy-
lene-triamine-penta-acetic acid), EDT A (ethylene-diamine-tetra-acetic acid),
acetic acid, ammonium acetate and nitrate (Davies, 1975; John, 1977; Keeney and
Walsh, 1977; Webber and Corneau, 1977; Symeonides and McRae, 1977; see sum-
mary by Sterritt and Lester, 1980). It must be mentioned, however, that "the leach-
able fraction does not necessarily correspond to the amount available to vegeta-
tion" (Pickering, 1981). One major reason for this is the lack of information about
the specific mechanisms with which the organisms actively participate in the re-
moving of nutrient from the solid substrate: in the case of plant root activities these
interactions with soil components include redox changes (Chaney et aI., 1972), pH
alterations (Moore and Carson, 1974) and organic complexing processes (Lindsay,
1974).
Experiments on the availability of particulate-associated forms of trace metals
to aquatic fauna have mainly been performed by Luoma and colleagues. Earlier
results from several chemical extractions of sediments from San Francisco Bay by
Luoma and Jenne (1976a) indicate that these speciation data do not correlate in
a simple manner with the bioavailability of the respective trace metal. Concen-
trations of Cd or Co in deposit-feeding clam, Macoma balthica, correlated signifi-
cantly only with the concentration of the metal extracted by 70% ethanol or I N
ammonium acetate; concentrations of Cd, Co and Zn extracted by weak acids
(0.1 N HCI; 25% acetic acid), reducing agents (1 N hydroxylamine hydrochloride
in 0.01 N HN0 3 ; sodium dithionite/citrate) or oxidizing agents (H 2 0 2 plus citrate)
correlated poorly with bioaccumulation (Luoma and Jenne, 1976b). On the other
hand, even quantitatively minor sinks within aquatic sediments may be important
sources of some metals for Macoma balthica; e.g., uptake rates of cobalt and zinc
from biogenic carbonates (crushed clam shells) were significantly greater than rates
of uptake from other sinks (Luoma and Jenne, 1977).
Data of Luoma and Bryan (1978) from sediments in 20 estuaries in southern
and western England indicate that the concentration oflead in the deposit-feeding
bivalve Scrobicularia plana is largely controlled by the concentration in the sedi-
ment as modified by the inhibitory effect of iron; the Pb/Fe ratio in 1 N hy-
drochloric acid extracts appears to reflect the availability of lead to Scrobicularia,
since this value is almost directly proportional to the concentration of lead in the
animal. More detailed investigations including statistical analysis of data per-
formed by Luoma and Bryan (1979), suggest that the correlation between metal
uptake and solid species distribution reflects competition for various metal sorp-
Solid Speciation and Bioavailability 57
tion sites within the sediment. It is assumed that the availability of zinc to Macoma
in San Francisco Bay is controlled by the competitive partitioning of Zn between
two forms of hydrous oxide: hydroxylamine hydrochloride-soluble iron oxide and
ammonium acetate-soluble manganese oxide; organic materials affect the bioavail-
ability of Zn when present in concentration greater than 1 percent. The availability
of Zn to Scrobicularia appears to be primarily controlled by the ratio of humic sub-
stance concentrations to total organic carbon; solute Zn and low salinities may en-
hance Zn levels in Scrobicularia at some stations, as may oxalate-soluble Mn when
present in high concentrations (Luoma and Bryan, 1979). It should be noted, how-
ever, that factors other than solid metal speciation can significantly affect availa-
bilities of even deposit-feeding organisms, e.g. interactions with other metals
(Heisinger et aI., 1979) or predominance of physiological regulations of metal up-
take, as has been shown for the Zn distribution in Nereis diversicolor (Bryan and
Hummerstone, 1973). Investigations of Tessier and colleagues (1982) in an unpub-
lished report of the University of Quebec generally confirm the findings of Luoma
and Bryan (1978; 1979). The data from studies on bivalves Elliptio complanata and
Anadonta grandii indicate, that (1) only a part of the metals in the sedimentary
substrate is available for the organisms, (2) hydrous iron oxides playa "protec-
tive" role for the metal uptake by the organisms as they compete with the biogenic
mechanisms for metal adsorption, and (3) the reagents used for the extraction of
hydrous oxide fraction widely reflect the "available" metal forms in sediments. The
study of metal uptake by the water plant Nuphar variegatum in the same work of
Tessier et al. (1982) provides even more controversial results with respect to the
question of solid species interaction and availabilities. There are practically no rela-
tions between the metal contents in the stems and rhizomes of the plants and the
total concentrations in the sediments; on the other hand, there are highly signifi-
cant correlations to the concentrations of metals in specific sedimentary fractions,
demonstrating the usefulness of the differentiated approach in these studies. How-
ever, the plant experiments cannot be utilized for the estimation of the potential
bioavailability of metals from sediments, since the direct uptake from the water
phase is probably masking the relationship between the metal concentrations in the
sediment and plants.
The present state of knowledge on solid matter speciation of trace metals is still
somewhat unsatisfactory with respect to the assessment of the quantitative extent
of bioavailable element concentrations. This is mainly due to the effect of competi-
tion between adsorption sites in the solid substrate and selective mechanisms of
metal uptake by the different organisms; which - as has been shown by the work
of Luoma and Bryan (1978, 1979) - cannot simply be derived from the chemical
extraction data. This situation cannot be improved by more sophisticated extrac-
tion schemes. On the other hand, the usefulness of a differentiated approach on the
interactive processes between water/biota and - even only operationally - defined
solid phases has been clearly evidenced. The possible environmental implications,
e.g., during dredging operations, after land disposal of waste material, from acid
precipitation, for redox changes in the subsoil, and organic complexing near sew-
age outfalls, which may lead to a partial remobilization of the particle-bound
metals, can be qualitatively estimated, particularly when the hydrochemical con-
ditions are known. With respect to the more important environmental parameters,
such as pH and redox potential (Pickering, 1981) a weak acid-reducing extractant

offers a relatively good indication of the mobile and potentially bioavailable frac-
tion of transition metals, equivalent to the non apatite inorganic P-fraction of the
solid phosphorous compounds (Salomons and Forstner, 1980). The study of
potential changes of the metal mobility due to higher concentrations of organic
chelating substances, e.g. by treatment with dilute EDT A or DTPA solutions, will
further complicate the interpretation of the analytical results; however, since par-
ticularly good relations have been found for the metal concentrations in the soil
substrate and in the plants growing on it, this approach should also been consid-
ered for practical applications, e.g., for surveys on a regional scale. Some of the
still obvious inadequacies in the correlation of data between the different solid sub-
strates and the organisms (or parts of them) can possibly be reduced by the study
of the intermediate water phase, and it seems to be particularly promising to con-
sider the different forms and availabilities of metals in this medium.
2.7.3 Transformation of Metals by Organisms
Organisms not only accumulate metals from the abiotic reservoirs (Fig. 5), but they
are also able to interact with metals and modify the processes affecting them. A
number of important processes are:
- the change in environmental conditions due to pH increase (e.g. algal blooms in
lakes, Chap. 5.4),
- the reduction of sulfate in sediments by bacteria to sulfide and subsequent for-
mation of metal-sulfide compounds (Chap. 3.7),
- redox conversions of inorganic forms (e.g. the oxidation of manganese, iron and
arsenic),
- conversion from inorganic to organic forms and vice versa, typically methyla-
tion and demethylation,
- the release of extracellular material by algae.
Apart from these chemical changes organisms are also able to introduce physi-
cal changes. Important in this respect are:
- the production of pseudofaeces by bivalves in tidal areas, changing the settling
properties of the suspended matter and enhancing sedimentation (Chap. 3.4),
- the bioturbation of upper sediment layers (see Jernelov, 1970; Renfro, 1973).
Redox conversions occur at many places in the hydrological cycle. Important
are processes at the sediment-water interface (Chap. 3.7.4), at the river/sea inter-
face (Chap. 6.5) and probably the formation of manganese nodules (Chap. 7.4.3).
Of economic importance is the reclamation of metals from low-grade ores (Brierly,
1978; Lundgren and Silver, 1980; Brierly, 1981).
Redox conversions, e.g. the oxidation of pyrite, cause environmental problems
with regard to acid-mine drainage (Lundgren et aI., 1972). The rate determining
step in acid-mine drainage being the production of ferric sulphate, which is a
Transfonnation of Metals by Organisms 59
Air
HO
Water
CH 3 - As3- - CH 3 + H - As3- - CH 3
Trimethylarsine Dimethylarsine
Bacteria
OH CH 3 C~3
I I I
HO - As5"" - OH r-As3+- OHr- HO -As3 +-OH r-HO - AS+-CH3
II Bacteria II Bacteria II Bacteria II
o 0 0 0
Arsenate Arsenite Methylarsenlc Dlmethylarsenic
acid acid
Sediment
Fig.36A
a:
a:
w
FISH
l-
I e
~
Hg ° cH:!Hg~(cH}JIg
I-
Z
w
aa;;;:.' \ '
aactarla ::Ii
aacterla / Q
~HII2+ + Hll o w
HII2+~ ~ CIl
2 Bactarla
Fig. 368
Fig. 36. A The biological cycle for arsenic. 8 The biological cycle for mercury. (Wood, 1974)
Fig. 37. Model for combined biotic/abiotic

methylation in the environment (Thayer and
Brinckman, 1982)
PseudDmDnas sp
powerful oxidant (Singer and Stumm, 1970). At high pH pyrite is oxidised chemi-
cally, but at pH values between 3.5 and 4.5 the ferrous-ferric oxidation is acceler-
ated by a factor of 200 by the bacterium Metallogenium, a further drop in pH (2-
3.5) causes an increase in the iron oxidation by 10 5 to 10 6 by Thiobacillus ferroxi-
dant. Therefore, the development of appropriate acidity in mining dumps is of
prime importance for the release of metals by microbial mediation.
Redox conversions pose severe problems for the management of pyrite-con-
taining soils (Pons and van Breemen, 1982). About 12.6 million hectares of soils
developed on coastal sediments are highly pyritic. These areas, mainly in the tro-
pics, are either poorly productive or unsuitable for agriculture because of their
acidity.
Methylation of inorganic metals is an important and relatively well-known bio-
geochemical phenomenon in natural systems and as been shown to occur for a
number of trace elements including Hg, As and Sn (Thayer and Brinckman, 1982).
The biomethylation of lead is still subject to controversy. Several investigators
have reported on the biological methylation oflead (Chau and Wong, 1978; Huber
et aI., 1978; Thompson and Crerar, 1978). However, experiments conducted by
Reisinger et ai. (1981) did not gave evidence for a biological methylation.
Mercury is the best understood example of an element that undergoes a com-
plex cycle in the biosphere and for which there is evidence for the biochemical and
molecular basis for the transformations (Summers and Silver, 1978). The biological
cycle of mercury is presented in Fig. 36A.
Bacteria in the sediments, capable of vitamin B 12 synthesis, are also capable
of methylmercury synthesis (Wood, 1972). The product is mainly monomethylmer-
cury under neutral and acidic conditions and dimethylmercury under basic con-
ditions (Beyer and Jernel6v, 1979). In addition to methyl mercury synthesis, de-
methylation is another biotransformation which can be carried out by micro-or-
Transformation of Metals by Organisms 61
ganisms in sediments (Billen et aI., 1974; Jernel6v et aI., 1975). Tin is another ex-
ample for which there is increasing evidence for biomethylation (Brinckman et aI.,
1982). Methyl-tin, produced by biological activity in the sediments, is able to react
with inorganic mercury and produce in this, abiotic, pathway methylmercury and
dimethyltin (Fig. 37).
The influence of organisms on the cycle of arsenic is complex. Arsenic is subject
to both reduction, oxidation and methylation (McBride and Wolfe, 1971; Chal-
lenger, 1945; Johnson, 1972). Its biological cycle is shown in Fig. 36B.
Arsenic behaviour in surface waters is strongly influenced by phytoplankton.
Sanders and Windom (1980) showed that the As(V) taken up by plankton is for
the greater part reduced, methylated and released to the surrounding medium. Cal-
culations based on measured rates indicate that 15-20% of the total arsenic is re-
duced by phytoplankton during spring and fall blooms on the continental shelf
(Sanders and Windom, 1980). A substantial amount of the arsenic taken up by ma-
rine algae is strongly bound to structural parts of the cell, up to 12 soluble organo-
arsenic compounds were formed by algae (Andreae and Klumpp, 1979). The over-
all cycle of arsenic in marine systems is similar to the phosphate cycle (Sanders,
1980).
Micro-organisms are known to produce large quantities of extracellular
polysaccharides which are organised in well-defined capsules around the cells or
are secreted as loose material. In a study on the toxicity of cadmium and copper
to the bacteria Klebsiella aerogennes (Bitton and Freihofer, 1978) it was found that
bacteria with polysaccharides on their cells exhibit less toxicity than cells without.
This was attributed to the complexation of cadmium and copper by the polysac-
charides preventing uptake by the bacteria. Experiments with the isolated capsular
polysaccharides showed that this material was able to complex between 18 and
54 % of added copper to the suspension and 9-18 % of the added cadmium. Since
these extracellular products are found abundantly in the natural environments
(Harris and Mitchell, 1973), they may contribute to the natural complexing capac-
ity of surface waters.
Polyphenols are excreted in large amounts by brown algae in seawater. Rates
of release may exceed 1 mgjkg fresh algae per day (Sieburth, 1969) and polyphenol
concentrations in nearshore waters may reach 2.5 mg per I. By complexing metals
and reducing the activities of metal ions, extracellular algal products could change
the speciation of metals and possible detoxify the cells' external milieu (Steeman
Nielsen and Wium-Anderson, 1971). Van den Berg et al. (1979) measured the sta-
bility constant for organic matter released by algae and observed log K values vary-
ing between 7.7 and 8.6 (for copper pH 7.6). The highest values were observed for
the organic fractions which were released in small quantities. The release of com-
plexing agents by 21 algal species and their copper complexins properties were in-
vestigated by McKnight and Morel (1979). Most eukaryotic species released mea-
surable amounts of a weak copper complexing agent, with a log K value of about
0.5. Modelling of the copper speciation with the measured log K value and a con-
centration of the weak complexing agent of 10- 6 (expected during of after dense
algal blooms) showed that most of the copper is present as the organic complex.
Of the seven blue-green algae studies, four produced very strong copper-complex-
ing agents with conditional equilibrium constants in the range of 10 8 to 10 12 . The
study showed that the complexation by extracellular algal products can dominate
the speciation of copper in natural waters and lower the toxicity of copper; how-
ever, a detoxifying role can be envisaged only when the organic copper complexing.
compounds are not rapidly degraded (McKnight and Morel, 1979). In a later study
(McKnight and Morel, 1980) it was shown that the excretion products of the blue
algae were siderophores. Siderophores playa role in the transport of iron, and a
low iron concentration in the water stimulated the release of siderophores by the
algae studied.
3.1 Introduction
Sediments are important carriers for trace metals in the hydrological cycle, an as-
pect which will be discussed in chapters dealing with individual parts of the hydro-
logical cycle. However, sediment research has certain aspects of its own, which
warrants a separate discussion. Therefore, we will discuss those aspects of metals
and sediments which are common to all parts of the hydrological cycle.
Sediments can reflect the current quality of the system as well as the historical
development of certain hydrological and chemical parameters. Comparative anal-
ysis of the total concentrations of longitudinal profiles and sediment cores is per-
formed to determine metal anomalies in zones of mineralization (Rose et ai., 1979).
as well as from pollution sources (Forstner and Wittmann, 1979). The study of
dated sediment cores has proved to be especially useful as it provides a historical
record of the natural background levels and the man-induced accumulation of
metals.
Sediment analysis play an important role within the framework of environmen-
tal forensic investigations (Meiggs, 1980) in those cases, in which a short term or
past pollution event is not or only insufficiently traceable from water analysis.
In addition to their significance as an indicator medium, sediments are, depend-
ing on environmental conditions, a sink or a source for trace metals in the surface
waters. Metals are not necessarily fixed permanently by the sediment, but may be
recycled via biological and chemical agents, both within the sedimentary compart-
ment and also back into the water column (James, 1978). The recycling of miner-
alised organic matter and pore-fluid transfer processes are essential components of
models that are devised to describe the nutrient and pollutant dynamics of aquatic
systems (Lerman, 1977).
From an economical viewpoint it must be realised that sediments are also a me-
dium in which certain substances can be concentrated from solution and thereby
represent profitable sources of raw materials.
3.2 Composition of Sediments

In view of their behaviour in nature, sediments can be divided in two distinctly dif-
ferent groups (Terzaghi and Peck, 1948; Raudkivi, 1976):
- fine sediments with particles smaller than about 50 11m, subdivided in silts and
clays; and
70
40
..
ii
60
.
D 50 ii
c D
·e c
·e
CD
> 40
:; CD
.~
E -.;
0c 30
~
c
/II
20 /II
i i
10
0 0
Nearshore sands (Gulf of Paria) Nearshore marine clays
Fig. 38. Mean mineralogical composition of nearshore sands and marine clays (Hirst, 1962)
- coarse sediments with grains exceeding 0.05 mm and subdivided into sands and
gravels.
Roughly these two groups differ in mineralogical, morphological, physico-
chemical and mechanical properties. Fine sediments mainly consist of clay min-
erals, organic matter and fine grained quartz, carbonate and feldspar particles. The
mineralogy of coarse sediments is in general less diverse, it consists mainly of
quartz with admixture of feldspar. The mean mineralogical composition of modern
nearshore sands and nearshore marine clays are shown in Fig. 38.
The organic matter plays an important role in the transport of metals, since it
is able to bind trace metals and takes place in diagenetic processes after deposition.
MoreQver, there is increasing evidence that suspended particles in natural waters
are covered with organic films which determine to a large extent their hydrodyna-
mic behaviour as well their adsorption characteristics (Neihof and Loeb, 1974;
Loeb and Neihof, 1977; Hunter and Liss, 1979; Balistrieri et aI., 1981; Hunter and
Liss, 1982).
Generally the coarse sediments consist of more or less rounded particles. The
shape and size of the fine particles is diverse (Lal, 1980; Lambert et aI., 1981). The
fine particles are charged, the charge depending on ionic strength and the surface
coatings. The surface charge is also responsible for the cohesion characteristics of
fine grained sediments.
In water, the particles tend to fall under the action of gravity, the velocity de-
pending on the size and the shape of the particles additionally the fall velocity is
influenced by the presence of naturally occurring surface coatings, solution elec-
trolyte and dissolved organic substances (Chase, 1979). Clay particles in an elec-
trolyte solution form aggregates of which the size depends on the type of mineral,
the strength of the solution and the hydraulic conditions (Whitehouse et aI., 1958;
1960; Einstein and Krone, 1962). Contrary, very fine and well dispersed particles
form colloids with a very low settling velocity. The formation of very well dispersed
iron colloids in estuaries may explain the transport behaviour of iron in coastal
areas (Mayer, 1982, see also Chap. 6.5). In the oceans, there is strong evidence that
Transport of Sediments 65
the larger particles scavenge during their fall through the water column small par-
ticles (Lal, 1977; Honjo, 1982). In concentrations exceeding about 5 kg/m 3 flocs
hinder each other, causing a decrease of the fall velocity. In concentrations of 150
to 400 kg/m 3 , the suspension is almost stable and acts as a heavy fluid, called fluid
mud. Fluid muds occur in some estuaries and are an important agent in the trans-
portation and deposition of fine grained sediments.
In deposited coarse sediments, the particles are simply stacked upon each other
but in fine sediments, the deposition of flocs, formed by inter-particle forces, leads
to a more open structure with cohesion. The microstructure of clay-rich sediments
has been studied with electron microscope techniques (Bowles, 1968; Mattiat,
1969). The micro-structure of undisturbed marine sediments from the Gulf of
Mexico are characterised by a loose, open, random arrangement of particles
(Bowles, 1968).
3.3 Transport of Sediments
The transport of sediments is highly related to hydrological and geomorphological

phenomena. The main processes to be considered are (Raudkivi, 1976):
- erosion of the sediments from a bottom or a bank;
- vertical transport of the particles in the body of the water in which it is carried;
- horizontal transport by the flow;
- deposition on the bottom, and
- compaction (consolidation) of the deposit.
All these phenomena interact and vary in space and time. Their result is the
geomorphology of an alluvial area. A proper understanding of the dynamics (ero-
sion, transportation, sedimentation) is not only essential within most sedimento-
logical contexts but additionally for the prediction of the fate of sediment-bound
contaminants.
In general, for sediment particles to start moving, the flow of water must exceed
a certain critical velocity. Similarly, deposition occurs when these characteristics
of the flow decrease below another critical value. This behaviour strongly depends
on the grain size of the sediment as is roughly indicated by Hjulstmm in Fig. 39.
It shows that the two thresholds are almost equal for coarse sediments but that a
relatively strong current is needed for the erosion of fine cohesive sediments while
the deposition ofthe small particles requires very quiet conditions.
The mode of transport shows significant differences between coarse and fine
particles.
In the usual flows in rivers and estuaries, sand and gravel move in a thin layer
along the bottom as, so-called, bed load. The average distance travelled between
erosion and deposition is relatively short. The range of vertical excursions of the
particles is smaller and they move rapidly.
Under the same conditions silt and clay (Einstein and Krone, 1962) are trans-
ported as suspended load in the whole body of water. Vertical movements reach
MEAN VELOCITY
(ii) IN m/sec
102r-----r-----~----~----,_----_r----~----_,
MOVEMENT
OF GRAINS
101~----~----T-----+----+4------r----~~~-1
0,2
161~----~----~~--+_~~1_----_r----_t----~
DIAMETER OF SAND GRAIN (d) IN mm
Fig. 39. The Hjulstmm curve
the whole water depth but the particles move very slowly. They remain in suspen-
sion for a long time and may travel over large distances, once eroded. The accumu-
lation of sediment in the water and its release take considerable time, leading to
a time lag between the rate of transport and the rate of flow. In general, the same
flow can transport a much greater quantity of fine sediments than coarse sedi-
ments.
The dependence of the mobility of the sediments on the hydraulic conditions
leads to a progressive sorting of sediments (and their associated contaminants)
with respect to composition and size. The most significant sorting is in the coarse
(sand, gravel) and fine (silt, clay) sediments. The former are found in the more en-
ergetic areas such as steep rivers, strong tidal currents and along exposed coasts.
Fine sediments (which in general contain higher metal concentrations) accumulate
in more quiet waters such as lagoons, tidal flats, flood plains and deep lakes. Of
course, the (non)availability of the typical fraction in the supply of sediments may
lead to another distribution; e.g. the muddy coast of Guyana.
After deposition the initial water content of sediments ranges from 40% (coarse
sediments) to more than 80% in fresh deposits of fine sediments.
Consolidation of the sediments, under their own weight and under the weight
of the overlying sediments, results in the expulsion of pore water. The particles of
coarse sediments form a rather rigid structure already at the moment of deposition.
Further deformation is relatively small and is reached very rapidly. Fine sediments,
especially the flocculated, form a very loose fabric with a very high porosity and
low permeability. Consolidation progresses slowly and may cause a 50% in reduc-
tion of the volume (see for instance Fig. 49). The compaction means a considerable
increase of interparticle contacts and, therefore, more mechanical strength against
erosion.
Distribution and Deposition 67
3.4 Distribution and Deposition
As sediments are transported by flows, the patterns of sediment transport are

strongly related to the structure of the relevant hydraulic system. The most simple
case is a river with unidirectional flow. Much more complicating are oscillating tid-
al flows. Waves are a further complicating factor in coastal areas, shallow seas and
lakes. Even more intricate are estuaries in which also the difference of the densities
of riverwater and seawater plays an important role. Spatially, the system is bor-
dered by the geometry of the body of water which can be complex and which may
change in time; rapidly because of the variations of the water level and slowly due
to morphological processes.
The discharge of rivers reacts to individual showers in small streams and to the
seasons in large onces. The sediment transport show a similar pattern, generally
with a maximum flux during the rising stage of a flood. The nature and amount
of the sediments depend on the yield of the catchment area and to the carrying ca-
pacity of the flow. A stretch of alluvial river receives sediments from upstream and
from erosion in its bed, especially from concave banks in its meanders. Deposition
occurs on the bed and on the flood plains. The different sources contributing to
the sediment load of a river during high discharge are also reflected in its trace
metal concentrations (Fig. 83).
In areas with tidal flows the velocities of the oscillating water bodies vary be-
tween maximum ebb in one direction and maximum flood in the other. With ex-
tremes of 1 mis, the horizontal excursion is about 15 km. During slack water the
velocity is about nil.
With the water, the sediments move to and fro with erosion and transport
around the maxima and deposition around the slacks (Fig. 40).
Coarse sediments moving as bed load closely follow the flows but the behaviour
of fine sediments is much more complicated (Einstein and Krone, 1962) as is
NEAP SPRING
Fig. 40. Velocities and sediment concentrations during a tidal cycle at neap and spring times (schemati-
cally)
schematically shown in Fig. 40. Not all the sediment is deposited around slack wa-
ter; erosion occurs around maximum flow. During spring tide the erosion lasts lon-
ger and the flow is stronger than during neaps, but the period of deposition is short-
er. The consequence is a much higher average concentration (and also greater vari-
ation) during the springs. The amounts of sediment carried during ebb and flood
show great variations during a fortnightly cycle.
In coasts and shallow seas, the orbital motion of waves is added to the other
flows; especially during periods of storm and high swell. They enhance the erosive
force of the water (Davis, 1978). The net transport caused by asymmetry of the
wave action itself is relatively small but the erosive action of the waves may facili-
tate the transport (in suspension) by flows, that themselves are too weak to carry
much sediments.
Estuaries are transitions from the river to the sea (Dyer, 1973): the freshwater
meets the denser saline seawater in a tidal area. The seawater intrudes along the
bottom, the riverwater flows seaward along the surface and there is mixing of the
two mainly caused by the tides (see also Fig. 115). Also the, sometimes very intri-
cate, systems of channels and shoals influence the flows. The seasonal variation of
the river discharge affects the salt intrusion and the pattern of resultant flows.
In view of this it is no surprise that transport patterns of sediments in estuaries
are very intricate and differ from case to case (Einstein and Krone, 1961). Floccu-
lation plays a role where fluviatile sediments encounter the salt from the sea. In
general estuaries are, geologically young, areas of accretion with zones of rapid de-
position where the river meets the tide, i.e. around the tip of the salt wedge (see
Fig. 113) and at the bar outside its mouth. Especially fine sediments are found on
the tidal flats and marshes.
All these transports of sediments playa part in the geomorphological develop-
ment of an area. The latter proceeds slowly compared with the apparent hydraulic
phenomena. As the study of transports shows the pathway along which sediments
travel, the study of the morphology of an area may reveal the sources and sinks
of the sediments. Both approaches lead to the observation that fine sediments,
which contain the highest trace metal levels, mainly come to rest in shallow or in-
tertidal areas which are ecologically important.
The construction of dams, canals, irrigation systems, deforestation, reclama-
tion ofland, navigation channels, harbour basins etc., changes the geometry of an
area. Such human interactions interfere with its geomorphology and so with the
patterns of flows and sediment transports. Erosion is induced in deforested areas,
downstream of dams and in trained rivers and estuaries. Deposition is enhanced
in reservoirs, irrigation systems, harbours and navigation channels.
The relative dimension of such works differs from case to case. The dredging
of a navigation channel in a very large estuary may hardly influence the general
system (McDowell and O'Connor, 1977) but in the course of time the construction
of harbours, e.g. near Rotterdam in the Rhine estuary, have given it a completely
artificial geometry.
Another important human factor is the displacement of sediments for construc-
tion works and maintenance dredging of harbours, navigation channels and re-
servoirs. Dredged material is dumped within an economically feasible distance of
transport. The most effective places of deposition are on land or in quiet water.
Grain Size Effects 69
Then, in fact, the sediments are withdrawn from the natural transport system. Less
drastic, but often cheaper, is dumping in deep water with the risk that (part of) the
sediments return to the location of dredging. Via the dredging process (polluted)
sediments may end up in places they never would reach by natural processes.
3.5 Grain Size Effects
Metals are not homogeneously distributed over the various grain size fractions,
and large differences in total metal concentrations are observed in sediments sam-
ples from a single locality. Within the grain size spectrum, the finer-grained frac-
tion - consisting mainly of clay minerals - show relatively high metal contents. In
the silt and fine sand fractions the metal concentrations generally decrease as that
fraction is dominated by quartz components with low metal contents. In the
coarser fractions the presence of heavy minerals may cause the metal portion to
increase once more.
Alteration of the grain size spectrum of some characteristic components of sed-
iments are presented in Fig.41 for Lake Constance and Lower Rhine River sam-
ples.
The relatively insignificant differences of the grain size distribution curves do
not imply that material inhomogenities cannot be sometimes very large. Since the
greater majority of the particles range in the grain size of 2 11m to 20 11m, the in-
creased values for the specific surface area, for example, climbs in this grain size
spectrum in Rhine River sediment to a value that is clearly higher in the overall
sample of the Lower Rhine (24.3 m 2 jg) compared to 7.2 m 2 jg in the Lake Con-
stance sample. Two especially important carriers for trace metals are shown in
Figs. 41c and 41d: iron oxyhydrates are distinctly enriched in the Rhine River se-
diment compared to the sample from Lake Constance. The Fe-oxides prefer the
fine grained particle surfaces, and the humic substances apparently tend more to
collect on fine- to medium-sized silt grains. For phosphate compounds (Fig. 41e)
there is a preference towards the fine grain fractions. In the latter case the strong
enrichment in Lower Rhine River sediments occurs as non-apatic inorganic P-as-
sociations. Detrital carbonates (Fig.41f) generally possess a diluting effect on
metal concentrations in the coarser sediment fractions of Lake Constance, where
they are 4-5 times more prevalent than in the sample from the Lower Rhine River.
Different methods for grain size correction are compiled in Table 9 (after De
Groot et aI., 1976; Forstner and Wittmann, 1979; Forstner and Salomons, 1980).
These methods will reduce (not eliminate) the fraction of the sediments that is
largely chemically inert, i.e. mostly the coarse-grained quartz, feldspar and carbon-
ate minerals, and increase the substances active in metal enrichment, i.e. hydrates,
sulfides, amorphous and organic materials.
Separation of grain size is advantageous because only few samples from a par-
ticular locality are needed. However, separation of the fraction less than 2 11m in
settling tubes is time-consuming (the remobilization of metals - as has sometimes
been suspected - is relatively low; Jenne et aI., 1980). The fractions less than 173 11m
and 204 11m contain considerable percentages oflarge grains which are usually low
Lower Rhine • •
%
Bodensee 0----0
25
Grainsize % Specific surface
distribution (m 2 g" )
20 40
15
10 20
% Humic substances % Fe
(0.1" NaOH Extraction) (0.3"HCI Extraction)
1.0 1.0
® @)
0.5 0.5
% Carbonate conUnt % Total· P

30 0.5
® CD
0.3
15
0.1
0.06 0.2 0.6 2.0 6.3 20 63 0.06 0.2 0.6 2.0 6.3 20 63
Grainsize (}J.m)
Fig. 41 a-f. Grain size spectrum of some components in sediments from Lake Constance and the Lower
Rhine (partly from F 6rstner and Patchineelam, 1980)
in trace metals. Therefore, the fraction < 63 /lm is recommended for the following
reasons (Forstner and Salomons, 1980):
trace metals have been found to be present mainly in clay/silt particles
this fraction is most nearly equivalent to the material carried in suspension (the
most important transport mode of sediments by far)
sieving does not alter metal concentrations - particularly when water of the same
system is used
numerous metal studies have already been performed on the < 63 /lm fraction,
allowing better comparison of results.
Table 9. Reduction of grain size effects in sediment samples
Method Reference (example)
I. Separation of grain size 204 11m (sieving) Thornton et a!. (1975)

fractions (mechanical) 175 11m (sieving) Vernet and Thomas (1972)
63 11m (sieving) Allan (1971)
20 11m (sieving) Jenne et a!. (1980)
211m (settling tube) Banat et a!. (1972)
II. Extrapolation from Metal/Percent 161lffi De Groot et a!. (1971)
regression curves Metal/Percent 20 11m Lichtfu13 and Briimmer (1977)
Metal/Percent 63 11m Smith et a!. (1973)
Metal/specific surface area Oliver (1973)
III. Correction for inert mineral Quartz-free sediment Thomas (1972)
constituents Carbonate/quartz-free Salomons and Mook (1977)
IV. Treatment with dilute acids 0.1 M hydrochloric acid Gross et a!. (1971)
or with complexing agents 0.3M HCI Malo (1977)
(determination of "mobile" 0.5MHCI Agemian and Chau (1976)
fraction) 25% acetic acid Loring (1977)
EDTA, DTPA, NTA Gambrell et a!. (1977)
V. Comparison with Metal/aluminium Bruland et a!. (1974)
"conservative" elements Sediment enrichment factor Kemp et a!. (1976)
(Al./ AI-backgr.)
ReI. atomic variation Allan and Brunskill (1977)
M/Cs, Sc, Eu, Rb, Sm Ackermann (1980)
AI./Standard-AI Li(1981)
Sc./Standard-Sc Schoer et a!. (1982)
Thomas and Martin (1982)
In respect to the assessment of metal pollution at a certain locality, the extra-

polation techniques both for the grain size and specific surface area of the material
require a large number of samples (10-15). Furthermore it is often not possible to
obtain the necessary amount of samples with differences in grain size composition
(surface area) to calculate a regression line.
The quartz correction method, the expression of the metal contents on the
quartz-free sediment fraction (determined by fusion with potassium-pyrosulfates
which preferentially removes the layered silicates (clays) organic and inorganic car-
bon and sulfides with a residue made up of quartz plus feldspar and resistant heavy
minerals such as zircon (Thomas et ai., 1976)) has to be extended to dilution effects
caused by feldspars, carbonates and opaline silica (Salomons and Scheltens, 1975;
Chester, 1978). An example of the quartz correction method is shown in Fig. 42.
It becomes quite clear that Lakes Superior and Michigan are only moderately polluted, Lake
Huron has a somewhat more intensive pollution rate in its eastern half, but Lake Erie and even more
Lake Ontario (southern part) show an unproportionally high pollution rate. The area around St. Clair
is presented on the map in Fig. 42. At the beginning of the 70's this lake was at the forefront of the mer-
cury discussion. In an extensive review of all industries and communities of the region, two main sources
of mercury pollution were found: one was the Wyandotte Chemical Co., which has a chlor-alkali plant
located on the Detroit River; the other is the Dow Chemical chlor-alkali plant on the St. Clair River
at Sarnia, Ontario. In 1978 mercury was still very much a problem in the Great Lakes region-even years
after closure of the point source discharge. This was due to the resuspension and continued transport-
ation of polluted sediments from Lake St. Clair. A high mercury level near the mouth of the Detroit
Mercury ~g/kg
D <50
o 50'100
• 100 · 500
• SOO'1000
• >1000
L.St.Clair
150km
Fig.42. Distribution of mercury in sediments of the Great Lakes (Thomas, 1978)
River results from a rapid deposition from the western flow as it enters Lake Erie. As the contaminated
water mass flows south along the Michigan-Ohio shore, it deposits progressively smaller amounts of
mercury into Lake Erie. In Lake Ontario, there is a distinct grouping of elevated mercury levels near
the southern bank of the lake, especially close to the mouth of the Niagara River. Investigations carried
out by Fitchko and Hutchinson (1975) have shown that the dispersion pathways point to the Niagara
River as the prime source of mercury to Lake Ontario. The eastward extension of the Niagara mercury
"plume" is probably due to coastal currents, whereas the enrichment of mercury at the mouth of the
Genesee and Oswego Rivers appears to result from the contamination within their catchment areas.
The asessment of both sources and environmental effects of trace metals in par-
ticulate matter must predominantly consider the most mobile fraction of these ele-
ments, which is introduced by man's activities and bound to the sediment in sorbed,
precipitated or co-precipitated (carbonates and hydrous Fe/Mn-oxides) and
in an organically complexed form. Goldberg (1954) suggested that a large portion
of the "hydrogenous" metal fraction in recent sediments can be dissolved by spe-
cific attack with dilute acids; a residue of relatively inertly bound metals from the
natural rock and soil detritus ("residual fraction") can be found predominantly in
the coarser grain sizes. The metal data thus obtained by acid extraction should
compare favourably with data from the separation of the fine-grained fraction of
sediments (see above).
Studies by Cross et al. (1970) on the distribution of manganese, iron and zinc
in sediments of the Newport River Estuary, North Carolina and by Cross et
al.(1971) on marine waste deposits of the New York Metropolitan Region were
among the first to consider the chemical fractionation of non-detrital/residually
bound metals in polluted sediments by the application of 0.1 M and 1 M hy-
drochloric acid, respectively. In more recent studies other acids or acid concen-
trations have come into use for the general differentiation of metal species associ-
ated with hydrous oxides, carbonates, sulfides and surficially sorbed materials
from the residual fraction (Table 9).
A practical example of this type of study is the initial assessment of trace metal
pollution in surface sediment from two Greek Gulfs by Chester and Voutsinou
(1981). The technique proposed by Chester and co-workers involved the leaching
of the samples with cold 0.5 M hydrochloric acid and has been shown to "provide
a rapid, inexpensive way of establishing the gross degree to which a sediment pop-
ulation has been subjected to trace metal pollution from the overlying waters".
From Fig. 43 it is evident that the highest non-residual concentrations of Cd and
Zn are found in sediments around Salonika and the industrialized area of the
northern Thermaikos Gulf, in particular in the region of the outflow of the Axios
River, which is an industrialized catchment area.
Investigation on sediment cores from Lake Erie (performed by Kemp et aI.,
1976) distinguished five types of elements according to their mode of distribution:
(a) diagenetically mobile elements, such as iron, manganese and sulfur; (b) car-
bonate elements, carbonate-C and calcium; (c) nutrient elements, organic carbon,
nitrogen and phosphorus; (d) enriched metals, such as copper, cadmium, zinc,
lead and mercury; and (e) conservative elements, e.g. silicon, potassium, titanium,
sodium and magnesium. The latter group of elements, labelled "conservative", are
of particular importance when determining comparative values of metals in de-
posits, e.g. in order to minimize grain size efects.
Aluminium was used in earlier studies, e.g. by Bruland et al. (1974), as a suit-
able reference element to trace the development of anthropogenic input into sedi-
ment profiles. Standardizing anthropogenic (and "abnormal" natural) metal con-
centrations to the contents of "conservative elements" such as aluminium and
potassium, i.e. on the percentage of clay minerals in dust samples or sediments has
at first glance one major disadvantage in that it gives a ratio value instead of a real
concentration. But it can be attempted - as Duce et al. (1975) have done for atmo-
spheric dust particles and Li (1981 b; 1982) for marine sediments - to standardize
the contents to a standard material, defining the enrichment factor, e.g. of element
"i" in the sample E~l as the concentration ratio of "i" to Al (Ci/C A1 ) compared
to the ratio in standard material. Average crustal igneous rocks (see Chap. 5.2.3)
is very often used as the standard material (Herron et ai., 1977; Weiss et ai., 1978),
but average shale (e.g. Turekian and Wedepohl, 1961) seems to be more represen-
tative of the continental soils (Lantzy and Mackenzie, 1979; Li, 1981 b).
On sediment samples from the Ems River Estuary in Northern Germany a
series of potential reference elements - Cs, Eu, Fe, Rb, Sc, Sm and Th (measured
by neutron activation analysis) - were tested by Ackermann (1980). Table 10 sum-
marizes the correlation coefficients "r" between metal contents and the percentage
of grain size fraction 20 )..lm and 63 )..lm, respectively, and the slope of the regression
lines, the quotient s(100%)/s(0%) from the ordinate values extrapolated for 100%
and 0% of the two grain size fractions (Fig. 44). The closer to 1.0 the correlation
coefficient r for a specific reference element lies and the larger the quotient s(100%
)/s(O%), the more exactly can a grain size correction be carried out. According to
Table 10, cesium appears to be the preferred reference element for 2 reasons: it is
particularly well correlated (r = 0.987) with the percentage of the < 20 )..lm fraction
and the quotient, s(100%)/s(0%) is greater than for the other elements. A test for
t
Zinc
N
I
• - I.~ -.'4
> 200 ppm
100- 200 ppm
70-100 ppm
50 -ppm
> 50 ppm In,mlle
Fig.43a,b. Distribution of 0.5 M HCI-extractable cadmium and zinc in sediments from the Gulf of
Thermaikos, Greece. (After Chester and Voutsinou, 1981)
the applicability of the correction procedure was made on a 140 cm long sediment
core from the brackish water zone of the Ems River Estuary near Emden (Fig. 44b)
by Ackermann (1980). The layers deeper than 10-20 cm are older than 20-25 years
(Cs-137 dating). The curve of Zn-concentrations in the total sample varies with
depth and does not give an indication ofthe Zn pollution, being fully superimposed
by the much stronger grain size effect (thick broken line). The Zn data corrected
for grain size (solid line), on the other hand, clearly indicate the very significant
increase of Zn pollution during the last 100 years.
b THESSALONIKI
• • •
t
N
0------1
In.mile
Fig.43b
Due to the very close geochemical relation between scandium and aluminium
(which is most often taken as a reference value), the measurement of these com-
ponents seems to be recommendable (Schoer et al., 1982; Thomas and Martin,
1982). An example is given in Chapter 5.2. for investigations on metal concen-
trations in sediments from the Elbe, Weser and Ems Estuaries and from the Ger-
man Bight (Southeastern North Sea).
Generally it appears that correction made with conservative elements is espe-
cially valuable. If separation of coarser grain sizes, for example up to < 63 ~m, is
mg/kg Zn-concentration mg/kg
,,
.
12 100 200 300
.--------.
Cs I
10
.".
.~ .-
,,0
/
0
~~• .;..:.. total sample
8
V,
6
4
.. •••
..............-.
,.
~ '"....
",0
2 "",-••
.........~.
,r-
......A.
r ~ 0,987
.t:.
Q.
50 0 ....
.... 0
\
/
•\
-3 I
0
I
•
,
O+-~---.--~-.--~--r--.---.--~-,
o 20 40 60 80 100 1: 0
•
.
%
A Fraction c 20",m
•E '0
I
/~rrected with cesium
li 100 0
\0 I
(/)
•\
I
0
\ •I
I I
•
0
B 0
\ \
•
150
Fig.44A, B. Correction of grain size by conservative element content: Relation to cesium. (Ackermann,
1980) A Regression line and correlation coefficient "r" of cesium and percentage of the fraction < 20
Ilm in sediment samples from the Ems Estuary (N. Germany). B Example ofa sediment core from the
Ems Estuary near Emden. Open circles: Zn in total sample; closed circles: Zn values corrected for
cesium contents
Table 10. Correlation coefficients, r and concentration ratios s(I00%)/s(O%) for some potential
reference elemen ts. (Ackermann, 1980)
Cs Sc Fe Rb Eu Th Sm
Fraction < 20 Ilm r 0.987 0.982 0.858 0.958 0.945 0.932 0.878
s( 100% )/s(O%) 14.0 7.3 6.4 3.4 3.1 3.2 3.1
Fraction < 63 Ilm r 0.919 0.937 0.789 0.900 0.947 0.944 0.911
s(I00%)/s(O%) >20 15 9.0 3.7 3.8 3.8 3.9
carried out prior to correction, still better results may be obtained. In our opinion
the separation of the fraction less than 63 Ilm offers an economical method for as-
sessing the distribution pattern of trace metals in a given area. To obtain more de-
tailed information it can be combined with the determination of the "mobile frac-
tion" and a further standarization with "conservative elements".
3.6 Anthropogenic Influences on Metal Concentrations in Sediments
3.6.1 Background Concentrations
To determine the extent of pollution in an aquatic system by means of the heavy

metal load in sediments, it is of primary importance to establish the natural level
of these substances, i.e. the "pre-civilizational" level and then substract it from ex-
Background Concentrations 77
isting values for metal concentrations in order to derive the total enrichment
caused by anthropogenic influences.
To obtain an ideal comparative basis for environmental studies, the following
criteria should be fulfilled so as to achieve representative values for metal concen-
trations: a large number of sediment samples must be analyzed which correspond
with recent deposits in their (i) grain size distribution, (ii) material composition
and (iii) conditions of origin. A fourth criterium is that the samples must be un-
contaminated by civilizational influences.
Several possibilities have been discussed to establish background values for
trace metals (Forstner and Wittmann, 1979):
(1) average shale composition as a global standard value;
(2) fossil aquatic sediments from defined environments as a standard, taking into
account natural allochthonous and autochthonous factors and mechanisms as
well as regional influences;
(3) recent deposits in relatively unpolluted areas;
(4) short, dated sedimentary cores, which provide a historical record of events oc-
curring in the watershed of a particular river or estuary. These would enable
an estimation of both the background levels and the changes in input of an ele-
ment over an extended period of time.
Table 11 gives a few examples of background concentrations for heavy metals
evaluated according to method (1) to (3). The most suitable data for a global stan-
dard (method 1) proves to be that for fossil shales and data compiled by Turekian
and Wedepohl (1961) are often used as a global basis for comparison for metal-
contaminated sediments. For some metals, e.g. manganese, zinc and lead, the
values for this so-called shale standard agree quite well with the average concen-
trations that have been measured in recent shallow water sediments in less polluted
regions. For other examples, especially elements enriched in basic rocks, the shale
Table 11. Background concentrations of heavy metals in sediments and soils
Metal Shale and clays (1) Sub-recent Lacustrine (3) Soils (4)
Rhine sediments (2) sediments (3)
Fe(%) 4.72 3.23 4.34 3.2

Mn 600 960 760 760
Zn 95 115 118 59.8
Cr 83 (*60) 47 62 84
Ni 68 (*32) 46 66 33.7
Cu 45 (*31) 51 45 25.8
Pb 20 30 34 29.2
Co 19 (*13) 16 16 12
Hg 0.2 0.2 0.35 0.098
Cd 0.2 0.3 0040 0.62
* Recent freshwater sediments

(I) Turekian and Wedepohl (1961) and from Handbook of Geochemistry (Wedepohl, 1969; 1980)
(2) Forstner and MUller, 1974
(3) Forstner, 1978
(4) Ure and Berrow (1982)
values appear to be too high for comparison with modern sediments from inland
and coastel waters. Such elements, e.g. Cr, Ni, Co and Cu are marked with an as-
terisk (*) in Table 11. The corresponding concentrations in fossil Rhine River sed-
iments (from a sediment core taken near Cologne, Forstner and Muller, 1974) and
in soils (Ure and Berrow, 1982) underline the tendency to lower background values
for these metals. Lithologic peculiarities of the respective catchment basins must
be considered, especially for investigations covering only a limited surface area.
3.6.2 Sediment Core Studies
The significance of sedimentary cores in the assessment of the quality of aquatic

systems is well illustrated by examples from the lacustrine environment. First ob-
servations of cultural effects on lakes, as indicated in the variations in the sediment
stratigraphic records, were made on Lake Zurich and described by Nipkow (1920).
Man-made effects have been evaluated from the distribution in sediment cores of
phosphorous and other nutrients (e.g. Frink, 1967), iron mono sulfide (Muller,
1967) and in changes of diatom assemblages (Stockner and Benson, 1967); pollen
variations in recent lake sediments reflect historical changes in land use (e.g. An-
derson, 1973). During the last decade, lake sediment analyses have increasingly
been employed as a tool to trace sources and input rates of less or non-degradable
pollutants, such as halogenated hydrocarbons (Leshniowsky et aI., 1970), poly-
cyclic aromatic hydrocarbons (Hites et aI., 1977), artificial radio nuclides (Picker-
ing, 1969) and heavy metals (compilation of examples, see F 6rstner and Wittmann,
0.5 2
0
1
I
-+- I
I
18.2mm/y ---+
I
10
20
1 av.7.7mm/y _ ~
r __ -+- -_1.8mm/y
~--
E 30 --r --
..
u
III
I
.r:
Co
~ 40
50
Fig. 45. Plot of 21O-Pb excess against depth in a sedi-
ment core from the German Bight, Southeastern
North Sea (Dominik et aI., 1978). Solid lines: best fit
60 to all values in the interval 7-50 cm. Dashed lines:
best fit for intervals 7-19, 19-28 and 28-50 cm
Quantification of Environmental Impact 79
1979). The study of sediment cores is especially suited for the differentiation of nat-
ural metal enrichment, for example, in zones of mineralizations, and anthropo-
genic effects occurring in certain areas as a consequence of mining and smelting
activities (Allan, 1974).
Sedimentary cores are particularly useful when the individual phases of de-
velopment, which are recorded in the different layers of sediment material, can be
dated by means of certain granulometric characteristic, by pollen assemblages or
by isotope measurements. Among the latter methods the determination of the 210-
Pb and 137-Cs distributions have proved to be advantageous: 137-Cs is an artificial
radionuclide introduced into the environments by nuclear tests. The 137-Cs dis-
tribution in a sediment core should reflect variations in the atmosphere flux, pro-
vided the sedimentation rate is constant and no mixing or diffusion occurs. The ra-
dioactive isotope 2l0-Pb is derived from the decay of 222-Rn, which comes from
the earth's surface; once in the atmosphere this rare-gas daughter of238-U decays
with a half-life of 3.8 days. The charged daughter ions thus produced are chemi-
cally reactive and soon become irreversibly associated with aerosol particles (Ture-
kian et aI., 1977). The abundances of2lO-Pb and other decay products of 222-Rn
give not only information on mean residence time of the aerosol, but once intro-
duced in the aquatic system and in the sediments, they can be used for dating pur-
poses.
The sedimentation rate is determined from the slope of the least-square fit for
21O-Pb excess values plotted versus depth and expressed in mm/y. An example is
given in Fig.45 from a sediment core taken from the southern German Bight
(Forstner and Reineck, 1974), where two sections with sedimentation rates of 15-
20 mm/y are interrupted by a section showing a very low sedimentation rate or even
an erosion period (Dominik et aI., 1978). The 21O-Pb method is well-suited for dat-
ing events occurring during the last 100-200 years (Krishnaswami and Lal, 1978).
3.6.3 Quantification of Environmental Impact
A first attempt to quantify the extent of heavy metal pollution in sediment on a

more global scale was made by Forstner and Muller (1973) by the comparison of
heavy metals consumption with the natural concentration of the respective ele-
ments in unpolluted sediments, which is then recorded in the "Index of Relative
Pollution Potential". It has been found that this index proves to be particularly
high for zinc, lead, mercury and cadmium. A similar approach was used by Niki-
forova and Smirnova (1975) by calculating the "technogenic migration" ofa metal
and the degree of its utilization through its "Technophility Index" that is, the ratio
of the annual output of a metal to its "Clarke" (mean concentration in the earth's
crust). The higher the TP of a metal, the more intensively it is involved in techno-
logic migration (all values x 10 7):
Mn= Fe<Ni < Cr< Zn < Cu < Hg= Pb< Cd
5 5 10 20 50 100 150 150 700
The TP-index varies with time, and thus each metal can be characterized by its own
rate ofTP growth. The TP ofPb, for example, has grown two and a halftimes from
Table 12. Sediment enrichment factors (SEF) of heavy metals in selected examples from lacustrine and
marine environments
Source Element Refer-

ence"
Cd Co Cu Cr Fe Hg Ni Pb Zn
LakeVanern 2.6 NAb 1.2 NA NA (38) 0.8 2.3 3.7 (I)

Lake Constance 2.9 0.5 1.1 3.0 1.0 2.0 0.9 2.7 3.1 (2)
Lake Geneva 4.6 1.5 2.7 1.3 NA 15 1.0 2.3 3.6 (3)
Lake Erie 7.3 1.6 3.7 2.9 1.5 8.3 2.1 4.7 3.6 (4)
Kieler Bight (Baltic) 7.5 1.4 2.0 NA 0.9 NA 1.6 4.1 2.7 (5)
German Bight (North Sea) 7.5 2.2 1.8 1.5 1.4 9.4 1.3 8.2 4.0 (6)
MeanSEF 5.3 1.4 2.1 2.2 1.2 8.7 1.3 4.1 3.5
a (I) Hakanson (\977), mean values from eight surficial samples (0-1 cm) versus natural background.
(2) Forstner and Miiller (\974), sediment core from central part (250 m water depth). (3) Vernet
(1976), mean SEF from coastal stations. (4) Walters et al. (1974), sediment core from central basin
(No. 13-2); Pb value from Kemp et al. (1976), mean of SEF from two cores of central basin. (5) Er-
lenkeuser et al. (1974), core A-GC from 28 m water depth. (6) Forstner and Reineck (1974), core 1/315
from 22 m depth
b NA=notavailable
the beginning of the century up to the present time and will have further increased
four and a halftimes by the year 2000.
In order to estimate the relative enrichment of trace metals by cultural effects
Table 12 depicts selected examples of core sediment studies on both lacustrine and
coastal marine environments. It is evident that zinc, lead, cadmium and mercury
are on the average particularly strongly enriched (the latter element more on a local
scale than the others). Suess and Erlenkeuser (J 975) have pointed out that the order
of enrichment in anthropogenically influenced sediments, cadmium> lead> zinc,
corresponds to the accumulation of metals in fossil fuel residues.
A quantitative measure of the metal pollution in aquatic sediments has been in-
troduced by M liller (1979), which is called the "Index of Geoaccumulation":
C n is the measured concentration of the element "n" in the pelitic sediment fraction
( < 2 11m) and Bn is the geochemical background value in fossil argillaceous sedi-
ment ("average shale", see Table 42; the factor' 1.5' is used because of possible
variations of the background data due to lithogenic effects. The Index of Geoac-
cumulation consists of 7 grades, whereby the highest grade (6) reflects 100-fold en-
richment above the background values (2 6 = 64· 1.5). In Table 13 two examples of
heavily polluted river systems in the Federal Republic of Germany are presented.
The index values of the upper Rhine (between Basel and Mannheim), before the
waters of the Neckar and Main Rivers enter the Rhine) lie at a maximum of 3 for
Cd and Pb. Cd reaches the highest grade (6) in the middle section of the river and
the lower Rhine (below the mouth of the Main River to the German/Dutch bor-
Table 13. Geoaccumulation indices for metals in sediments from Rhine River and Elbe River
Igco I.eo class Upper Rhine" Lower Rhine b Elbe (Hamburg)C Elbe (Stade)d
>5 6 Cd Cd,Hg
4-5 5 Zn, Pb
3--4 4 Pb,Zn Cu Cd
2-3 3 Cd,Pb Hg Hg,Zn,Pb
1-2 2 Zn,Hg Cu Cr
0-1 1 Cu Cu,Cr
<0 0 Cr
" Base1-Mannheim
b Mainz-Emmerich (MUller, 1979)
C < 63 !lm-fraction (ARGE-Elbe, 1980)
d < 2 !lm (MUller, 1980)
der), which can be traced to influents from the Neckar River and from the Ruhr
area. The indices for Pb and Zn attain 4, and those for Hg, Cu and Cr each increase
by one (Fig. 86 shows the development of the Igeo indices in longitudinal profiles
of the Rhine River)
In the deposits in the Hamburg harbour area, which originate from the Elbe River,
the index of Cd and Hg is 6, whereas Zn and Pb have a geoaccumulation index rat-
ing of 5. The example of Elbe River sediments near Stade (given by Miiller, 1980)
shows a clear decrease of metal contents in estuarine sediments which is chiefly the
result of an increasing mixing of heavily contaminated fluviatile sediments with less
contaminated marine sediments in the tidal area (see Section 6.4).
In accordance with a suggestion by Tomlinson et ai. (1980) for the classification
of heavy metal levels in estuaries and the formation of a pollution index based on
enrichment factors in intertidal algae or fauna within an estuary it was possible to
obtain contamination factors by referring to baseline metal levels, as shown in
Table 11. The Pollution Load Index (PU) is at first determined for the different
metals at each site by calculating highest contamination factors (C.F. = metal con-
centration in polluted sediment/base value for that metal) are calculated, deriving
the n-th root of the n factors multiplied together: n cn· cn ... ' Cfn. Such site in-
dices can be treated in the exact same manner to give a zone index, and an estuary
index from the zone indices, e.g. Pollution Load Index for the zone = n site 1
. site 2 ... · site n; for the estuary = n zone 1· zone 2 ... · zone n, where n = the
number of contamination factors, sites and zones, respectively. The use of such an
index in simplified from is illustrated in Fig. 46 (from Tomlinson et aI., 1980).
The estuary is divided into three zones of approximately equal area - each zone
would normally consist of a number of sites - but in this example only one site is
given for each zone. Fig. 46 illustrates such indices using Fucus sp. calculated for
the east coast estuaries of Ireland. It is shown that the Avoca Estuary at Arklow
is by far the most polluted with regard to heavy metals, whereas Malahide and
Dublin are the least polluted. It has been inferred by the authors of this study that
unusually high levels of a single pollutant might result in an unusually low index
level if other pollutants in the system are present at near baseline concentration.
According to Tomlinson et aI., 1980 such a fault might be overcome by using a sub-
b POLLUTION LOAD
INDICES
Dundalk .w..; 1.88
a CuPbZnNi
z~ne ttSx1x2x6=2.78 2.78
IRISH
SEA
1.30
1.41
Estuary index=tl2.78xl.41x2.91=2.2S
Fig.46. Classification of Pollution Load Index (PU) after Tomlinson et al. (1980) and example for the
east coast ofIreland. For explanation see text
script to the index identifying any pollutants present in abnormally high concen-
trations; thus the index for the Avoca Estuary at Arklow (Fig. 46) would become
5.6 Cu Zn, indicating that copper and zinc were the major pollutants to give rise
to the relatively high Pollution Load Index.
It has been suggested by Tomlinson (1980) that while an index value cannot at
present provide information on the effects of the combination of pollutants on the
estuarine biota, it may enable the public to understand factors influencing the qual-
ity of a component of their environment, and it can indicate trends over time and
area. For the use of sediment parameters it will be necessary to determine an en-
richment factor corrected for grain size with the help of conservative elements
(Chap. 3.5). A further step in the application of these indices in assessing of pollu-
tion potentials would be the consideration of the mobility of a given element and
its environmental toxicity.
In this respect Tada and collegues (1983) classified pollution of Japanese rivers
by heavy metals in bottom mud using the values of 0.5 M-HCl-soluble metals in
a cluster analysis. This classification was in agreement with the pollution index de-
veloped by Nishida et al. (1980), which is based on the statistical concept that the
upper 10% of the probability distribution for a standard group would fall within
a critical region. Application of the 0.5 M-HCl-soluble data in this pollution index
should consider the aspect of "mobility" to some extent.
A sedimentological approach for an "ecological risk index" was introduced by
Hakanson (1980) and tested on 15 Swedish lakes representing a wide range in term
of size, pollution status, trophic status etc. These estimations - considered as a first
step in this field and undoubtedly open for many criticisms - are based on four
"requirements", which are determined in a relatively rapid, inexpensive and stan-
dardized manner from a limited number of sediment samples:
I. The concentration requirement compares data from the uppermost sediment
layers (minimum 5 sediment samples providing an even area cover of the lake/
basin) with a standardized set of natural background levels ofthe respective pol-
lutant.
2. The number requirement is built on the idea that for practical purposes only a
limited number of substances can be used, which are determined from sediment
samples as "total concentrations". In practice, the sum of selected contaminants
and their concentration factors (PCB, Hg, Cd, As, Cu, Pb, Cr and Zn) represent
the "standard degree of contamination".
3. The toxic requirement differentiates the various contaminants according to an
"abundance principle", i.e., saying that there exists a proportionality between
toxicity and rarity (determined from concentrations in soils, water, plants and
animals) and to their "sink-effect", i.e. their affinity to solid substrates, which
may be evaluated, for example, from the quotient between the natural back-
ground concentrations in freshwater and the pre-industrial reference values for
aquatic sediments. After a normalization process the "sedimentological toxic
factor" is calculated in the following sequence: Zn = 1 < Cr = 2 < Cu = Pb = 5
< As=10 < Cd=30 < Hg=PCB=40.
4. The sensitivity requirement indicates that different lakes/basins have different
sensitivities to the different toxic substances. In this context the "bioproduction
index" as determined from the data on nitrogen content and loss of ignition is
used as the critical parameter for the "toxic-response factor" of a certain con-
taminant. (Other effects, such as the influence of pH, Eh, salinity, etc., which
may have a considerable impact on the toxicity of various metals, are not yet
included in these expressions mainly due to the insufficient knowledge on many
of these parameters.) Except for As, all the selected metals seem to be related
to the degree of bioproductivity in a similar way, i.e., the negative effects tend
to increase with decreasing bioproductivity; this effect is assumed to be the
greatest for Hg and on the same order of magnitude for the other metals.
To quantitatively express the potential ecological risk of a given contaminant

in a given sedimentary environment, ths risk factor E~ is defined as follows
where T~ = the toxic-response factor for a given substance; and C} = the con-
tamination factor (see 1).
Five steps, ranging from low to very high, describe the potential ecological risk
factor (E~) for a given contaminant; the four-step potential ecological risk index
(RI) is the sum of the individual risk factors, i.e. of the selected contaminants, for
a certain lake/basin. The examples from Swedish lakes in Table 14 show that within
the different classes of risk indices (RI-values) there may be quite characteristic
"contamination profiles" with prevalences for certain pollutants. For example,
Lake Norra Barken is characterized by high potential ecological risk factors orig-
inating from elevated contents of PCB and Cd, while in Lake Varmslandssjon -
in the same group of very high risk index - the concentrations of Hg pose the pre-
dominant problems. It has been stressed by Hakanson (1980) that this approach
could at first indicate the overall pollution impact in a certain aquatic environment,
expressed by the RI-status, but then - even more important in the practice of pol-
lution control- the risk factors point to those substances to which the most atten-
tion should be paid.
Table 14. The potential ecological risk factors (Er'-values) and risk indices (RI-values) of the 15 Swedish lakes. All figures marked· are hypothetical ~
Lake RI Potential ecological risk factor (E:)
Moderate Low
E:>320 320>E:> 160 160>E:>80 80>E:>40 E:<40
Risk index (RI) very high RI > 600

Vasman 1,201 Hg Cd PCB*>Pb As* Cu>Zn>Cr
Norra Barken 813 PCB*>Cd Hg Pb>As* Zn>Cu>Cr
Ovre Hillen 741 Hg PCB* Cd As· Pb>Cu>Zn>Cr
Varmlandssjon 652 Hg Cd>PCB* As*>Pb>Cu>Zn>Cr
Stora Aspen 650 PCB* Cd>As* Hg>Pb>Cr Zn>Cu
Risk index (RI) considerable
300<RI<600
Vanern 511 Hg Cd>PCB* As* > Pb> Cu>Zn>Cr
Osterjon 415 PCB*>Hg Cd>As* Cr>Cu>Pb>Zn
Hjalmaren 380 PCB* Cd* Hg*>As*>Pb>Cu>Cr>Zn
Amanningen 370 PCB· Cd>Hg>As* Pb>Cr>Zn>Cu
Freden 365 PCB* Cd Hg As*>Cr>Pb=Cu=Zn
Malaren 326 PCB*>Hg Cd As*> Cu> Pb> Cr>Zn
Blacken 305 PCB* Cd>Hg As* > Cu > Cr > Pb > Zn
Risk index (RI) moderate
150<RI<300
Haggen 275 Cd PCB*>Hg As*> Pb>Cu >Zn > Cr f
Vattern 248 PCB* Cd*>Hg As* > Pb>Cu> Zn>Cr [
Bysjon 231 PCB* Hg>Cd As· > Pb> Cu =Zn> Cr g-
Risk index (RI) low RI < 150
o
f
...,
E:::
~
Sampling of interstitial waters 85
3.7 Early Diagenesis of Trace Metal Compounds in Sediments
The term "early diagenesis" denotes a large spectrum of mechanisms and effects
by which sedimentary constituents after deposition from the water column are
changed in their chemical form, involving new equilibrium between solid and their
dissolved species.
As a result different metal compounds are formed and also pore waters may
acquire high concentration of some trace metals. With regard to the processes af-
fecting metals in the hydrological cycle, the most relevant processes within the
broad spectrum of diagenetic processes are:
- the influence of deposited sediments on the composition of surface waters;
- the influence of deposited sediments and their interstitial waters on benthic life.
The more general aspects, common to all parts of the hydrological cycle will
be discussed in this chapter, the more specific details will be treated in the individ-
ual chapters dealing with separate parts of the hydrological cycle.
3.7.1 Sampling of Interstitial Waters
Several methods exists for sampling of pore waters:

- in situ methods,
- indirect methods.
Two different methods are used for the in situ collection of pore waters; the
dialysis and the direct-suction methods. With the dialysis method a half open con-
tainer, containing one or more dialysis bags, is pushed in the sediment, and left
there for some days (Mayer, 1976; Hesslein, 1976; Zimmerman et aI., 1978). The
attractive features are, among others, that no pore water flow is induced in the sed-
iment by sampling, and analysis of dissolved gases is possible. Disadvantages are
the disturbance of the sediment structure and the relative large size of the dialysis
samplers in comparison with the sediment layer structure (Brinckman et aI., 1982).
The direct suction method consists in principle of a tube with a number of inlets
which is pushed into the sediments, and the pore water is extracted by applying a
vacuum to the inlet ports (Sayles et aI., 1976; Zimmerman et aI., 1978; Rutgers van
der Loeff, 1980; Brinckman et aI., 1982). Indirect methods include the squeezing
of sediment cores in the laboratory (Siever, 1962; Hartmann, 1965; Manheim,
1966; Presley et aI., 1967) or centrifugation (Edmunds and Bath, 1976; Holdren et
aI., 1977). Recently a squeezer was modified to extract directly organo-tin com-
pounds from the pore waters (Salomons and Brinckman, unpublished results). In
the last 10-15 years the problems inherent to low level trace metal analysis and
sampling have been recognised for surface waters. However, for interstitial waters
the problems are aggravated. In addition to the presently well recognised problems
inherent to trace metal work, with sediments new additional problems are encoun-
tered. Interstitial waters are reduced, with generally high concentrations of reduced
manganese and iron. The introduction of even small amounts of oxygen during
sampling will result in a fast precipitation of iron hydroxides (Bray et al., 1973;
Troup et al., 1974). These iron hydroxides are able to adsorb trace metals and
phosphorus from solution. Also the temperature during squeezing may affect the
composition of the pore waters (Bischoff et al., 1970; Fanning and Pilson, 1971).
3.7.2 Diagenetic Environments
The most intensive early diagenesis reactions are usually found in sediments where
variations of the redox conditions take place. Characteristic examples have been
described both from the still "natural" sediments of the deep-sea and from highly
polluted environments - e.g. deposits of dredged materials. Examples of redox pro-
cesses - involving the elements C, N, 0, S, H, Fe, and Mn - are arranged in Fig. 47
(Stumm and Baccini, 1978) in the sequence of reactions observed in an aqueous
system at various Eh-values. Since the reactions considered (with the possible ex-
ception of the reduction of Mn0 2 and FeOOH) are biologically mediated, the
chemical reaction sequence is parallelled by an ecological succession of microor-
ganisms - aerobic heterotrophs, denitrifiers, fermentors, sulfate reducers, and
methane bacteria (Stumm and Morgan, 1981). Driving force of reduction process-
es is the decomposition of organic matter by nonphotosynthetic organisms,
thereby obtaining a source of energy for their metabolic needs. The energy yields
can be evaluated from a combination of processes given in Fig. 47; reduction pro-
cesses involving oxidation of organic matter follow the sequence "aerobic transpir-
ation" (A + L -29.9 Kcal/equiv.), "denitrification" (B + L -28.4 Kcal), "nitrate re-
duction" (D + L -19.6 Kcal), "sulfate reduction" (G + L -5.9 Kcal) and "methane
fermentation" (H + L -5.6 Kcal). In this succession the formation of soluble
Mn(II) by reduction of Mn(III,IV)-oxides parallels or follows nitrate reduction,
whereas the formation of soluble Fe(II) by reducing Fe(III)-oxides takes place near
the conditions for sulfate reduction; the combination of the latter constituents for
insoluble iron sulfides is characteristic for more strongly reducing environments
(see below).
The sedimentary environments corresponding to these processes are, respec-
tively: "Oxic", "post-oxic", "sulfidic", and "methanic" (Berner, 1980).
The sequence of events affecting these transformations can be evaluated both
from pore water analyses and from mineral concentrates of typical diagenetic
phases in short sediment cores.
The succession of typical pore water constituents has been depicted by Froelich
et al. (1979) from the study of deep-sea sediment cores from the eastern equatorial
Atlantic (Fig. 48): Oxygen is consumed in the uppermost deposits during decompo-
sition of organic matter. This process - which involves dissolution of carbonate -
will release ammonia, which is subsequently oxidized to nitrate; N0 3 diffuses down
to be denitrified in the lower part of the core.
Not far below the nitrate maximum organic carbon starts to become oxidized
by simultaneous reduction of Mn0 2 , upward diffusing Mn 2 + -ions will be precipi-
tated in the stronger oxidizing part of the sediment sequence, an observation made
at first by Lynn and Bonatti (1965) on pelagic sediments. Since Mn0 2 -reduction
involves a small but characteristic effect on carbonate precipitation, the concentra-
Diagenetic Environments 87
-0.5
I
oI
+0.5
I
+1.0
I
E H Volt
-10 -5 o +5 +10 +15 +20 pE
<I O 2 - Reduction IA
Reductions
< Denitrification IB
MnOV)oxlde - I
MOl) C
N03 Reduction 1D
< Femn oxide - Fe OlliE
Reduct•. org. Mat.1 F

I
<SO! Reduction IG
<CH Fermentation IHI
4
<
N2-NH 4 IJ
< H 2 Formation I K
-r- - -- -- -- I - - - f--
L I Oxldat. org. Mat.
~ 1Sulfide - SO 4
N pxldat of Fe Ol~
0INH; -NO a/
p lOxldat of Mn on)
al N2 -NO-
R 1O2 - Formation
Oxidations
I -5 o +5 +10 +15 +20 pE
oI 5
I
10
1
20
I
K cal.! equivalent
Fig. 47. Sequence of redox reaction. (Stumm and Bacchini, 1978)
tion of Mn2+ in pore fluids of both lacustrine and marine sediments may be con-
trolled by the solubility of Mn-carbonate rhodochrosite (Callender et ai., 1974;
Holdren et ai., 1975). Stair-step profiles of dissolved manganese, as observed by
Klinkhammer (1980) in sediment cores from the eastern Pacific (Fig.43), indicate
that the pore water chemistry of this element is more complex than simple oxida-
tion/reduction reactions predict and may suggest that Mn2+ is produced and con-
sumed in more than one zone. At greater sediment depth, the process of iron re-
duction to d Fe 2 + begins, thus indicating the persistence of iron oxides, but not
__ CONCENTRATION
:z::
.....
IL
W
o
Fig.48. Schematic succession of concentration profiles of

oxygen, nitrate, manganese and iron in pore waters from
deep-sea sediment cores. (Froelich et aI., 1979)
3000 75
50 4 Fe
:::::
~ 2000
~~. :::::
l
~ 50
i
~~
~... ~o ~5(.....
1000 ......"':':.:::
::::-:"7 r-.
0
¥ '.,~~
~. 1=..... ~c;.
o o
o 60 120 180 240 300 360 o 60 120 180 240 300 360
75 Cr 75 As
f,.--- ~
..,.".-"
0-
..- ,.
.~.~
::::: / "'-0"
~
"" _.... .....

01 50 50
:::L /~. :::L
i 25
"'. _0- ~
ej,....
/"
k";......
"...
n
i 25
11 1'-.0
o~ o ~\ .n. .nil.
o 60 120 180 240 300 360 o 60 120 180 240 300 360
75 30
DOC O-P04
_0
::::: :::::
o
.. .. •.--
a- l~
01 50 01 20
..
~;:::-",.
E E
I\~ G ",'
.~;,;;...o"
i
-~
25 .~
~- :-::
~- ,::..; P''-
~o" ~~ ~o
o o ~o
o 60 120 180 240 300 360 o 60 120 180 240 300 360
days days
Fig. 49. Changes in the composition of pore waters in original freshwater (0), brackish water (... ) and
marine (0) sediments dumped into a marine environment over a 360 day period. (Kerdijk and Salomons,
1983)
manganese oxides, under anoxic conditions (Berner, 1981). It has been inferred,
however, by Froelich et al. (1979) that only a relative small portion of Fe is avail-
able for the reduction processes - namely Fe in oxidic coatings, not in the silicate
compounds. As for the MnOz-reduction, the change from Fe 3 + to Fez + usually
involves small effect on the carbonate solubility. Under certain conditions,
Fe(OHh and FeC0 3 (siderite) might be expected to coexist (Jones and Bowser,
1978). For deep-sea sediments, however, Klinkhammer (1980) suggests that
MnC0 3 saturation is seldom reached in the upper 40 cm of the cores and the pore
waters are always undersaturated with respect to siderite.
In stronger reducing environments the metal distribution should be controlled
primarily by the formation of (highly insoluble) sulfides; at lower HzS concen-
trations, it should be controlled by the stability of carbonate and phosphate
phases. The early diagenetic reactions involving stronger reduction processes have
been studied experimentally in the field by Salomons and Kerdijk (1983). Three
large pits (80 x 30 x 6 m) were dug in the Rhine River estuary below the water table
and were filled with freshwater (Waalhaven), brackish water (Botlek) and marine
(Maasmond) sediment. The consolidation rate and the changes in pore water com-
position were studied over a one-year period (Fig. 49).
The changes in the concentrations with time can be divided into three cate-
gories:
I. The concentration shows a decrease; this is the case for sulfate in all cases, nickel
in the sediments from the Maasmond, and arsenic from the Botlek and Waal-
haven sediments.
2. The concentrations show a continuous increase; this is the case for o-P0 4 ,
NH 4 , silicon, chromium, BODs and DOC.
3. The concentrations show a maximum and then afterwards decrease; this is the
case for iron and manganese in all three examples, for copper from the Botlek
and Waalhaven sediments, and cadmium in the Maasmond sediments.
A rapid increase in iron and manganese concentrations is observed in the first
few weeks (Fig. 4ge); during this period no sulfate reduction takes place as is shown
by the constant levels of sulfate. The electron acceptors for the degradation of the
organic matter are apparently oxygen and nitrate. The low oxygen levels cause a
reduction of iron and manganese and a subsequent appearance ofFe2+ and Mnz+
in the pore waters. Sulfate concentrations start to decrease after about 2 months.
The decrease is most rapid in the sediments with the highest organic matter con-
tents (Botlek and Waalhaven) but is slower in the Maasmond sediment. With the
decrease in sulfate concentrations, and the production of sulfide, the iron and
manganese levels start to decrease, possibly as the result of the formation of sulfidic
minerals. Silicon and ortho-phosphorous concentrations show a continuous in-
crease. The phosphorous release probably takes place as a consequence of the
breakdown of the organic matter; about 10-20% of the total phosphorous in the
sediments is organically bound (Salomons and Gerritse, 1981). The behaviour of
arsenic differs strongly between the three sediment types. In the Botlek and Waal-
haven sediment the concentrations decrease continuously, whereas in Maasmond
sediments, the same type of behaviour as for iron is found, suggesting specific in-
teractions between these two elements. Chromium shows a continuous increase in
its concentrations, which is probably due to the reduction of Cr6 +-compounds to

more mobile Cr 3 +; no sulfides of chromium are stable under natural aquatic con-
ditions.
Iron and manganese solubility at the sediment/water interface was experimen-
tally studied in an in situ bell jar system by Balzer (1982). From the onset of anoxic
conditions to the precipitation of FeS a high release was observed of iron from the
sediments; this release could only take place during the short time from the onset
of reduction of the top layer of the sediments to the first precipitation of FeS, con-
firming the findings presented in Fig. 49. Contrary to iron, manganese being solu-
bilised in the reduced sediment layers can penetrate oxic strata due to slow oxida-
tion kinetics. The maximum concentration of dissolved manganese under anoxic
conditions is controlled by a solid phase with solubility properties similar to
MnC0 3 (rhodochrosite).
The last steps in the "Redox Titration" in biologically mediated "diagenetic
processes" are sulfate reduction and methane production. From a series of cores
collected from the White Oak River Estuary in North Carolina, Martens and
Goldhaber (1978) found that in the riverbed stretches under marine influence, sul-
fate reduction is a major process, owing to the availability of seawater sulfate; up-
stream, however, sulfate is rapidly exhausted and methane generation becomes
more important. Consistent with these trends is a decrease in sedimentary pyrite
in methane-rich sediments.
The early diagenetic environment is characterized by highly complex inter-
actions of metal ions, metal-organic complexes, sulfur compounds, organic and in-
organic solids. It is of primary importance to consider that dissolved organic mat-
ter can significantly alter the distribution between oxidized and reduced forms of
metals. The example of the interactions with iron are shown in Fig. 50 (after Theis
and Singer, 1974): (a) Organic compounds formed by decay of humic material are
capable of inhibiting the kinetics of Fe(II)oxidation; it is shown that the extent of
Fe(II) stabilization is a function of the concentration of organic material. (b)
Complexation ofFe 2 + by organic substances competes with the oxidation reaction
of Fe(II), by which the thermodynamically stable phases of Fe(II) should be
formed. (c) Organics are also capable of complexing oxidized forms of metals,
thereby increasing their apparent solubility beyond the limitations imposed by the
solubility product, and also enhancing their colloidal stability (Singer, 1977).
Another important interaction of metals in the early diagenetic environment is
with the various sulfur species. The oxidation of FeS 2 can be considered as the
starting point of several reactions involved (presented here without the exact mech-
anistic steps; Singer and Stumm, 1970):
1. Initiator reaction
2. Propagation cycle
F e2+ (aq) + O 2 (aq) bacteri') F e3+ (aq)
Fe3+(aq)+FeS2(aq) _____ Fe2 +(aq)+SOi- +H+(aq) (acidity)
FelUl- Org ~ Fe(lIIl- Org _ Fe 2+ + Oxidized Org
... !lorg
-.....
..!
Fe 2+
.=-e
~
Fe(OHI 3
Oxidation - reduction
Fig. 50. Diagrammatic description of the behaviour of iron in the presence of organic matter (after Theis
and Singer, 1974)
Fe(IILOrg~ +3
02/ _Fe
Fe'~o.g ~ 1)OH
~oxidized Org
Fe (OH)3
Fig. 51. Model of geochemical leaching of FeS 2 as it may take place in a tailings pile (after Andrews,
1977)
The sulfidic component is oxidized to sulfate, where by H + is generated and

Fe 2 + -ions are released. Once the reaction has been initiated, a cycle is established
whereby Fe 2 + is oxidized to Fe3+; the ferric ion is capable of oxidizing pyrite-
thereby taking over the initial role of oxygen - to produce additional Fe 2 + and
acidity. For each mole of iron sulfide oxidized, four moles of acid are produced.
Fig. 51 (after Andrews, 1977) shows the interactions of sulfidic species with the
iron species in the systems affected by organic matter, mainly designed to demon-
strate the possible pathway of acid mine drainage (Chap. 5.4.6.). The characteristic
process is the reduction of the Me3+ by oxidation of additional MeS 2 (s), in the
presence of H 2 0 but without need of O 2 as an initiation agent (reaction "d"). Com-
pletion of this step, allows initiation of a cycling between Fe 2 +, Fe 3 + and FeS 2 (s).
It has been demonstrated that with FeS 2 (pyrite or marcasite) the rate determining
Table 15. Geochemical classification of sedimentary (early diagenetic) environments. (Berner, 1981)
Environment Characteristic phases
Hematite (Fe203);goethite (FeOOH);

Mn02-type minerals, no organic matter
II. Anoxic (Co, ~ 10 - 6)
A. Sulfidic (CB,s> 10- 6 ) Pyrite, marcasite (FeS2); rhodochrosite (MnC0 3);
alabandite (MnS); organic matter
B. Nonsulfidic (CB,s < 10- 6)
1. Post-oxic Glauconite and other Fe +2 - Fe+ 3 - silicates (also siderite,
vivianite, rhorlochrosite); no sulfide minerals;
minor organic matter
2. Methanic Siderite (FeC0 3); vivianite (Fe3(P04h, 8H 20);
rhodochrosite; earlier formed sulfide minerals; organic
matter
step in this system is the oxidation of ferrous ( + 2) iron to ferric ( + 3). In an abiotic
system, the oxidation of ferrous iron is roughly a factor of 10- 6 slower than in a
system mediated by bacteria (Singer and Stumm, 1970). Methods of controlling the
problems of acidic mine drainage include thermodynamic measures (elimination of
oxygen and the maintenance of reducing conditions), kinetic effects - the latter
methods clearly having the most advantages - and especially the application of
bactericides.
A scheme for the recognition and distinction of early diagenetic environments
has been proposed by Berner (1981) on the basis of typical mineral associations
(Table 15).
Mn0 2 -type minerals constitute a good indicator of truly oxic conditions. Post-
oxic (weakly reducing) conditions, involving successively the reduction of nitrate,
manganese and iron, are characterized by the presence of Fe 2 + Fe 3 + -silicates such
as glauconite, the absence of sulfide minerals and only minor contents of organic
matter (authigenic Fe2+ -Fe3+ -silicates, siderite and vivianite are stable neither in
the oxic nor in the sulfidic environments). Sulfidic and methanic (both strongly re-
ducing) environments typically contain significant amounts of organic matter, in
addition to either newly formed or pre-existing (from former diagenetic processes)
sulfidic iron minerals such as pyrite, mackinawite and greigite. Methane, vivianite
and siderite form more readily in non-marine sediments than in marine deposits
(Emerson and Widmer, 1978), due to an initially lower sulfate concentration in the
water. The mathematical modelling of diagenetic processes in sediments has been
given by Berner (1980).
3.7.3 Diagenetic Mobilization of Trace Metals
The behaviour of iron and manganese in pore waters is fairly well known (Berner,
1980; Presley and Trefry, 1980). The manganese profiles reported in the literature
fall into the four categories shown in Fig. 52 (Presley and Trefry, 1980).
Diagenetic Mobilization of Trace Metals 93
Fig. 52. Typical interstitial Mn I

profiles in sediments. (Presley and
Trefry, 1980)
SEA WATER
SEDIMENT
:m:
Case I is observed in a stratified water column with anoxic bottom waters, as

is the case for the Black Sea and some lakes (see Chap. 5.4.5). Here, iron and
manganese may be reduced and solubilized in the water column. Case II represents
oxic waters overlying an anoxic sediment, maximum metal remobilization occurs
at the sediment-water interface; in case III, mildly reducing conditions allow the
development of a well defined oxic zone, where-in remobilised metals may be
trapped and greatly concentrated over natural levels. Well known is the increase
in manganese and iron in the top layer of these sediments (Berner, 1980; Presley
and Trefry, 1980; Sundby, 1981) and phosphorus (Salomons and Gerritse, 1981).
Robbins and Callender (1975) showed that for Lake Michigan sediments, the neg-
ative interstitial manganese gradient below the AB horizon may be controlled by
the precipitation of rhodochrosite (MnC0 3 ). Case IV is an example of a slowly ac-
cumulating sediment where a thick oxidised zone occurs with possible discrete
anoxic segments.
The type of mechanisms involved in diagenetic mobilization of trace metals is
not yet fully clear. Experimental data of Lu and Chen (1977) on the migration of
trace metals between the interface of seawater and polluted surface sediments sug-
gest that under reducing conditions the concentrations of trace metals in the inter-
stitial waters are controlled by sulfide complexes for Cd, Hg and Pb, by organic
complexes for Fe and Ni, chloride complexes for Mn, and by hydroxide complexes
for Cr. The high values measured for dissolved copper in comparison with the cal-
culated values (see Hallberg, 1973; 1974; Elderfield and Hepworth, 1975; Emerson,
1976; Lyons et ai., 1980) may be explained by slow precipitation or nucleation, or
may be due to the presence of humic-copper complexes (see below). Theoretical
Fig. 53. Erfccts of pH and redox
64 potentia l on exchangeable d-I09
in Mississippi River sedimen t su -
pension . (after Gambrell et aI. ,
1977)
48
'#.
:;; 32
...
ell
ell
::»
o
....
ell
a:
~ 16
a"l
<::>
calculations on trace metal complexes in anoxic marine pore waters showed the im-
portance of bisulfide and polysulfide complexes as chief agents for trace metal sol-
ubility (Gardner, 1973; Boulegue, 1983; Emerson et aI., 1983).
In contaminated estuarine sediments of Bellingham Bay, Washington, Bothner
et ai. (1980) observed interstitial mercury concentrations up to 3.8 J.lg/l, from 16 to
126 times higher than the concentrations in overlying seawater. This is similar to
the enrichment of mercury in contaminated anoxic sediments of Mobile Bay, Ala-
bama. It has been suggested that, in general, higher Hg fluxes were associated with
low oxygen or reducing conditions in the overlying seawater (Bothner et aI., 1980)
and the chemical form of dissolved mercury in such sediments has been calculated
to be predominantly (98%) HgS2 (Lu and Chen, 1977). However, other complexes
of mercury with polysulfides and dissolved organic matter have also been postu-
lated for this type of environment (Andren and Harriss, 1975; Bothner et aI., 1980;
Elderfield, 1981; see below).
Holmes et ai. (1974) reported that the cadmium introduced into Corpus Christi
Bay Harbour from industrial effluents in the summer when the harbour water was
stagnant reach the surface sediment with the sulfide ions and precipitates as CdS;
in the winter months, however, the increased flow of oxygen-rich water into the bay
result in the desorption of some of the precipitated metal.
The pH-redox dependencies of exchangeable cadmium were studied ex-
perimentally by Gambrell et ai. (1977) with Mississippi River sediment (Fig. 53).
A much greater proportion of the incubated cadmium isotope 109-Cd was re-
covered in the readily bioavailable form than for any other potentially toxic heavy
metal studied.
It is suggested that considerable cadmium release to relatively mobile forms
may occur as cadmium-contaminated sediment is transported from a near-neutral
pH, reducing environment to a moderately acid, oxidizing environment. Under
these conditions, cadmium levels of subsurface drainage water from upland dis-
posal of dredged materials may be increased, and cadmium availability to plants
growing on the material enhanced.
Significant enrichment of trace metals in pore waters of sediment samples from
Southern California basin, Saanich Inlet (British Columbia) and Loch Fyne (Scot-
land) has been explained by complexation effects with organic substances (Brooks
et aI., 1968; Presley et aI., 1972; Duchart et aI., 1973). In a comparative investiga-
tion Nissenbaum and Swaine (1976) found that with the exception of Fe, Ni, and
Co, which occur mostly as sulfides under anaerobic conditions, the elements con-
centrated in the interstitial solutions are those which are also enriched in sedimen-
tary humates. The transport of dissolved metals in the pore waters is, therefore,
strongly influenced by the vertical gradient of dissolved humic substances (Krom
and Sholkovitz, 1978).
Recent data of Elderfield (1981) from anoxic sediments of Narragansett Bay
R.I. indicate that approx. 80% of the total Fe and Cu, approx. 40% of the total
Ni, 10% of the total Mn were organically bound in the interstitial water of surface
sediments.
The concentrations of trace elements copper and iron in pore waters of sedi-
ments from a salt marsh along the Delaware estuary have been found to be con-
trolled mainly by sulfide formation; calculations show that copper is strongly com-
plexed probably with organo-sulfur ligands, whereas iron might be complexed as
such sulfur species to a much lesser extent than copper (Boulegue et aI., 1982).
While microprobe studies of zinc in anoxic sediments performed by Elderfie1d et
aI. (1979) have suggested that it is more likely for metals to be scavenged by Fe sul-
fides than to form discrete sulfide minerals, more recent investigations by Luther
et., 1980 on sediments of Newark Bay, New Jersey, using scanning electron micros-
copy with energy dispersive X-ray analysis evidenced zinc sulfide minerals; this was
the first report of framboidal sulfide minerals which contain a cation other than
iron as the major constituent in recent estuarine sediments. Nickel and manganese
however, were incorporated into the structure of pyrite and iron mono sulfide crys-
tals, respectively (Luther et aI., 1980).
Data of Hart and Davies (1977) indicate that the major portion of cadmium
in the interstitial water from a sediment sample of an urban creek at Melbourne,
Australia, was associated with colloidal labile species and more strongly bound
complexes; zinc and lead to the major proportion was associated with the colloidal
phase, 20% in labile forms and 10% in more tightly bound (organic) forms. Water
samples from the Woronora River of New South Wales (Australia) by Batley and
Giles (1980) including speciation studies, indicate an increasing solubility of bound
species of lead and copper in the anoxic interstitial water (mangrove sediment)
compared with oxic surface water; this should be the result of organic complexa-
tion, with which the increase in "labile" metal species is also associated. Character-
istic differences in the behaviour of copper and zinc are also observed in ex-
periments on sand filters by Forstner et al. (1979). The sand filter columns were
fed with river water containing added doses of humic acids and dissolved copper
and zinc. After 10 hours the copper concentrations in the filter outlet had increased
significantly, whereas no increase in the zinc concentrations were observed over the
whole 24-hours measuring period. Anodic stripping voltametry determinations
showed that zinc in the inflowing solution is basically labile bound, whereas copper
was in a more stable association with the complexing (organic) ligands. The labile-
bound zinc strongly interacts with the FejMn hydroxides of the filter particles,
whereas the more stable organic-copper complexes are only partially affected by
physico-chemical interactions with the filter material. Most of the organically-as-
sociated metals are "colloidal", equivalent to the high molecular weight organics,
presumably; if this colloidal material is genetically related to the dissolved organic
fraction, it has been proposed that it is dear that the alteration of the latter to the
former takes place very rapidly during diagenesis (Elderfield, 1981). It is possible
that this rapid coagulation is promoted by very high concentrations of interstitial
iron, as shown experimentally by Picard and Felbeck (1976).
Since the larger proportion of the metals was found to be associated with high
molecular weight organic material it appears, on balance, that diffusion of organi-
cally-associated metals will not be a major factor in metal transport; only in
situations where transport is by biological "advection" and not diffusion, metal-
organic complexes may be very important (Elderfield, 1981). Flux calculations
from pore water concentration gradients suggest that benthic fluxes of nickel, cad-
mium, and copper are close to zero or are negative, due to the above-mentioned
behaviour of metal scavenging by sulfides (Elderfield, 1981 b).
The studies carried out on metal behaviour in pore waters show the importance
of both complexation by organic matter and precipitation as sulfidic minerals on
pE
Sediment I Water interface
CI
.SCI)
Us::
:::10
"gN Fig. 54. Schematic presentation of the cycling che-
II:
lated heavy metals above the redoxcline (Hall-
berg, 1982, modified after Hallberg, 1972)
their behaviour. Hallberg (1982) has discussed in detail the metal cycling in the top
layer of sediments as being the result of a competition of trace metal complexation
by organic matter and precipitation as sulfidic minerals, stressing the importance
of trace metals in pore waters as a dynamic system. As sediments accumulate, the
oxidizing surface layer is buried and gradually becomes deficient in oxygen due to
oxygen consumption and ultimately H 2 S is produced by sulfate reducing bacteria,
as is shown by a decrease in sulfate concentrations with time (see Fig. 54). The H 2 S
moves upward and encounters the oxidised layer as a consequence the metal com-
pounds existing as hydroxides, oxyhydroxides and various carbonates have a lower
stability and are redissolved (Hallberg, 1982). Furthermore, the microbiological
decomposition of organic matter produced intermediate compounds (as is evident
from the increase in DOC levels in the pore waters Fig. 49), which may act as metal
chelators. If a metal chelating compound has an upward transport rate which is
greater than that of the H 2 S, chelated metal will escape the H 2 S-zone. Thus a min-
eral cycle exists above the redoxcline where the chela ted metals are transported up-
wards (Fig. 54).
In this way the complexed metals escape from being trapped and fixed as solid
sulfide compounds and are concentrated in the uppermost layers. Sedimentation
causes an upward movement of the enriched metal layer: the metals climb with the
accumulation of sediments (Hallberg, 1982). Metals differ in their ability to chelate
so that the more easily chela ted ones tend to becom e enriched in the uppermost
layer. In such a dynamic system, the metals are chelated and/or complexed before
they meet the sulfide environment.
This dynamic approach can also explain the enrichment of iron, manganese
and phosphorus in the oxidised surface layer of marine sediments (Salomons and
Gerritse (1981). High concentrations of iron, manganese and phosphorus are
found in oxidised surface layers of marine sediments in the North Sea compared
with the underlying reduced layers (Table 16).
High dissolved iron, manganese and phosphorus concentrations are observed
in the pore waters of the reduced layer, these migrate upward as a consequence of
concentration gradients between the pore waters and the surface waters, a process
enhanced by consolidation. When the upward migration metals and phosphorus
encounter the oxygen-rich surface layer, they are reprecipitated. After renewed de-
position, the former surface layer becomes reduced and mobilization of Fe, Mn,
and P takes place. The released trace metals start migrating upward again and be-
come precipitated in the new surface layer. This process results in an upward mi-
gration of an enriched surface layer. Also adsorption of upward migrating chela ted
Table 16. The concentrations of Fe, Mn and P in surface layers (upper

2 mm) and in the underlying reduced layer (2-10 cm) in marine sediments
from the North Sea (Salomons and Gerritse, 1981)
Phosphorus Manganese
/!g/g /!g/g
Surface layer \,720± 140 25,900±600 1,230±220

Reduced layer 660± 90 21,120±470 580± 45
trace metals on the manganese and iron hydroxides in the surface layers seems
likely. Such an oxidised surface layer, therefore, may act as chemical barrier
against the upward flow of some trace metals and phosphorus to surface waters.
The difference in metal chelating ability of copper and zinc was used by Hall-
berg (1974) to trace anoxic and oxic conditions in recent and fossil sediments.
Under anoxic conditions the more easily chela ted copper may escape the sediments
to the surface waters. In this way the Cu/Zn will differ between sediments deposited
under oxidizing from sediments deposited under anoxic conditions in the bottom
waters.
It has been stressed by Beveridge et al. (1983) that a significant portion of the
organic matter of aquatic (both marine and freshwater) sediments consists of small
colloidial aggregates which are composed of highly cross-linked heteropolymeric
materials of biological origin and are very resistant to degradation. These most du-
rable polymeric networks - partly of bacterial origin - would interact with and se-
quester dilute metals from the aqueous phase, thereby concentration metals into
the sediment. Within a series of microbial or chemical transformations, sedimen-
tary diagenesis eventually would either recycle the metals to the overlying water
column or immobilize them in authigenetic mineral phases. In an experimental
series to simulate low-temperature sediment diagenesis of metal-loaded cells (using
an admixture of synthetic inorganic sediment which consists of calcium carbonate,
crystalline quartz, as well as of elemental sulfur and crystalline magnetite as redox
buffers) Beveridge et al. (1983) found the formation of a mixed assemblage of crys-
talline metal phosphates, metal sulfides, and polymeric, metal-complexed, organic
residues. Calcite raised the pH of the fluid phase of the sediment, which influenced
phosphate mineralization and inhibited metal sulfide genesis. This is the first in-
stance that metal sulfide framboid production has been definitely correlated to bi-
ological material.
The sometimes conflicting opinions on trace metal behaviour in pore waters re-
ported in the literature and the lack of a coherent set of data (e.g. analysis on both
solid and liquid phases including speciation) makes it difficult at present to present
a clear picture of the processes affecting trace metal concentrations in pore waters
and of the processes at the sediment-water interface.
However, the recognition of pore waters as a key factor in the geochemical cyc-
ling of trace metals in oceans, lakes, estuaries and their importance for the assess-
ment of dumping strategies will undountedly increase research in this area.
4.1 Introduction
The influence of the atmospheric deposition on trace metal concentrations is found

in all parts of the hydrological cycle (e.g. soils, rivers, lakes, estuaries and the
ocean). In this respect the atmosphere plays a unique role. Additionally, transition
metals act as catalyst in the atmosphere (e.g. the oxidation of sulfur dioxide)
(Graedel and Weschler, 1981; Lindberg, 1981). Compared with other parts of the
hydrological cycle, metals in the atmosphere have a short residence time, estimated
to vary between days and weeks (Hidy, 1973). However, within this short time span,
these trace metals are able to trave11arge distances.
Several sources contribute to atmospheric trace metals. Most of these sources,
like forest fires, windblown dust, vegetation and sea salt sprays, influence the com-
position of the lower troposphere. The upper boundary of the troposphere, the tro-
popause, is found at 11-17 km above the earth's surface. Volcanic eruptions may
inject particulate metals through the tropopause boundary to the stratosphere.
Particles in the stratosphere will be subject to a global distribution, whereas the
particles in the troposphere will be transported in the zonal circulation before re-
turning to the earth's surface (Cawse, 1982). Compilations on the amounts of trace
metals brought into the atmosphere have been made by Nriagu (1979), Lantzy and
Mackenzie (1979) and Weisel (1981). Some estimates of anthropogenic and natural
sources of trace metals emitted to the atmosphere are presented in Table 17. The
data are order of magnitude estimates, since some are based on broad assumptions
and/or isolated literature data which have been extrapolated to global emissions.
Nevertheless these data provide an estimate of the relative importance of the vari-
ous sources.
Table 17. Atmospheric emissions of trace metals (x JOY g(y). Data are based on Nriagu (1979), except
for the Zn, Pb and Cd inputs from seaspray. (Weisel, 1981)
Natural sources Industrial

sources
Metal Windblown Forest Volcanogenic Vegetation Seasalt
dust fires particles sprays
Cd 0.1 0.012 0.52 0.2 0.4 7.3

Cu 12 0.3 3.6 2.5 0.08 56
Ni 20 0.6 3.8 1.6 0.04 47
Pb 16 0.5 6.4 1.6 5 449
Zn 25 2.1 7.0 9.4 JO 314
4.2 Natural and Anthropogenic Emissions of Trace Metals
It is known that the atmosphere has been contaminated with lead since about 4500
BP (Fig. 55) when technology for smelting lead sulfide ores and cupellation of silver
from lead were developed in Southwest Asia (Patterson, 1971). Until 2600 BP the
annual production oflead was about 200 tons/year, while it rose to 10,000 tons af-
ter the discovery of the use of silver coinage in the eastern region of the Mediter-
ranean (Patterson, 1972). During the period 2100 to 1800 BP, the Romans mined
and smelted lead at a rate of about 80,000 tons/year and during this period the con-
centrations in the atmosphere probably increased about 5-fold above natural levels
(Patterson, 1972). Around 1940 there was a sharp increase in atmospheric lead con-
centrations due to lead emissions from automobiles (Murozimi et aI., 1969). The
present input of lead into the atmosphere is estimated at 400,000 tons/yr (Ng and
Patterson 1981).
There are less detailed historical records available for other trace metals and
hence other methods have been employed to assess the anthropogenic concen-
trations in the atmosphere. Three approaches have been reviewed by Galloway et
aI. (1980, 1982).
1. Compare the actual metal emission rates of natural and anthropogenic process-
es. This is the approach which has been used by Lantzy and Mackenzie (1979).
10 7
6 Spanish Production
10
of Silver /
in New World
"i:
~·i
5
0 10
iI:
.5
":s 10 4
.'l\\
./ t. ./.........
I " It
ell
g Industrial
"..a.
Revolution
/
0 Exhaustion S.·I
.
:0. 10 3
of Roman
lead Mines
I ve~
~roductlon
In Germany
"-
.a
·--t
II.
. 10
III
c: 2
0
Discovery ./ Use of
of /" coinage
cupell/tion•
1
10 ~ Rise and Fall Roman Republic
• of Athens \ and Empire
10° ------J H I... I ~I

5000 4000 3000 2000 1000 o
Corrected C14( solar) Years before Present
Fig. 55. Historical development in the use oflead during the last 5500 years (Settle and Patterson, 1980)
Natural and Anthropogenic Emissions of Trace Metals 101
Table 18. Natural and anthropogenic emissions of trace metals in the atmosphere and
the mobilization factor. Based on Lantzy and Mackenzie (1979) and Galloway et al.
(1980). The values in brackets refer to vapour emissions of the volatile species (Ag,
Hg and Se) from land and sea (The data on lead are from Ng and Patterson, 1981)
Emissions (l08 g/yr) Mobilization factor
Natural anthropogenic
Ag 0.6 50 83
As 28 (210) 780 3.3
Cd 2.9 55 19
Co 70 50 0.71
Cr 580 940 1.6
Cu 190 2600 13
Hg 0.4 (250) 110 0.44
Mn 6100 3200 0.53
Mo 11 510 45
Ni 280 980 3.5
Pb 40 4000 100
Sb 9.8 380 39
Se 4.1 (30) 140 4.7
Sn 52 430 8.3
V 650 2100 3.2
Zn 360 8400 23
2. Compare the ratios of atmospheric concentrations to those in the natural sour-

ces contributing to it. This approach was used by Duce et al. (1975) in compar-
ing the metal concentrations in the atmposphere with those in crustal material.
3. Determine the temporal trend in the composition of metals in atmospheric de-
position. One of these techniques is the use of lake sediments as a historical re-
cord for trace metal emissions (see also Chap. 3.6.2).
In Table 18 natural (soil dust, volcanic dust and volcanic emanation fluxes) and
anthropogenic emission rates are presented. Also given is the Mobilization Factor,
which is defined as the ratio of the flux from anthropogenic sources to that from
natural sources.
The second approach is the comparison of trace metals in the atmosphere with
those in one of its natural sources: crustal material. In this comparison aluminium
is used as a reference element. The enrichment factor EF (crust) is defined as:
EF (crust) = (X/ Al)air/(X/ AI)crust
where (X/Al)air and (X/AI)crust refer, respectively to the ratio of the concen-
trations of metal X to that of Al in the atmosphere and in average crustal material.
Data for EF (crust) values for Bermuda and Eniwetok atoll are presented in Fig.
56.
Values of EF (crust) near 1 suggest that continental weathering is likely its
source in the particles (Duceet aI., 1975; Rahn, 1976). Values of EF (crust) larger
than about 4 are called (anomalously) enriched elements and have some other
source than crustal weathering, which may be anthropogenic.
104
DNorth Atlantic Westerlies
o South Pole
103
102
~v ~~
to
"'-u'" 101
B it'"
<OJ
10° ---tr-- :~----tt---------------------------------

Mn
10"1
Element
Fig. 56. EF (crust) values for metals in the atmosphere at Bermuda and the South Pole (Duce ct aI., 1975)
Table 19. Expected enrichment for trace metals III the atmosphere and III atmospheric
deposition. Galloway et al. (1982)
Techniques Expected enrichment in atmospheric deposition
Low Moderate Large No data
Mobilization CO,Mn, As, Cr, As, Cd,Cu, Be, Te,

factor" Hg Ni, Se, Mo, Pb, Sb, 11
V Se, Sn, Zn
Enrichment Co,Mn, Cr, V Cd, Cu, Pb, Ag,As,
factor Ni Sb, Se, Zn Be, Hg,
Mo, Sn,
Te, TI
Historical Co,Mn, Cr, V, As, Cd, Pb, Mo, Sn,
factor b Ni,Be CU,As, Sb Te, TI,
Zn, Se Hg
Note: Low = < 2 x enrichment; moderate = 2 to 4 x; large = >4 x.

a The MF is based on the comparison of global emission rates. On a reduced scale, such as
for the United States, the relative order will change; for example, Hg, As and Se would be
expected to be in categories of higher enrichment
b Relative degrees of enrichment taken from Heit et al. (1981) and Galloway and Likens (1979)
However, several other sources apart from anthropogenic inputs and crustal
material contribute to the atmospheric trace metals. These include low temperature
volatilization. Particles released by vegetation and coal and fly ash have relative
concentrations of trace metals similar to average crustal material (Bertine and
Goldberg, 1971). Enrichment factors must therefore be used cautiously in attempts
to ascertain atmospheric trace metal sources (Duce et aI., 1976).
Atmospheric Particles 103
Historical records of atmospheric pollution are found in dated sediment cores

from remote lakes, and in ice cores from the Arctic and from Antarctica.
A number of studies have shown considerable increases in metal concentrations
in these lake sediments compared with background values (see Chap. 3.6.2; 5.4.3)
It should be noted, however, that part of the increase may be due to increases in
weathering as a consequence of increased input of acid from the atmosphere (acid
rain) and deforestation.
A comparison of the enrichment of atmospheric trace metals as derived from
the mobilization factor, the crustal enrichment factor, and dated lake sediments
has been made by Galloway et al (1982). Their results are presented in Table 19.
The results show that the elements Ag, Cd, Cu, Pb, Se, V, As and Cr should
show elevated concentrations in the atmosphere. For the eastern United States the
rates of atmospheric deposition of Ag, Cd, Cu, Pb, Sb, V and Zn are strongly in-
fluenced, if not controlled by anthropogenic processes (Galloway et aI., 1980).
4.3 Atmospheric Particles
Most metals in the atmosphere are present in association with particles; an excep-
tion is mercury which is highly volatile and perhaps some volatile methylated spe-
cies of certain trace metals. The behaviour of trace metals in the atmosphere there-
fore is closely related to the behaviour of the atmospheric aerosol. Estimates on
the amount of particles introduced into the atmosphere are presented in Table 20.
Based on the size and nature of particles the following terminology is in use
(Cawse, 1982). Coarse range particles (diameter, d> 1 !lm) produced by disintegra-
tion of minerals or from resuspension of soil particles are called dust. Fine particles
formed from the gas phase by condensation are termed "smoke" and "fume". In
the case of fume the particles are generally from 0.01 to 1 !lm diameter, and are
often agglomerates of smaller particles. Suspended particulate matter < 15 !lm dia-
meter is usually defined as smoke. Mists (d > 40 !lm) and fogs (d = 5-40 !lm) are liq-
uid droplets. Finally, small hygroscopic particles, or condensation nuclei, are clas-
sified into Aitken nuclei (d<0.2 !lm), large (d=0.2- 2 !lm), and giant (d>2 !lm)
types (Cawsc, 1982).
Table 20. Sources of particulates in the at-

mosphere (Nriagu, 1979, except industrial
activities (Lantzy and Mackenzie, 1979))
x 10 12 g/year
Windblown dust 5000

Forest fires 36
Volcanic particles 10
Vegetation 75
Seasalt sprays 1000
Industrial activities 200
r I I I
10- 2 10- 1 10° 10 1 10 2
--+ radius, I'
-
10 5
/ , ,-- .......
1/ ...........
r\."~"
10·
10 3
~
/ I
continental aerosols
I
10 2
",
! maritime aerosols
'~'"
!
i ;
10 1
II
u 10° !;?
-~
u
2i -1
:> 10
u
sea-salt particles
~
a. 10- 2
~
"
III
5!
\
'a
10- 3
"
K "
Z
ct
\ "\
10-·
air electricity
A
10- 5
1\
large Ions
\
10- 8
."'. . " -<

10 -7
.
sIze range
~m~~~'~ haze particle/'(' I
10- 8 ~
for cloud physics

condensation nuclei
Approximate size ranges of predominant chemical constituents
continental 50.-, NH.+, Ca++ un soluble mineral

aerosols <{ organic components particles from soil
maritime continental
aerosols <{ aerosols? sea salt
Fig. 57. The average size distribution of aerosols over the continents and oceans and of seasalt particles
(Junge, 1974)
The size-distribution of particles in the atmosphere can be approximated with

a log-normal distribution
The average size distribution of aerosols collected over the continents and over
the oceans, and the size distribution of seasalt particles are presented in Fig. 57.
The total number of particles is dominated by those present in the fractions less
than 0.1 11m radius, whereas the total mass by those larger than 0.1 11m radius. Sea-
salt is the major component of aerosol particles over the ocean, but decreases over
the continents, where it is replaced by sulfate, calcium, ammonium and other ions
(Junge, 1974).
Chemical Conversion
r::::I of Gases to low
T-
Volatility Vapors
Condensation
Wind blown Dust

+
Emissions
+
Sea Spray
+
Volcanos
+
Plant Particles
.002
Particle Diameter , micrometer
TRANSIENT NUCLEI OR ACCUMULATION MECHANICALL Y GENERATED

--ALTKEN NUCLEI RANGE ~I'" RANGE ---i·~I""''''- AEROSOL RANGE -
..." ' f - - - - - - - - - FINE .. - - - COARSE PARTICLES _

PARTICLES ----------,J.*I~
Fig. 58. Schematic diagram of processes involved in the formation of the three modes of atmospheric
particles and an example of a surface area distribution of the particles (Whitby 1977)
The curve shown in Fig. 57, which was used quite extensively before the 1970's,
masks the true structure of aerosols, because it erroneously suggests that the whole
distribution can be plotted as a continuous function (Whitby, 1977). In fact two or
three modes are usually observed in the mass or volume distribution ratio (for a
review see Whitby, 1977). The approximate range of these three particle modes and
the processes leading to their formation are summarised in Fig. 58. The physical
separation of the fine and the coarse mode originates because condensation pro-
cesses produce fine particles while mechanical processes produce mostly coarse
particles. The fine particle mode can be subdivided into a nuclei mode and an ac-
cumulation mode.
Table 21. Summary of processes acting upon the contaminants present in particle size classes of
airborne particulates (Hosker and Lindberg, 1982)
Size range (diameter) Properties
<0.3 11m Nucleus mode:

Condensation nuclei, secondary particles. Transported like gas molecules,
and adhere to surfaces. Movement is independent of solubility or phase.
Controlling forces are Brownian motion and phoretic effects. Gas transfer
can be modified by attachment to these small particles.
The nucleus mode is maintained by the dynamic equilibrium by particle
production through condensation processes and particle removal by
adsorption on larger particles. It is important in urban and near-urban
areas.
0.3 to 3.0 11m Accumulation mode:
Coagulated small particles such as fly ash. Momentum of particles
relative to both gas motion and gravitational settling must be considered.
Brownian motion and phoretic effects continue to be important. Both
soluble and insoluble types adhere to surfaces
>3.0 11m Coarse particle mode:
Large dust particles. Gravitational settling and particle momentum are
important. Re-entrainment possibly significant.
The small particles are formed by condensation processes. However the rate of
transfer from smaller to larger particles by coagulation decreases sharply for par-
ticles larger than about 0.5 !lm diameter. To transfer the mass present in the accu-
mulation mode to the coarse particle mode would require weeks (Whitby, 1977).
Thus for the usual few days residence time of fine particles in the atmosphere, the
accumulation mode particles are not a major source of particles in the coarse mode.
These particles are generated in a different way; they consist of wind blown dust,
primary emissions like fly ash, sea spray, volcanic dust and particles released by
vegetation (Fig. 58). As a consequence the nuclei mode of particles is important
for urban and near-urban areas. In aged aerosols found over rural and remote
areas, the accumulation mode and the coarse mode dominate. A summary of the
various processes acting upon the contaminants in the various particle size classes
is given in Table 21.
The bulk composition of the aerosol collected within different particle size
ranges is variable, for example the composition of a rural aerosol as shown in Fig. 59.
The soil related elements dominate in the two larger size ranges and amount
to more than 50% of the smallest size range. Flocchini et al. (1981) also observed
seasonal variations in the soil component concentration, being about three times
higher in summer than in the winter. No distinct seasonal pattern was observed in
the concentrations of sulfur, which is dominant in the small particle size fraction.
The mineralogy of urban aerosols from the S1. Louis area (USA) has been stud-
ied using X-ray diffraction analysis (O'Conner and laklevic 1981). The most fre-
quently observed component in the fine fraction «2.4 !lm) were (NH 4hS04 and
the double salts (NH 4hS04' PbS0 4 and 3 (NH4)2S04' H 2S0 4, The major com-
ponents they observed in the coarse fraction (2.4-20 !lm) were the minerals calcite
and quartz, reflecting the composition of surface rocks in the region.
15 - 3.5 Micrometers 3.5 - 0.5 Micrometers 0.5 - 0.1 Micrometers

2 1
4
2
3
5 5 4
m Sulfate 1 =SO. 5= K2 O 9= P
10 = 81
[J Soil related 2= MgO 6= CaO
3= AI2 0 J 7= Fe2 0 2 11 = Pb
4 =SiO 8 = Na 9a, 12=Other
Fig. 59. Size fractionated mass balance for Zion, Utah (U.S.A.). Redrawn after Flocchini et al. 1981
Ammonium sulfate was the largest chemical component (41 %) of the fine aero-
sol (d < 3.S flm) in the urban aerosol of Charleston, West Virginia USA (Lewis and
Macias 1980). Carbon was a large component of both fine and coarse particles con-
stituting 16 and 12% respectively.
Considering the diversity in the sources of trace metals, it is not surprising that
concentrations are not uniform according to particle size. An example for air over
Bermuda is shown in Fig. 60.
Iron, aluminium, manganese and chromium are found in the coarse size parti-
cles (around 1.S flm), cadmium, lead, zinc and antimony in particles smaller than
0.2S flm. For trace metals and other constituents, the particle size distribution can
be approximated by the mass median diameter (MMD): the particle size for which
SO% of the mass occurs on larger and SO% on smaller particles. A summary of
available MMD values for metals in the atmosphere is presented in Table 22. Some
data are also given in Fig. 64.
The metals found in rural to urban atmospheres and in marine air occur mainly
in the accumulation mode of particles. In the marine atmosphere the MMD is less
than 1 flm, and slightly higher in urban-rural areas. Compared with other com-
ponents of marine atmospheres like sodium (MMD about 4-S flm), the metals are
present in much smaller fractions. (see also Chap. 4.6.3.3)
Information on the mode of occurrence of trace metals in urban particulates
has been obtained with selective chemical leaching techniques (based on the sedi-
ment leaching methods described in Chap. 2.6). Standard Reference Material 1648,
urban particulate matter, was analysed with a sequential extraction procedure
(Lum et aI. 1982).
The results show high proportions of soluble metals, especially for Zn, Pb and
Cd. Co and Cr are more tightly bound in the residual fraction.
This high solubility of trace metals in atmospheric particulates is a general phe-
nomenon (Wallace et aI., 1977; Crecelius, 1980; Gatz et aI., 1982; Hodge et aI., 1978;
Ochs and Gatz, 1980), and shows that deposition on wet surface (e.g. leaves) and
in surface waters will results in a release of trace metals to the ecosystem.
Fig. 60. Trace metal concentration

as a function of particle size in Ber-
muda marine air (Duce et aI., 1976)
3.6 1.5 0.750.480.25<0.25 3.6 1.5 0.750.480.25 <0.25pm
Equivalent aerodynamic radius cutoffs at 50% collection

efficiency for particles with a density of 1g/em 3
Table 22. Mean MMD values for a number of metals. The data for marine air
are from Duce et al. (1979). The data from Eniwetok atoll are from Merrill
and Duce (1982) and those for rural to urban air from Rahn (1976) as cited by
Galloway et al. (1980)
Metal Marine air Eniwetok atoll General

(rural to urban)
Na 1
Ag 1
As 2
Cd 0.5 2
Co 0.75 4
Cr 3
Cu 0.8 0.96 1.8
Hg 0.5
Mn 0.4 0.88 2
Mo 1.2
Ni 1.5
Pb 0.4 0.25 0.4
Sb 0.35 1
Se 0.53 0.8
Sn 1.2
V 0.5 0.76 1
Zn 0.04 1.5
Deposition of Atmospheric Particles 109
Co Cr Ni Mn Cu Zn Ph Cd
Fig.61. Mode of occurrence of trace metals in Standard Reference Material 1648 (urban particulate
matter). (Drawn after table 2 in Lum et aI., 1982). 1 Exchangeable fraction, 2 Surface oxide and car-
bonate-bound fraction, 3 Associated with Fe-Mn oxides, 4 Organically bound fraction,S Residual frac-
tion
4.4 Deposition of Atmospheric Particles
Trace metals are removed from the atmosphere by dry and wet deposition. The dry
deposition velocity of particulates (and gases) has been defined by Chamberlain
and Chadwick (1953) as the deposition flux F, divided by the airborne concentra-
tion C.
V=FjC.
The reference heights for airborne concentrations have historically been about
1.5 m for land surfaces and 10-15 m for ocean surfaces. The deposition velocity is
not the same as the gravitational settling velocity, since it is the summation of all
processes causing the flux to the surface; it is equal to or greater than the gravita-
tional settling velocity. Measured dry deposition velocities in the field vary by or-
ders of magnitude (for reviews see Sehmel, 1980; McMahon and Denison, 1979;
Slinn et aI., 1878). These variations are not surprising considering that Sehmel
(1980) listed close to 100 factors which influence the dry deposition removal rates.
The deposition velocity in polar regions (Greenland) is estimated at 0.5 cm s - 1
(Davidson etaI., 1981), and for ocean areas the estimates using different methods
are 0.8 cm s -1 (Crecelius, 1982) over vegetated areas it is much larger.
Three main processes cause removal of particulates from the atmosphere (Hidy,
1973; Galloway, 1980):
Sedimentation
The most common process by which particulates are removed from the atmosphere
(and also from water) is gravitational settling. The sedimentation velocity falls off
drastically for particles smaller than a few microns, so that this process is particu-
larly important for particles in the coarse-particle mode (larger than 5 11m diame-
ter).
Diffusional Transport
In the same way that gas molecules are transported by diffusional processes, the
smaller particles migrate by their own thermal agitation (Brownian movement) or
turbulent eddying in the air. Deposition by this process is especially important for
particles smaller than 0.3 11m in diameter.
Inertial Impaction and Interception
Impaction and interception are caused by the fact that particles do not follow ex-
actly the gasflow on objects and hence collide and are removed from the atmo-
sphere.
The removal at the surface of the earth depends on its nature. Large differences
in deposition velocities are observed for water surfaces and forest areas.
As already discussed, all three processes are not equally efficient for all particle
sizes. The smaller particles (less than 0.3 11m) are efficiently removed by diffusion
and impaction processes, and the large particles by sedimentation processes. How-
ever, there is a minimum deposition velocity for particles approximately in the
range of 0.3 to 0.5 11m; these particles have longer residence times since both dif-
fusion and inertial deposition and sedimentation are weak in this range.
The particle size of aerosols depends not only on their source and origin but
additionally on the humidity. Continental aerosols contain 15-30% of sulfate in
the accumulation mode, while the value for marine aerosols is 30-60%. Sulfate in
excess of 15-30% makes the particles hygroscopic and at normal humidities they
increase in size due to adsorption of water. The increase in size due to humidity
changes must be taken into account when considering the deposition of particles
over natural waters, since the relative humidity increases towards the water sur-
face.
Three cases of particle behaviour are shown in Fig. 62, namely for:
- hydrophobic particles, their size is not affected by humidity changes
- particles that will grow to the equilibrium size of ammoniumsulfate particles for
a relative humidity of99%
- the expected behaviour of ammoniumsulfate particles for a relative humidity of
100%.
One of the main features of the curves is the minimum in the deposition velocity
for particles in the accumulation mode. It should be noted that particles originally
hydrophobic may obtain a wettable/soluble surface coating after aging (Slinn and
Slinn, 1980), and show behaviour similar to hydrophilic particles. The high water
solubility of trace metals in both coal combustion emissions and ambient aerosols
has been shown by Lindberg and Harriss (1980, 1981).
Dry deposition of atmospheric pollutants is a continuous process, while wet de-
position is an intermittent process. In fact, only dry deposition may always be re-
lied upon to remove airborne pollutants and is always cleansing the atmosphere
(Sehmel, \980).
Deposition of Atmospheric Particles III
.-.
I.,
-,.
10
E Rat. limited b,.
o
.
"III
:.
C;
o
'i
:.
c::
o
;:
..o 102
•,.
Do
.
"III
CI
Dr,. particl. radius • ad 'pm)
Fig.62. Predicted deposition velocities of particles to natural waters as a function of wind speed and
of particle size (Slinn and Slinn, 1980)
In discussing the wet removal of aerosols and their associated pollutants, it is

necessary to make a distinction between the formation of cloud droplets and the
subsequent formation of rain drops and ice crystals which later on are removed
from the cloud. The aerosol particles and cloud droplets collide with each other
and with larger particles. The efficiency of this collision process depends on the size
of the collector particle and but even more so on the size of the particle to be col-
lected (Fig. 63). The efficiency is very low for submicron particles, but very high
for particles between 5 and 10 ~m in diameter. For efficient wet removal of metals
it is important that they are associated with soluble aerosol particles. A lead aerosol
particle with a MMD of 0.5 ~m has a very low collision frequency. However when
it is attached to a soluble aerosol particle with MMD of 0.5 ~m, it will grow in the
cloud to sizes of 10 ~m very rapidly with an associated collision efficiency of ca. 1.
The processes causing coagulation of particles are similar in nature to deposi-
tional processes, hence the similarity in the curves given in Fig. 62 and 63.
The formation of rain drops involves coalescense processes rather than conden-
sation of vapour on individual droplets. In this way the pollutants in the individual
droplets are not diluted but become concentrated in raindrops. A I mm raindrop
is the product of approximately one million collisions with cloud droplets (Scott
1981). This means that one gram (or one cm 3 ) of rain scavenges about one m 3 of
air. Estimates on the wet removal of aerosols are often made utilizing the washout
ratio (factor) or scavenging ratio W, where:
W = C(R)· DjC(A)
and C(R) = concentration of material in rain (~gjkg)

C(A) = concentration of material in air (~gjm 3)
D = density of air (e.g. 1.2 kgjm 3 at 20 DC, 1 atm) .
:0-
U
'u•
I:
......
;:
I:
o
~
'0
(,)
Radius of unit density particles ( pm )

Fig. 63. Collision efficiency by collector particles of 0.1 and I mm as a function of particle size (Slinn,
1977)
..:
2000r--------r--------,--------,--------,--------,
~ 1600
:!
•E
!
.
~c 1200
•E Mg
...
.! Gatz, St. Louis, to 7.2
a"i 800 50 km NW
it
I
8
! 400
:e.u
~
•
3 4 5
MMD, ~m
Fig. 64. Washout ratios as a function of the MMD. (Gatz 1975)
Fig. 64 shows the washout ratio as a function of the MMD for a number of
trace metals (Gatz, 1975).
Young aerosols have low MMD's and consequently a low washout ratio (the
results for 15 km from St.Louis). With an increase in age the MMD increases, and
probably also the attachment of the metal containing particulates to soluble
aerosols with a subsequent increase in washout ratio.
Metal Concentrations in Urban, Rural and Remote Atmospheres 113
Table 23. Mean data on the contribution of dry deposition

to the total deposition of trace metals from the atmo-
sphere. [Duce (1979). Feely and Larsen (1979) as cited by
Galloway et al. (1980)]
Metal Reported measurement of dry fractions
Marine Rural Urban
As 0.2
Cd 0.4 0.4 0.6
Cu 0.5
Mn 0.5 0.5 0.5
Ni 0.6 0.5 0.5
Pb 0.6 0.3 0.2
V 0.4
Zn 0.7 0.4 0.5
Data on dry versus wet deposition of trace metals have been reported by Duce
(1979) for the marine environment and for rural and urban areas by Feely and
Larsen (1979). Some data ofthese studies are presented in Table 23.
The data indicate that dry and wet deposition both may contribute about
equally to the flux of atmospheric trace metals to the surface of the earth. Davidson
et al. (1981) reported data for polar areas and showed that dry deposition contrib-
uted less than 25% of the total deposition for elements with large enrichment
factors (e.g. trace metals). These data should be interpreted cautiously. Various
methods are in use to sample separately dry and wet deposition, with large differ-
ences in efficiency. The various methods to discriminate between wet and dry de-
position as well as the collection of atmospheric particulates have been discussed
in detail in the reviews by Hosker and Lindberg (1982), Cawse (1982) and Noller
et al. (1981).
4.5 Metal Concentrations in Urban, Rural and Remote Atmospheres
Trace metal concentrations at different localities may vary by orders of magnitude

in the atmosphere. Low concentrations are found at remote sites and over the
oceans, whereas the highest concentrations are observed at urban sites. Annual av-
erage concentrations at a rural site in the United Kingdom (Wraymires) are com-
pared in Table 24 with levels recorded at background European (Jungfrau), remote
South Pole and city atmospheres (Cawse, 1981). The results show the strong mari-
time influence (high concentrations of Cl, Na, K and Mg for the non-urban site
in the U.K. compared with the other non-urban sites. A comparison with city at-
mospheres shows that urbanisation and industry has resulted in order of magni-
tude increases in air concentrations of Br, Co, Cr, Cs, Ni, Pb, Sb and Zn (Cawse,
1981 ).
Galloway et al. (1982) made an inventory of all available data on atmospheric
metal concentrations in rural, remote and urban areas. To show the relative con-
Table 24. Concentrations of elements in air at non-urban and urban locations (ng kg - 1 air) Cawse (1981)
Element Non-Urban Urban
Wraymires, Jungfrau S. Pole 20 sites Central

Lake District, Central Europe remote average, Swansea
UK, 1980 Inland Background site in UK
Al 105 42 0.67 6.4 370

As 2.4 0.19 0.006 6.4 15
Br 17 1.1 1.1 320
Ca 310 0.40
Cd < 1 0.4 2.8
Ce 0.19 0.80
CI 1450 5.9 2.1 4600
Co 0.11 0.037 1.4 4.5
Cr 1.2 0.29 <0.03 14 6.1
Cs 0.024 0.012 0.024 0.27
Cu 16 0.72 0.51 19 57
Fe 96 29 680 940
Hg 0.047 0.024
I 1.6 0.22 0.068
In 0.027 0.0008 < 0.7
K 600 16 0.56
Mg 160 8.2 0.59
Mn 4.0 1.2 31 25
Mo < 0.4 0.24
Na 710 18 2.7 1960
Ni <3 13 66
Pb 38 3.6 340 500
Sb 0.79 0.16 7.3 4.0
Sc 0.031 0.0063 0.16
Se 0.81 0.034 0.005 2.7
Ti <7 2.0 0.08 39
V 3.7 0.24 17 21
Zn 19 8.1 0.027 260 310
Reference Dams and De J onge Maenhaut McInnes Pattenden,
(1976) and Zoller, (1979) (1974)
(1977)
Note: 1 m 3 air at 15° C, 760 mm Hg (Standard Cubic Metre) = 1.226 kg
tribution of anthropogenic sources on various elements, the ratios of urban/remote

and rural/remote are presented in Fig. 65.
The ratio of urban/remote follows the order Zn > Pb > Cu > Mn > Co > Sb >
Cr> As > Ag > Ni > V > Se > Hg > Cd. The ratios for rural/remote follow a similar
order, but are about one order of magnitude lower. An exception is cobalt, which
shows very little enrichment. It seems probable that this is due to the high MMD
(Table 22) and consequently high washout ratio near its sources.
Information on long term trends and seasonal fluctuations in trace metal con-
centrations in the atmosphere are available for the United Kingdom. The seasonal
fluctuation in absolute concentrations of elements in air is shown in Fig. 66 A, B
andC.
Metal Concentrations in Urban, Rural and Remote Atmospheres 115
Fig. 65. The ratio of metal concentrations

in urban/remote and rural/remote atmo-
spheres (Galloway et aI., 1980, 1982)
.Urban/Remote
.Rural/ Remote
10.000 .---W-R-A-YM-IR-E-S--N-O-N-U-R-B-A-N-----------------. 10.000
...
CI
\
1000 Na\......l
"'
"
....
1000
I
m
jf.
iii
..
o
c
-
100 Zn .'
'
.s
z
o
i=
«
a:
I-
zW
(,)
Z
o
(,)
0.1 1 234123
1971 1972
10.000.....--------------------------,10.000
WRAYMIRES-NON URBAN
.j 1000 1000
...
I
m
jf.
iii 100
.
o
c
.s
10 10
~
i=
«
a:
I-
z
W
(,)
Z
o
(,)
Fig. 66. Seasonal fluctuations and long term trends in metal concentrations in the atmosphere (Cawse,
1981)
Table 25. Total deposition rates of atmospheric trace metals.

Oceanic regions from Crecelius (1982). Greenland from Davidson
et al. (1981) and forest area from Lindberg and Harris (1981)
(mg· m- 2 . yR -1)
Oceanic regions Greenland Forest area
Pb 0.22 0.06 15
Zn 1.3 0.17 9.3
Cu 0.28 0.026
Ni 0.076 <0.072
Cr 0.10
V 0.076
Cd 0.050 0.0061 0.5
Mn 0.022 0.22 35
The element bromium showed the greatest increase in winter, to almost three
times its concentrations in summer. Increases for the elements As, Cr, Pb, Sb, V
and Zn are 11 to 2-fold compared with the summer period. This variation is at-
tributed to increased combustion of fossil fuels and the persistence of inversion
layers in winter (Cawse, 1981).
The long term records at the various stations (Fig. 66) show that downward
trends are evident for several elements over the last 8 to 10 years. Downward trends
are found for AI, Br, Co, Cr, Mn, Pb, Sc, V and Zn for all sites. The downward
trend is most marked for zinc. A decrease in industrial emissions owing to the eco-
nomic recession is considered the be the most likely cause of lower trace element
concentrations in air (Cawse, 1981). The deposition of trace metals from the atmo-
sphere depends on dry versus wet deposition and on local atmospheric conditions.
A large amount of data on the total deposition of trace metals have been reported
and some of them are summarised in Table 25.
4.6 Environmental Impact of Airborne Trace Metals
Atmospheric metals have a global distribution and affect all aquatic ecosystems.
To illustrate the impact of trace metals on the hydrological cycle, three areas where
the atmospheric input is dominant will be discussed:
- terrestrial ecosystems
- ocean areas far away from the input of rivers and other point sources
- the polar regions.
Atmospheric trace metals are also one of the many sources of trace metals in
lakes, rivers, estuaries and near coastal environments. This will be discussed in the
relevant chapters.
Terrestrial Ecosystems 117
4.6.1 Terrestrial Ecosystems
The influence of atmospheric trace metals has been studied in a number of forest
ecosystems. In these systems two pathways for the atmospheric trace metals can
be distinguished:
- the dry deposition of trace metals directly on the forest soil and on the leaves
of the trees and other vegetation;
- the wet deposition of trace metals. This will also remove the dry deposition from
leaves.
Trace metals deposited by both dry and wet deposition will interact with the
vegetation. Some metals appear to be taken up through the leaves, whereas others
are leached from the leaves (foliar leaching).
Within the forest ecosystems, trace metals are incorporated in the above
ground cycling fraction (leaves, needles etc), in the non-cycling fractions of the veg-
etation (wood, bark), in the organic-rich surface layers and in the soil. Part of the
metals accumulated in the forest ecosystem will be leached away from the soil and
enter streams and rivers. However, if the rate of input is not matched by the rate
of output, an accumulation of metals will occur.
Areas which have been studied in detail include the Walker Branch Watershed
(Lindberg et aI., 1979) in the USA and the Solling forest in W-Germany (Mayer,
1981 ).
The Walker Branch Watershed (surface area 97.5 ha) is located in Eastern Ten-
nessee and is situated within 20 km of two coal-fired power plants (annual coal
consumption about 7 x 106 tons) and within 350 km of22 coal fired power plants.
The Solling forest is located close to the major industrial region of Europe (the
Ruhr area). Using a mass balance approach it was shown (Andren and Lindberg,
1977) that no more than 5% of the total composition of the aerosol in the Walker
Branch Watershed could be accounted for by the local coal-fired power plants,
however they accounted for up to 20% of the concentrations of individual ele-
ments. The enrichment oflead in the aerosol could be accounted for by automotive
emissions, and zinc and possibly mercury by the three nearby power plants. How-
Table 26. Characteristics of atmospheric particles above the forest canopy at Water
Branch Watershed. The relative solubility is defined as (water-soluble concentra-
tion) ·IOOj(acid-leachable concentration). The acid leaching was carried out at a
pH of 1.2 and includes both soluble and acid leachable components (Lindberg
and Harriss, 1981)
Metal MMD Atmospheric concentration Relative

(j.tm) solubility
Total acid leachable Water soluble alone
(ngjm 3 ) (ngjm 3 ) %
Cd 1.5 0.17 0.14 82

Mn 3.4 9.4 8.6 83
Pb 0.5 112 84 76
Zn 0.6 9.9 8900 89
lIS Metals in the Atmosphere
ever, these local sources still could not account for most of the As, Cd, Cu, Hg,
Se, V and Zn in the aerosol. Recent atmospheric trace metal concentrations at Wal-
ker Branch Watershed, together with the results of a speciation scheme are given
in Table 26.
The extraction scheme consists of an extraction with distilled water and an acid
extraction at a pH of 1.2. The results show the very high relative solubility of trace
metals in the atmospheric aerosol. The relative solubility increased with decreasing
particle size (Fig. 67) (Lindberg and Harriss, 1981), as also shown for coal combus-
tion emissions (Lindberg and Harriss, 1980).
The dry deposited particles on the leaves contained significant fractions larger
than 5 Ilm in diameter and also numbers of particle aggregates. The relative low
solubility of the deposited particles (for lead) is in accordance with the relative
coarse particle sizes. Similar high solubilities of metals in aerosols have been found
by Gatz et al (1982), who studied the solubility in rainwater. The distribution of
RELATIVE SOLUBILITY OF
PARTICLE ASSOCIATED
LEAD (%)
60
40
20
Fig. 67. The relative solubility of lead in the aerosol

over the Walker Branch Watershed as a function of
particle size and for the dry deposited particles
0~"'7"'---3"--- 1 OA .0.4
-----. -----
AERODYNAMIC DIAMETER
(,11m)
AMBIENT DRY
AEROSOLS DEPOSITED
PARTICLES
Table 27. Summary of mean data for the precipitation at the Walker Branch Watershed. (Lindberg
and Harriss, 19SI)
Metal Dry deposition Precipitation Atmospheric

deposition
rate Velocity Incident Throughfall mg·m- 2 ·yr- 1
Ilg· m2 · d - 1 cm· S-I
Ilg .1- 1
Cd 0.60 0.37 0.44 1.41 0.5

Mn 28 6.S 3.46 135 35
Pb 6.8 0.06 6.85 I1.S 15
Zn 1.5 0.46 6.13 15.4 9.3
pH 4.13 4.26
the percent soluble metals showed the order Zn = Cd > Cu > Pb and differences for
all metals between sample types were in the order: wet> bulk = dry. The dry depo-
sition rate, the dry deposition velocity, the trace metal concentrations in the pre-
cipitation above and below the canopy (throughfall) and the total atmospheric de-
position for the Walker Branch Watershed is shown in Table 27.
The dry deposition rate follows the general relationship that the higher the
MMD the higher the deposition rate. Also the mean deposition velocities (as de-
termined from deposition on inert flat surfaces) reflect the influence of MMD. It
should be noted however, that the deposition velocities increase by a factor of
about 2-3 if the full canopy effect (larger surface area) of the forest during summer
is taken into account (Lindberg and Harriss, 1981). Mayer and Ulrich (1982) ob-
served higher deposition rates in a spruce forest compared with a beech forest. This
deposition excess of the spruce forest is mainly found during the winter period,
when beech has lost its leaves and therefore has a reduced surface area compared
with the evergreen spruce canopy. The dry deposition particles or their water sol-
uble metals are washed from the leaves during rain periods and are part of the flux
to the forest floor. Important with respect to potential negative effects for the veg-
etation are dew periods and small rainfall events. In those cases the dry deposition
particles are not washed offfrom the leaves, but instead dissolve partly in the water
film on the leaf. The dry deposition particles contain high concentrations of soluble
metals and as a consequence elevated metal concentrations occur in the water film,
which increase after subsequent evaporation (Table 28).
The metal concentrations are one up to several hundred times higher than typi-
cal rain concentrations in this area (Lindberg and Harris, 1982). The physiological
effects of surface deposited materials on vegetation either in particulate or dis-
solved form requires considerable study, as they are poorly understood (Lindberg
and McLaughlin, 1982). Possible effects may be damage to micro-organisms on the
leaf surfaces, epiphytes or the leaves themselves (Mayer and Ulrich, 1982).
The flux of metals to the forest floor differs from the sum of wet and dry pre-
cipitation, showing the effects of interactions between the precipitation and leaf
surfaces (Lindberg and Harriss 1981, McColl and Bush 1978, Heinrichs and Mayer
1980, McColl 1981). The enrichment in manganese is particularly high (see Table
27); for zinc and cadmium smaller enrichments are observed. Also the pH increases
in the throughfall precipitation.
The uptake of H + by the leaf surfaces and the concomitant loss of several ele-
ments suggests a combination of ion exchange and leaching processes. This foliar
leaching is important for manganese, zinc and cadmium in the Walker Branch Wa-
tershed (Fig. 68).
Table 28. Concentrations of metals on leaf surfaces

after 1.3 mm of rain (deposites on a 50 cm 2 leaf, about Metal Concentration
6 ml of water) following a 2.4 days dry period (Lindberg Ilg/I
et al., 1982)
Cd 13
Zn 120
Pb 230
Mn 1300
I ATMOSPHERE I
Incident precipitation Dry deposition
2 12
Foliar
leaching
I LEAVES
L~
49
'\ MANGANESE
Wash - of dry
depOsition I
~
LEAF
SURFACE
11 I
Leaf fall
31 To Ground
Idormant parlod )
\ It It
J V It
FOREST FLOOR
l ATMOSPHERE I
Incident precipitation Dry dep081tion
36 8
Foliar
I •• chlng
LEAVES I ZINC
I 32
Wash-of dry
depOsition I
~
LEAF
7
I SURFACE
1
Leaf f.1I
24 To Ground
\ / (dormant parlod)
V \V
FOREST FLOOR
I ATMOSPHERE J
Incident precipitation Dry depOsition
34 1
Foliar
leachi ng
I LEAVES
L 55 Wash-of dry
CADMIUM
depo81t1on I
~
LEAF
6
I SURFACE
1
Leaf fall
3 To Ground
\ It (dormant period
V V
FOREST FLOOR
Fig. 68
If the flux of cadmium by the annual leaf fall is taken as being representative
of the total cadmium in the le<\,ves, then almost 20 times as much cadmium present
in the leaves at any time is leached from it to the forest floor during the summer
period. This indicates the high replenishment of cadmium (and also of manganese
and zinc) in the leaves.
The behaviour of lead is different from the other metals studied. For lead the
annual flux to the canopy exceeds the flux to the forest floor by a factor of 1.3. This
balance study, as well as leaf washing experiments, suggest canopy assimilation for
some of the deposited lead (Lindberg and Harriss, 1981). In the SoIling forest
(Heinrichs and Mayer, 1980), an assimilation oflead, copper and cadmium was ob-
served.
Part of the total flux to the forest floor will accumulate in the soil. However
part will be removed by leaching processes.
A compartment model and balances were constructed for two experimental
forest systems in Western Germany (Mayer, 1981). Part of the results of the balance
study are presented in Table 29.
The input given in Table 29 is the total deposition from the atmosphere on the
ecosystem. The throughfall is the input of trace metals to the forest floor. The ac-
cumulation in the soil is the balance of inputs through the through fall, litter fall,
and losses through uptake by roots and to the groundwater. The total balance is
the atmospheric input minus the losses to the groundwater. It differs from the ac-
cumulation in the soil, since this term also incorporates the storage in growing
plants. The balance (input> output) is positive for Cr, Fe, Ni, Cu and Pb, negative
for Mn and Co, and fairly balanced for Zn and Cd. The considerable seepage losses
of Mn, Co, Zn and Cd are caused by anthropogenic factors (e.g. the acid precip-
itation). Mayer (1981) showed that within forest ecosystems the micro-organisms
and vegetation with its root system are endangered by the heavy metal accumula-
tion at the soil surface; the accumulation has reached levels where deleterious ef-
fects are to be expected. Mobilization of the accumulated metals may follow any
kind of ecosystem manipulation like clearcut, fertilization, deposition of waste
products, spreading of deicing salts into roadside forests etc.
The significance of long-range atmospheric transport to the supply of trace
metals to terrestrial ecosystems may be illustrated by some recent data from Nor-
way (Steinnes, pers. comm.).
In a national study of trace element deposition using moss analysis (Rambaek
and Steinnes, 1980), it was found that areas in the southernmost part of the country
receive about ten times as much lead, arsenic and antimony as most areas north
of the 62° N. A similar trend but somewhat less pronounced was evident for zinc,
cadmium, silver, vanadium and selenium. In a simultaneous study (Hanssen et aI.,
1981) these elements were shown to be strongly intercorrelated in aerosols collected
at Birkenes, Southern Norway. A sector analysis confirmed that the highest air
concentrations of these elements in Southern Norway occur with trajectories from
..
Fig. 68. Processes affecting the annual flux of cadmium, zinc and manganese to the forest floor in the
Walker Branch Watershed. Based on data from Lindberg and Harriss (1981). Values represent the frac-
tion of the total annual flux to the floor that a given process contributes
Table 29. Metal balance for two experimental forest systems in Western Europe (Mayer 1981). A = Beech forest and B = Spruce forest. All data in g/ha/y N
N
Mn Ni Cu Zn Cd Pb
A B A B A B A B A B A B
Input 1750 5150 123 140 470 659 1632 1732 16 20.1 437 733
Throughfall 3840 5190 33 39 162 227 2169 2121 12.6 20.1 302 467
Accumulation in 2900 1300 88 78 310 300 110 246 1.4 3.2 49 76
lea yes and roots
Soil accumulation -6790 -8230 14 -4 54 249 397 -878 -2 -9.3 413 720
Seepage 5900 11100 21 66 106 110 1125 2364 16.5 26.2 24 13
Balance -4150 -5950 102 74 364 549 507 -632 -0.5 -6.1 413 720
s:::
(1)
E
'"
S·
g-
>
~
~
if
(l
the south and south-west, clearly indicating a major contribution from areas in
Central and Western Europe.
In another national survey the geographic distribution of lead in natural sur-
face soils, shown in Fig. 69, was found to be very similar to that of the airborne
deposition oflead (Allen and Steinnes, 1979).
Other volatile trace elements such as cadmium, arsenic, and antimony, were al-
so found to be strongly enriched in surface soils in the southernmost part of Nor-
way as compared to more northerly areas of the country, whereas less volatile ele-
ments such as copper and nickel did not exhibit this kind of trend. Most probably
this enrichment of the volatile-group elements is due to deposition of metals from
long-distance atmospheric transport and subsequent strong fixation in the organic
fraction of the soils, which is in most cases above 50%. This conclusion is support-
ed by similar findings from a study of trace element profiles in ombrotrophic bogs
from different parts of Norway (Hvatum et aI., 1983).
Not only are the soils affected by the regional differences in trace element de-
position, but also organisms living in the areas concerned. The content of lead and
cadmium in forest trees and heather is about 3-5 times higher in southernmost
Fig. 69. Regional distribution of lead in natural surface soils

in Norway, indicating strong contribution of atmospheric de-
position from distant sources (Allen and Steinnes, 1979)
Norway than in ecologically equivalent localities in Middle Norway whereas no

significant differences are evident for the essential trace elements copper and zinc
(Solberg and Steinnes, 1983). Lambs from different parts of Norway, slaughtered
after having spent their first summer season on natural pasture land, showed liver
concentrations of lead and cadmium in good accordance with the patterns of air-
borne deposition, whereas other trace metals investigated did not show clear re-
gional differences (Froslie et ai., 1983). Not only natural ecosystems may be endan-
gered by atmospheric trace metal inputs, also agricultural land receives metal in-
puts from the atmosphere. Atmospheric supply from natural and anthropogenic
processes may considerably affect the exchangeable fraction and in some cases
even the total content of the element concerned in the surface layer of soils. This
has been clearly shown for elements associated with the marine environment such
as Na, Mg, Cl, Br, and I (Lag, 1968; Lag and Steinnes, 1976). As mentioned before
the supply oflead, cadmium, arsenic and antimony from long-distance atmospher-
ic transport strongly affected their regional distribution in Norwegian soils (Allen
and Steinnes, 1979) as well as their vertical distribution in the soil profile (Solberg
and Steinnes, 1983). For selenium, the regional distribution in Norway indicates
atmospheric supply from a natural source, possibly marine, in addition to the an-
thropogenic input (Lag and Steinnes, 1974; Steinnes, 1980; Hvatum et ai., 1983).
Cawse (1982) made calculations for the United Kingdom and showed that for
some elements a 30 year period of continuous atmospheric metal input may pose
problems with regard to recommended maximum additions of trace metals to ag-
riculturalland.
4.6.2 The Arctic and Antarctic Aerosol
The arctic and antarctic areas are influenced mainly by the atmospheric deposition
of trace metals and from (small) local sources. One of the differences between the
arctic and antarctic is that the latter is situated far away from major land masses
in the southern hemisphere which is less subject to pollution than the northern
hemisphere. Metal concentrations in dated ice cores taken from the North and
South Pole areas may provide, when sufficient precautions during sampling and
analysis are made (Ng and Patterson, 1981), a valuable record of the historical
changes in metal concentrations in the atmosphere. It has been proved that Pb/Si
ratios increased by about 300-fold in Greenland snows during the last 3000 years
(Murozumi et ai., 1969; Ng and Patterson, 1981). Present day concentrations oflead
in antarctic snows are only several times higher than prehistoric levels as a conse-
quence of inputs of industrial lead emissions. This is because the fraction of the
total world emission of industrial lead is small in the southern hemisphere and the
barrier to the transport of these lead aerosols to south polar regions presented by
the antarctic circumpolar atmospheric convergence is strong (Patterson, 1982, pri-
vate communication). No reliable data appear to be available to show whether
other trace metals like cadmium and zinc have also increased in polar snows (Bout-
ron 1980).
A second indication of pollution of the arctic atmosphere is the occurrence of
the arctic haze, a reduced visibility in northern regions due to the scattering oflight
The Arctic and Antarctic Aerosol 125
by atmospheric particles. Reports on it were first filed by airline pilots and it was
first reported in the scientific literature by Mitchell (1956). It has now been posi-
tively identified as being part of a global air pollution phenomenon.
4.6.2.1 Concentrations in Arctic and Antarctic Areas

Mean concentrations in arctic and antarctic aerosol are given in Table 30.
The data from the arctic have been examined by factor analysis (Heidam, 1981).
Corresponding to the factors, the results split up into three distinct and easily re-
cognizable groups. Factor 1 included the elements Na, Mg, Cl, K, Ca and Sr, and
measures the influence of oceanic sources. The second factor included the elements
AI, Si, Ti, Mn, Fe which are all indications for crustal or soil derived aerosol com-
ponents. The third factor (S, V, Cr, Ni, Cu, Zn, Br, I, Pb) can be interpreted as
an industrial or anthropogenic-derived aerosol component.
The concentrations and size distribution of trace metals in the South Polar at-
mosphere have been described by Maenhaut et aI. (1979). By comparing the aero-
sol composition with the mean crustal composition it was possible to show that V,
Mn, Fe, Co, Cr have a crustal source (enrichment factor less than 10). A large num-
ber of elements (including most heavy metals) have an enrichment factor> 50
(AEE, Anomalously Enriched Elements). These are believed not to have a crustal
or a marine source (Maenhaut et aI., 1979). A likely source for the AEE enrichments
elements appears to be volcanism, as pollution sources can be ruled out to a large
extent.
Principal component analysis of trace metal concentrations in snows (Boutron
and Martin, 1980) has shown that the AEE (Pb, Cd, Cu, Zn and Ag) are not derived
from either oceanic or crustal sources. By measuring metal concentrations along
profiles in antarctic snows over a period covering the last 100 years, it was possible
Table 30. Metal concentrations (picogram per cubic meter) in arctic and
antarctic aerosol. Arctic data from the station Thule for the period 1 september
1978-15 january 1979 (Heidam, 1981). Data from the Antarctic for
1974--1975 (astral summer) (Meanhaut et aI., 1979)
Arctic Antarctic
(Greenland) (Geographic South Pole)
Aluminium 4380 820

Silicon 48600
Sulfur 96400 49000
Potassium 10100 680
Calcium 10500 490
Titanium 1200 100
Chromium 66 <40
Manganese 274 13.3
Iron 16100 620
Nickel 33
Copper 104 29
Zinc 454 33
Lead 953 27
to show that the variations in concentrations were related to reports of major ant-
arctic volcanic eruptions (Boutron, 1980).
4.6.2.2 Seasonal Changes

Numerous studies have been carried out on the arctic aerosol, and more detailed
information on its composition and seasonal variation is available than for the less
polluted antarctic aerosol. Studies conducted during the last 5 years have shown
that the arctic aerosol contains an abundance of pollution derived components,
especially during the winter half year. A distinct seasonal cycle is observed for sev-
eral components of the arctic aerosol (Fig. 70). Vanadium is a good indicator of
pollution derived from mid latitude areas for the arctic aerosol, because it is de-
rived from the combustion of residual oil which is too viscous to be used in arctic
areas.
Thus an increase in its concentrations shows that during the winter the con-
ditions for atmospheric transport from mid-latitude (industrial) areas to the arctic
are more favourable than the summer period. The variation in the V concentration
at Barrow (Alaska) is about 50 (Fig. 70), whereas the seasonal changes at its source
in mid-latitude regions is only 3-4. This implies that seasonal variations of trans-
port plus removal is more than an order of magnitude greater than the source vari-
ations (Rahn and McCaffrey, 1980). In the model to explain these seasonal varia-
tions, the rate of removal of the aerosol was made proportional to the mean pre-
cipitation. Their calculations showed that during winter, the transport over land
is more efficient for the aerosol than transport over the ocean, because there is less
precipitation and hence less removal over the interior of the continents. During the
1000
Winter / Summer
New York City
/0 . . . 0 1972 -74
1'1
Ie
100
-3 0..,.,0- 0
'-0 °0 -0 _ _0 ,
,o~
/'0....... Northeast U.S.
0
11\
c:
,; ° 1974 - 77
~o '-0--0--
. 10 ';0 0 ........ 0 0 0 0
i 0/ '\ Spitsbergen
.
III
::I
II °/ O~OI
1973-74
c:
0 1.0
c: '::o1!-/' /-\
III
/.--...... \ 1976-77
•• "0.
•
III
-50 _
/
II
Ie
-
III 0.1 -5
0.01
/-/ ~ Fig. 70. Monthly mean concentration of
excess vanadium in arctic and non-arc-
A S 0 N D J F M A M J J tic sites (Rahn and McCaffrey, 1980)
summer periods more material is removed by rain and the flux of pollutants to the
arctic is greatly reduced. Thus an aerosol travelling to the arctic via the North At-
lantic will be removed by an order-of-magnitude greater efficiency than will the
same aerosol travelling the same distance over Eurasia. A similar rapid removal
can be expected for an Eastern Asian aerosol traversing the North Pacific (Rahn
1981 ).
Another characteristic of the arctic aerosol is its highly aged character (travel
time to the arctic is around 10-20 days). The aged character can be derived from
the particle size distribution which favours the occurrence of submicron particles,
that have a low scavenging efficiency. The high concentrations of sulfate are also
an indication of the aged character, since the sulfate is derived from the oxidation
of S02 during transport (Rahn and McCaffrey (1980). The high concentrations of
21O-Pb during winter (in view of the lower production of its precursor 222-Rn pre-
cursor) can also be explained by the unusually long residence time of the arctic
aerosol, so that 21O-Pb produced in the arctic accumulates with little loss due to
precipitation (Rahn and McCaffrey, 1980). Vanadium and sulphate are not the on-
ly elements to show this seasonal change in concentrations but trace metals like
copper and zinc show similar trends (Barrie et al. 1981).
An interesting characteristic of the arctic aerosol is the high concentration of
soot (Rosen et aI., 1981), which causes the blackness of air sampling filters in the
winter period. The soot also shows the seasonal changes in concentrations
(Fig. 71).
Most of the carbon in the arctic aerosol consists of graphite carbon. Raman
spectroscopy showed that the graphite structures are similar to carbon black and
are derived from combustion processes. In fact the concentrations are in the same
order of magnitude as observed for major cities such as New York and Los
Angeles.
The presence of graphite carbon has important implications for the light scat-
tering properties of the arctic aerosol. Depending on the amount and vertical dis-
tribution assumed for the soot, the rates of heating of the local atmosphere have
been estimated to lie between 0.2 and 1 °C' d - 1 during spring (Rahn and Shaw,
1980). Future development of mining, petroleum extraction, refining and manu-
facturing is expected to double every 15-20 years, and in another 50 years arctic
40
.. ° ° - Biweekly averages
/0/
Barrow 1979 - 1980
c
•..
II
• 30
/°
D.
c
° r~New
°..
York
/°
Fig. 71. Seasonal varIatIOns of
0,°/"0
-'II
graphite carbon as a percentage of "
Co) 20
°
the total carbon content of the
aerosol particles at Barrow,
Alaska. The values are compared
~
:E
.."
D.
°
/ +-- Los Angeles
to the average values obtained for

New York City and Los Angeles
CJ
10 ,,0,/
(Rosen et aI., 1981)
° °
Oct Nov Dec Jan Feb Mar Apr Mar June
haze may be serious enough to cause significant heating of the atmosphere of the
northern polar regions (Shaw, 1981).
4.6.2.3 Origin of the Arctic Aerosol

The three main potential source areas for the arctic aerosol according to Rahn
(1981) are:
- Eastern Asia (Japan, Korea, China etc.)
- Eastern North America
- Eurasia (the Western Europe and U.S.S.R)
Possible pathways for the transport of pollution to the arctic during winter are
presented in Fig. 72.
Pure meteorological, meteorological-chemical and observational evidence for
Eurasia as a source of the pollutants in the arctic has been presented by Rahn
(1981). We will discuss in this Chapter the more relevant compositional evidence
with regard to metal cycling. Composition evidence has been obtained using three
lines of reasoning:
- The Pb-210 concentrations are too high to have come from North America via
the North Atlantic, but are consistent with a Eurasian source (Rahn and McCaf-
frey, 1979, 1980).
- Both simulated values of the ratio S04/V in the arctic during winter and ob-
served values in the Atlantic are too low to account for a North American pol-
lution source (Rahn, 1981).
90 ·
Fig. 72. Possible pa thways for the

tran port of poll utan ts from mid-
120 ·
la titude regions to the arctic dur-
ing winter ( Rahn. 19RI)
- However, the most direct and powerful evidence has been obtained by using the
Mn/V ratio of the aerosol (Rahn, 1981). Vanadium is the best indicator elements
since it is derived from only one significant source: combustion of residual oil
(Zoller et aI., 1973), whereas Mn has a variety of sources (Evendijk, 1974).
The elementl Al ratio has also been used to differentiate between various sour-
ces. However in the case of the arctic aerosol it is not possible to use the VIAl or
the Mnl Al ratio since the ratios between the various sources do not differ to a great
extent. More important, however, is the fact that aluminium is a crustal element
and does not occur in the same size fractions as vanadium. During transport, dif-
ferential settling processes will occur, resulting in a loss of aluminium and a change
in ratio VIAl as a function of the ageing of the aerosol. Aerosols are best traced
using two elements with the same mass-size function, so that their ratio will remain
nearly the same during transport (Rahn, 1981). For tracking pollutants an ideal
pair would be Pb and V since they are almost entirely derived from pollution and
are mostly found in submicron urban aerosols. However, data on lead are lacking
(Rahn, 1981). Therefore the ratio of noncrustal manganese to noncrustal vanadium
is used to trace pollutant sources. The noncrustal concentrations can be calculated
from the total concentrations using the formula (Rahn, 1981):
Xaer . noneru.tal = Xaer• total- (~l) crust

Al aer
where x and Al stand for concentration of element X and Al respectively, in the

aerosol or in the crust. The resulting concentrations of noncrustal Mn and V are
plotted as a scatter diagram in Fig. 73.
The Mn/V ratio is larger than unity in Eurasia and less than unity in the north-
east USA. Mean ratios for the two areas are 2.0±0.8 and 0.41 ±0.09 respectively,
1000r-----~-.------r-._----~--r_----~~
/
/
/
/
/
,/0 /
/
100
~:)./
C'I
I
E
g!
c EURASIA
C
... 1./
...
•
..
:E 10 /, /
ia NORTH • /' •
.
III
::I
U
AMERICAN
ARCTIC .~
• .:.
/.
SHETLAND IS
NE USA
.
C
o \
Z "V'\. / ~ NORTHERN NORWAY
10 • / ~ /
~ /-)
Fig. 73. Scatter diagram of at- </~~ NORWEGIAN ARCTIC
/
mospheric concentrations of /
/
noncrustal Mn and V in O.1~/ ____ ~ __ ~ ____ ~~~ ____ ~~ ____ ~~
Eurasia, the northeast USA., 0.1 10 10 100 1000

and the Arctic (Rahn, 1981) Noncrustal V, ng m- 3
: 2 o 40
i ;:
.>-
~ fI
a:
..
~
:ii.
1
til
:
:I
20 Zn
V
c Cu
o v
3.-----~,--------------,
I
q~:n
o o 20
;:
~ 2 fI
a: a:
til til
til
: 10
~
v/v ~r
1 :I ~
V
IV
O~--~~~~~--~~-r~
ONDJFMAM o N D J F M A M
1979 1980 1979 1980
Fig. 74. Mass ratios of various elements and of blackness (soot) to excess (non-soil) vanadium in sus-
pended particulate matter collected at Mould Bay. Redrawn after Barrie et al (1981)
a factor of 5 ± 1 different. However, as already discussed, the ratio of Mn/V is not

the ideal tracer due to differences in their size fractions. As a consequence there are
changes in the Mn/V ratio during transport. The Mn/V ratio of the North Ameri-
can aerosol decreases by a factor of about 3-4, the ratio of the Eurasian air by a
factor of about 3-4 also. Taking this into account the aerosol in the Norwegian
arctic appears to be derived from aerosols in Eurasia. Also, the Mn/V ratios of the
aerosol in the Shetland Islands and Northern Norway, which are geographically
between Eurasia and the Norwegian Arctic, fall between the Eurasian and Norwe-
gian Arctic ratios (Rahn, 1981). The high Mn/V ratio of aerosols collected in the
North American Arctic, as high as those in Eurasia, are still a puzzle (with aging
taken into account, and they should be lower). Rahn (1981) concluded that the
North American Arctic must be influenced by a previously unrecognized source
with a very high Mn/V ratio. Based on the patterns of air flow it was concluded
that the industry in central USSR is a probable source.
More detailed information on the sources affecting the aerosol in the arctic has
been obtained from a seasonal study of several elements in the aerosol at Mould
Bay in the Canadian arctic, as presented in Fig. 74 (Barrie et aI., 1981).
Large changes in the mass ratios of elements in air particulate and in the black-
ness are observed. Three periods have been analysed in detail, combined with air
parcel trajectory analysis.
- The period from December 1, 1979 to January 6, 1980 and the period from
10-17 February;
- the period from 7-28 January 1980 and the period after mid February.
Metals in the Oceanic Aerosol: Continental or Ocean Derived? 131
The first period is characterised by high Mn/V ratios and high concentrations
of soot. Both characteristics point to a coal-burning industrialised area (Siberia).
The high Mn/V ratio cannot be explained by North American sources. Trajectory
analysis confirmed these conclusions (Barrie et aI., 1981). In January the Mn/V
ratio dropped to low values of 0.6. During this period no trajectories linking the
arctic with European sources were observed. Both the trajectory analysis and the
Mn/V ratio suggest a North American source. The increase in the Mn/V ratio from
0.6 to 2 in the week of 10-17 February could be attributed to Siberian sources and
the subsequent decrease during March and April to mainly European with possibly
some Siberian sources. Barrie et al (1981) concluded that the arctic atmosphere can
be described with the "bathtub" model. The arctic atmosphere is a horizontally
mixed reservoir into which air from mid-latitudes is periodically injected. Due to
the annual variation in scavenging processes, the flux of particles into the reservoir
and their residence time while in it are lower in summer than in winter. They
gradually increase in fall and decrease in spring. Consequently the reservoir be-
comes progressively dirtier throughout the winter. The air parcel trajectory anal-
ysis led to the conclusion that elemental ratios of soot, Pb, Zn,Cu,Ni and Mn to
non-soil vanadium in arctic aerosols are highest, intermediate and lowest for Si-
berian, European and North American sources, respectively.
4.6.3 Metals in the Oceanic Aerosol: Continental or Ocean Derived?
4.6.3.1 Formation of the Oceanic Aerosol

The oceanic aerosol originates from continental sources and from seaspray. It has
been estimated that the sea produces between 1000 and 10.000 tonneslyr of atmo-
spheric sea salt particles (Eriksson, 1959, 1960; Blanchard, 1963; Petrenchuk, 1980).
The influence of continents on the oceanic aerosol has been well demonstrated for
the North Atlantic Ocean which is influenced by Saharan dust storms (Schlitz et
aI., 1981) and also for the Pacific Ocean where certain areas are influenced perio-
dically by dust storms originating from the mainland of China (Duce et aI., 1980).
The formation of sea spray is caused by processes following the entrainment
of air bubbles in the water by wave action, their subsequent rise to the surface and
bursting. Other processes like the direct shearing of wave crests by the wind are of
minor importance (Wu, 1981a). In coastal waters, bubble generation by decaying
organic matter on the sea floor may also be significant (M ulhearn, 1981).
The minimum size of the bubbles is about 14-18 /lm (Wu, 1981) and the maxi-
mum size may be up to several mm's. The size spectrum of the bubbles is very simi-
lar in shape to that of the water droplets in the sea spray, except that the absolute
size of the latter is about 10-20% of that of the bubble (Wu, 1981a). The processes
associated with the bubbles bursting at the water-air interface are complex. Inten-
sive studies have been carried out by Woodcock and Blanchard (Woodcock et al.
1953; Blanchard and Woodcock, 1957; Blanchard, 1963; Blanchard and Woodcock,
1980; Cipriano and Blanchard, 1981) and by MacIntyre (MacIntyre, 1970, 1972,
1974). When the bubble is at the surface of the water, water drains from the film
cap which is exposed to the water surface and the bubble subsequently breaks pro-
TOP JET DROP

• 5em EJECTION HEIGHT
•
50 .. m DIAMETER
•
FILM CAP
•
•
• • •
•
• •
• •
•
• FILM DROPS
• 15-20 PRODUCED
SUBMICRON TO
• 10 .. m DIAMETER
500 .. m DIAMETER
";.
RISE VELOCITY
3.5 em / sec.
Fig. 75. Processes involved in the breaking of an air bubble at the water surface and the formation of
an aerosol (Winchester and Duce, 1977)
ducing very small film drops. With the breaking of the bubble, a high speed jet of
water is produced which moves upward from the bottom of the bubble cavity. This
jet rises rapidly, becomes unstable and produces between 2 and 5 drops (jet drops)
whose size is about 10-20% of the size of the original bubble (Wu, 1981). The pro-
cesses involved in the breaking of the bubble at the water surface and the formation
of an aerosol are schematically shown in Fig. 75.
Cipriano and Blanchard (1981) have shown that most of the smaller sea salt
particles are film drops and these are derived from large bubbles (1 mm and larger),
which may produce as many as 100 or more film drops per bubble. Film drop pro-
duction reaches a maximum for bubbles with roughly 2 mm diameter; bubbles
smaller than 1 mm or larger than 5 mm are relatively inefficient. The production
of jet drops falls off rapidly as the bubble diameter exceeds 1 mm. The total flux
of salt to the air in the model experiments of Cipriano and Blanchard (1981) was
dominated by the jet drops, suggesting that most of the oceanic salt mass flux de-
rived from it. It should be noted, however, that although the total mass transported
into the atmosphere is dominated by jet drops, the film drops will have the largest
residence time. Important with respect to the composition of the oceanic aerosol
is the fact that the film cap skims off a portion of the surface layer of the water,
and in the formation of the jet drops the surface layer of the water is also skimmed
off (interior of the bubble cavity). Macintyre (1970) estimated that the top jet drop
is composed of material from the interior of the bubble surface to a depth of 0.05 %
of the bubble diameter. Therefore, the composition of the sea surface micro layer
determines to a large extent the composition of the marine component of the
oceanic aerosol.
4.6.3.2 Sea Surface Microlayer
The sea surface microlayer may be operationally defined to extend from 3 A (the
diameter of a water molecule) to about 3 mm, which is near the extreme limit of
non-turbulent kinetics with no wind and also the penetration depth of jets from
small bubbles (MacIntyre, 1974).
Various ingenious methods have been designed to sample the surface
micro layer, which remove the layer varying in depth from 1 mm to 300 A (Lion
and Leckie, 1981a). This variation in sampling depth makes it difficult to compare
reported concentrations and enrichments of metals with the concentrations in the
bulk seawater. However, a recent survey showed that despite the large differences
in sampling methods, in most cases the concentrations of trace metals and organic
matter in the surface micro layer are enriched in comparison with the bulk seawater
(Lion and Leckie, 1981 b).
The absolute amount of trace metals in the surface layer may be quite high, and
in marsh areas high enough to necessitate taking it into account for flux calcu-
lations (Pellenbarg and Church, 1979).
The surface microlayer in oceans receives material from the water column by
rising bubbles (flotation) and from the atmosphere. The flotation process is similar
to the one used for the recovery of ore minerals in the mining industry. Organic
matter and particulate matter become attached at the water-air interface of the
bubble and are transported in this way to the surface.
In laboratory studies, Wallace and Duce (1975) showed that over 50 percent
of the particulate AI, Mn, Fe, V, Cu, Zn, Ni, Pb, Cr and Cd present in Narrangan-
sett Bay water could be scavenged by bubbles and transported to the surface
microlayer. These results were similar to those obtained for the Sargasso Sea (Wal-
lace and Duce, 1978). The upward bubble flux of trace metals was in the same order
of magnitude as the flux of atmospheric trace metals to the water surface.
In the experiments, large particles were formed, which could not be broken up
by vigorous shaking. This shows that bubbles in the sea may concentrate particu-
late trace metals, increase the size of particulate matter and hence the flux. The
downward flux from the sea surface layer was in remarkable agreement with the
independently estimated flux of particulate trace metals to deep waters associated
with sinking organic matter (Wallace etal., 1977). Bacon and Elzerman (1980) com-
pared 210-Po/21O-Pb ratios in bulk seawater, the surface layer and in atmospheric
fallout. The atmospheric ratio was much lower than the ratio in bulk seawater,
whereas the ratio in the surface layer showed only small deviations from that in
bulk seawater. This comparison suggests that the ocean is an important source of
trace elements in the ocean surface micro-layer.
Hunter (1980) made a detailed study of various processes affecting metal con-
centrations in the surface micro layer by considering atmospheric deposition,
Brownian diffusion, gravitational settling, bubble flotation and mixing. A sche-
matic presentation of these processes is shown in Fig. 76.
Both iron and manganese were strongly depleted in the surface micro-layer of
the North Sea on all occasions studied by Hunter (1980). The phase bearing these
two trace metals and probably also part of the other particulate trace metals (PTM)
consists of river-derived terrigenous material present on large particles. These par-
atmospheric
• deposition
CI a 7-\:
• •• U interfaclcal
Brownian diffusion •••• sedimentation boundary ~ 50 11m
---}------------;~~:-~----~-------~-~~!!~---------
o
~ ~0
~
i
r
mixing processes ". 0
eddy
I }
0°
0 bubble
It diffusion" 0 0 flotation
'......... °0
o
__________~~!!!.!I_~~!~~a.!.!!.!'~~~e_______ ~~~_~~_________ _
Fig. 76. Schematic presentation of the processes affecting trace metals in the surface microlayer (Hunter
1980)
ticles are transported to the micro layer by mixing processes but settle relatively
rapidly. The fact that other trace metals are enriched (Ni, Cu, Zn, Pb and Cd)
shows that for these trace metals the gravitational settling process is minor com-
pared with the other processes controlling these element concentrations in the sur-
face microlayer. By comparing residence times for both flotation and atmospheric
deposition necessary to cause a two-fold enrichment (times varying between 1 min
to 28 minutes for the enriched elements by flotation and 24 to 1500 minutes for the
atmospheric deposition) it was shown that bubble flotation was the major process
for the enrichment of particulate trace metals in the surface layer. Foggy con-
ditions, accelerating the scavenging of suspended particles in the atmosphere en-
hanced the atmospheric flux. After the fog had cleared, the metal concentrations
in the surface microlayer declined (Hunter, 1980).
Metals in aerosols are partly soluble (Fig. 67). Solubility of metals in aerosols
in seawater studies by Crecelius (1980) and by Hodge et al. (1978) indicate, that
the deposition of aerosol particles contributes both to the particulate and dissolved
metals in ocean surface waters.
Model calculations on the speciation of trace metals in the sea surface
microlayer have been carried out by Lion and Leckie (1981). In the bulk seawater,
both Cd and Hg are strongly complexed with chloride. Copper and lead compete
more effectively for dissolved complexing agents. If transport to the surface layer
takes place by dissolved organics, then the transport of copper and lead is favoured
over cadmium and mercury. These results support the fact that in surface layers
the enrichment by copper and lead has been more consistently observed than en-
richment of cadmium and mercury (Lion and Leckie, 1981).
4.6.3.3 Composition of the Oceanic Aerosol

The composition of the marine components of the aerosol depends on the compo-
sition of the film and jet drops. They both skim off part of the surface layer, but
Table 31. Source strength for trace metals in the marine

aerosol (x 109 g/y} (Weisi:!, 1981)
Element Ocean
mean min max
Cadmium 0.4 0.1 7

Lead 5 0.2 20
Vanadium 9 5 20
Zinc 10 0.5 100
additionally the bubbles scavenge the water column during their rise to the surface.
Piotrowicz et al. (1979) and Weisel (1981) observed a strong dependence between
the EF (sea) (the enrichment factor in the aerosol with respect to the composition
of the bulk seawater) and the depth at which bubbles were generated in an ex-
perimental set-up in the field for the metals Zn, Cd and Pb. Copper gave a positive
intercept in the graph depicting the relation of EF (sea) value to the bubble gener-
ating depth, which was attributed to microlayer enrichment of this trace metal
(Piotrowicz et al. 1979). Very high EF (sea) values for copper were found in areas
with visible slicks. It was concluded that the enrichment of copper on sea salt
aerosols may be related to biological and/or organic processes and that Cu and Zn
may be scavenged by rising bubbles (Piotrowicz et aI., 1979). The data from Weisel
(1981) on lead also suggest that rising bubbles play an important role in its enrich-
ment in the aerosol.
Therefore it appears that the marine component of the aerosol depends not on-
lyon the composition of the surface layer, but also on the bubble generation depth.
If the EF (sea) value for trace elements is known, the contribution of the sea
salt spray to the marine aerosol can be easily calculated from data on the amount
of sea spray produced annually. Since data are not available on the total number
of bubbles generated and the depth of submergence, Weisel (1981) made calcu-
lations for minimum EF (sea) values of metals by using the data obtained from ex-
periments conducted just below the sea surfaces and for maximum EF (sea) values
from experiments conducted at a depth of two meters. This depth was chosen be-
cause studies by Blanchard and Hoffmann (1978) suggested that at 2 meters the
bubble surface appears to be saturated and ceases to scavenge additional material.
The results of calculations by Weisel (1981) are shown in Table 31. Estimates
of natural and other fluxes are given in Chap. 4.1, Table 17.
The results show that upwards of 10% of the total global atmospheric con-
centrations of cadmium may come from the oceans; for vanadium there also may
be a significant marine input.
It should be noted, however, that anthropogenic sources are localized and that
their influence may be less for pristine marine environments than global data sug-
gest. Interesting results have been obtained on the relative strength of the various
sources contributing to the aerosol at Eniwetok in the North Pacific. The compo-
sition of the atmospheric aerosol at Eniwetok shows strong seasonal changes
100r---------------------,
.....
Fig.77. Atmospheric concentrations of sea salt
and dust at Eniwetok (Merrill and Duce, 1982)
g! Salt • • • • •
... 10
!! E
'E• .!
.a
II
C
g:.
II
;:
"II
II.
II
1.0 .. Dust
• E
.cII. .."
~ f 0.1
E Is
cE
0.01 '--__-'--_-'-__--'-_----L._--'
April 1 May 1 June 1 July 1 Aug 1 Sep 1
Sample Collection Date, 1979
(Fig. 77). The concentration of salt with a MMD of 3-4 !lm was nearly constant,
whereas the dust concentration showed strong variations.
The MMD of the dust particles ranged from 0.7 to 1 !lm, which is consistent
with a very long atmospheric transport path (Merrill and Duce, 1982). The alter-
ations could be explained by seasonal changes in large scale wind patterns over the
North Pacific and the seasonal character of dust storms in desert regions of China
(Duce et ai., 1980). The dust storm activity is apparently greatest in the spring in
China due to the combined effects of low rainfall, the increased occurrence of high
surface winds and wind erosion of soil freshly ploughed for planting (Merrill and
Duce, 1982).
Some trace metals (e.g. AI, Sc, Mn, Fe, Eu, Ni, Co, V, Hf, Cr, Th, Cu, and Rb)
were also found to be associated with the dust storms. Their EF (crust) values
varied between 1 and 3; Zn, Cs, Sb, Ag, Pb, Cd and Se had EF (crust) values higher
than 4, and apparently had some source other than continental weathering. The
MMD data, the EF (crust) data and the mean atmospheric concentrations at En-
iwetok are shown in Table 32.
The elements associated with crustal material showed seasonal cycles that re-
flected the input of dust from mainland China. However, the enriched elements did
not show these strong seasonal variations. These elements apparently have con-
tinental sources which are not as seasonal in nature, but are more evenly dis-
tributed throughout the year (Merrill and Duce, 1982) The MMD of the enriched
elements is <0.5 !lm, which is consistent with a possible pollution source. If they
were associated with sea spray, the MMD would be higher.
The sources for lead were unravelled by Settle and Patterson (1982) by using
isotope lead ratios. The 206-Pb/207-Pb ratios in the surface waters (0.184) differed
from that in the dry deposition (1.226) and showed that most of the dry deposition
originated from lead-rich particles which are transported from land. Experiments
with a bubble generating device confirmed this conclusion: both methods indicated
that only 1-15% oflead in air at Eniwetok originates from sea water lead in sea-
spray.
The deposition velocity of the lead indicated that it must be associated with
large diameter (7 !lm) particles. However, the MMD diameter of lead in the atmo-
Table 32. Selected data for trace elements in the atmosphere at Eniwetok (Merrill and Duce, 1982)
Metal MMD EF (crust) Mean atmospheric concentration
March - June Rest of the year

ng/m 3 ng/m 3
Al 0.8 75 3
Fe 0.72 1 50 2
Mn 0.88 0.9 1 0.04
pg/m 3 pg/m 3
Sc 0.70 0.8 20 1
Cr 1.8 200 30
Co 0.75 1.0 25 1
Cs 0.79 4.8 15 0.5
Rb 1.1 3.0 200 40
Th 0.84 2.0 20 1
V 0.76 1.6 120 20
Zn 0.04 4.6 250 80
Cd 57 10 2
Cu 0.96 2.3 50 10
Pb 0.25 45 150 100
sphere was only 0.25 Jlm (Table 32). The small lead-rich sub-micron particles are
transferred to large sea salt particles during cloud forming condensation processes
(Settle et al. 1981). These processes make aerosols injected into the atmosphere by
bursting bubbles as efficient as plant foliage on land in sequestering small anthro-
pogenic lead-rich particles and makes the dry deposition flux of lead to the oceans
important (Settle and Patterson, 1982).
The 206-Pb/207-Pb ratio also showed seasonal changes. During the dry season,
when the silicate dust concentrations were highest, the ratio was similar to the ratio
in lead aerosols emitted from Asia and Japan. During periods oflow dust concen-
trations, the ratio of206-Pb/207-Pb was more like the ratio in lead aerosols emitted
from the United States.
In a comparison of experimental data with the atmospheric concentrations at
remote regions like Eniwetok, Weisel (1981) concluded that up to 10% of the lead
is from a marine source, for cadmium and vanadium this contribution is in excess
of 30% and zinc 10 to 20%. The marine component at Eniwetok is found mostly
on large particles.
Weisel (1981) estimated that for the oceans as a whole the oceanic contribution
is 10% for cadmium, 3% for zinc and 1% forlead present in the oceanic aerosol.
5 Metals in Continental Water
5.1 Introduction
Although the volume of continental waters is insignificant with respect to the mass
of the hydrosphere, these waters have their particular importance as the basis of
our freshwater supply as well as geochemically, since they are responsible for most
of the weathering and erosion of the land masses. In the latter sense terrestrial
waters are the major medium involved in the "exogenic cycle", i.e. processes on the
earth's surface and uppermost lithological units, in which solid and dissolved
weathering products are transported, deposited and solidified, and - after diagen-
esis and tectonic uplift - may be exposed to weathering and erosion again. While
most of these processes of deposition and rock formation take place in the marine
milieu, there are characteristic geochemical interactions in the soils and, particular-
ly interesting, in the lacustrine environment.
The input of material into the ocean is mainly affected by river discharges.
Table 33, where the different modes of transport are distinguished according to an
estimation made by Judson (1968), clearly demonstrates, that - in particular for
the river transport rates - there is an enormous effect of human activity on
weathering and erosion processes as a result of ploughing agricultural soils, defor-
estation, and all types of engineering on the earth's surface. On the global average
the concentration of dissolved constituents is 114 mg/l (Gibbs, 1972), while the
contents of solid are approx. 330 mg/l (Judson, 1968); of the latter more than 90%
are transported in suspension.
It should be noted, however, that there are very significant regional differences
with respect to transport and erosion efficiency in rivers. Table 34 (after Judson,
1968) shows rather similar distribution patterns for dissolved and solid mass trans-
port as well as for erosion rates in the examples from Amazon and Mississippi
River catchments, whereas the low and high denudation rates in the Congo River
basin on the one hand, and in the Colorado River basin on the other hand are
mainly affected by the strongly different modes of particle erosion and transpor-
tation.
These differences become even more spectacular when the seasonal influences
are considered. Table 35 (from Garrels and MacKenzie, 1971) compares the material
transport in selected tributaries to Amazon River (data from Gibbs, 1967): while
the material concentrations in the mountainous rivers are higher by a factor of ap-
prox. 12 to 14 compared to the tropical rivers during the dry season both for the
dissolved and suspended load, and this ratio is only insignificantly changed in the
dissolved concentration at stronger rainfall, there is a very strong increase in the
Introduction 139
Table 33. Annual discharge of material into the oceans (Judson. 1968)
(10 6 tonnes/year)
By rivers: Before human influences 9,300

After human influences 24,000
By Wind 60-360
By glaciers 100
From extraterrestrial sources 0.35-140
Table 34. Transport and erosion efficiency of large rivers (after

Judson, 1968)
Transport in Erosion in
tonnes/Ian 2 / year cm/l,OOO years
Dissolved Solid
Amazon 37 87 4.7
Congo 40 14 2.0
Colorado 23 417 17
Mississippi 39 94 5
Table 35. Material transport in Amazon River tributaries. (Garrels and MacKenzie, 1971; after Gibbs,
1967). Data in mgjl
Dissolved load Suspended solids
Wet season Dry season Wet season Dry season
Mountainous rivers 112 192 600 70

Tropical rivers 9 16 10 5
solid matter concentrations of the mountainous rivers during the wet season. This
influencing factor is significantly affecting the overall balance of material transport
in the lower Amazon River system and also the material discharges into the ocean.
The much higher variability of the solid matter transport, which is reflected by
an exponential increase with water discharge or flow velocities (Muller and Forstner,
1968), generally effects significantly larger differences in the mechanical denuda-
tion than in the chemical erosion rates for a particular catchment area (Garrels and
MacKenzie, 1971). With respect to the transport of metals in continental waters
it has been noted by Yeats and Bewers (1982) from a study of the St. Lawrence
River that the variability in the concentrations of dissolved metals is unrelated to
changes in water flow and therefore the dissolved fraction of metals exhibits a cer-
tain degree oflong-term stability, whereas particulate AI, Fe, Mn, and Zn concen-
trations characteristically depend from water discharge. This could make the cal-
culations of the flux rates particularly difficult for those elements, which exhibit
a strong tendency for solid associations (Martin and Meybeck, 1979).
Table 36. Global metal fluxes in dissolved and particulate matter. (After Yeats and Bewers, 1982),
and solid/solution ratios. Fluxes in 106 kg/year
Fe Al Co Mn Ni Cu Zn Cd
Dissolved
St. Lawrence" 2,200 3,000 7 250 57 88 330 4
Amazon/Yukon b 1,400 3 630 11 61
Mississippi" 160 320 51 63 320 3
Particulate
St. Lawrence" 990,000 1,400,000 280 26,000 780 1,700 6,700 30
Amazon/y ukon b 1,100,000 - 750 21,000 2,200 6,300
Mississippi" 860,000 24,000 1,000 770 3,300 26
Avg. 22 rivers d 730,000 1,500,000 320 17,000 1,500 1,600 5,400
Ratio particulate/dissolved fluxes 510 480 100 55 35 35 15 8
a Yeats and Bewers (1982)

b Gibbs (1977)
" Trefry and Presley (1976)
d Martin and Maybeck (1979)
However, the data in Table 36 (after Yeats and Bewers, 1982), which represent
the best contemporary estimates of global river-borne metal discharges (the data
of the individual rivers are scaled for the ratio to the global discharges) show a re-
markable degree of similarity. Despite the fact that the rivers vary from tropical
to subarctic, from natural to highly industrialized, and from suspended loads of
10 mg/l to 580 mg/l, the calculated metal discharges seldom vary by more than a
factor of three (Yeats and Bewers, 1982).
In the last line of Table 36 the ratios of average particulate and dissolved fluxes
of the individual metals are arranged in decreasing order; this sequence reflects an
increase in the relative mobility of the metals with Al and Fe being the least reactive
examples, Co, Mn, Ni, and Cu at intermediate mobilities, and Zn and Cd exhibit-
ing a relatively high percentage of the total flux in dissolved state. It should be
noted that some of these ratios - which resemble the "sink-effect-values" in the
"ecological risk index" of Hakanson (1980) - can be significantly different in rivers
affected by higher inputs of anthropogenic waste materials (see Chaps. 5.3.1.).
5.2 Metals in Rocks and Soils
Metals released through weathering processes and their transport to rivers and the
oceans are one of the major fluxes in the hydrological cycle. The mass transport
rates of metals in these processes, however, depend significantly on their occur-
rence in igneous, metamorphic and sedimentary rocks (in a more regional view on
the distribution of these basic rock types in the particular watershed) and on the
intensity of the weathering processes and the mode of transport. During transport
anthropogenic additions can be made to the metals released by natural weathering
Igneous and Metamorphic Rocks 141
processes and the natural weathering intensity can be greatly enhanced by anthro-
pogenic effects such as acid precipitation, land use or deforestation.
5.2.1 Igneous and Metamorphic Rocks
The evolution of igneous rocks from molten magma - in a sequence from ultra-
mafic rocks to the series of gabbro-diorite-granodiorite-granite (the latter called
"felsic" rocks) - involves the continuous and discontinuous reaction of common
minerals as crystallization proceeds ("reaction principle", Bowen, 1928) (Fig. 78).
Rarer minerals which crystallize in this sequence include apatite, fluorite, mon-
azite, titanite, xenotim and zircon (Bowen, 1979). Later the elements which have
not been trapped in major or accessory minerals crystallize out separately, in small
amounts, forming pegmatites; these elements - e.g. Be, Cs, Li, Sn, U, W, Zr - have
unusual ionic radii which lead to their natural segregation. With respect to crystal-
lochemical factors, such as ionic radius, valence and electron configuration typical
elementary associations are found in igneous rocks (Krauskopf, 1979):
(i) Cations with large radii and low electric charges tend to substitute for potas-
sium, hence are concentrated in felsic rather than mafic rocks; these elements (Rb,
Cs, Ba, Tl) are often called the "large-ion lithophile" group (LIL);
(ii) several cations with smaller radii and mostly with higher charges (U, Th,
B, Be, Mo, W, Nb, Ta, Sn, Zr) also are concentrated at the felsic end of the series,
not because of extensive substitution but rather because their size and charge make
it difficult for them to substitute for any major ions in common silicate structures
("incompatible" elements);
(iii) many elements with intermediate radii, especially metals of the transition
groups, substitute readily for iron and magnesium, hence they are abundant in the
earlier members of the differentiation sequence; some (Cr, Ni, Co) are enriched
with Mg in ultramafic rocks, others (Mn, V, Ti) have maximum abundance in gab-
bros and basalts;
(iv) part of the metals, which substitute to some extent for major cations in sili-
cate structures, are left to accumulate in the residual solutions that may eventually
form sulfide ores ("chaicophile" elements);
(v) some minor elements indicate properties similar to major elements, e.g.
gallium/aluminium, cadmium/zinc, hafnium/zirconium, and are found in their
structures without significant differentiation.
Decreasing temperature---_
olivine _pyroxene_hornblende _ b i o t i t e \
quartz
7eldSpar)
Fig.78. The sequence of min-
erals formed during the crys-
tallization of a mafic magma Ca· plagioclase Na.plagioclase
(Bowen. 1928)
With respect to supergenic (weathering, pedogenesis) chemical processes three

"distributive" types of elements in minerals have been distinguished (Lelong et aI.,
1976; after Goldschmidt, 1954):
Camouflaged Elements, which exhibit the same ionic radius, but a similar or differ-
ent charge: e.g. Rb, Cs, Pb may replace K + in feldspar; Mn, Co, Zn, Li, Cr and
V may replace Fe 2 + , Fe 3 + , Mg or Al in Fe-silicates; .
Autonomous Elements are located outside the structure of the essential minerals,
but incorporate into accessory ones: e.g. Sand Cu are found in sulfide minerals,
B is found in tourmalines, Zr in zircone, Cr in chromite and rare earths in apatites
and monazites;
Fissural Elements are linked to the lattice surface, retained in an adsorbed form on
intercrystalline surfaces inside the physical discontinuities of the crystals or inside
the fissures; e.g. Ni, Co and Mn inside the microfissures of antigorite (serpentine
asbestos), Cu, Cr, Wand V inside microfaults in biotite.
This qualitative distribution of elements conditions their behaviour during the
chemical weathering processes; the release of camouflaged elements depends on the
degree of decomposition of the parent minerals as opposed to fissural elements,
which are generally very rapidly released during changes of the chemical environ-
ment.
Characteristic examples of trace metal concentrations in minerals of magmatic
origin are given in Table 37 (after Wedepohl, 1972, 1974):
(i) The data do not indicate that copper has a strong tendency to be incorpo-
rated in any particular crystal structure of rockforming silicate minerals, but it
seems to be enriched in the earlier counterparts (olivine, pyroxene) of the magmatic
differentiation series rather than in the later crystallization products (alkali feld-
spar, quartz);
(ii) zinc, on the other hand, is preferentially incorporated into a distinct struc-
tural position of silicates and oxides, where it replaces ferrous iron and magnesium.
Biotites and amphiboles are often very rich in zinc;
(iii) lead, in the silicate structures, replaces the positions of large monovalent
or divalent metals, especially potassium. This explains the enrichment in both
muscovite and alkali feldspars.
The major occurrence of elements in common minerals formed in magmatic
crystaIIization and differentiation are summarized in Table 38 (from Bowen, 1979).
During the magmatic evolution of the major constituents the contents of Mg
and AI decrease, while those ofSi and K increase.
Fig. 79 (adapted from Wedepohl, 1966) shows some characteristic development
trends of trace elements in the magmatic differentiation (as well as the respective
element concentrations in argillaceous sediments). In accordance with the princi-
ples of element distribution in minerals, as discussed above, zinc fluctuates relative-
ly little within the magmatic differentiation series. In contrast, the concentrations
of chromium and nickel in ultrabasic and gabbroid rock are 100 to 1000 times
higher than in granitic rocks. From bedrock of this type, therefore, a characteristic
enrichment of chromium, cobalt (as well as of nickel, copper and other elements)
can be derived in their erosion products and sediments. Granitic rocks, in contrast,
Igneous and Metamorphic Rocks 143
Table 37. Distribution of selected elements in rock-forming minerals (date from Wedepohl, 1972, 1974)
% in earth's crust Cu Zn Pb
Range Mean Range Mean Range Mean

ppm ppm ppm ppm ppm ppm
1 Olivine 6- 960 115 50- 82 63 0.2- 7.2 2

4 Pyroxene 4-1,000 120 16- 200 97 0.3- 20 6
5 Amphibole 1- 300 78 34- 690 196 1 - 70 11
4 Biotite 1- 480 86 34--4,000 527 7 - 95 21
2 Muscovite 5- 152 36 24- 200 59 6 - 70 20
42 Plagioclase 8- 700 62 I- SO 17 - 70 20
22 Alkali feldspar 1- 20 4 10- 24 15 2 -700 53
18 Quartz 2 4- 11 7 0.1- 3 1
Table 38. Common mineral formed in magmatic crystallization (major constituents in capital letters)
and their co-crystallized elements (Bowen, 1979). With permission of Academic Press, London
Stage of Mineral Ideal formula a Elements

co-crystallized
crystallization
1 OLIVINE Mg zSi0 4 Fe(lI)

2 Pyrite FeSz Ag, As, Cd, Co, Cu, Mo, Ni, P, Pd, Sn, Te
3 Pyrrhotite FeS
2 Magnetite Fe304
2 Chromite FeCrZ04
2 Ilmenite FeTi0 3
3 FELDSPAR MAISi 30 s Ba, Ca, K, Na, Rb, Sr
3 AMPHIBOLE L14Si1604(OH)4 Ca, F, Fe, Li, K, Mg, Mn, Na, Sr, Ti
3 PYROXENE L zSi0 6 K, Li, Mn, Na, Ti
3 MICA KMg 3(OH}zAISi 30 1o Ba, F, Fe, Li, Mn
3 QUARTZ SiOz
3 Apatite Cas(OH)(P04h As, F, Pb, Se, V
3 Fluorite CaF z
3 Monazite CeP0 4 La-Eu, Th
3 Titanite CaSiTi0 6H z F
3 Xenotime YP0 4 Gd-Lu
3 Zircon ZrSi0 4 Hf
4 Miscellaneous Au, Be, Cs, Hf, La-Lu, Li, Nb, Sn, Ta,
pegmatites U, W, Y,Zr
5 Volatiles Ar, C, H, He, Hg, N, 0
a L-Ca, Fe(Il) or Mg; M-K or Na
are enriched in lead and beryllium by a factor of 50 compared to ultrabasic rocks.

The increase of alkaline earth metals (with a large ion radius) barium and ru-
bidium, is even greater following the magmatic differentiation sequence.
Metamorphism involves the conversion of magmatic and sedimentary rocks to
metamorphic rocks at higher temperatures and/or pressures. Although the changes
in elemental composition during these changes have not been thoroughly studied,
they are probably relatively minor ones (Bowen, 1979).
In order to assess the influence of different magmatic rocks on the composition
of aquatic sediments, the relative percentage of individual rock types must be taken
into consideration. These calculations are still relatively controversial. Taylor
(1964) suggested that the crust consists of half basalt and half granite; Wedepohl
(1969) prefers a crust consisting of 44% granite, 34% granodiorite, 13% gabbro
and 8 % quartz diorite (see compilation of Bowen, 1979).
5.2.2 Weathering and Element Migration
Weathering includes all physical, chemical and biologic actions which abrade or
dissolve rocks. The main agent of chemical weathering is water, especially when
it contains a small amount of dissolved carbon dioxide which makes it more acidic.
Sodium is readily leached from rocks, while calcium, magnesium and potassium
are dissolved somewhat more slowly; the other common rock constituents, alumin-
ium, iron and silicon are much less soluble (Bowen, 1979).
A general sequence of relative mobility of common elements during weathering
processes, corresponding to the ratio of the element in river water to that in rock,
was established in 1937 by Polynov (Table 39).
It is indicated that the sesqui-oxides of Al z0 3 and Fez03 are least mobile (ap-
prox. 10- 4 to chlorine) and silica moderately, whereas the basic cations of KzO,
MgO, NazO and CaO can be readily removed. This development is paralleled by
the migrational series during the weathering of silicious rocks in temperate cli-
mates, as established by Perel'man (1967).
The susceptibility of the minerals to chemical weathering generally shows a se-
quence which is reverse to the reaction series of Bowen (1928, see Fig. 78); least
stable minerals of the discontinuous series are olivine and pyroxene, of the contin-
uous series Ca-plagioclase (Goldich, 1938). The weathering stability for soil min-
erals has been found higher for most clay minerals - especially for aluminous
chlorites and kaolinites - than for quartz; on the other hand, calcite and, particu-
Weathering and Element Migration 145
Table 39. Relative mobility of common elements during

weathering processes (Lelong et aI., 1976; after Polynov,
1937)
Group Element Relative mobility
Sesqui-oxides A1 z0 3 0.02
Fe303 0.04
Silica Si0 2 0.20
Basic cations K 20 1.25
MgO 1.30
NazO 1.40
CaO 3.00
Anions C0 3 57
CI 100
Table 40. Solubility products (S.P.) of the hydroxides and some compounds (Lelong et aI., 1976). With
permission of Elsevice Publ. Co.
Category' Ele- S.P. S.P. S.P. S.P. Category' Ele- S.P.

ments hydrox- carbon- sulfurs varied ments hydroxides
ides ates com-
pounds
A Na+ 2.9 C Be z + 20.8

(</1 <2) Cs+ 2.8 (3<rP <7) Ce 3 + 22.3
K+ 2.6 Hg2+ 25.5 (HgO)
Li+ 1.4 Sc3+ 26.3
TI+ 0.2 20.3 Cr 3 + 30
Ba2+ 2.3 8.8 10.0 Bi3+ 30.4
Sr 2 + 3.5 9.6 (BaS0 4 J AI 3+ 32.5
Ca 2 + 5.3 8.4 4.5 In3+ 33.2
(CaS0 4 ) y3+ 34.4
Ga3+ 35
Fe3+ 38
Ti 4 + 40
Th 4 + 44.7
TI3+ 45
B Ag+ 7.6 49.2 9.8 U4 + 45
(2<</1 < 3) (Ag 2O) (AgCl) Mn 4 + 56
Mg2+ 11.0 5.1 Sn 4 + 56
Mn 2+ 12.7 10.2 12.6
Cd2+ 13.7 11.3 27.8
Ni 2 + 14.7 6.9 25.4
C0 2 + 14.8 12.8 20.4
Fe 2 + 15.1 10.5 17.2 D y5+ 14.7 (V 205)
Pb2+ 15.3 13.1 27.5 8.0 (7<¢<11) Si 4 + 8.0 (Si0 2)
Znz+ 17.0 10.8 22 (PbOP4 ) Ge 4 + 2.3 (Ge02)
La+ 19.0 12.7
Cu2+ 19.7 9.3 36.1
E B3+
(¢ > 11) As 5 + < 0
p 5+
• Arranged according to ionic potentials "</1" (ratio of the charge to the ionic radius)
lady, gypsum are much less resistant than the least-resistant silicates (Jackson,
1968).
The element mobility depends, in the second place, on their solubility limits,
which are mainly a function of pH and, for elements such as Fe and Mn, of the
Eh (Lelong et aI., 1976). Solubility limits are mainly determined by the value of sol-
ubility products of the hydroxide compounds of the M(OH)n type, classified ac-
cording to their ionic potentials (IP; Table 40).
(Ions in solution attract water molecules, cations to the negative, anions to the
positive part of the polar molecule. Package density depends on size - as larger the
ion the more water molecules being attracted. The smaller the ionic radius and the
higher the charge of the central ion the more acid are its oxides. If the ionic poten-
tial, i.e. the positive charge on the surface of an ion is high enough, they repulse
part of the protons of the water molecules, thus giving neutral central ions, i.e. in-
soluble hydroxides. At higher repulse all protons are deprived from the water mole-
cules and an oxy-acid-anion formed, which is soluble).
In the presence of anions, such as bicarbonate, sulphate, hydrogen sulfide etc.
the values of Table 40 are no longer valid; the same pertains to the presence of com-
plexing agents, e.g. organic acids, where an increased mobility is noted for slightly
soluble or insoluble elements, such as metallic elements belonging to the Fe- or Al-
group (Pedro and Delmas, 1970; Lelong et aI., 1976; Saxby, 1976). The following
divisions of the elements have been proposed:
- elements forming soluble hydrated or simple cations in the full range of pH;
these are alkaline and alkaline-earth elements (ionic potential below 2);
- elements forming insoluble hydroxides in a certain range of pH; these are (with
increasing solubility product) Fe2+, Mn 2 +, Ni 2 +, Co2+, Pb 2 +, Zn2+, Cu2+,
Cr3+, AI3+, V3+, Fe3+, Ti 4 +, which have an ionic potential between 2 and 7;
most of them are only soluble at acid or very acid pH;
- elements forming simple or complex anions, which have IP above 7 and are more
or less soluble within a large range of pH, e.g. (N0 3)-, (S04)2 -, (P0 4)3-.
Of importance too, are the redox conditions that evoke a significant "migration
contrast" (Perel'man, 1967) for some elements; e.g., the migrational intensity for
uranium and zinc in oxidizing environments is "strong", but in strongly reducing
environments it is "weak" or "very weak". Copper, nickel and cobalt pass from
a moderate migrational intensity in an oxidizing milieu to near immobility in
strongly reducing environments.
A further mechanism for migration intensity during weathering is the "entrap-
ping of elements in secondary mineral products" (Lelong et aI., 1976). From a com-
prehensive data compilation by Tardy (1969) specific accumulation stages for
the various chemical elements in the major facies of weathering can be derived
(Table 41).
Chiefly the iron and manganese phases in crusts and their deposition on clay
minerals (mainly montmorillonite) are significant carrier substances for many
trace metals. Also of global importance in the are the amorphous weathering prod-
ucts in the selective entrapping of some elements: Si-Mg-gels from experimental
weathering of peridot contain high concentrations of Mn, Fe, Co, Ni, Zn and Cu
(Lelong et aI., 1976). The process of reverse weathering (Mackenzie and Garrels,
Weathering and Element Migration 147
Table 41. Partition of chemical elements between the main facies of weathering: oxi-hydroxides, clay
minerals, salt and alkaline silicates (Lelong et aI., 1976; after data from Tardy, 1969) with permission
of Elsevier Publ. Co.
Bauxite Iron crust Manganese crust Calcite crust Sulfates Sodium carbonates
AI-Ga-B Fe-Ti-V- Mn-Fe-Co- Ca-Sr-Ba- Ca-Sr-Ba Sodium chlorides
Cr-Mo Pb-Ba-Sn- Zn Na-Rb-Li
Ni-Cu
Kaolinite Montmorillonites Zeolites

Magadiite
SiOz-Ti-Al-Fe-Mg-Ni- Mg-montmorillonite
Zn-Pb-Cu Si0 2 -Mg-Na-Ca
Humid climate Arid climate

Upstream Downstream
Top of profiles _ _ _ _ _ _ _ _-'I"'oc:!!re""as""io...
g m"'o""b""ili~ty_ _ _ _ _ _ _--+, Bottom of profiles
1966), in which marine clay minerals recrystallize from amorphic weathering prod-
ucts, is considered a decisive factor in the chemistry of major cations in ocean
waters.
It is important to note, however, that the bulk of the detrital trace elements
never leaves the solid phase from initial weathering to ultimate deposition. There-
fore, detrital minerals from magmatic, metamorphic and sediment source rocks
may significantly affect the metal composition of aquatic sediments. Placer de-
posits, which result from the residual accumulation of heavy, stable minerals dur-
ing weathering and from their absolute accumulation during formation of alluvial
fans by sedimentation are major sources of economic concentrations of metals
such as gold, platinum, zirconium, thorium, tin and tungsten (Hails, 1976). How-
ever, even in "normal" sediments the heavy mineral fraction can contribute signifi-
cantly to the enrichment of metals. Investigations performed by Loring (1978,
1979) on sediments of the St. Lawrence Estuary and open Gulf of St. Lawrence in-
dicate that 61-98% of total Zn, Cu, Pb, Cr, Ni and V concentrations are held de-
tritally in various sulfidic minerals (pyrite, chalcopyrite), oxide minerals (mag-
netite, ilmenite, chromite) and ferromagnesial silicates (amphiboles, chlorite,
pyroxene and garnet). Detrital host mineral concentrations are highest in the estu-
ary, decreasing seaward from the interior sources of terrigenous clastic material.
The products of weathering in the sequence given in Table 41 are equivalent to
the major groups of sedimentary constituents, as classified by Goldschmidt, 1954;
see also Degens, 1965; Bowen, 1979:
- Resistates, or unchanged minerals from primary rocks;
- Hydrolysates, mostly clay from weathering of aluminosilicates minerals;
- Oxidates, precipitates ofFe(OHh, e.g. as "coatings" on detrital grains;
- Carbonate precipitates, mostly calcite, e.g. as skeletons of marine plankton;
- Evaporates, mostly salt or gypsum from drying salt lakes.
In addition to this classification "Bioliths" or resistant organic matter, includ-
ing peat and petroleum, which are mainly deposited in anoxic regions where spe-
cialized bacteria remove oxygen atoms from dead organic matter; typical elements
adsorbed are uranium in some peats, and Mo, Ni and V in some petroleum
(Bowen, 1979).
5.2.3 Chemistry of Sedimentary Rocks
During diagenesis the weathering products are converted to sedimentary rocks by

processes involving loss of water, decrease in organic matter, recrystallization and
cementation. The effects of these conversions during the stage of early diagenesis
were treated in section 3.2.3; the changes of the elemental composition in the later
stages, i.e. cementation of sandstones and formation of shales, has not been stud-
ied. From a comparison of analyses of marine clays with the shale composition
there seem to exist gains ofBa, Hg, Se, Sr and U, and losses ofB, Br, Cu, Mn, Mo,
Ni, Pb and rare earths; if these not very distinct changes are really due to diagenetic
effects is not sure (Bowen, 1979). There seems to exist more evidence for elemental
changes during the diagenesis of plant remains; Nicholls (1968) suggests that or-
ganic matter adsorbs - according to higher concentrations at the margin of coal
seams - B, Ge, Mo and some Co and Ni, while sulfidic mineral impurities absorb
As, Co, Cu, Ni Pb and Zn, and other elements such as Cr, Ba, and V may be ad-
sorbed by clay mineral impurities.
Bowen (1979) has noted the close similarity in elemental composition of aver-
age igneous rocks and "average" sedimentary rock, the latter being calculated as
74% shale + 15% limestone + 11 % sandstone. Table 42 shows in the first two col-
umns that sedimentary rocks are depleted in sodium (which remains behind in the
ocean), but are somewhat enriched in calcium and a number of "volatile" elements,
which may well be associated with the organic matter in sediments - As, Sb and
Hg.
Argillaceous rocks consisting essentially of clay minerals (apart from finely dis-
persed detrital organic matter and iron oxyhydrates) constitute nearly 75% of all
sediments. Their elemental composition, therefore, dominates the calculations of
the average sedimentary rock (columns 2 and 3 in Table 42). Except for the loss
of sodium, the increase in potassium and lithium, and the characteristic enrichment
of tin, arsenic, antimony and mercury in the shale composition are similar to the
mean crust data (column 1 in Table 42). The strong enrichment of arsenic, antimo-
ny and selenium has been explained by the high adsorptive capacity of sedimentary
iron accumulations for these elements; the hydrous manganese oxides, which as
colloids are negatively charged (whereas ferric oxides generally exhibit a positively
charged colloid) mainly adsorb cations, e.g. Ba, Zn, Ni, Cu, Pb, Co and Mo (Ma-
son, 1966). This mechanism provides an explanation for the increase of trace ele-
ments observed in the deep-sea clays (column 4 in Table 42) compared to the shale
levels (see also Chapter 7.4 on "Oceanic sediments").
Probably more representative for the chemistry of allochthonous inputs into
natural aquatic systems - and therefore used as a proper reference basis for the cal-
culation of anthropogenic effects - are shallow water argillaceous sediments, both
occurring in continental basins and in coastal marine environments. The data listed
Table 42. Elemental composition of the earth's crust and sediments (major cations in %; minor and trace elements Ilg/g)
Element Mean crusta Mean sediment b Average shale c Deep-sea clayc Shallow water River sus- Sandstone f Limestone f Soil h
()
sediment d pended sed. e ::r
§.
Silicon 27.7% 24.5% 27.3% 25.0% 25.0% 28.5% 32.7% 3.2% 33.0% '"
::;
8.2% 8.4% 4.3% 0.7% 6.7% '<
Aluminium 7.2% 8.0% 8.4% 9.4% 0
Iron 4.1% 4.1% 4.7% 6.5% 6.5% 4.8% 2.9% 1.7% 3.2% ....
rn
4.1% 2.9% 3.1 % 34.0% 20% n
Calcium 6.6% 2.2% 2.9% 2.2% e:
Magnesium 2.3% 1.4% 1.5% 2.1% 2.1% 1.2% 1.2% 0.6% 0.8%
~
t:I
Sodium 2.3% 0.6% 1.0% 4.0% 4.0% 0.7% 1.0% 0.1% 1.1%
p;-
Potassium 2.1% 2.0% 2.7% 2.5% 2.5% 2.0% 1.5% 0.3% 1.8% ...
'<
Titanium 0.6% 0.4% 0.5% 0.5% 0.5% 0.6% 0.4% 0.03% 0.5% ~
550 0
Phosphorus 1,000 670 700 1,500 1,150 440 700 800 n
;0,-
Manganese 950 770 850 6,700 850 1,050 460 620 760 '"
Barium 500 460 580 2,300 600 320 90 568
Strontium 370 320 140 110 160 150 320 610 278
Zirconium 190 150 160 150 240 220 20 345
Vanadium 160 105 130 120 145 170 20 45 108
Chromium l00(?) 72 90 90 60 100 35 11 84
Nickel 80(?) 52 68 250 35 90 9 7 34
Zinc 75 95 95 165 92 350 30 20 60
Copper 50 33 45 250 56 100 30 5.1 26
Cobalt 20 14 19 74 13 20 0.3 0.1 12
Lithium 20 56 66 57 77 25 38 7.5 31
Scandium 16 10 13 19 12 18 1 1 10
Lead 14 19 20 80 22 150 10 5.7 29
Cesium 3.0 4.2 5 6 6 0.5 0.5 3
Beryllium 2.6 2 3 2.6 3 < I I 1.5
Uranium 2.4 3.1 3.7 1.3 3 0.5 2.2 2.2
Tin 2.2 4.6 6.0 1.5 2 0.5 0.5 5.8
Molybdenum 1.5 2.0 2.6 27 1 3 0.2 0.2 1.9
Arsenic 1.5 7.7 13 13" 5 5 I I 11.3
Tungsten 1.0 1.7 1.8 1.1" 1.6 0.6 1.1
Antimony 0.2 1.2 1.5 1.0 2.5 0.05 0.3 1.7
Cadmium 0.11 0.17 0.22" 0.42 1 0.05 0.03 0.6
Silver 0.07 0.06 0.07 0.11 0.25 0.12 0.4
Mercury 0.05 0.19 0.18 i 0.08 0.29 0.16 0.1 :;
Selenium 0.05 0.42 0.06 0.17 < 0.01 <0.03 0.4 '"
a Bowen (1979) C Turekian and Wedepohl (1961) e Martin and Meybeck (1979) • Marowski and Wedepohl (1971)
b Bowen (1979) after Wedepohl (1968) d Wedepohl (1969, 1978) f Bowen (1979) after Wedepohl (1968,1969,1974) h Ure and Berrow (1982)
in Table 42 originate chiefly from the Handbook of Geochemistry (Wedepohl,

1969; 1972; 1974; 1978); a comparison of these data (5th column in Table 42) with
the shale values (3rd column) shows considerable discrepancies for Cr, Ni, Co and
Cu, i.e. especially for elements derived from mafic (basaltic) rocks. An estimate of
average river particulate matter composition (6th column in Table 42; from Martin
and Meybeck, 1979) is based on analyses of material from the Amazon, Congo,
Ganges, Magdalena, Mekong, Parana and Orinoco rivers, to which were added lit-
erature data for 13 other major world rivers, covering the whole spectrum of mor-
phoclimatic features. The data are similar to the shale values, except for zinc, cop-
per and lead, where anthropogenic effects on the composition of the riverine ma-
terial cannot be excluded.
Compared to the shale values, the trace metal content in sandstone (column 7
in Table 42) is more or less "diluted". This is chiefly the result of the extremely low
trace metal concentrations encountered in quartz or feldspar components. A rela-
tively small decrease is observed on the content of Mn, Ba, Cu, Pb, Wand Ag
which have up to a third of the shale levels. In contrast, the trace metal content
of Sr, Ni, Co, As, Be, Mo, Sb and Hg in sandstone exhibits only a tenth or less
of their respective values in shales. This is strongly reflective of the grain size effects
which must be taken into consideration when comparing different samples (Chap.
3.5).
Most carbonate rocks (data for limestone are given in Table 42, 8th column)
also show a "dilution" of trace metals compared with the corresponding shale
levels. Only manganese and strontium are enriched; there is little difference in the
Pb, U, W, and Ag values. The concentrations of Cr, Li, Cu, As, Be, Hg and Cd,
in contrast, are greatly reduced, having approximately one-tenth of the amount in
shale. A very strong reduction is observed in the limestone concentration of cobalt,
which is only 1/200 of the respective amount in argillaceous rocks. Analyses of
coexisting calcite and dolomite by Bratter et al. (1971) suggest small diagenetic en-
richment of trace metals during diagenesis; enrichment factors of 1.2-2.4 have been
found for AI, Cr, Sc, U and V, of 2.4-4.8 for Co, Fe and P, and magnesium and
sodium are enriched more than 4.8-fold in the dolomite phase compared to calcite.
5.2.4 Metals in Soils
In the present chapter composition and processes of soils will be treated only so
far as their behavior in the aquatic cycles of metals are concerned. In this context
soils occupy an intermediate position between atmospheric fallout and terrestrial
waters, and act as substrates of plants which, on the one hand are the basic level
of the terrestrial food chain, and on the other hand, by their decomposition prod-
ucts, influence the chemical equilibria in the soil itself and in the aquatic environ-
ment. In the transfer of pollutants from the atmosphere to the receiving waters soils
may play several roles, e.g. as a medium of preconcentration, followed by mechan-
ical erosion and discharge into the surface water, or by combined effects or direct
inputs and chemical leaching of pollutants from terrestrial solids and subsequent
transport in dissolved or complexed form to both groundwater and surface water.
Metals in Soils 151
5.2.4.1 Soil Constituents and Metal Binding

Of the six major constituents of soils as distinguished by Gieseking (1978), namely,
(1) coarse inorganic particles, (2) colloidal inorganic particles, (3) organic matter,
(4) living organisms, (5) the soil solution, and (6) the soil atmosphere, the compart-
ments (2) and (3) are particularly important for the aquatic cycling of trace metals.
Colloidal Inorganic Particles
The more important weathering products in the colloidal fraction (less than 0.2 ~m
in diameter) in soils are clays and hydrous oxides. Clays are aluminosilicates with
layer structures many of which swell in water and function as cation exchangers
(their cation exchange capacity (CEC) is between 10-20 meq/l00 g for kaolinite
and approx. 80-100 meq/IOO g for montmorillonite). The hydrous oxides of AI, Fe,
and Mn also have limited ion-exchange properties, as well as acting as specific ad-
sorbents for phosphate and some of the rare elements (Bowen, 1979). Hydrous iron
oxides strongly absorb As, Cr, Mo, Se, and V in acid soils, hydrous manganese oxi-
des carry most of the Co as Co(III), together with some Ba, Ni and lanthanides;
in alkaline soil, calcium phosphate adsorbs As, Ba, Cd, Fe, Pb and other elements
(Bowen, 1979).
Organic Matter
Small organic molecules are the products of partial decomposition of organic mat-
ter by bacteria and fungi. The binding of metallic cations by soil's organic matter
has a profound influence on the physical and chemical properties of soil com-
ponents. The cation exchange capacity of organic soils is largely due to organic
matter and its contribution to the CEC of mineral soils may be > 200 meq/IOO g
of organic matter (Helling, 1964; Bloom, 1981). Soil organic matter is largely com-
posed of polymeric weak acids of the type of humic and fulvic acids, which appear
to be quite similar in composition but with different molecular weights. In the pH-
range found in soils, metal ions are bound largely by carboxyl groups, some of the
more strongly bound ions may also bind to phenolic groups.
From a review given by Bloom (1981) two typical examples for the association
forms of metals within humic substances are given in Fig. 80.
ot-
/!
___ c:
,. ~
H20 o-!--
I I o
H20 -
/OH2
Mn 2 +-OH 2 H20- Cu 2+ -OH 2
/OH 2
'\:\
-: c
H20 / I I y
H20 / o
H20 ot-
---c:
/!
~ot-
Fig. 80. Possible binding sites for Mn 2 + (left) and Cu 2 + (right) in soil organic matter. (Bloom, 1981)
The complex formed between humates and Mn2+ can be described as an outer
sphere complex where the ligand does not interact directly with the Mn 2 + electron
(Fig. 80). This is not a chelation complex, since the latter would be an inner com-
plex where functional groups donate electron pairs to a metal ion. On the other
hand, it is likely that both water and carboxyl oxygen form coordinate bonds with
Cu2+ and that the charge on some carboxyl ions is shared by two (or more) metal
ions (Fig. 80). The formation of such an inner sphere complex affects the behaviour
of metals, in that, for example, copper mobility is more restricted than that of
manganese in the humate environment. Inner sphere complexation has been sug-
gested to exist also for Pb 2 + and V0 2 + while most other divalent ions are bound
in outer sphere complexes.
The affinities of metals to humates appear generally to follow the Irving-Wil-
liams order (Stevenson, 1977) and it has been found that Hg(II), Cu, Pb and Sn(II)
are exceptionally tightly bound by humates, while Mn(II) and the alkali and alka-
line earth metals are at most loosely bound (Bowen, 1979). Soils rich in organic
matter are reported also to concentrate Ge, Mo, Se, U and V, and most of the io-
dine and bromine in soils appears to be in the organic fraction (Vinogradov, 1959).
5.2.4.2. Trace Metal Concentrations in Soils

Numerous investigations (see summary by Ure and Berrow, 1982) have evidenced
that the total element content of a soil is basicaly determined by the content of the
parent material when it has been only slightly weathered. This relationship holds
for metallic trace elements as well as for those such as Band Se which exist in rocks
and soils largely in anionic forms. While this relationship is basically maintained
even in more strongly weathered soils in temperate climate, the soil composition
under tropical conditions is very dependent upon pedogenetic factors (see section
5.2.2). Selected data on the composition of soils have been summarized in Table 42
from the compilation of Bowen (1979) and U re and Berrow (1982). It seems that
As, Cd, Pb, Sb, Se and Sn may be somewhat enriched in soils compared to rock
composition, while Ca, K, Mg, Hg, Ni, Sr and U may be slightly depleted.
Adsorption processes and specific sites of organic and inorganic substrates as
well as anthropogenic effects are responsible for the relative enrichment of trace
elements. With respect to the latter effect it has often been found that heavy metals
such as Ag, As, Cu, Hg, Sb and Zn are enriched in the upper layers of soils (Bowen,
1979); sources of metals include agricultural additions, such as lime, fertilizers,
manure, herbicides, fungicides, and irrigation waters, as well as other materials
such as sewage sludge, composts, fly ash, mine waste, and atmospheric depositions
(Ure and Berrow, 1982). On the other hand, elements reported to be enriched in
the lower layers of soils, where clay minerals and/or hydrous oxides accumulate,
include AI, Fe, Ga, Mg, Si, Sc, Ti, V, and Zr.
Residence times of readily leached elements such as Ca, Cd, Mg and Na are in
the range of 75-380 years. Hg has a residence time of 500-1000 years, while other
elements such as As, Cu, Ni, Pb, Se and Zn have residence times of the order of
1000-3000 years in temperate soils; in tropical rain forests, where nutrient cycling
is particularly rapid, residence times of about 40 years have been estimated for all
nutrient elements (Bowen, 1979).
Metals in Soils 153
5.2.4.3 Metal Transfer from Soil to Plants
Soils act as the major suppliers of nutrients as well as contaminants to those classes
of organisms which are supported by soil (see summary of Haque and Subra-
manian, 1982). Any change of the concentration or chemical status of such sub-
stances, therefore, has a direct impact on the health of the organisms which follow
up in the food chain. With respect to the pollutant input the situation can become
even more serious, as removal of contaminants from soils is nearly impossible.
When metal transfer from soil to plants is estimated or plant uptake is mea-
sured this is usually done in terms of the "available fraction" of the total soil ma-
terial. A large number of studies have been performed on these relationships and
(as already mentioned in Chapter 2.6 on the speciation of particulate metals) a
similar number of chemical extraction methods have been proposed (e.g. Jackson,
1958; Mitchell, 1964; Mortvedt et aI., 1972; Viets and Lindsay, 1973; Anderson,
1976; Purves, 1977; Farrah and Pickering, 1978; Sterritt and Lester, 1980; Picker-
ing, 1981), generally belonging to one of the four broad categories (Shuman, 1980):
(1) complexing agents, (2) dilute acids, (3) chelating agents, (4) neutral salts.
Among the more widely used extractants in soil/plant studies, the combined soil
test DTPA leach - 0.005 M diethylenetriarnine penta-acetic acid, 0.01 M CaCI 2
and 0.1 M triethanoleamine - seems to give overall best correlations with transi-
tion metals such as Cu, Zn, Cd, Pb, Co, Ni, Fe and Mn.
A global investigation on the interactions of micro nutrients such as Mo, B, Cu,
Fe, Mn and Zn between soils and food plants was undertaken by Sillanpaa (1982)
with the objective of finding extreme situations with respect to both deficiency and
oversupply (from pollution or lithological sources) for characteristic examples of
elements. The example of the evaluation of the zinc data is presented in Fig. 81.
The plant-available zinc was determined by extraction with DTPA and correlated
with the zinc content in pot-grown wheat. Fig. 81 shows that there is a highly sig-
nificant correlation between the two data sets (r = 0.732 on the basis of 3537 sam-
ples), suggesting that the DTPA- extract is well suited to estimate the micronutrient
status of zinc with respect to the plant uptake from the respective soil material. The
regression graph has been divided into five zones (I-V) in such a way that the nu-
merical product of plant micronutrient content multiplied by soil micronutrient
content is constant at every point on the line separating two zones. The locations
of the zone limits have been determined so that five percent of sample pairs of the
whole international material falls below the line separating Zones I and II, i.e. into
Zone I. Accordingly, ten percent of the material falls below the line between Zones
II and III, i.e. five percent into Zone II. The next 80 percent of the material falls
in Zone III and the highest ten percent of the values in Zone IV and V, i.e. five per-
cent in each. The most likely cases of deficiency are to be found among samples
falling in Zone I and the most probable cases of toxicity in Zone V. In the example
for zinc no real cases of deficiency seem to exist, however, the pollution impact is
predominantly found in the examples from Malta and Belgium. It should be noted
that these examples do not necessarily reflect toxic conditions, since critical defi-
ciency and toxicity limits vary from one plant species to another. Further statistical
evaluation of the data sets with respect to the influence of characteristic parameters
such as soil texture, organic carbon content, cation exchange capacity, CaC0 3
200
1\
\
Interndt.
Zn n=3537
1\ y=s = 18.33+10.77
x=s = 1.97+705
109 y=1.280+0.321 109 x
100 r=0.732···
90
\ .,/
80
70 1\ \ V"
60 \ \ io"
E
Q. 50
Q. \ 1\ L
~
..: \ [\ L V
IV 40
,r
~
--
GI
~
~
30
1\
i" ~ 1\
•• ~
1\
0
C
-
GI
20
~
..
V-• •• 1\1\
1\
c
~~
0
u
c
N
~ ""~~ 1\
V 1\
10 ./
9
8 V \ ~
7 \ \
1\
~
\
~ ,
6
I \ ][ ][ \ Dr 1\ Jz:
0.1 0.2 0.4 0.6 1 2 3 4 6 810 20304060 100
Zn in soil, mg/I (DTPA)
Fig. 81. Correlation between DPTA-extractable Zn in soils and the Zn concentrations in wheat
(Sillanpiiii, 1982)
equivalent, and pH-values indicate particularly strong effects of the latter factor,
but significant influences also from the other parameters (Sillanpiiii, 1982).
The various factors affecting the transfer rates of copper, lead and zinc from
soil to plants were reviewed by Haque and Subramanian (1982):
- Soil pH has a direct relationship to the availability of metals as it affects their
solubility and their capacity to form chelates in the soil. For example, Lindsay
(1972) reported that the solubility of Zn in soil solutes increased 100 times for
each unit decrease in pH; on the other hand the chelation activity was greater
at higher pH-values (Norvell and Lindsay, 1972).
- Soil organic matter has an essential function in the accumulation and transport
of metals as well as in delaying their circulation in the soil. Therefore, the toxicity
of metals may be both increased as well as decreased by organic substances
under specific environmental conditions.
- Phosphate content of soils also exhibits ambiguous effects on metal availa-
bilities; examples of both increase and decrease of the metal uptake at elevated
phosphate contents have been reported.
Metals in Soils 155
- Plant species differ widely in their physiology and hence accumulation of metals
is never the same for two plants growing under similar conditions. Ecotypes of
various plant species have been observed to develop characteristics which give
them the capacity to resist or withstand excess metals in soils.
- Relative accumulations in parts of the plants has often been observed; generally
roots exhibit higher metal concentrations than shoots. Soil pH, species of che-
lators, and quantity of metal in soil affects the passage of metal from root to
shoot.
- Exposure period has a direct influence on the accumulation of metals by plants.
It has been found, for example, that the zinc uptake in rice increased slightly at
maturity over the level at the young stage, while copper and lead uptake de-
creases with maturity (Takijima and Katsumi, 1973).
- Competition and synergisms of metals has been evidenced, for example, from
studies by Brar and Sekhon (1976) which found that copper competed for ad-
sorption with zinc in wheat and rice seedlings, and by Miller et al. (1977) indi-
cating an increased cadmium uptake by corn shoots at elevated soil lead concen-
trations. According to Haque and Subramanian (1982) it is suggested that anta-
gonism is due to competition for the same site of element, the sites being nor-
mally those which are responsible for adsorption or translocations; synergistic
effects are then thought to be due to the damage caused by one of the various
elements.
In addition to these factors cation exchange capacity (see above) may be con-
sidered; however, CEC does not act as an independent property of soil but is re-
lated to clays, hydrous oxides, organic matter, pH and presence of other ions in
the soil (Haque and Subramanian, 1982).
Until now there has been no information about the effects of contaminated soil
systems (soil particulate matter, soil solutes, plants and their decomposition prod-
ucts) on the metal concentration in receiving waters. The only quantitative
evaluations on the interactions of soil and surface waters as well as of their effects
on plants have been performed on agricultural areas irrigated by polluted surface
waters or affected by the deposition of contaminated sediments, e.g. from flood-
ings or disposal of dredged materials. These aspects will be treated in the conclud-
ing section of this chapter.
5.2.4.4 Problems with River-borne Metal Pollutants on Agricultural Soils

The predominant soil-related pollution problems are the enhanced levels of cad-
mium in agricultural products. Obviously cadmium is taken up by plants more eas-
ily than most of the other heavy metals and there is a good correlation between
the cadmium concentrations in soils and plants found in nearly all studies. Root
crops such as carrots and potatoes, but also cabbage and lettuce are particularly
susceptible for elevated cadmium contents. Unlike zinc, copper, nickel or boron,
cadmium accumulations in vegetation can reach levels that are toxic to animals be-
fore the vegetation itself shows any signs of damage. Generally food consumption
is the most important pathway for the overall Cd uptake of humans, under unfa-
vourable conditions - e.g. consumption of kidneys, shellfish and uncultivated
mushrooms or food from polluted areas (see below) the tolerable daily intake of
60-70 Ilg Cd can be surpassed. Therefore, guidelines limiting cadmium applica-
tion, e.g. sewage sludge in agriculture, tend to be relatively conservative (Forstner,
1980).
Catastrophic poisonings by cadmium-polluted food has first been reported
from Japan. During 1947 an unusual and painful disease of "rheumatic nature"
was recorded in the case of 44 patients from villages on the banks of the Jinzu
River, Toyama Prefecture. The cause of this disease was completely unknown until
1953 when a close relationship between the disease and metal pollution from min-
ing wastes was postulated; further investigations found a definite overlapping of
limited localizations with Itai-Itai disease (as the disease was called) and polluted
environments such as soil, crop, and river water (Yoshioka, 1964). It has been evi-
denced that the Cd drain from the mine (together with other metal pollutants) had
been poured into the stream of the Jinzu River and had accumulated in paddy field
soils in the basin, and was later absorbed by crops such as paddy rice and soybeans
grown on the polluted soil (Morishita, 1981, with a compilation of the data on the
cadmium pollution in the Jinzu River Basin).
Another case study, which is reported here in more detail, has been performed
by Asami (1981) on the Ichi and Maruyama River basins situated between the Ja-
pan Sea (in the north) and Seto Inland Sea (in the south). Also here, rivers draining
mine wastes have been used to irrigate paddy fields. The cadmium concentrations
in the surface layers of paddy soil (sediment data are also given) are shown in Fig.
82.A.
In the paddy soil of the Ichi River basin, the Cd concentration was higher in
the upstream area where the Ikuno Mine was situated and decreased gradually
downstream: the maximum concentration of more than 10 mg Cd/kg was observed
in one sample in Kuri, Okochi Town, about 7 km downstream from Ikuno Mine.
The highest concentration of Cd in the Maruyama River basin was observed in the
upper reaches near Ikuno Town, where the soil sample contained 12.5 mg Cd/kg;
however, the Maruyama River basin exhibits a lower overall contamination level
for cadmium than the Ichi River basin. In addition to direct effects of mine ef-
fluents, serious pollution by cadmium in paddy soils originates from ore smelting
and dressing. Altogether, the paddy soil of both river basins, where Cd-rich waters
were used for irrigation, were thoroughly polluted by cadmium and other metals
such as copper and zinc; in some instances, subsoils were found to be even more
polluted than surface soils (Asami, 1981).
The cadmium concentrations in unpolished rice produced in the basins of the
Ichi and Maruyama Rivers were analyzed every year from 1972 by Asami and col-
leagues. Fig. 82 B shows the maximum Cd concentrations in unpolished rice pro-
duced in each village from 1972 to 1979. These data significantly correlate with the
distribution patterns of Cd in soil samples; according to Asami (1981) a cadmium
concentration below 0.1 mg/kg in unpolished rice means that the rice is not pol-
luted; Cd concentration between 0.11 and 0.19 mg/kg are suspected pollution and
unpolished rice which contains above 0.2 mg/kg Cd will not be produced in unpo-
luted fields under normal conditions. The present maximum allowable limit for un-
polished rice in Japan is 1.0 mg/kg. These levels are surpassed in many examples,
mainly from the upper reaches if the Ichi River. However, it has been stressed by
Metals in Soils 157
JAPAN SEA
Ikuno Mine ------"=''____=_
Cd in rice
• > 1.00 ppm
Cd In soil • 0.99-0.70 ppm
• > 5.00 ppm .. 0.69-0.40 ppm
.. 4.99-3.00 ppm o 0.39-0.20 ppm
o 2.99-1.00 ppm o 0.19-0.11 ppm
A SETO INLAND SEA "" < 0.99 ppm B SETO INLAND SEA "" < 0.10 ppm
Fig. 82. A Cadmium concentrations in surface layers of paddy soil and, B Maximum cadmium concen-
trations in unpolished rice. (Asami, 1981)
Asami (1981) that these limits may be probably too high, since the average Cd con-
centration in highly endemic areas of Itai-Itai disease of the Jinzu River was 0.53
mg/kg and the effects of renal dysfunction evidently occur at even lower levels; the
latter disease has been found in many examples in the upper portion of Ichi River
basin.
It has to be added that problems with river-borne cadmium contamination of
agricultural soils are not restricted to Japan. Salomons and colleagues (1982) have
summarized the experience in the Netherlands as follows:
The river flood plains along the rivers Rhine and Meuse, about 40,000 hectares,
are flooded almost yearly. The upper soil layer consists entirely of contaminated
river sediment. The flood plains are mainly in use as pastures for grazing dairy
cattle; a limited part is used for the cultivation of maize.
The sediments dredged out of the harbours and waterways of Rotterdam, situ-
ated in the Rhine estuary, are partly deposited on land. Depending on local con-
ditions these polders contain layers of dredged material up to a thickness of 10
meters. About 300 hectares of these disposal sites potentially have agronomic
destinations.
Detailed investigations during the last years indicate that the heavy metal bur-
den of the cattle in the flood plains is higher than that of the cattle at the reference
pastures. Data of the heavy metal contents of the milk, kidney, liver and brains,
however, revealed that this did not result in elevated concentrations of metals. On
the other hand, cultivation of consumable crops on sediments heavily polluted with
heavy metals may involve risks of intolerable high levels of these contaminants in
the products. Pot experiments and field data have shown that significant accumu-
lation of most metals in the crops occurs as compared with non-contaminated sub-
strates. Particularly in the green, leafy vegetables, wheat grain and other cereals
and in most green fodders, the cadmium concentrations must be considered too
high for human and animal consumption.
5.2.4.5 Land Disposal of Metal-Contaminated Waste Materials

A short review will be given here of the actual situation in the land disposal of pol-
luted solids, with special regard to dredged sediments and sewage sludge. Here too,
cadmium is presently posing the greatest potential hazards and is regulated by
more conservative guidelines than the other metals.
The problems evolving from upland disposal of cadmium-contaminated
dredged materials have been described by Khalid (1980). Upland disposal sites ef-
fect on cadmium availability to terrestrial and marsh plants. Chemical fraction-
ation studies indicate that the retention of dredged material under oxidizing con-
ditions changes from less available organic and sulfide-bound to more readily bio-
available forms, induding exchangeable, carbonate, and easily reducible fraction
(see Chap. 2.6). The exchangeable fraction is considered to be readily available to
aquatic organisms and plant species, while carbonate and easily reducible com-
pounds will also be readily available as a result of pH and redox potential changes.
Short-term effects, therefore, include cadmium discharge in oxidizing effluent
waters from upland disposal sites into adjacent receiving waters. The potential
long-term impacts of cadmium at upland disposal sites include its uptake by the
plant communities established at the disposal sites, ground-water leaching of cad-
mium solubilized under oxidized, acid conditions, and the transport, due to ero-
sion, of suspended material rich in cadmium to the adjacent surface waters. Until
now - other than for open-water disposal- criteria to assess the long-term release
and leaching of cadmium and other toxic material from upland disposal sites are
essentially nonexistent (Khalid, 1980).
Although it is apparent that guidelines for land application of sewage sludge
should be based on parameters such as soil pH, cation exchange capacity, organic
matter content or on extractability rather than on total metal concentrations, it is
also clear that legal regulations using such differentiations are considered as being
rather problematic. However, US Environmental Protection Agency has included
regulations for cadmium in domestic sewage earmarked for land disposal ("Pro-
posed Classification Criteria - Solid Waste Disposal Facilities, Federal Register
43,4942, 1978"):
"Any site that is currently or will in the future be used for the production of
food chain crops complies with either subparagraph 1 or subparagraph 2 of the
paragraph 257.3-5 (a) 1:
Trace Metals in River Water 159
(i) The annual application of cadmium from solid waste does not exceed the
maximum addition below:
Present to December 31, 1981 2.0 kg/ha
Jan 1, 1981 to Dec 31, 19851,25kg/ha
Beginning Jan. 1, 19860.5 kg/ha
(ii) The maximum cumulative amount of cadmium applied to any hectare of
land does not exceed 5 kg on soils with a cation exchange capacity (CEC) of less
than 5 meq/100 g, 10 kg on soils whose CEC is between 5 and 15 meq/l00 g, and
20 kg on soils whose CEC exceeds 15 meq/100 g.
(iii) Solid waste containing cadmium concentrations in excess of 25 mg/kg dry
weight is not applied to sites where tobacco, leafy vegetables, or root crops are or
will be grown for direct human consumption.
5.3 Metals in Rivers
5.3.1 Trace Metals in River Water
Trace metal analysis on continental waters were commenced in the USA, in central
Europe, the USSR and Japan, mainly in areas where local anomalies from ore min-
eralizations had been expected. Huff (1948) studied the concentration of Cu, Pb
and Zn in five samples from the Colorado River; Turekian and Kleinkopf (1956)
analyzed the abundance of Cu, Mn, Pb, Ti and Cr in surface waters of Maine. In-
vestigations and literature compilations have been performed during the 60's and
early 70's by Merril et aI. (1960; Be - Delaware and Hudson Rivers), Durum and
Haffty (1961), Livingstone (1963; surface waters), White et aI. (1963; subsurface
waters), Silvey, (1967; California), Turekian et aI. (1967; Neuse River, North
Carolina), Bradford et aI. (1968; Sierra Nevada), VoegelI and King (1968; Mo -
Colorado), Angino et aI. (1969; lower Kansas River basin), Lindstedt and Kruger
(1969; V - Colorado), Weller and Chawla (1969; Great Lakes), Durum et aI. (1971;
surface waters), Bradford (1971; California), Mills and Oglesby (1971; Cayuga
Basin), Robbins et aI. (1972; tributaries to Lake Michigan), Mathis and Cummings
(1973; Illinois River), and Proctor et aI. (1973; Missouri River). In central Europe
early investigations have been performed by Heide and Singer (1954) and Heide
et aI. (1957) on the concentrations of Cu, Zn and Pb in the Saale River (German
Democratic Republic), by Heyl (1954) in the Siegerland mining area (Federal Re-
public of Germany), and by Fricke and Werner (1957) in the mineral waters of
Nordrhein-Westfalen (FRG). Both the European and Asian surface waters of the
USSR have been studied intensively; compilations and original data are given by
Konovalov (1959), Udodov and Parilov (1961), Kontorovich et aI. (1963),
Konovalov et aI. (1976a-b), Konovalov and Ivanova (1972), and Konovalov and
Nazarova (1975). An early review of data on acidic mine drainage was given by
Smirnov (1954). Of the early Japanese investigations on trace metals in natural
waters one should particularly mention the studies performed at Nagoya Univer-
sity (Morita, 1955; Sugawara et aI., 1956; Sugawara and Okabe, 1960; Kanamori
and Sugawara, 1965).
Table 43. Metal concentrations in river water (examples). Values in IlgjI
Metal Background Mississippi River' Rhine River b Witwatersrand C
AI 64 d 56
As I' 3 13 250 r
Cd 0.02" 0.1 5.5 52
Cr 0.5" 0.5 33 4,000
Cu Ih 2 34 5,400
Fe 55 d 5 35 550,000
Hg O.Oli 0.1 0.65
Mn 6d 10 5.2 200,000
Ni O.3 k 1.5 20 6,400
Pb 0.2' 0.2 57 290
Zn 10 (0.5)"(1) 10 330 26,000
, Trefry and Presley (1976) g Schell et al. (1977) - Puget SoundjWash.

b Anon (1982) and Heinrichs (1975) h Boyle (1978) - Amazon River
C Wittmann and Forstner (1976) i Forstner and Wittmann (1979) -literature
d Yeats and Bewers (1982) - St. Lawrence River review
, Copeland and Ayers (1972) - Lake Michigan k Gibbs (1977) - Amazon and Yukon Rivers
r Aston et al. (1975) - acid mine drainage in I Kennedy and Sebetich (1976) - streams in N.
Cornwall California
During the last few years the number of trace metal analysis on river waters has
greatly increased in both geoexploration and environmental management (com-
pilation see Rose et aI., 1979, and Forstner and Wittmann, 1979). This progress
has been to a large extent due to improvements in analytical techniques which have
significantly lowered the costs and increased the effectiveness of these methods.
However, following the findings of Patterson et ai. (1976) on lead values from
oceanic samples, it has been argued that the same contamination effects associated
with marine sampling and analysis also exist in fresh and estuarine waters, and "it
is safe to assume that many of the natural water values quoted in the literature are
high solely for this reason" (Martin et aI., 1980).
For a general overview metal data from both less contaminated and polluted
water samples are given in Table 43.
Due to the variety of rock formations and the fluctuations in water discharge
it is even more difficult to establish natural background values for metals in inland
waters than in seawater. The examples for background values in Table 43 partly
stem from large inland water masses such as Lake Michigan; however, contamina-
tion from both atmospheric and river inputs cannot be excluded (see Sect. 5.4.6).
More reliable background values of those from Amazon and Yukon River (Boyle,
1978; Gibbs, 1977), where the effect oflarge catchment areas meets the prerequisite
oflow pollution activity.
It can be seen that the "dissolved" metal concentrations in the Rhine River (sta-
tion Bimmen at the Dutch/German border, 1970-1973) were enriched by a factor
200-500 for Zn, Cd and Pb, 30-60 for Ni, Hg, Cu and Cr, approx. 10 for As. Much
higher concentration factors have been analyzed in inland waters affected by acidic
mine effluents, e.g. in the Witwatersrand Goldfields in South Africa (Table 43),
where the levels of dissolved Ni, Mn, Fe (and Co) exceed the normal surface water
Dissolved and Solid Transport 161
concentrations by a factor of more than 10,000, values of Zn and Cr (and Fe, sul-
fate) are increased 1000-fold, whereas Pb and Cd in many instances are encoun-
tered at values exceeding a 100-fold enrichment. Lowering of pH-values on a re-
gional scale by acid precipitation is probably the most important single effect on
metal mobility in surface waters, particularly for AI, Cd, Mn, and Zn (see Sect.
5.4.6)
5.3.2 Dissolved and Solid Transport
It has been suggested that the source of trace metals in aquatic systems significantly
determines their distribution ratio between the aqueous and solid phases. This is
especially true for river systems, where equilibrium between the solution and the
solid phases can often not completely be achieved due to the short residence times;
Bowen (1977) has noted the example of the Thames River flowing 250 km in 14
hours, while chemical equilibrium would require more than 100 hours in some in-
stances.
5.3.2.1 Geographical Variability

Metal contents of river solids depend nearly exclusively on allochthonous in-
fluences. After the composition of source rocks the most decisive factor is the grain
size (discussed in Chap,2.2). In a comprehensive study by Martin and Meybeck
(1979) the average values in the suspended matter composition of 20 major rivers
were determined. The geographical variability of elements in the suspended matter
differs widely. The most constant elements are mostly the rare earths, Si and Thi;
AI, Fe, K, Ga, Hf, Sc, Ta, Ti and U do not vary much. On the other hand, As,
Cr, Mg and Na vary moderately and Ca, Cs, Cu, Li, Mo, Ni, Pb, Sr and Zn are
highly variable. The most constant elements are, in general, essentially carried in
rivers by the particulate matter. The highly variable elements are those either car-
ried mostly in solution (Ca, Na, Mg, As, Sr, Li), or significantly enriched in the
suspended material (Zn, Pb, Mo, Cu). The variations of the major chemical ele-
ments (AI, Fe, Mg, Ca, Na, Si, Ti) are due to the climatic features in the river
basins; there appear to be two different types of rivers according to the intensity
of the weathering action (Martin and Meybeck, 1979). In tropical rivers the con-
tents of AI, Fe and Ti in the suspended matter are the highest, while contents of
Ca are the lowest; for this type of river the particulates mainly originate from soil
material enriched in insoluble rather than the more soluble elements, as these have
been leached away. On the contrary, contents of AI, Fe and Ti in temperate and
arctic rivers are much lower, while here the contents of Ca are higher; as the sus-
pended load of these types of rivers is mainly derived from rock debris or poorly
weathered particles, particularly in mountainous areas, the average composition of
their particulates is much closer to the average contents of surficial rocks.
Computations by Martin and Meybeck (1979) of the ratio of dissolved trans-
port to total transport have led to the establishment of the so-called Dissolved
Transport Index (DTI), which shows that more than 90% of the total load of P,
Table 44. Dissolved transport index (DTI) in rivers (Martin and Meybeck, 1979): Percentage of
dissolved transport over total transport (ranked in decreasing order)
90-50% Br, 1*, Sa, CI*, Ca, Na, Sr

50-10% Li, N*, Sb, As, Mg, B, Mo, F*, Cu, Zn, Ba, K
10- 1% P, Ni, Si, Rb, U, Co, Mn, Cr, Mn, Th, Pb, Y, Cs
1- 0,1 % Ga, Tm, Lu, Gd, Ti, Er, Nd, Ho, La, Sm, Tb, Yb, Fe, Eu, Ce, Pr, Al
* Estimates based on elemental contents in shales
Table 45. Percentage particulate-bound metal of total discharge
Amazon Mississippi Polluted rivers in

Rivera River b
% % US' FRG d
% %
Cadmium 88.9 30
Zinc 90.1 40 45
Manganese 83 98.5 8-97
Chromium 83 98.5 76 72
Copper 93 91.6 63 55
Lead 99.2 84 79
Iron 99.4 99.9 98 98
a Gibbs (1977)
b Trefry and Presley (1976)
, Kopp and Kroner (1968)
d Heinrichs (1975)
Ni, Si, Rb, U, Co, Mn, Cr, Th, Pb, V and Cs is carried by river particulates, while
Fe, Al and the rare earths are almost exclusively transported in particulate forms
(Table 44). A similar sequence of the ratios between particulates and dissolved
metal phases has been found for polluted systems (Table 45). Typically, however,
the dissolved discharges in polluted waters are significantly higher than the less pol-
luted systems (example from the Lower Mississippi River), particularly for cad-
mium, zinc and copper.
The relative importance of the particulate forms in the decreasing sequence
AI> Fe > Mn > Co > Zn > Ni > Cu > Cd has also been found by Yeats and Bewers
(1982) from St. Lawrence River in Canada. According to these authors the lower
proportions of the metals in particulate phases from St. Lawrence compared to the
data from the Amazon (Gibbs, 1977) or the Mississippi (Trefrey and Presley, 1976)
rivers are a direct reflection of the contrasting levels of suspended matter in the St.
Lawrence (10 mg/I), Amazon (65 mg/I) and Mississippi (580 mg/I). The work of
Yeats and Bewers (1982) on the discharge of metals from the St. Lawrence River
also confirms earlier suggestions of Trefry and Presley (1976) that the dissolved
fractions are exhibiting a certain degree of long-term stability and are - at least in
less polluted systems - not significantly related to water flow.
Dissolved and Solid Transport 163
5.3.2.2 Seasonal Variability

The metal concentrations in river particles are highly determined by the runoff. As
an example, particulate metal concentrations as a function of the water discharge
of the Rhine River in Germany and in the Netherlands are shown in Fig. 83.
It is clear, that during periods of high discharge metal concentrations decrease
strongly in this highly polluted river. Especially for cadmium, which shows in-
creases of more than IOO-fold over base-line levels (Salomons and De Groot, 1978;
see also Sect. 5.3.4.) the influence of the discharge is very strong. Similar studies
on suspended matter from the middle Rhine Riveer near Koblenz, which were per-
formed by Schleichert (1975), indicate practically the same development for chro-
mium as was found in the lower section of the Rhine River.
However, even the moderate cadmium contents in the winter period exceed the
maximum values for the spring/summer, despite the much higher water discharge.
RHINE AT KOBLENZ
18~-----------------,
1500r-------------------,
..gig
12 .. gig
gOO
8
4
300
O~~ ____ ~ __ ~ ____ ~ O~~ ____ ~ __ ~ ____ ~
2000 4000 2000 4000

-----. m 3/s ---. m 3/s
• Autumn-Winter Period
x Spring Period
RHINE IN THE NETHERLANDS « NIEUWE MERWEDE )
100~-------------------, 2000r-------------------~
..gig Cd 119/g Cr
•
75 1500
50 1000
.:
•
25 500
,
• I •
O~--~~~~~~~~~ O~--~~~--~~~~
o 2000 4000 o 2000 4000
Fig. 83. The relationship between the water discharge and the metal concentrations in the suspended
matter. Above: Rhine River at Koblenz. (Schleichert, 1975) Below: Rhine River in the Netherlands.
(Salomons and Eysink, 1981)
Such a development is due to the suspended sediments, rich in cadmium, being held
back in periods of poor flow, for example, mainly during the summer, in the lock-
regulated Neckar and Main rivers; in autumn/winter the tendency is reversed, the
material is carried by high water flows into the Rhine River in increased quantities.
From investigations in two Cornish estuaries (Boyden et aI., 1978) found that
- except for Ni and Pb - there are higher trace element concentrations in high and
low water surface and bottom samples in winter compared to summer; it is sug-
gested that this probably reflects increased weathering and transport in the catch-
ments in winter.
Studies performed by Grimshaw et ai. (1976) on the River Ystwyth in mid-
Wales, where strong metal pollution from past mining operations is still obvious,
indicate that metal concentrations in solution are highest during low flow periods,
suggesting a dilution effect. For brief periods during initial stages of storm runoff,
there is a very significant increase of the metal concentrations in solution, ap-
parently due to a flushing effect.
Data on the temporal variability of metal transport from the Susquehanna
River to Chesapeake Bay (Carpenter et aI., 1975) showed that the trace metal con-
centrations correlate well with the amount of solids discharged. When data are cal-
culated for weight concentrations of metals in the solid fraction, it is found that
all metals generally peak during December and January and secondary peaks occur
for Co, Cr, Ni, Cu and Mn in July. Troup and Bricker (1975) suggest that this effect
is due to decaying organic matter which is abundant in the Susquehanna River dur-
ing these two periods.
5.3.3 Metals in River Sediment
In their comprehensive study on the geochemistry in mineral exploration Rose et

ai. (1979) have described several procedures to assess "Anomalies in Drainage Sed-
iments". The various procedures pertain to deposit types with different sediment
character, differing metal-introducing processes and applications. Sediments in
seepage areas and near springs, where important interchanges between water and
sediment may occur, tend to furnish strong anomalies and are particularly useful
in detailed survey stages. Active stream sediments are dominated by clastic mate-
rial eroded from banks of streams and are the most widely used medium for recon-
naissance explorations. Sediments on flood plains are similar to active sediments
in many respects, but may be distinctive in sorting, weathering, or content of or-
ganic matter. Iflakes occur in a drainage pattern, sediments collect in them as clas-
tic particles and as adsorbed or precipitated material (see work of Coker and
Nichol, 1975; Allan, 1977).
5.3.3.1 Factors Affecting Compositions

Generally, the variation in trace metal content of stream sediments can be charac-
terized as a function of potential controlling factors by the following formula
(Dahlberg, 1968):
T=f(L,H,G,C,V,M,e)
Metals in River Sediment 165
in which T represents the resulting trace metal concentration, L the influence of

lithogenous units, H the hydrologic effects, G the geologic features, C the cultural
(man-made) influences, V the type of vegetation cover, M the effects of mineralized
zones and e the error plus effects of additional factors not explicitly defined in the
model. In mineral exploration, the main problem is to maximize the factor M, i.e.
to eliminate other effects as far as possible. As has been demonstrated in a large
number of investigations in the field of mineral exploration, traditional mining re-
gions are particularly susceptible to contamination by metals. It is usually difficult
to distinguish between contamination of industrial or domestic, "natural" pollu-
tion, and pollution resulting from mining activities. Airborne dust and particulate
material from smelter stacks, wind-blown particles and leachate from the tailing
ponds all contribute to an increase in the metal concentrations in river sediments.
5.3.3.2 Variability of Data

At the same time, seasonal variations in stream sediments seem to be relatively
slight and not sufficient to cause serious problems in routine application of geo-
chemical sediment surveys (summarized by Chork, 1977). This study demonstrated
that measurement errors for Cu, Pb, Zn, Co, Ni, Mn and Fe resulting from sam-
pling, sample preparation, and analysis are small compared to the regional vari-
ation. The sampling error, which constitutes the main source of procedural errors
(Miesch, 1967), is greatly in excess of the laboratory error for these elements.
Investigations by Schoer and Forstner (1980) on a large number of sediment
cores from the lock-regulated middle section of the Neckar River in southern Ger-
many show that even with relatively similar grain size conditions there are signif-
icant variations of the measured data. In Table 46 selected data for the upper 10 cm
from five locks clearly show that the percent standard deviation consistently lies
above 20%. For cadmium in fine-grained sediment, this value has been determined
to be as high as 67%.
Thus, it becomes apparent that for the investigation of temporal developments
the consecutive method of measuring pollutants in samples from the same location
at different times is significantly less accurate than the simultaneous determination
of older and younger deposits from sedimentary core profiles (see below).
Table 46. Procentual standard deviation of metal data in multiple sampling in selected reservoirs of
the middle Neckar River (FRG); samples from a sediment depth of 0 to 10 cm (Schoer and Forstner.
1980)
Reservoir River No. of Cu Pb Cr Ni Cd Zn

kilometer samples % % % % % %
Horkheim 117.7-117.9 4 23 34 25 29 41 18
Lauffen 125.3-125.6 7 62 56 76 38 93 49
Poppen weiler 165.0--166.3 6 38 28 33 21 41 38
Obertiirkheim 189.7-190.7 5 81 26 45 9 64 38
Plochingen 200.5-200.7 4 24 22 20 12 95 21
Mean percent standard deviation 46 33 40 22 67 33
5.3.3.3 Influence of Grain Size

A large number of sediment analysis which have been performed both for the in-
ventory, survey, assessment and monitoring of metal pollution within the last few
years (Forstner and Wittmann, 1979) have clearly shown that it is imperative, par-
ticularly for river sediments, to base these data on a standardized procedure with
regard to particle size (a compilation of methods was been presented in Chap. 3.5).
In examples from the Saddle River presented in Fig. 84 (after data from Wilber
and Hunter, 1979), the grain size dependencies of heavy metals are compared in
samples taken upstream and downstream of an urbanized area.
In the less contaminated material (e.g. from river mile 16.6) a general decrease
of metal concentrations is found with increasing particle diameter. In the polluted
material there is a typical increase of metal concentrations in the clay and silt
fractions; it is conceivable that the metal enrichment is due to organic matter not
removed during sewage treatment processes. A characteristic feature of the pol-
luted sediments (e.g. from river mile 0.5) is the increase of metal concentrations (ex-
cept for Mn) in the medium and coarse sand fractions, particularly significant for
Pb, Cu, Ni, Cr, Cd and Zn (Fig. 84, right), but also evident for iron (Fig. 84, left).
This is probably due to the input of coarse waste particles.
The decrease of metal concentrations in the range 10 Ilm-IOOO Ilm grain diam-
eter should be even more pronounced if the mechanical fractionation would more
accurately separate individual particles according to their grain size. However, this
Fe Zn •
% ."",
7 • IRON mg/kg
ZINC
4000
- RIVER
5 MILE 3000
_ RIVER
0.5 MILE
0.5
4 X . 270ppm
o,
0 .........
,,
1
2000
,,
.,,
3 "'0...
RIVER/" ,
MILE • '. ,,
2 16.6 \ b, /'
1000
.~/ ~. RIVER', \
MILE - " , '\.
/-
'0- - - 0- - - 0 _ - ... '0

16.6 O,,'\. ..".
i 04ppml .........0~
_ _ _ :-:-:_/
__" _
0.02 0 .15 5.8 63 125 250 500 1000 I'm 0.02 0.15 5.8 83 125 250 500 1000 t'-m
GRAIN SIZE FRACTION
Fig. 84. Grain size distribution of iron and zinc in two sediment samples from Saddle River, upstream
(mile 16.6) and downstream (mile 0.5) from an urbanized area of Lodi, New Jersey (Forstner, 1982; af-
ter data from Wilber and Hunter, 1979)
Metals in River Sediment 167
is not the case and "coatings", for example, of iron/manganese oxides, carbonates,
and organic substances on relatively inert material in respect to heavy metals, such
as quartz grains, act as substrates of heavy metals in coarser grain size fractions
(Forstner and Patchineelam, 1980). Furthermore, an aggregate formation of finer-
grained substances occurs in which the relatively metal-rich clay particles partici-
pate as well.
Therefore it must be said that the selection of certain grain size fractions - espe-
cially in the tracing of sources of pollution - remains controversial for the following
reasons (see Fig. 84):
1. Since the larger sediment fractions are less affected by scour and transport, they
may reflecting the effect of urbanization on the distribution of heavy metals
over an extended period of time at a given location (Wilber and Hunter, 1979).
2. The fine sand fraction (approx. 20 ~m to 200 ~m diameter) seems to be of par-
ticular interest for the differentiation of natural and pollutant metal transport,
firstly because it comprises most of the total sediment, and secondly because
there are most obvious differences between individual metal examples (in Fig.
84, Fe is not affected in this grain size interval by man-made effects, whereas
the typical "anthropogenic" metals, e.g. Pb, Cr and Zn are significantly en-
riched in the same grain size fractions of the polluted material).
3. The silt and clay fractions comprise the major carriers for both natural and an-
thropogenic metal compounds (although in relatively small portions); they are
widely distributed within the sedimentation area and are least affected by grain
size effects (Banat et aI., 1972).
5.3.3.4 Metal Forms

Only part of the metals present in river sediments may take part in short-term geo-
chemical processes and/or are bioavailable. For the differentiation of the relative
bonding strength of metals in different phases, sequential extraction procedures
have been developed which - in combination with biological uptake data - could
also enable the estimation of the toxicity of metal pollutants (see comprehensive
discussion in Sect. 2.6).
Extraction sequences related to Engler's scheme have been used for the speci-
ation of particulate metals in Lake Michigan (Filipek and Owen, 1979), the Rio
Grande (Popp and Laquer, 1980) and Tokyo Bay and Osaka Bay (Kitano et aI.,
1980; 1981). The latter studies have shown, that the transformation of oxides and
hydroxides to sulfides under anoxic conditions within the sediment is significant
for the fixation of copper and zinc discharged through human activities into the
sediment. The heavy metal (Cu, Zn, Fe and Mn) contents of the silicate fraction
from core samples are almost constant with sediment depth.
Eisenreich et ai. (1980) studied trace metal transport phases in the upper
Mississippi River during 1977/78 at sites representative of natural bog/marsh
drainage, agricultural drainage, urban runoff, and municipal and industrial dis-
charges. The solid organic phase of metal transport increased at the site receiving
sewage input. It is suggested that copper, cadmium and lead in the river discharged
as soluble complexes in the sewage effluent may associate with solid organic mat-
Table 47. Chemical forms of cadmium in aquatic solids. (Forstner et aI., 1981)
Sediment fraction Weser Estuary Rhine R. Rotterdam Hr. Neckar R.

(I) (2) (3) (4) (5)
% % % % %
Cation exchangeable 8 18 27 12 13
Easily reducible 32 49 42 61 64
Moderately reducible 45 14 2 13 10
Organic/sulfidic 12 17 17 12 12
Residual fraction 3 2 2 2
Total Cd (mg/kg) 3.0 4.3 9.0 18.1 33.6
(I) Dredged sediment; (2) suspended matter; (3) station Wesel (Dutch/German border); (4) Broek-
polder; (5) lock reservoir Lauffen
ter. This has the effect of increasing metal transport and the overall quantity of
metal accessible to the biota. With the exception of iron and aluminium, more than
90% of the manganese, copper, cadmium and lead occurred in transport modes
thought to be available to aqueous and biotic interactions.
Suspended sediment samples were collected by Tessier et al. (1980) at 12
stations on the Yamaska and Fran<;ois Rivers - located in southeastern Quebec -
and analyzed according to their elaborate scheme (Tessier et aI., 1979), which in-
cludes partition of five fractions: (1) exchangeable, (2) bound to carbonates, (3)
bound to Fe-Mn oxides, (4) bound to organic matter, and (5) residual (see Sect.
2.6). Although suspended sediment levels as well as total soluble and particulate
trace metal concentrations were highly variable in time and space, speciation pat-
terns for each metal proved reasonably constant. Deviation from the general be-
haviour were occasioned by man-induced perturbations (e.g. inputs of municipal
sewage or mine waste waters). At stations influenced by such factors, total particu-
late metal concentrations increased and the relative contribution of the residual
fraction decreased. The trace metal content of the fraction "bound to Fe-Mn-oxi-
des" proved to be particularly sensitive to anthropogenic inputs.
A scheme similar to that of Tessier et al. (1979) has been used by Forstner and
Salomons (1980) for the differentiation of metal species in fluvial and coastal ma-
rine sediments. A distinction is made between "easily reducible" (including carbon-
ate-associated metals) and "moderately reducible" metal fractions. Examples for
the solid phase partition of Cd have been given in Table 47, for samples from areas
of major dredging activities (Forstner et aI., 1981; Forstner and Calmano, 1982).
Compared to other metals, such as Pb and Cu, cadmium is characteristically
enriched in the more mobile fractions "cation exchange" and "easily reducible
phases", and is, therefore, more mobile than most of the other heavy metals.
A simplified scheme consisting of an extraction with 0.1 M hydroxylamine-H CI
(pH 2) followed by an extraction with hydrogen peroxide (30%, pH 2.5) and am-
monium acetate was used for the study of sediments from the Rhine, Meuse, Ems
and Scheidt Rivers from the North Sea (Salomons and De Groot, 1978). This
scheme, including an additional step for exchangeable cations ("Standard Extrac-
tion Method" after Salomons and Forstner, 1980), was used to study the speciation
Fig. 85. The speciation of trace metals in 18 different river sediments. (after Salomons and Forstner,
1980)
of particulate trace metals in 18 different river systems, including major rivers in

France, the Magdalene, Orinoco, Zaire Rivers, and the Ottawa River. In Fig. 85
the rivers are arranged according to their approximate geographical positions from
North to South. (Most tropical rivers contain low amounts of cadmium and here
it was not possible to obtain a reliable speciation. For the Rio Magdalena and the
Orinoco River, insufficient material was available for the determination of the ex-
changeable fraction; the acidified hydroxylamine step therefore contains also the
"exchangeable metals"). The results show an increase in the relative amount of
metals present in the resistant (lithogenous) fraction for the less polluted river sys-
tems. In nearly all examples the "reducible phase" is an important sink for trace
metals; copper more than other trace metals shows a tendency to refer the "organic
phase".
5.3.4 Impact of MetaIs in River Systems
The major part of this chapter will cover the case history of the metal pollution in
the Rhine River which is not only a characteristic example of origin, distribution
and fate of trace metals in fluvial systems but also gives evidence for the fact that
in many critical cases this type of pollution - which has caused considerable public
concern during the 1970s - has passed its climax and is now decreasing as a result
of recent improvements of waste water treatment.
5.3.4.1 Distribution of Metal Pollutants

River Rhine, which poets of former centuries called "Dear Old Father Rhine" be-
cause of its majestic scenery particularly in its middle reaches in western Germany,
flows through the most densely populated area of Europe, receiving water of mu-
nicipal and industrial wastewater treatment plants lined up at the river bank like
links of a chain (Anon., 1976). Simultaneously, it is a major source of municipal
and industrial water supply, mainly in the lower section of the river, flowing
through the western part of Germany and the Netherlands. Human activities have
not only changed the pollutant load of the river, but also the pathways along which
dissolved and particulate metals are transported into the direction of the Southern
North Sea, in particular, by the enclosure of the Zuiderzee in 1932 (the present IJs-
selmeer, receiving about 10% of the discharge of the Rhine River, see Sect. 5.4.4)
and the Haringvliet in 1970. The distribution of the water of the Rhine in the
Netherlands is controlled by weirs and sluices in the enclosure dams, and as a con-
sequence of these changes, the Rotterdam Waterway is at present the main estuary
of the Rhine and Meuse Rivers.
The major part of the heavy metal load originates from anthropogenic sources.
Evidence for the different influences are gained from the "mapping" of metal con-
centrations in the sediments of the Rhine River of the "Index of Geoaccumulation"
(see Chap.3.6.3) by Muller (1979): Fig. 86 shows that nickel remains in class 0
(background concentrations) along the total course of the river, whereas cadmium
is not to be found in classes 0 and I (up to double the background values) at all
and shows a general tendency to increase downstream. It finally reaches the Igeo-
Impact of Metals in River Systems 171
Fig.86. Index of geoaccumulation SEDIMENT - QUALITY

in sediments of the Rhine River
HEAVY METALS
(M iiller, 1979)
RHINE - 1979
I geo - classes
Neckar
12
0 1
Aare Glatt Bodensee

Do
class 6 (i.e. more than lOO-fold enrichment compared to natural background
values) of the lower Rhine, downstream from the mouth of the Rhine tributary,
the Ruhr River.
The different sections of the course of the Rhine River can be characterized as
follows (Forstner and Muller, 1981):
Neckar River-Main River: This section is characterized by a strong increase of
the cadmium concentration (from class 3 to 5), mainly due to the inputs from the
middle section of the Neckar River (Forstner and Muller, 1973). Chromium in-
creases from class 0 to 2, an effect which is probably due to the inflow ofWeschnitz
River, a water body that is highly polluted by waste from tanning and other indus-
tries (Forstner and Muller, 1974).
Main River-Ruhr River: Zinc and lead are now mainly in class 4, i.e. are en-
riched about 20-fold compared to natural concentrations. However, important
point sources do not seem to be present either along the main course of the rivers
or at the inflow point of either tributaries.
Ruhr River-Lippe River: Cadmium is registered for the first time in the highest
class (see above).
Lippe River-Dutch border: Lead and mercury also advance one class, and cop-
per occurs in class 3 for the first time. It has been found that more than 90% of
the concentrations of copper, zinc, lead and mercury and more than 99% of cad-
mium originate from man-made sources in this section of the lower Rhine River.
5.3.4.2 Historical Evolution

By analyzing sediments that have been systematically collected since 1922,
Salomons and de Groot (1978, additional data for more recent years by Salomons
et aI., 1982) have been able to trace the development of metal polluti on in the lower
Rhine section in the Netherlands (Fig. 87).
The samples taken from the river flood plain at the beginning of the 20th cen-
tury show that the concentrations of copper, zinc, lead and cadmium and mercury
were apparently already then anthropogenically influenced. This becomes evident
upon comparison with sediment data from polders reclaimed in the 15th and 18th
centuries. Between 1922 and 1958 all trace element concentrations determined in
Rhine River sediments had undergone an increase. Cadmium, copper and chromi-
um continued to increase between 1958 and 1975. The concentrations oflead, zinc,
mercury and arsenic decreased however; in the case of arsenic, its strong decline
is probably due to a ban on the use of this element in pesticides. Similar develop-
ments have been reported by Salomons and Eysink (1981) from the rivers Scheidt,
Meuse and Ems in the Netherlands. The zinc concentrations in the sediments of
the River Meuse are higher than those in the Rhine River and show a large increase
between 1958 and 1979.
2000
----z::--.--~
Zn
1000 . !
500
/~~'
.,<~::::::.
x--
/ . _0- ,\
200
III
"- 100
.
III As
::L.
50
t.'
i 20
~~~- Hi
CO _D~?\
~
10 "-"~:/"" \
5
2
f: H,
Fig.87. History of traee metal pollution in
.
1 <>
the Rhine River in the Netherlands as re-
o 0 0 0 0 0 0
.... 0
0 (If CO) II) D co fleeted in its sediments (after Salomons et
...
III
... ... ... ...
III III III III
... ... ...
III III III
ai.,1982)
Impact of Metals in River Systems 173
Table 48. Tentative metal balance for the rivers Rhine and Meuse and of dredged material of fluvial
origin from the Rotterdam harbours in 1977 (Salomons et aI., 1982). In tonnesjyear
Zinc Copper Lead Cadmium
Input Rhine + Meuse 10,051 1,215 1,707 195

Transport to land-fill 1,269 223 280 24.3
Percent of input 13% 18% 16% 13%
Transport to North Sea 462 78 116 7.6
Percent of input 5% 6% 7% 4%
Of the total amount of metals transported by the rivers Rhine and Meuse,
about 2/3 accumulates in the Netherlands, which in fact acts as an effective "treat-
ment plant" for these river discharges (Salomons et aI., 1982). This situation may
be regarded as beneficial for the North Sea, but poses problems for the manage-
ment of inland waters and the land-fill areas in the Netherlands. The problems with
polluted sediments are intensified by the closing of lagoons, the extension of har-
bour areas, the deepening of navigation channels and the channelization of the
rivers. The total amount of dredged material from the Rotterdam harbour is pres-
ently about 20.10 6 m 3 , which represents a 20-25 fold increase compared with 70
years ago. The most severely contaminated spoil from the easterly harbours, with
high admixtures of fluvial sediment, is dumped on land. Thus the land-fill areas
are an important sink for fluvial (and partly marine) particulate metals. A tentative
balance for trace metals of fluvial origin in spoils from the Rotterdam harbour is
presented in Table 48.
Problems arise from the metal concentration in sediment both with land dis-
posal and marine dumping. From pot experiments under controlled conditions and
by surveying the contents of contaminants in the crops grown on polluted sedi-
ments under field conditions it has been shown that agricultural use of the land-fill
areas is restricted due to cadmium accumulation in crops, particularly in the green,
leafy vegetables, wheat grain and other cereals and in most green fodders. With re-
spect to the contamination of groundwater in disposal areas the transport of pol-
lutants was calculated with a one-dimensional dispersion programme (Kerdijk,
1981); chloride, showing conservative behaviour, will become apparent in the ad-
jacent polders in the year 2100 approximately, the heavy metals one to three cen-
turies later, and pesticides several thousand years later.
As a result of increasing efforts to reduce the waste-water input the metal dis-
charges in highly polluted rivers are now decreasing after a maximum in the early
1970s. From a review of data from the Rhine River at the German-Dutch border
it is shown by Malle and Muller (1982) that the suspended solids contents have
hardly changed since 1973, while the contents of Cr, Cu, Zn, Cd, Hg and Pb are
retrograde (Fig. 88).
The decrease in the Cr and Hg contents mainly occurred in the suspended sol-
ids, Zn and Cd concentrations were found to be reduced in the liquid phase.
,,
Fig. 88. Changes of metal load (dis-
\ Cr Cu solved and particulate) in the Rhine
3000 '. 2000 "" River at the Dutch-German border
·····:~o" ....~~
from 1971 to 1979. (Malle and Miiller,
2000
1982)
1000
,72 74 76 18 12 14 76 18
18000 ,,
,,
.......
Zn 200
,,
12000
'"
........ '~100
C/I
'"c:: 6000 --- --~
0'"
\72 14 76 78 ,12747678
· . :~ooo ..~:~:~
80
\ Hg 2000
60
40
20
~
72 14 16 18 12 14 16 18
year
o D
soluble suspended
solids
5.3.4.3 Metal Budgets and Local Inputs

An example of the heavy metal budget in a densily populated region is given for
the 4488 km 2 large Ruhr River catchment area, a tributary to the Rhine River, by
Imhoff et al. (1980). The Ruhr River is the main source of drinking and process
water for population (about 6 million people) and industries. At the same time the
Ruhr and its tributaries receive treated waste waters from 2.2 million people and
2 million industrial population equivalents. Among other industries about 300
plating plants have settled in the Ruhr basin; these plants discharge a considerable
amount of heavy metals, affecting metal concentrations in the river water casually
up to critical levels (e.g. for nickel, which appears in Ruhr water in higher concen-
trations than in other rivers). Fig. 89 shows that approx. 55% of the heavy metals
(Pb, Cu, Zn, Ni, Cr, Cd) in the Ruhr River are discharged from municipal and in-
dustrial waste water treatment plants; 45% are of geochemical origin.
The municipal treatment plants receive 31 % of the heavy metals from domestic
and 69% from industrial waste water. The origin of the elements and their relative
fraction of the total load varies considerably. For example, 90% of the chromium
in the Ruhr River is discharged by industries; 66% nickel and cadmium derive from
industries, while only 50% copper and zinc originate from industrial waste-water
(Imhoff et aI., 1980).
3'
'0
~
o
....,
~
~
<;;
Input Output + Retention ;;-
~
~ .
...,
Industrial 'a'"
discharge ~ 1%
6t / a ~
Percentage of the
catchment area
j :; : ; j ;
I~ I; I; II;;I; I ; I ;I ; I ;Ii: I :
:::: Exported with::::
::::drinking water!:::
non point ~ : :: over the ::: :
sources ~4% :::: watershed ::: .
O
20 t / a :.:' 50 tt a :,':
,',',',',','
,! I ! I" !! I I !
,', ',', ',', ',',',II I:'
! ,
Sum: 483 t/a Sum: 483 t / a

• partly •• tlm.t.d
-..J
Fig. 89. Balance of heavy metal load in the Ruhr River catchment. (Imhoff et aI., 1980) V.
Cd DUiSbUJ9 Copper Plant Effluent Fig. 90. Cadmium-concentra-

1-'9 / 9
• tions in suspended sediment
30 • from the lower Rhine River
(Cologne to Rotterdam). Data
•.,. • • from RIWA-Report on the sam-
20
•
•• • •• • •
pling campaign from 23.4.1980
••• to 24. 4. 1980
• • ••
, •.
• • • ••
10 •
e. .. . ..". C>
"
3*n
C
c:
~*7i Rhine R. -km

II
800 * 1000
*
C'
0
Rotterdami
Q.
~
The Dutch Rijncommissie Waterleidingbedrijven (RIW A, 1980) during a sam-

pling campaign during 23rd and 24th April, 1980 localized significant increases in
the concentrations of copper, lead. zinc and cadmium in the lower Rhine down-
stream from the Ruhr influent. The characteristic example of cadmium contents
in the suspended matter is given in Fig. 90.
At Rhine River kilometer 680 (distance from Lake Constance outlet) the con-
centrations of cadmium in the solid matter were approx. 6-7 Ilg/g (dry weight).
Near river kilometer 790, the Cd-concentration jumps to more than 30 Ilg/g, and
- after 30-40 km - drops down to approx. 15-20 Ilg Cd/g, which generally does not
change all the way to Rotterdam. It has been suspected that this very significant
increase of the cadmium concentrations was mainly caused by the copper plants
in Duisburg (km 776), which were known to have discharged considerable amount
of heavy metals into the Rhine River.
5.3.5 Complexing Agents in River Systems
Although many investigations have shown that increased inputs of natural organic
substances can affect the metal mobilization from the sediments, the introduction
of synthetic complexing agents can have an even more serious impact on heavy
metal remobilization.
Among these substances, nitrilotriacetic acid (NT A) as a possible alternative
to the polyphosphate in detergents was intensively discussed during the last few
years (Forstner and Wittmann, 1979). The extent of these effects depends on the
concentration of the complexing agent, its pH value, the mode of occurrence of
trace metals in the sediments and on competition by other cations (Salomons and
van Pagee, 1981). The influence is twofold:
1. The complexing agent may actively desorb heavy metals from the suspended
matter and the deposited sediment. Similar processes may occur within the de-
posited sediments (increased mobilization of trace metals to the interstitial
waters).
Complexing Agents in River Systems 177
2. When both NT A (or any other complexing agent) and metals are discharged in-
to a river system, the complexing agent may negatively influence the naturally
occurring adsorption processes, causing enhanced dissolved metal concen-
trations.
The active remobilization has been studied by many investigators and seems to
exhibit reliable results at NT A-concentrations above approx. 1-2 mg/1. Such con-
centrations of NT A could rarely be expected in normal river waters, but may occur
at even higher levels in sewage treatment plants. Recent data from experiments per-
formed by Dietz (1982) on sediments from the Ruhr River at relative high concen-
trations of solid matter (1 gil) and NT A-contents of 1 mg/l are summarized in
Table 49. Mobilization mainly occurs for zinc, nickel and copper, leading to four-
fold increase of the concentrations of zinc, three-fold for nickel and double for cop-
per concentrations in the water phase. Following the calculations of Dietz (1982)
the formation of 1: I complexes of metals with NT A - which has to be expected
from thermodynamical data - would consume total available NT A in the solution,
and, therefore, it would seem that calcium and magnesium complexation will not
play any significant role in these processes.
The "passive" effects of NT A on the sorption of metals on solid surfaces was
studied by Salomons and van Pagee (1981) using natural river water, metal dosages
of 5 and 10 l!g/l, respectively, for Cd and Zn, 200 mg/l solid matter, pH-values of
7 and 8, respectively, and variable NT A concentrations from 20 l!g/l to 5 g/1. Three
different systems were studied:
(a) The influence of NT A on the adsorption of trace metals on sediments. This
process occurs when NT A and dissolved metals are discharged simultaneously into
the river system, or when a pH change occurs when both NT A and metals are
present;
(b) the influence of NT A on the desorption of "labile" bound metals. This pro-
cess may occur during transport when, after a discharge of trace metals, NT A is
discharged further downstream. Over a period of 4 weeks trace metals were ad-
sorbed on sediments. Then NT A was added. The pH was not controlled (pH was
about 7.8).
Table 49. Remobilization of metals from Ruhr River sediments. (Dietz, 1982)
Metal Cone. in Cone. in Remobilized after 45 h

sediment orig. water
mg/kg ~g11 Control NTA- Released Metal/NTA
experim. expo byNTA I: I-complex
~g/l ~g/l ~g/l ~g/l NTA
Zinc 3,040 70 75 353 278 813

Nickel 260 22 25 78 53 173
Copper 610 22 12 24 12 36
Cadmium 25 < 1 < 1 1 1 2
Lead 460 <10 <10 < 10 < 10
Chromium 270 <10 <10 < 10 < 10
Iron 46,000 25 30 34 < 10
Consumption of NTA: 1,024 ~g1l
60 100 20
( .....
00
•-...... pH - 6 desorption Zn Cu ,pH - 7 _.-.
."", pH -7 2 days ..)
% Pb, pH-8 --0
pH - 8 8 days
,ug/l //
Zn t .~~ t /
/1 '
~o4°1 :a~ . I
50 10
.,. .
0
V ",'
.". " i
20-4
\
..... -.-- • .". ~.'
~.. '
/,/ ~ ..... '
.....,
.... • r~~o
-..---- ..-. ."-...,
0 . -------.:. -'- o ..A
. o 0
60 100 100
pH -6 desorption Cd Zn, pH - 7 _. - .
pH - 7
. ---~.-.-.
pH - 8
% 2 days
8 days
,ug/l N i , pH - 8 --0
......
.......j
Cd t t ..... .I
O~o • .... _.--.-. .... . rI
50 50 •
.-
.-.-' ." . /
..... ~
~J .-'-.'-'-'."'- ,.
.-.-.-.--:a. ~.
20 .-
'. .
._-----.----'., ~ .....~.-
, ~ •
We::..:.:=.·
~
O~i
.. i i i i "1 o.l...Ay I I i i I 0 '"E.
20 50 200 500 2000 20 50 200 500 2000 20 50 200 500 2000 5000 '"S'
--+ p.g/l N TA --+ p.gll NTA --+ p.g/l NTA n
o
a
S'
Fig. 91. Results of the experiments on metal-sediment-NT A interactions, presented as adsorption in % of added metal or as dissolved metal concen-
tration in fig/I. (Salomons and van Pagee, 1981)
'"
a
e.
~
~
;;l
Introduction 179
(c) The influence of NT A on the desorption of trace metals from sediments as

a function of pH.
The data of the adsorption experiments (Fig. 91a and b) indicate, that already
at NT A concentrations of 200 to 500 Ilg/l, and particularly at the higher pH -level
(PH 8) the normal rate of metal adsorption is drastically reduced; in a river water
at pH 8, for example, one should expect that with 500 Ilg/1 NT A the adsorbed zinc
content is lowered from 55 percent (no NT A) to 22 percent, while the respective
reduction for cadmium is from 50 percent to 35 percent, under the same con-
ditions. These experiments show that, if all phosphates in detergents in the entire
drainage basin of the Rhine were replaced exclusively by NT A (maximum predict-
ed concentration, according to Salomons and van Pagee, 1981, is 580 Ilg/l), an in-
fluence on metal behaviour cannot be excluded. Thus, the authors propose that on-
ly a partial replacement of approx. one third maximum should be considered in this
area.
5.4 Metals in Lakes
5.4.1 Introduction
Lakes, like estuaries, must be regarded as dynamically evolving land-forms that go

through a life-cycle which ends in a progressive upfilling with sediments. The for-
mation oflacustrine deposits is dominated by the interaction ofa number ofphysi-
cal processes whose relative importance is influenced, particularly, by the form of
the basin, its orientation and size and by climatic conditions (Sly, 1978). Sedimen-
tary processes in lake systems differ from those in marine systems in three major
aspects: (I) Despite the great size of a few lakes, the small size of most lakes sig-
nificantly limits the generation of long-period wind waves and therefore maintains
such energy levels much below that of marine systems; the occurrence of sorted
coarse sands and gravels is largely confined to shallow water areas. (2) Lakes are
almost tideless, tidal currents are generally negligible, and littoral zones are much
reduced or absent. (3) Lakes are essentially closed, or nearly closed systems with
respect to sediment transport and, because the ratio between land drainage and
lake area is often high, sediment loadings and sedimentation rates appear sub-
stantially higher than in marine environments, even when accumulation is re-
stricted almost entirely to fine sediments (typically mid-lake sedimentation rates
are at least 10 times that of oceanic environments). Geologically speaking, there-
fore, most lakes are transitory features. This is shown from examples offossillakes
in the United States in Table 50.
The sediments from the "deepest hole" of the lake can be taken for mineralogi-
cal indication of the trophic level, or perhaps to assess diagenesis of lake bottom
materials, but they are probably not representative of the lake as a whole, nor are
they likely to be definitive about sediment source. Temporal changes in materials
available for sedimentation, such as clastic sediment associated with spring runoff
or the accumulation of organic remains after a high period of biological produc-
Table 50. Areas and approximate durations of typical lakes (Picard and High, 1972)
Rock unit, lake Location Age Area Duration

(in mi 2 ) (in m.,'y.)
Lake Bonneville Utah, Nevada, Idaho Pleistocene 19.750 (max) 1.0

Searles Lake California Pleistocene 385 0.l7(?)
Lake San Augustin New Mexico Pleistocene 225 0.65
Lake Uinta Utah Eocene 7,700 13.3
(Green River, lower
Uinta fms.)
Gosiute Lake Wyoming, Colorado Eocene 1,700 (max) 4.0
(Green River Fm.)
Flagstaff Limestone Utah, New Mexico Paleocene-Eocene 7,000 (max) 2.75
Todilto Limestone Colorado, Arizona La te Jurassic 34,600 0.02
Popo Agie Formation Wyoming, Utah Late Triassic 50,000( +) 3.0(?)
Lockatong Formation New Jersey, Pennsylvania Late Triassic 2,250 5.1
tivity, cause variations in the sediment mineral composition over scales ranging
from fractions of a millimeter to several centimeters. If burrowing or bottom stir-
ring zoo benthos are absent from the sediment such temporal variations can be pre-
served as laminated sediment [varves, if the period of obvious compositional vari-
ation is I year (Jones and Bowser, 1978)]. The composition of the sediments de-
pends on the composition of the particulate fluxes. However, after deposition
physical processes may cause a redistribution of the sediments over the lake bot-
tom; slumps may occur on river deltas in lakes resulting in turbidity currents; in
shallow lakes the energy of the wind may be sufficient to cause a resuspension and
redistribution of the bottom deposits.
Sources for trace metals in lakes are the atmosphere, riverine inputs and various
waste discharges (Fig. 92). Metals are introduced in the lake both in solution
and in particulate form. The allochtonous particles will partially settle to the bot-
tom. Whereas the dissolved trace metals are subject to removal processes by ad-
sorption, uptake by biota and incorporation in authigenous phases, in the oxic
epilimnion there is a strong interaction between the carbon cycle and the metal
cycle. The production of algal material causing an increase in pH, reprecipitation
of calcium carbonate, thus causing removal of trace metal by their incorporation
in algal tissues and in new mineral phases and by providing active surfaces for ad-
sorption. During their fall through the water column a partial dissolution of the
trace metals may take place, in the same way as in the oceans. In the lakes with
an anoxic hypolymnion there is a strong interaction between the metal and the re-
dox cycle. In the anoxic waters a strong redissolution of iron and manganese takes
place, which diffuses upward and precipitates at the oxic/anoxic interface in the
lake. The resulting hydrous iron and manganese particles are able to remove dis-
solved metals.
Metal research on trace metal in lakes has in most cases been based on sediment
analysis particularly using dated profiles to determine rates of input and the histor-
ical development of trace metals. Relatively less attention has been paid to process-
es which determine trace metal behaviour in lakes. Therefore, this chapter will start
a-d
0-
C
"g.
::>
ATMOSPHERIC INPUT ~ INTERNAL LAKE CYCLE

FLUVIAL INPUT we t/ dry
dissolved / particulate deposition
DISSOLVED METALS EPILIMNION

ME. L++MEL
00
Fig. 92. Processes affecting trace metals in lakes
also with a discussion of the occurrence of trace metals in sediments and their ac-
cumulative phases.
5.4.2 Accumulative Phases in Lake Sediments
The mineralogical composition of lake sediments reflects lithological and hydro-

chemical influences. Clastic sedimentation prevails both in extremely arid and in
humid zones. Clay mineralogy and the contents of Fe/AI-hydroxides and -oxides
vary widely (Forstner, 1981 b). Lake sediments of the humid zone are characterized
by higher concentrations of organic carbon, whereas in the arid regions organic
material is scarce or even absent. The chemical composition of clastic lake sedi-
ments is similar to that described in the section on river sediments (Table 42), also
with respect to the geographical variability and grain size effects on metal data (see
above).
Authigenesis of minerals occurs mainly in moderately humid and in semi-arid
climatic zones. Muller et al. (1972) have shown that formation and diagenesis of
carbonate minerals can be regarded as proper criteria for distinguishing the differ-
ent types of lacustrine geochemical evolution. Precipitation of sodium-carbonate
minerals is restricted to hypersaline alkaline lakes, such as in the East African Rift
Zone and in the Western States of the U.S.A. (Eugster and Hardie, 1978). Forma-
tion of primary Ca-Mg minerals (calcite, high-Mg calcite, aragonite, hydrous Mg
carbonates) and of secondary carbonates (dolomite, huntite and magnesite) is de-
pendent on the Mg/Ca ratio and pH of the lake or pore water, respectively. Other
typical endogenic or authigenic formations (Jones and Bowser, 1978) in lakes are
Fe/Mn oxide minerals, phosphorous compounds and sulfides.
A compilation of examples of autochthonous mineral formations and their ef-
fect on the enrichment or dilution of heavy metals in recent lake deposits, is pre-
sented in Table 51 (adapted from Forstner, 1981a, b; 1982). These data, however,
should not be generalized to cover all cases since phase separation is often not com-
pletely satisfactory; the dilution of most heavy metals by opaline silica, carbonates
and sulphates is often significant and must be considered too. Incorporation into
pyrite minerals seems to provide a distinct mechanism of enrichment for transition
metals (examples from Black Sea sediments). Unstable iron sulfide of the hydro-
troilite type (FeS' H 2 0) is, for the most part, finely dispersed (black mud) and in-
stantly oxidized under aerobic conditions, which usually makes the separate anal-
ysis of these components and their trace metals impossible. Coarse-grained aggre-
gates of iron sulfide from Lake Constance surface sediments, separated by sieving
from the fine-grained matrix, indicate an approximate six-fold enrichment of iron
in the concentrate in comparison with the composition of the surrounding sedi-
mentary material. Similarly, Cu, Co and Cr levels were two times and Ni 1.5 times
greater; on the other hand, Pb, Zn and Mn did not undergo a significant increase.
It may be concluded, therefore, that coprecipitation with iron sulfide is less effec-
tive in concentrating trace metals than incorporation into hydrous iron oxides (see
below).
The concretions and nodules ofFe/Mn oxyhydrates are autochthonous phases,
for which diagenetic effects - selective dissolution of Fe and Mn by redox changes
Accumulative Phases in Lake Sediments 183
Table 51. Effects of autochthonous mineral phases (Fe/Mn oxyhydrates not included) on the
enrichment ( +, + + ) or reduction ( -, - - ) of heavy metals in lake sediments
Mineral phase Type of source" Lake example(s) Effect (examples)
Endo- Authi-
genic genic
Carbonates
Aragonite x Aci Crater GI b (Turkey) - - all heavy metals
Calcite x x Bande-Amir b (Afghanistan) All heavy metals
Mg calcite x x L. Balaton b (Hungary) Fe, ± heavy metals
Dolomite x L. Neusiedl b ± Mn, Zn, - Ni, Cr, etc.
(Austria/H ungary)
Rhodochrosite x L. Michigan C + to + + heavy metals
Siderite x Black Sea d, Birket Ram e + Mn, ± heavy metals
(Israel)
Sul/ates
Gypsum x Australian lakes b - - all heavy metals
Glauberite x Curtain Springsf (Australia) - - all heavy metals
Alunite x L. Brown b Australia ± Pb, - heavy metals
Opaline silica x Lake Malawi b - - heavy metals, - Cu
Sulfides
Hydrotroilite x x L. Constance f + Ni, Cu, Cr
Pyrite x Black Sea" ± Pb, Zn, Mn; + + Cu, Ni, Co
Lake Kivu h ++ Ni
Non/mllite x Lake Malawi f ± heavy metals; + Co, Mn
Phosphates x Lake Geneva; + Fe, Co, Cu, Zn, Pb(?)
a After Jones and Bowser (1978) f Forstner (unpubl. data)

b Forstner (1978) " Volkov and Fomina (1974)
C Callender et al. (1974) h Degens et al. (1972)
d Stoffers and MUller (1978) ; Near sewage outfall- J.-M. Jaquet, Univ. Geneva
e Singer and Navrot (1978) (personal comm.)
(Harris and Troup, 1969) and upward migration in the pore water (Lynn and
Bonatti, 1965) both mechanisms being mediated and enhanced by organic diagen-
esis, - are assumed to occur for both shallow marine water (Calvert and Price,
1977) and lacustrine formations (Callender and Bowser, 1976)
The basic oxide mineralogy of lacustrine ferromanganese deposits appears to
be similar to marine ferromanganese nodules (Burns and Burns, 1977; Jones and
Bowser, 1978). Goethite is the dominant iron phase, whereas the manganese oxides
include todorokite, birnessite and psilomelane (Callender and Bowser, 1976).
Compared with the deep-sea nodules, ferromanganese oxide deposits in near-
shore and lacustrine environments indicate:
a higher variability of the Mn/Fe ratios,
higher contents of organic matter, and
characteristic lower contents of many minor elements.
Table 52. Chemical composition of freshwater ferromanganese nodules (after Callender and Bowser,
1976; Forstner, 1978)
Swedish Lake Grand Lake Lake Lake F

lakes Oneida Lake George Ontario Michigan (max)
(1) (2) (3) (4) (5) (6)
Iron 34.1% 23.5% 16.6% 33.5% 20.0% 20.6% 6

Manganese 10.8% 14.4% 33.0% 3.6% 20.5% 13.9% 347
Zinc (mg/kg) 50 150 1,635 1,177 460 1,490 23
Nickel (mg/kg) 40 40 268 704 725 1,670 22
Cobalt (mg/kg) 40 70 195 220 305 366 15
Copper (mg/kg) 155 80 12 1,314 90 96 24
(1) Ljunggren (1955); (2) Dean (1970); (3) Harris and Troup (1969); (4) Schiittle and Friedman (1972);
(5) Cronan and Thomas (1970); (6) Rossmann (1973)
F = max. factor of enrichment compared with crustal element abundance
The examples in Table 52 show the composition of limnic nodules and con-
cretions to be highly variable with respect to the concentration of minor elements.
The highest contents of nickel, copper and zinc are found in the deeper lakes,
whereas the lower contents occur in the shallow Canadian lakes. This divergence
partially results from the primary metal supply to lake water, but at the same time,
it is a consequence of varying growth rates of the concretions or nodules (Man-
heim, 1965) and may be affected, for example, by the complexation with organic
substances or anthropogenic influences (Cronan and Thomas, 1972).
The majority of freshwater nodules show concentric bands of alternating Fe-
rich (lighter) and Mn-rich (darker) laminations; minor transition metal cations,
such as those of Cu, Co, Ni and Zn are associated with the Mn phase, whereas ele-
ments with aqueous anionic charge such as silica, phosphate and arsenic are related
to the iron laminas (Callender and Bowser, 1976; Damiani et aI., 1977).
There is little data on the presence of metal in limnic phosphate deposits al-
though significant enrichments of trace metals, e.g. of uranium, arsenic and cad-
mium have been found in marine phosphate deposits (Altschuler et aI., 1978). By
EDAX-analysis Jaquet (priv. comm.) has found characteristic enrichment of Fe,
Co, Cu, Zn (and probably Pb) in spherical phosphate aggregates in sediments from
Lake Geneva in the immediate neighbourhood of a sewage outfall.
High positive correlation between the contents of organic matter and heavy
metal concentrations may be interpreted as being due to direct bonding of heavy
metals to organic substances with some exceptions (Forstner, 1977). For instance
in deep-water sediments from Perch Lake in Lanark County, Ontario, Jonasson
(1976) found that gelatinous colloidal substances, which are formed from dissolved
organic acids, spores, pollen and decayed leaves, take up metal ions from water.
Similar effects have been observed by Tobschall et ai. (1978) from gels and sedi-
ments in subarctic lakes in northern Norway. In the latter example the heavy
metals, Ni, Cu, Zn, Pb, Hg, Th and U were enriched in the organic gels by factors
of2 to 500 in comparison to concentrations in the organic sediment. It may be con-
cluded, therefore, that organic substances - although not in long-term accumula-
tive phases - perform a major function in the transfer of metals between mineral
Trace Metal Fluxes as Reflected in the Sediments 185
phases, thereby making a significant enrichment of metal possible in hydrous oxi-

des and sulfides.
5.4.3 Trace Metal Fluxes as Reflected in the Sediments
Lake sediments reflect the history of metal pollution and the study of metal con-
centrations along profiles has extensively been used to elucidate the pollution his-
tory oflakes (Forstner and Wittmann, 1979). An example of such a study is shown
in Fig. 93.
This example is of the central basin of Lake Erie near Cleveland, Ohio at the
mouth of ·the Cuyahoga River and seems to be representative of a moderate pol-
lution in that area (Walters et a1., 1974). According to the distribution of mercury
in the sedimentary record, early industrial activity might have taken place begin-
ning in about 1835. Major increases in the values of zinc, arsenic and copper during
1939-1955 reflect the general growth of industry during World War II and the
Korean conflict. Strong enrichment of chromium and other metals occurred dur-
ing the late 1940's which corresponds for the most part to the growth of the Cleve-
land electroplating industry. It is assumed that the establishment of chemical
plants in the Cleveland area caused a characteristic increase in the Hg concen-
trations of the river sediments in 1949. The major break in 1955 would then cor-
respond to the opening of the Detrex chlorine-alkali plant near Ashtabula, Ohio
(Walters et a1., 1974).
Evaluation of both geochemical and civilizational input of metals into aquatic
sediments is more and more frequently established by means of flux calculations.
The sedimentary flux of any metal may be calculated by the formula (Hamilton-
Taylor, 1979):
F = R(l-4» (! . C [Ilg - cm - 2 . yr - 1].
where R is the sedimentation rate (cm/yr), 4> the porosity, y the dry density of the
sediment (g/cm - 3) and C is the metall concentration (in mg/kg). An important
requirement for the determination of these data is the extraction of undisturbed
sediment core samples and accurate dating (best with the Pb-210 method,
Chap. 2.3).
Nriagu et a1. (1979) give an example of such an investigation in this case on
Lake Erie. A comparison of natural and anthropogenic fluxes for the three partial
lake basins is of note (Table 53): the present flux of metals to the sediments is cal-
culated as the product of sedimentation rates and metal concentrations in the top
1.0 cm layer. The anthropogenic component was derived by substracting the pre-
colonial flux (below the ambrosia horizon ca. 1850 AD) from the total elemental
flux to the surficial sediments. Because of the higher overall sedimentation rates
the average anthropogenic flux of metals into the Eastern Basin sediments is higher
than those entering the other two lake basins. As shown in Table 54 the anthropo-
genic input of zinc, lead and cadmium into the Western Basins exceeds that for pre-
colonial sediments five fold, whereas in the central and Eastern Basins the anthro-
pogenic fluxes of these metals are approx. two to three times greater than the nat-
ural inputs. Metal pollution in Lake Erie originates from tributary inflow, coastal
LAKE ERIE (near Cleveland) 00
0\
-
Hg Zn As Cu Ni Cr
0.2 0.6 ppm 10 20 30 2 3 20 40 60 40 60 80 20 40 60 ppm
o I ... ..', ... .'. I L ••.• .' ..•• .Ie .....c...: I••••• ! ...."""""""= I •••• .' •••••
C:: F_._._._.J_._._._._.~._._._._._'._. LOIiii [ •.•.•.•.•.'•.•.•.•.• .1......... I
20
40
60
em
Fig. 93. History of metal pollution of Lake Erie as reflected in its sediments (Walters et aI., 1974)
~
CI>
e.
'"
::i"
(')
o
E!-
5'
CI>
::>
e.
~
a
CI>
;;l
Trace Metal Fluxes as Reflected in the Sediments 187
Table 53. Inventory of sources and sinks of heavy metals in Lake Erie and their residence times
(N riagu et aI., 1979)
Source Flow rate (x 103 kg/y)
Cadmium Copper Lead Zinc
Detroit River (import from upper Lakes) 1,660 630 5,220

Tributaries USA 100 52 271
Tributaries, Ontario 31 19 140
Sewage discharges 5.5 448 283 759
Dredged spoils 4.2 42 56 175
Atmospheric inputs 39 206 645 903
Shoreline erosion 7.9 190 221 308
Total, all sources 2,477 1,906 7,776
Export, Niagara river and Weiland Canal 1,320 660 4,400
Retained in sediments 1,157 1,246 3,776
Retained in % of input 50% 65% 35%
Residence time (days) 104 180 152
runoff, industrial and domestic effluent discharges, atmospheric fallout, shipping

operations and the recreational use of the lake. The inventory of the sources and
sinks of metals in the lake agrees, give or take one order of magnitude, with the
loading rates recorded in the sediments (Table 53; Nriagu et aI., 1979). It is inter-
esting to note that direct atmospheric inputs account for 8%, 34% and 13% of the
Cu, Pb and Zn, respectively, delivered annually to the lake. The annual con-
tributions ofCu, Pb and Zn from sewage effluents are 18%, 15% and 11 %, respec-
tively.
Anthropogenically derived changes in the sedimentary flux of metals has been
discussed by Rippey et aI. (1982) from dated cores from Lough Neagh, Northern
Ireland and from comparison with other lacustrine situations. The alteration of a
lake's sedimentary regime, as a result of deforestation or other similar agricultural
change in the catchment, has been recorded as increased sedimentary K, Mg, and
Na concentrations, and by increased accumulation rates. The Mg-profile of core
B41 from Lough Neagh (Fig. 94) indicates that a small but detectable increase in
the erosion rate occurs at 52-54 cm (corresponding to 1670 A.D.) and stabilizes at
44-46 cm. Above 24-26cm (ca. 1880 A.D.) Mg concentrations decrease again,
suggesting a change in the erosion regime; there is, however, no evidence for any
major land-use changes in the last 100 years. The increase in erosion rates above
52-54 cm not only produces increasing Mg concentrations but also relates to in-
creasing Cu and Pb concentrations (Fig. 94). Above 24-26 cm (around 1880), Cu,
Pb, Zn, and Hg concentrations increase toward the surface and suggest that con-
tamination of the sedimentary material is occurring. Phosphorous, on the other
hand, behaves differently to trace metals (Fig.94) and appears to reflect the in-
creasing P loadings to the lake over the last 100 years or so as a result of sewered
population increase and the introduction of phosphate-rich detergents. Calcu-
lations of recent net sedimentary and background fluxes show that background at-
I 00
00
mg Mg g-1 ~g Cu g-1 I.lg Pb g-1 I.lg Zn g-1
I
ng Hg g-1 mg P g-1
-
Minerals %
14 16 18 50 100 150 50 100 200 300 500 1000 90 94 98
E
t)
&.
0.
~ 50
Fig.94. Metal concentrations along sediment cores in Lough Neagh (North Ireland).
(Rippey et aI., 1982)
~
~
:or
()
o
a
s·
o
::l
E.
~
~
Metal Cycling in Lakes 189
Table 54. Selection of data on the sedimentary fluxes in lakes. The Lake Huron and Ontario data
are from Kemp and Thomas (1976), the Lake Erie data from Nriagu et al. (1979), the Loch Neagh
data from Rippey et al. (1981), the Woodhull Lake data from Galloway and Likens (1979) and the
Windermere data from Hamilton-Taylor (1979)
Lake Cr Ni Cu Zn Cd Hg Pb V
mgm- 2 a-I
Lake Huron:
Anthropogenic 2 - 14 7 - 57 0 -D.05 8 - 42
Natural 4 - 8 12 - 17 0.01-D.04 5 - 8
Lake Ontario:
Anthropogenic 22 - 33 109 -217 0.9-3 0.20-1.4 62 -169
Natural 13 -17 29 - 48 0.3-D.4 0.01-D.05 8 - 12
Lake Erie:
Anthropogenic 1.5-120 10 -362 0.1-5.4 - 2 -118
Natural 5.9- 78 6.8-148 0.1-1.6 - 3.8- 43
Lake Neagh:
Anthropogenic 84 58 61 164 1.8 0.5 72
Natural 61 56 15 47 1.2 0.08 12
Atmospheric 3 8 23 75 0.3 27
Woodhull Lake:
Anthropogenic 11 6.3 65 1.2 56 12.6
Natural 1.1 2.7 11 0.05 5.4 5.4
Atmospheric 3.6 13 50 1.2 25 16
Windermere:
Anthropogenic 18 169 0.49 99
Natural 12 75 0.05 26
Atmospheric 32 120 <0.24 55
mospheric flux could be a significant component for Cu, Zn, Hg and Pb in this
area (Table 54).
5.4.4 Metals Cycling in Lakes
Comparatively little information is available on processes affecting dissolved and

particulate trace metals in lakes and their incorporation in the sediments. Nriagu
in a recent article on metals in lake Ontario (Nriagu et aI., 1981) could only cite
three references dealing with the behaviour of dissolved trace metals in the Great
Lakes, the largest freshwater body on earth. Two of these articles dealt with limited
aspects only: the surface microlayer.
Well studied oxic lakes include a number of lakes in Switzerland and two fresh-
water lakes in the Netherlands. The Usselmeer is a former coastal lagoon (Fig.
130), which was transformed into a lake in 1932 when it was shut offfrom the sea
by the Enclosure Dike. Gradually the surface area of the lake has decreased as a
Table 55. Fluvial and atmospheric input of some trace metals (tonsjyr) in the I1sselmeer (Salomons,
1983)
As Cd Cr Cu Ni Zn
Fluvial input 13.5 11.4 112.8 85.2 83.1 688

Atmospheric input 0.45 0.27 0.18 5.0 0.9 52
Table 56. Mean metal concentrations in bottom deposits of the I1sselmeer (corrected for grain size
differences; metal concentrations refer to 50% 16 11m (see Chap. 3.5)
P Al Ni Zn Cu Cr Pb Cd Hg
% % Ilgjg
Ketelmeer 0.45 3.64 68 1,840 250 490 290 35 6.0

I1sselmeer 0.16 1.94 29 420 40 90 70 3.0 1.1
Base line 29 68 13 72 21 0.25
Table 57. Mean concentrations (based on monthly measurements in 1978) of dissolved metal con-
centrations and metal concentrations in the suspended matter in 11 sselmeer (Salomons, 1983)
Dissolved metals (Ilgjl)
Zn Cu Cr Cd Ni As pH
IJssel 40 5.1 1.6 0.6 7.4 0.76 7.4

Enclosure dike 4.3 1.5 0.2 0.04 4.5 0.90 8.4
Suspended matter (Ilgjg)
Zn Cu Cr Cd Ni As Mn
I1ssel 2,160 280 650 47 93 36 1,790

Enclosure dike 583 50 145 4.3 47 20 3,444
consequence of reclaiming parts of the lake. The present surface area is 1250 km 2
which makes it the largest lake in Western Europe. Its main source of pollutants
is the river 11 ssel, a distributary of the river Rhine which carries about 10% of its
pollutant load into the lake. Other sources include the input from the atmosphere.
However, compared with the fluvial input the input from the atmosphere is low
(Table 55).
The Rhine has been polluted with heavy metals since the early part of this cen-
tury (Fig. 87), thus the I1sselmeer has been subject to a increased metal input for
more than 50 years, and large amounts of trace metals have accumulatedd in the
bottom sediments. Especially the the mouthing area of the river I1ssel (Ketelmeer,
Fig. 130), is heavily polluted with trace metals (Table 56).
The increases in chromium and nickel are relatively minor or absent, this is be-
cause these metals are relative "newcomers" in the metal pollution of the river
Rhine (Fig. 87).
The IJsselmeer is a well mixed reservoir. Its shallow depth of 4 m allows an easy
resuspension of the deposited sediments with an intensive mixing of recent and
older deposits. During stormy periods suspended matter concentrations of several
grams per litre are observed (Salomons and Eysink, 1981).
A five year study has been carried out in this lake (1977-1982) to identify and
quantify the processes which affect the dissolved and particulate metal concen-
trations. Jointly with this geochemical study a biological study was carried out
(Marquenie, 1981) to determine the relative importance of the various reservoirs
of trace metals (e.g. deposited sediments, suspended matter, dissolved metals and
metals in the pore waters).
With the exception of manganese all particulate metal concentrations in the wa-
ter leaving the lake are lower than in the river IJssel (Table 57). Dissolved metal
concentrations, with the exception of arsenic, are also lower than in the river IJssel;
e.g. the removal of dissolved metals does not cause an increase in particulate metal
concentrations in the lake. The changes in particulate and dissolved metal concen-
trations are directly or indirectly determined by the carbon cycle in the lake. Its in-
fluence is threefold:
A. Changes in the composition of the surface waters

The high nutrient load of the river IJssel causes extensive algal blooms. As a con-
sequence the pH of the waters increase gradually in the direction of the Enclosure
dike. The increase in pH causes an adsorption of chromium, zinc and cadmium on
the suspended matter (see also Chap. 2.5) and thus a decrease in the concentrations
of these elements in the surface waters, in fact a good correlation between dissolved
zinc and the pH is observed (Fig. 95), because the pH shows seasonal cycles (high
pH values in summer).
9
x
x
pH x
x xx
x
x
8
X X
x x
Zn
20
X+observed
(.119/1) .+calculated
x
•
x
10
• •
Fig. 95. Seasonal cycles in pH and dissolved zinc con-
••
X X •
~,..
x.
centrations in the IJsselmeer. The calculated values
were obtained from a simple black box calculation
with adsorption as the only process. (Salomons, 1983) J A J 0
Table 58. Mean metal concentrations in algae from the I1sselmeer and the Haringvliet (corrected for
admixtures of inorganic suspended matter), compared with the concentrations in the suspended
matter
Zn Cu Cr Pb Cd Ni Mn
I1g/g
Algae 246 29 12 27 1.5 26 631

I1sselmeer 220 26 20 35 2.0 14 220
Haringvliet
Suspended matter 583 50 145 132 4.3 46.6 3,444
I1sselmeer 1,828 163 496 440 21.6 72.0 2,927
Haringvliet
Table 59. Dissolved concentrations in the pore waters of the 2 cm top layer
of the sediments and the theoretical flux from the sediment to the overlying
waters in the I1sselmeer. Fluxes of zinc, copper and nickel are small or absent
Metal Pore water Overlying surface Flux

2 cm top layer (mg/m3) water (mg/m3) (tons/year)
Cr 6.3 0.6 8
Cd 1.2 <0.2 1.4
As 21 0.9 28
Fe 21,000 20 33,000
Mn 9,160 50 13,000
P 5,380 145 7,000
B. Metal uptake by algae

Trace metals are taken up by algae (either through adsorption on the outside of
the cell walls or through incorporation in their tissues, a distinction between these
two processes however, is not yet possible). Mean metal concentrations in algae
from the lake are presented in Table 58, the low concentrations are in the same or-
der of magnitude as found for other lakes (Baccini, 1976). This metal uptake by
algae causes a further removal of dissolved metals.
C. Production ofauthigenous phases in the lake

The admixture of the algal material to the suspended matter causes a dilution of
the particulate metal concentrations because the metal concentrations in the algae
are lower than in the inorganic suspended matter from the river. The high pH of
the water, induced by algal blooms, causes a precipitation of calcium carbonate.
Calculations showed that the total amount of calcium carbonate produced in the
lake is about 440,000 tons/year, which is twice the sediment supply by the river IJs-
sel. The admixture of low metal carbonates to the suspended matter causes a fur-
ther dilution of the metal concentrations in the suspended matter.
o 50 % 100
zinc!lillllllll!III!!IIIIIIIII!llllillllllll!111111111II1I
Chromium 1'111111 iIII! I t t l .Iii1IIII111111111111 I

Cadmium 1111111111111111.llllflllllllllllllllllllllllll
Copper 1=• =I11~·~~

=
•••
· ______________~
iIml Removal by
mml adsorption D in solution
(not removed)
Fig.96. Fate of dissolved cadmium, zinc, chromium and copper in the IJsselmeer. (Salomons and
Mook,1980)
Thus the production of authigenous phases in the lake causes a decrease in par-
ticulate metal concentrations by dilution. The pH increase causes a removal of
those trace metals, whose adsorption depends on the pH over the range (7.4 to 9)
observed in the Usselmeer. However, the increase in particulate metal concen-
trations due to adsorption is offset by the dilution effects.
A balance calculation showed that adsorption processes are mainly responsible
for the removal of cadmium, zinc and chromium, whereas copper, whose adsorp-
tion characteristics do not depend on the pH over the range observed in the Ussel,
is hardly removed through physical adsorption processes (Fig. 96).
A second major factor which influences metal concentrations in the lake is the
bottom sediments. After deposition of the suspended matter, diagenetic processes
take place, causing a release of trace metals to the pore waters (see also Sect. 3.7).
Concentrations in the pore waters are high for manganese, iron and arsenic
(Table 59).
A simple flux calculation showed that the pore waters are able to release signif-
icant quantities of these three elements to the surface waters. Iron is known to pre-
cipitate in the surface oxidised layers in the sediments, however the oxidation of
manganese is much slower, and manganese is able to enter the surface waters,
where it precipitates/adsorbs on the suspended matter, causing the high particulate
manganese concentrations. Also arsenic is released to the pore waters. The adsorp-
tion of arsenic on sediments depends strongly on the pH (Pierce and Moore, 1982),
with maximum adsorption (on iron hydroxides) at pH values of about 8. The ar-
senic from the pore waters (PH 7 and lower) enters high pH surface waters (pH 9),
as a consequence little adsorption is expected to take place. The data on arsenic,
manganese and iron suggest that their concentrations are determined strongly by
kinetic processes and by the particular conditions in the lake (e.g. for arsenic the
pH in the pore waters and in the surface waters are shifted from the optimum ad-
sorption conditions).
PARTICULATE METALS DISSOLVED METALS
100 100 c:::J Haringvliet

Cu EZZI Ysselmeer
% Zn Cr % r
r r
Cu Cd
50 50 Zn
~ Cr
Cd /.
/'
0 ~ ~ 0 ~ h ~
Fig. 97. Balance calculation for the IJ sselmeer
suspended
matter
Zn -338 -166
_150.000 , -285.000 ---350 ---47
315.000 1472
water water t
sediment:::··· .
Fe Cu
-6000 -4588 _44.5 _14.2
---250 ---140 ---40.7 - --21.7
~1535 !47.3
Mn Cr
_318 _1097 -97.3 _41.3
---660 ---280 ---15.5 ---3.0
t400
I
~67.6
P
-1133
---3586
J1852
- Cd
-6.7
---4.7
'6.9_9.1
-1.3
---0_2.2
::;:::::::::::;:::::::;:;:;:;:::;:::::::::::;:::;:;:;:::::;:::::.:......
Hg Ni
-0.95 _0.34 _13.3 _13.3
---0_1.1 ---0_1.1 --_69.8 ---47.3
JO.61 , 16.7
As
- part iculate -5.2 -5.8
---8.3 ---1D.4
- -_ dis sol v e d t1.8
I
Fig. 98. Particulate and dissolved metal concentrations in the waters leaving the Haringviet and the IJs-
selmeer to the North Sea expressed as percentages of the concentrations in the incoming waters.
(Salomons, 1981)
Balance calculations on the amount of metals entering the lake and by the river
Ussel and leaving the lake to the Wadden Sea showed that the lake acts as a sink
for copper, zinc, cadmium, chromium, mercury and nickel but as a major source
for manganese and arsenic (Fig. 97).
The Haringvliet lake in the Netherlands (see Fig. l30) was created in 1970 and
is fed by both the highly polluted rivers Rhine and Meuse. About 50% of the total
pollutant load of these two rivers enters this freshwater lake. The metal concen-
trations in the suspended matter and in solution leaving this lake through the
sluices, however, is different from that in the Usselmeer (Fig. 98). Both the particu-
late and dissolved metal concentrations in the Haringvliet are much higher.
This reflects differences in hydrodynamic and geochemical conditions in this
lake. The Haringviet is deep, thus the resuspension oflow metal containing bottom
sediments is almost absent. The residence time of the water is in the order of weeks,
much less than that of the six months in the Usselmeer. Fewer algal blooms are
observed, with a resulting smaller production of organic matter. The pH also does
not reach values much higher than 8 and no calcium carbonate precipitation takes
place. The smaller production of low metal authigenous material causes less dilu-
tion of the metal concentrations in the fluvial suspended matter. Finally, the rather
low pH causes less removal of dissolved trace metals by adsorption processes, thus
dissolved metal concentrations stay high.
The removal of dissolved trace metals from solution is also reflected in metal
uptake by the bivalve Dreissena polymorpha (Fig. 99). Between Lobith and Kam-
pen (river Rhine and river Ussel) the pH increases slightly, affecting the distribu-
tion of dissolved cadmium over the dissolved and particulate phase (e.g. the dis-
solved metal concentrations decrease and those in the suspended matter increase).
Rhine
100
so
so
Fig. 99. Cadmium accumulation by B
Dreissena Polymorpha (Marquenie,
1981), compared with changes in dis-
particulate
solved and particulate metal concen-
trations in the river Rhine, its distribu·
100
tary the river IJssel and in the IJssel-
meer (Salomons et aI., 1982)
%
Fig. 100. Removal of di solved
r- and particulate trace metals In
la ke Alpnach (Baccini 1976)
80
60
- -
-
40 r- -
20
DO issolved
Fe Cu
11
Zn
n~ Cd Pb
010131
Although the total cadmium burden of the organism stays constant, the actual up-
take decreases, showing that dissolved trace metal fractions are more bioavailable
than the particulate forms.
In contrast to the extensive removal of a number of dissolved trace metals in
the Usselmeer, far less removal of dissolved metals has been observed from lake
Alpnach (Fig. 100).
The metal input in this lake is also predominantly by rivers. While iron is re-
tained almost completely, nearly 50% of the copper, zinc and cadmium is trans-
ported further. A comparison of the dissolved parts (Fig. 100) shows that copper
and cadmium are retained only to a small extent, zinc is retained for about 40%.
Temporal variations in metal distribution in the three phases - biomass, allochton-
ous particulate and dissolved phase, were calculated in a model in which particu-
late iron serves as an indicator for the allochthonous particulate material phase and
particulate organic nitrogen for the biomass phase. The major conclusions from
this simulation were:
- copper and zinc introduced in solution form are partly taken up by algae and
settle as part of the particulate organic matter to the bottom. The biogenic por-
tion of the total concentration varies between 5 and 15% for copper and 5 and
20% for zinc.
- the decomposition of the particulate organic matter during settling permits a
partial return of the metals to solution and the amount in the solution phase rises
in the hypolymnion (Fig. 101).
- the allochthonous particles are deposited on the lake bottom relatively un-
changed.
However, in contrast to the results from the Usselmeer study and from studies
in estuaries (see Chap. 6.7), adsorption plays a minor role in the removal of trace
metals from solution in Lake Alpnach; this lake does not act as a major sink for
dissolved copper and zinc.
In a laboratory study (Baccini et ai., 1982), the adsorption properties of sedi-
ment particles from Swiss lakes were compared with those of y-aluminium oxide
EPILIMNION HYPOLIMNION
2.5-10m (depth) 25- 55m (depth)
J J D
%
80
60
40 mil Biomass
• Allochthonous particulates
I I
20 D Dissolved phase
Fig. lOt. Simulated seasonal variations of copper concentrations in biomass, allochthonous particles
and water of the Lake Alpnach. (Baccini, 1976)
Cd ng/kg Pb ng/kg Cu ng/kg

0 10 20 0 50 100 0 200 400 600 800
0 0 0
oc! 'pt? 0
0/ fo
50 0 50 hb 50
I \1>0
\
0
100 b 100
tfl j 100
:g
..,c...
&.
150 I
0 150
II
1>0 150
I II
to
;\
200 0 200 200
I
250
0
I
250
1>0
250
9'"
o total
I>filtered
Fig. 102. Profiles for trace metals in the Bodensee (Sigg et aI., 1982)
in the presence of natural organic matter (NOM). Under natural lake conditions
the adsorption of copper, zinc and phosphate was reduced significantly by the pres-
ence of natural organic matter. It was postulated that the binding sites of mineral
surfaces are occupied almost completely by NOM under natural conditions, pre-
venting other ions being adsorbed. Differences in adsorption by zinc and copper
could be explained by differences in speciation due to the presence of NOM. These
experiments confirmed the field observations that allochthonous particles in Swiss
lakes are not very efficient scavengers while passing through the water column.
The first profiles of dissolved and particulate trace metal concentrations in deep
lakes have recently been obtained for the Bodensee (Germany) (Sigg et aI., 1982).
The results for cadmium, lead and copper are presented in Fig. 102.
Table 60. Inputs, deposition rates and concentrations of heavy metals in the Bodensee compared with
the North Atlantic Ocean (Sigg et aI., 1982)
Cu Pb Cd Zn
Bodensee
Atmospheric input} _ 2/ 714 11,000 20 8,400
Deposition ng cm y 6,500 9,500 100 36,000
Concentrations in the lake ng/I 300-800 50-100 6- 20 1,000-4,000
North Atlantic
Atmospheric
. .input'
. } ngcm -2/ y 25 310 130
VertIcal transItIOnal flux 234 330 1,040
Concentrations in the ocean ng/l 100 3 10 100
(30-300) (1- 15) (1-120) (10- 6(0)
, Buat-Menard and Chesselet (1979)
The results are similar to profiles obtained for ocean systems: a removal of trace
metals in the surface layers by biological activity and partial decomposition during
settling of the authigenous particles to the bottom (compare with Fig. 135). How-
ever, for the Bodensee, the high atmospheric input results in high levels of copper
and lead in surface layers. Although the input of trace metals in lakes are one or
two orders of magnitude higher than that of the oceans (Table 60), the metal con-
centrations are of the same order of magnitude. Therefore apparently highly effi-
cient removal processes are operating in lakes (Sigg et ai., 1982).
5.4.5 Metals Cycling in Stratified Lakes
Density variations in lakes that generate anoxic conditions below a thermo-halo-

cline are recognized as the main prerequisite for a possible feedback mechanism be-
tween oxidizing and reducing environments. This may have led to ore accumula-
tion of economic value in the geological past (Degens and Stoffers, 1977). The con-
cept of "stratified waters as a key to the past" has been developed by Degens and
Stoffers (1976) based on studies on sediment cores from the Black Sea and some
deep East African rift lakes (Fig. 103). In the modern, fully oxygenated ocean,
where at great depths molecular oxygen is recharged much faster than it is con-
sumed by the oxidation of organic matter, sand and clays are deposited in the shal-
low areas and carbonates are found at greater water depth (Fig. 103 a). In such
situations, the lack of distinct chemical contrast prevents significant feedback
mechanisms. Upon stratification of the water, anoxic conditions develop below the
interface and euxenic sediments form in the H 2 S zone, whereas carbonates may de-
velop in the shallow oxic zone (Fig. 103 b). These two contrasting environments dif-
fer not only in oxygen and hydrogen sulfide contents, but in a number of chemical
ingredients such as mineral nutrients (nitrate, phosphate, ammonia and silica),
some common and trace elements, and dissolved gases. Lowering the interface
(Fig. 103 c) will result in the transfer of dissolved chemical species into the upper
layer. Primary productivity will be stimulated and a series of minerals will precipi-
tate.
Metals Cycling in Stratified Lakes 199
m sand
~.~~ ... a ..
b
m clay
~ carbonate
fl!!lil!I marl
_ bituminous, shale
Fig. 103. a-il. F ormation and evolution of stratified waters. (Degens and Stoffers, 1976)
Metals, most notably those that are affected by changes in Eh/pH conditions,
may become concentrated or removed from the water column or sediment-water
interface. This pertains mainly to the behaviour of iron and manganese, however
as these scavenge other ions in their hydrate, oxide and hydroxide forms, this af-
fects the distribution of trace elements as well (see Chap. 2.5).
Metal behaviour in lakes which exhibit a pronounced stratification with anoxic
conditions in the hypolymnion are complicated as is shown by a number of recent
studies (Baccini and JoIler, 1981; Davison, 1981; Davison et aI., 1981; Sholkovitz
and Copland, 1981; Davison et aI., 1982; Davison and Woof, 1982). An analogue
of lakes with anoxic conditions in the hypolymnion is the Black Sea, which was
studied intensively in the late sixties (Spencer and Brewer, 1971; Spencer et aI.,
1972). The Black Sea is permanently stratified and does not exhibit the autumn
overturn of most freshwater bodies; as a consequence some aspects can be studied
in more detail.
The Black Sea is the world's largest anoxic basin. The surface salinity varies
from 17.2%0 to 18.3%0, the salinity of the deep water is relatively constant at 22.4%0
(Spencer et aI., 1972). Owing to the strong density gradient through the main halo-
cline, cold surface waters formed during the winter do not mix downward to great
depths as is the case for most freshwater lakes. The deep water of the Black Sea
is renewed only by Mediterranean water flowing in through the Bosporus.
Profiles of the particulate manganese, zinc and dissolved copper, zinc, cobalt,
manganese and cobalt are presented in Fig. 104.
The profiles with depth are plotted relative to oxygen zero and the stations for
particulate metals identified into "near shelf' and "far shelf' groups. The concen-
trations of dissolved manganese and iron in the deep water exceed those in the sur-
face waters, which is attributed to the greater solubility of the sulfides and hydroxi-
des of the reduced species as compared with the solubility of hydroxides and oxides
of the oxidized species (Spencer and Brewer, 1971).
The concentrations of copper and zinc are depleted in the deep water by pre-
cipitation as insoluble sulfides. This precipitation of zinc starts below the oxygen
zero boundary and reaches maximum values of 2322 ng/kg at 35 m below the
boundary. Manganese is precipitated in the oxic layers above the boundaries, sug-
gesting an upward flux of dissolved manganese by diffusive and advective flow;
concentrations increase from less than 1 Ilg/kg to about 450 Ilg/kg at 30-40 m
above the oxygen zero boundary. The lack of a peak in the particulate zinc profile
100 300 500 ~9/kg 10 20 30 40 5O~g/kg

I I I
I
-200j
o - ~-~---1___...
-500 ATLANTIS II -500 I

CRUISE"49
BLACK SEA
o
ffi -1000 -1000
N
z
w
~ -1500
• -1500
S
Mn Fe
g
w
>
-2000 .. -2000
....~
-Flo'.
1 2 3 4 5 6 ~g/kg 1 2 3 4 5 6 ~g/k9
Ii!
III
II:
-200
.
l!!
..
I o o
-200 ••
~
~
~
o
-500 -500
..
•
-1000 -1000
-1500 -1500
,
-2000 Zn -2000 • Cu
Fig. 104. Profiles of dissolved copper, zinc, cobalt, and manganese in the Black Sea. (Spencer and
Brewer, 1971; Spencer et aI., 1972)
at 30 m above the oxygen zero boundary (manganese precipitation) is an indication

that this element is not being coprecipitated or adsorbed to any great extent by the
particulate manganese. The pronounced peak in particulate trace metals is proba-
bly caused by the formation of a very finely grained precipitate with low settling
velocities. Similar flocculates oflow settling velocities, resulting in sharp maximum
of particulate iron along depth profiles have also. been observed in freshwater
lakes (Davison et aI., 1981; Tipping et aI., 1981). The distribution of cobalt and
nickel does not appear to be greatly affected by redox reactions. From their
observations the authors (Spencer and Brewer, 1971; Spencer et aI., 1972)
concluded that the trace element composition of the particulate matter is controlled
by the following four processes:
Metals Cycling in Stratified Lakes 201
- the presence of detrital silicate particles (Sc, La and partly iron) which is also
controlled by the other three processes;
- precipitation as sulfides in anoxic deep waters (Zn and Cu);
- coprecipitation with or adsorption by particulate manganese which is being
formed above the oxygen zero boundary (Co and Sb);
- concentration by marine organisms in the surface waters.
Processes in lakes may be different due to the fact that the salinity in the Black
Sea is higher and that lakes are subject to annual turnovers and the Black Sea is
not. In fact the present day salinity conditions in the Black Sea were established
about 3000 years ago (Spencer and Brewer, 1971).
Baccini and Joller (1981) studied the transport processes of copper and zinc in
the highly eutrophic and stratified lake Baldegg; this lake is, like the Black Sea,
characterised by a permanent anaerobic hypolimnion (Fig. 105).
The lake is in an anaerobic state all year (Fig. 105A). During spring the in-
creased oxygen flux into the hypolimnion causes a decrease in dissolved manganese
(Fig. 105B) and dissolved iron (Fig. lOSC). With increasing reducing conditions,
the redissolution of manganese starts in April and of iron in May. Large differences
in the behaviour of dissolved copper and zinc are observed. Zinc decreases in the
summer period and does not show a distinct variation with depth. Dissolved cop-
per on the other hand is higher in the epilimnion than in the hypolimnion. Further-
more particulate zinc does not show much variation with depth whereas particulate
copper concentrations increase with depth.
The authors offered the following transport processes as an explanation for
these variations: Both copper and zinc are removed from solution by the biomass
in the epilimnion. The metals removed from solution by the biomass are partly
mineralised during settling to the bottom. However, copper is additionally being
sorbed on the newly formed iron particles in the upper hypolimnion, causing an
increase in particulate copper, which is sedimented. (see also the general scheme
of lake processes in Fig. 92). Laboratory experiments showed that neither of the
other newly formed particles in the lake (calcium carbonate and manganese hy-
droxides) adsorb/coprecipitate under the conditions observed in Lake Baldegg.
However, the iron hydroxides are able to remove copper from solution (not zinc).
An empirical one diffusion-dimensional diffusion model was able to simulate the
observed copper profiles in the hypolimnion (Baccini and J oller, 1981).
A well studied lake with a seasonally anoxic hypolimnion is Esthwaite Water
(English Lake District). The particulate chemistry in this lake is controlled by three
biogeochemical cycles (Sholkovitz and Copland, 1981):
- The activity of phytoplankton in spring and summer results in the in situ gener-
ation oflarge excess concentrations ofP, S, Mg, Ba and K in the epilimnion.
- As the hypolimnion becomes anoxic, the release of ferrous iron from sediments
results in the formation of particulate iron hydroxides which scavenge by ad-
sorption and/or co-precipitation of S, P, Ca, Ba and K, and particulate organic
carbon (POC) from solution. The concentrations of these components follows
that of the excess particulate iron. As reducing conditions become more intense,
the iron hydroxide particles are solubilized along with the above mentioned
components.
1-
0. S (mllll) d~n (10- 8 MIll
A B
d-Fe (10- 8 MI l) d-Cu (10- 0 MI ll
c D
p-Cu (10- 0 Mi ll p-Zn (10- 8 MI ll
E F
Fig. 105. Isolaths of oxygen and sulfide (A), dissolved manganese (B), dissolved iron (C), dissolved
copper (D), particulate copper (E) and particulate zinc (F) (Baccini and Joller, 1981)
- The anoxic conditions induce a large build-up of bacteria populations and in the
last stage of anoxia (before turn-over) bacteria supported POC and excess P,
Mg, Ca and K appear to become important components in the hypolimnion.
The flux of iron and manganese to the sediments in Esthwaite Water was stud-
ied by Davison et al. (1982) using sediment traps. The iron cycle is similar to that
found in the formerly discussed Lake Baldegg. During winter most of the iron and
manganese which flows into the lake is transported to the sediment. However, in
summer there is a vertical transport offerrous iron from the sediment (see also Fig.
92) by eddy diffusion, an oxidation to Fe(III) by oxygen, sinking of the particulate
iron and redissolution in the anoxic hypolimnion. The manganese cycle differs to
Atmospheric Inputs in Lakes 203
a large extent from the iron cycle. In winter, the manganese reaching the sediment
is rapidly reduced and is released to the overlying oxic waters. Only about 10% ac-
cumulates in the sediment. During summer the particulate manganese never
reaches the sediment, since it become redissolved in the anoxic hypolimnion. Near-
ly all manganese which enters the lake is washed out again; however, during its resi-
dence time in the lake it will have undergone a redox cycle (Davison et al., 1982)
However, not in all lakes with anoxic conditions in the hypolimnion an iron
cycle as described for Esthwaite Water and Lake Baldegg is observed. Davison and
Woof (1982) found in the hypolimnion of Rostherne Mere a complete removal of
oxygen and accumulation of Mn(II) for five months during the summer period.
However, both ferrous iron and dissolved sulfide were absent. They suggested that
this is due to the high concentrations of nitrate observed in the lake. The reduction
of ferric to ferrous iron usually only occurs after all the nitrate in the system has
been consumed (see Chap. 3.7). Their study showed convincingly that deoxygena-
tion of water above an active reducing sediment can be insufficient to ensure release
of iron or sulfide from the sediment. Rostherne Mere appears to be a finely poised
system which shows manganese reduction and the initial stages of denitrification.
5.4.6 Atmospheric Inputs in Lakes
The importance of the atmospheric input of trace metals in lakes is clearly shown
by the data in Table 54. A characteristic example depicts the atmospheric input of
trace metals in lake Michigan compared with a number of other sources in Fig. 106
(Eisenreich, 1980).
The atmospheric loading is especially important for lead (60%) and is a signif-
icant source for zinc (33%), for copper it contributes 13% and for cadmium and
manganese 11 %. The atmosphere is a minor source for aluminium, iron and co-
balt.
This correlates with the data of Sieve ring et al. (1980; 1981) who have studied
the input of atmospheric trace metals over Lake Michigan in detail (see also Win-
chester and Nifong, 1971; Gatz, 1975). Calcium and magnesium are for more than
90% lake derived and aluminium almost entirely soil derived. It is estimated that
Pb Zn Cu Mn Cd AI Co
D Atmosphere 100
f
D Tributary
I
f
f
f
f
f
D Erosion % I
I
I
I I
I
I
I
Fig. 106. Relative importance of the I
input of trace mcta ls in Lake Michi -

gan by various sources. (Bascd on
Eiscnrcich. 1980) o
Table 61. Annual metal input to southern Lake Michigan by dry

deposition compared to wet deposition and surface runoff (Sievering
etal.,1981)
Element Loading (tonnes/yr)
Dry deposition Precipitation Total lake runoff
Al 550
Ca 2,000
Fe 1,100 950 1,450
Mg 700
Mn 60 55 450
Pb 500 90 100
Zn 200 50 180
over 95% of the lead, 75% of the zinc and manganese and more than 50% of iron
are of anthropogenic origin (Sievering et ai., 1980).
Sievering et ai., 1981 compared the dry deposition loading with wet precipita-
tion and surface runoff (Table 61):
They found that the atmospheric input by dry deposition contributes 75% of
the total loading for Pb and 50% for the total loading of zinc to the lake ecosystem.
The interaction between the dry deposition and the lake waters is highly complex
due to processes in the surface micro layer (see Chap. 4.6.3.2). Moreover part of the
particles are highly soluble, and contribute in this way to the dissolved trace metal
loading of the lake.
The acidic deposition from the atmosphere affects the pH of soft water lakes.
Thousands of lakes and streams in southern Scandinavia and eastern North
America and Canada are affected by it; fish populations are lost and other vital
ecosystem components and processes are disturbed. With regard to heavy metal
behaviour three processes can be distinguished:
- the increased leaching of trace metals from soils in the drainage basin causing
elevated metal concentrations in the receiving waters;
- the changes in the distribution of trace metals over the particulate and dissolved
phase in lakes (e.g. more trace metals will be leached from atmospheric particu-
lates entering the lake);
- and the active leaching of trace metals from sediments in the lake.
Changes in pH affect the distribution of trace metals over the dissolved and
particulate phase (see Chap. 2.4.1); however, the actual changes in the lake depend
to a large extent on its buffering capacity. Kramer (1976) used the carbonate
alkalinity of lakes to access their susceptibility to acid input. In Fig. 107 this clas-
sification is superimposed on the relationship between pH and alkalinity for Min-
nesota and northern Wisconsin lakes (Glass et ai., 1980).
Also shown in Fig. 107 is the relationship between adsorption of trace metals
on silica and the pH. This shows that only a small shift in pH can cause a large
shift in adsorption equilibria.
pH
9.0 r - - - - - - , - - - - - - - r - - - - , - - - - - , - - - - - - - ,
NOT SUSCEPTIBLE
8.5 POTENTIALLY SUSCEPTIBLE
.. ' . .'. -.. ,. .
SUSCEPTIBLE
8.0
•• 0·... ;. :::. . 0
• • ••- 0·. •• • 0 •
<.-" ~.!o~ 8"6&/ ... -•••

o
•~
.. . .'.
,. ."-i',
.. ,0'. it~·.
. .. -. » .
7.5 'f,
...
'... ·o":'I.:r~~ :"! •
7.0 NORTHERN MINNESOTA LAKES
•
..
'o~-f~~!_
~~.
'tI9o ....
Spring 1979 n(")o105
%i1-
8.5
:. 'i16
8.0
. 0:>£
NORTHERN WISCONSIN LAKES ~I
'ei
5.5
Sununer 1979 nr)o350 •
';fJ
..;:I
5.0 t
b I
4.5L------~------~hP------~------_..~------~
pH
!
50 37.5 25 12.5 o
1000 750 500 250
a ppm CaC03
ALKALINITY - - - - - - -
,lJeq HCOa/1
Fig. 107. Relationship between pH and alkalinity in 105 northern Minnesota lakes and 350 northern
Wisconsin lakes (Glass et ai., 1980) (a), and the adsorption of trace metals on silica as a function of
the pH (b)
Cameron and Ballantyne (1975) studied the fate of dissolved lead and zinc orig-
inating from oxidizing mineral deposits during their flow in a river and lake system
in a permafrost region of northern Canada.
With an increase in pH the dissolved metal concentrations decrease and those
in the sediments increase. As is expected from Fig. 108, the reduction for lead is
stronger than for zinc. Similar observations on the distribution of trace metals over
the dissolved and particulate phase as a function of the pH have been observed for
the I1sselmeer (Netherlands) (Salomons and Mook, 1980). They found that an in-
crease of 0.5 pH units was sufficient to cause an almost complete removal of dis-
solved cadmium from river water entering the lake (see Fig. 95). In acidifying lakes
the reverse may be expected. Haines (1981) made a survey of the literature on re-
ported metal concentrations and the pH in lakes. Some of his results are presented
in Table 62.
In acidified lakes, metal concentrations are signifcantly higher than in non-
acidified lakes. Large changes are found for the dissolved manganese and alumin-
ium concentrations in particular.
In Swedish lakes a pronounced correlation was observed between dissolved
metals levels and pH in lakes (Fig. 109).
1:11
~
.....
..
1:11
E
C
GI
1000
o~~o 0
Zn in lake sediment / "-..... ____ '\
E
:sGI \. 0 0
1/1
.5
c
100
o
/0
N
1000
..
GI 100
i
.5
g
..
:;:
~
C
GI
10
U
C
o
o
1
/e-••---.----.-
7~------------------------------------------~
5
.--.---- ........... --.-.-.
::t:
Co 3+-~------------------~~------------~ri
o 1 2 3 4 5 6 7 km
Fig. 108. Decay of zinc and lead concentrations in lake and stream water, Northwest Territories, Ca-
nada, and corresponding increase ofPb and Zn in lake sediments (from Cameron and Ballantyne, 1975;
after Rose et aI., 1979)
Table 62. Metal concentrations in acidified and non-acidified lakes in

Scandinavia and in North America (Haines, 1981)
Al Cd Mn Zn
flg/ I
Lakes with pH 6.0-7.8 <50 <0.1 < 100 < 30

Lakes with pH 4.1-5.3 Up to 600 0.6 400 120
0.3 300
~
::::: :::::
IJI IJI
~
'0
0.2 ~200
"
CJ ~
• •
i i
.-----..-.-
0.1 100
0.05 •
<0.05
6.0 7.0 8.0
0
4.0
•8.0
4.0 5.0
----+ pH ----+ pH
.
30 5
::::: 4
IJI
:::::
~
C IJI
3
•
N 20 ~
i
4
D. 2
.. i
10 ••)-. 1
0 ~. •
4.0 5.0 6.0 7.0 8.0 5.0 6.0 7.0 8.0
----+ pH ----+ pH
Fig. 109. Metals in 16 lakes on the Swedish west coast with similar deposition but with a different pH
(Dickson, 1980)
Davis et aI., 1982 studied the influence of acidic precipitation on the release of
lead from sediments. Compared with the results on pure mineral particles (Fig. 107
B), the adsorption edges were shifted to lower pH values. Significant desorption
only occurred at pH values < 3.0 in sediments from Woods Lake and < 2.0 in sed-
iment from Lake Sagamore.
The input of acidity in lakes is not a continuous process; especially in spring
with the melting of snow large influxes are observed. Johannessen and Henriksen
(1978) showed with laboratory and lysimeter experiments that 50-80% of the pol-
lutant load is released with the first 30% of the meltwater. The average concen-
trations of pollutants in this fraction is 2-2.5 times the concentration in the snow-
pack itself. This phenomenon has been attributed to ion separation during melting
(Hultberg, 1977) or to a freeze-concentration process (Johannessen and Henriksen,
1978).
Norton et aI., (1981) in a study of New England lakes (USA) observed a de-
crease in zinc concentrations from near-recent sediment to present in lakes with pH
values < 5.5, which was explained by a leaching of zinc from the sediments by
acidic deposition. Three processes were suggested for this release:
Ion exchange:
ZnX + H + = Zn 2 + + HX (where X is a cation exchange surface)
Solution of a host (solid solution phase):
(Zn,Mn)O(OH)+H+ = Mn2+ (dominant) + Zn 2 + +e- +H 2 0.
Congruent solution of a Zn-phase:
ZnS+2H+ =Zn2+ +H 2 S
Langtjern Hoyvata ppm
% ppm
20 40 60 80 100 50 100 150 o 20 40 60 80 100 SO 100 150
o
4 4
E E
2
:z: 8 iI-
8
ez
~ "-
w W
Zn
o 12 12
I-
Z w
w :!;
:!;
15
til
16 iii 16
<f) en
20
Langtjern % ~g / g Hovvata % ppm
o 20 40 60 80 100 40 80 40 60 80 100 4.0 8.0

o
1 4
E E
2 8 2 8
:z:
....
"-
til Co ~ Co
o 12 ~ 12
I-
Z
w !ztil
~ 16 ~ 16
til
<f) iiien
20 20
Lake Ramsey % ppm Lake Wavy % ppm
o 20 40 60 80 100 2000 4000 o 20 40 60 80 100 2000 4000

o O~-~--.----r--~~~'--r--'--'
E
2
8 E 8
2
i=
"-
w
o
12 ~
til
12
I-
o
Z I- Ni
UJ Z
:!; 16 w 16
~
15 15
UJ
en w
(J)
20 20
25-30 L _ ___ 1ffiIiIj5ffi1ffi1ffilB...._ _ _----1 30-35
Leaching agent/CHEMICAL FORM
E:::::J Ammonium acetate/ CATION EXCHANGE
E3 Hydroxylamine hydrochloride/ EASILY REDUCIBLE FRACTION
~ Oxalate buffer/ MODERATELY REDUCIBLE FRACTION

IiIiIiU Hydrogen peroxide/ ORGANIC + SULFIDIC PHASES
C==:J RESIDUAL FRACTION
Fig.BO. Historical evolution of chemical forms of trace metals in lake sediments of areas affected by
acid precipitation. Above: Zinc and cobalt in sediments of Hovvatn and Langtjern (Norway). Below:
Nickel in sediment cores from Lake Ramsey and Lake Wavy in the Sudbury mining and smelting area
(Ontario/Canada)
Fig. 110 (from Reuther et aI., 1981) presents data from two lakes in Southern
Norway and shows the different behaviour of zinc at different pH values. Lake
Hovvatn had before lime treatment in 1980/81 a pH of 4.4 and had been barren
of fish since the 1940's. Upon comparison with Lake Langtjern (PH 4.95) it is evi-
dent that zinc is remobilised from the upper sediment layers at that degree of acid-
ity, mainly from the easily reducible fractions (see Chap. 2.6). A significant de-
crease of the reducible fractions is also observed for cadmium, cobalt and nickel,
whereas lead and copper are affected by these changes only to a small, insignificant
degree. The fact that these effects are not discerned in Lake Langtjern indicates
that an increase in pH of half a point (0.5) may be enough to reduce the mobility
of these elements (see also insert in Fig. 107).
The impact of acid precipitation on lake sediments and the effects of metal re-
lease were studied by Nriagu et ai. (1982) and Reuther et ai. (1982) from examples
of the Sudbury area in Ontario/Canada. In the past uncontrolled open-air roasting
of copper and nickel ores released significant quantities of pollutant metals to the
air and the fumigation of the surrounding areas with the S02 - the biggest single
source of S02 of the world - had destroyed the vegetation. In 1972 a 381 m super-
stack was installed; however, in 1977 the smelters in Sudbury still emitted about
2.6 tons ofNi, 2.6 tons ofCu, 0.7 tons ofPb, 6.3 tons of Fe and 2500 tons ofS0 2
per day (Nriagu et aI., 1982). The substantial reduction in vegetation biomass
around Sudbury associated with the emission of S02 from the smelter stacks has
been well documented (Ontario Ministry of Environment, 1978); the contribution
of the laJ:ge-scale input of pollutant metals to the reduced primary production of
these lakes, however, remains to be fully assessed.
Sediment cores indicate characteristic pollution records, which are mainly af-
fected by the emissions of the Sudbury stacks. The onset of accelerated deposition
of both Ni and Cu began about 90-100 years ago in most lakes studied; the discon-
tinuation of the use of roasting beds and the building of the 170-m stack around
1923 brought a first change of the distribution of copper and nickel in the sediment
cores, followed by a sharp increase due to the expansion of the Sudbury's metal
industry in the 1950s. The maximum concentrations observed in Kelley Lake near
Sudbury include 440, 12,000 and 50,000 ppm for Cu, Ni and Cu, these are among
the highest values recorded in recent sediments anywhere. The concentration ofNi
and Cu in the surficial sediments tends to decrease with increasing distance from
Sudbury; the enrichment factors for Ni in sediments of unlimed lakes range from
2.5 for Windy (furthest from Sudbury) to 38 for Ramsey (closest to Sudbury); as
expected, considerably higher enrichment factors have been found in sediments of
lakes which have been treated with lime. The recent decrease of metal input to the
lakes in the immediate surroundings of the Sudbury smelters and the increase of
Cu and Ni in sediments of lakes further from Sudbury (Vermillion and Windy
Lakes) may be related to the installation of the superstack in 1972 (Nriagu et aI.,
1982)
In our study on the chemical forms of metals in sediments of the Sudbury area
(Reuther et aI., 1982) two examples were selected for core samples: Lake Ramsey,
within the reaches of the township of Sudbury, indicating pH-values of6 to 7 dur-
ing sampling, and Lake Wavy, 25 km southwest of Sudbury, exhibiting pH of 4.0
to 4.5 in its waters. The example of the nickel distribution demonstrates the typical
OO~~OT~~rr~TTTr~r-~~~T-~~rr~~~~~~~~~~~
10
20 Zn Cd Pb Cu Ni Co Fe Mn Cr AI
-
.I:
1:1.
CI:I Ramsey lake
-
c
c
CI:I
E
0rr~-.r-~~~~~~~~~-r~--~~'-TT~~~-r~~-r-
AI
20
I '1
Wavy lake
Fig. HI. Contour lines of metals in sediments from Lake Ramsey and Lake Wavy
differences in the interactions of water and solid metal components as they have
developed during the last hundred years (Fig. 110): Both profiles are nearly iden-
tical in the older, pre-industrial deposits containing approx. 50% of nickel in resid-
ual fraction, 10-15% associated with organic and sulfidic phases, 35-40% in mod-
erately, and 5% in easily reducible phases. The raising input of metals shifts the
chemical form of nickel in the direction of the non-residual associations, which at
the same time are more reactive. At the climax of the metal emissions - in the 1950s
and 1960s - nearly 50% of the nickel contents exist in exchangeable form in the
sediments of Lake Ramsey; with the decrease of total Ni in these sediments since
1972 also the exchangeable components are decreasing. In Lake Wavy sediments,
on the contrary, the residually bound nickel fractions are relatively low even at
higher bulk concentrations, probably due to the enhanced remobilization at ele-
vated SOz-inputs and decreasing pH-values. According to the differences of the re-
sidual fractions in the uppermost deposits one may estimate that about 50% of the
nickel input in the solid matter of Lake Wavy has been remobilized. Similar mo-
bilities can be assumed for manganese and cobalt from the distribution curves,
whereas the contents of cadmium and zinc seem to be more stable, associated with
the solid matter, and the mobilization of Cu, Pb, Fe and Cr should only be signi-
ficant at much lower pH-values than those presently occurring in the waters of
Lake Wavy.
In Fig. III the contour lines of other metals in sediments from Lake Ramsey
and Lake Wavy are compared for the total metal concentrations. It is obvious that
also for metals other than nickel there is a distinct decrease in the upper layers of
the sediments from Ramsey Lake, e.g. for copper, chromium, cobalt, cadmium and
to a lesser extent for lead and zinc; the characteristic increase of the manganese
content in the uppermost layers of the deposits in Lake Ramsey possibly reflects
a change in the redox conditions, which is, however, not strong enough to affect
similar changes in iron content. The most evident feature in the metal contours of
Lake Wavy's sediments is the gradual decrease of the manganese concentrations
in the upper 20 cm; this evolution probably reflects the increasing acidity in the
lake water (as well as in the precipitation and in the contributing waters), which
also involves the interactions with sediments deeper than expected from the nickel
data (Fig. 110). It seems that the behaviour of manganese can be used as the most
sensitive indication not only for redox conditions but also for changes to increasing
acidity. Strong effects are also observed for zinc and cadmium in the core from
Lake Wavy, where the concentrations are strongly reduced in the upper layers,
whereas the concentration oflead is still increasing in this part of the sediment core.
However - as has also been stressed by Nriagu and colleagues (1982) from their
data on these and other lake examples of the Sudbury area - this documentation
that the contaminated sediments can release substantial quantities of toxic metals
to the overlying water must have interesting ramifications with regard to the lim-
nological impact of acid rain. Increased inputs of trace metals in lakes from the at-
mosphere and their subsequent incorporation in bottom deposits will affect ben-
thic organisms mainly. However, the combined input of metals and acids will affect
both benthic and pelagic organisms because the acid will cause a lowering of the
pH and metals will remain in solution and/or will be solubilized from the sediment.
6.1 Introduction
Like lakes, estuaries are ephemeral in respect to geologic time. They must be re-
garded as dynamically evolving land-forms that go through a life cycle from valley
creation, followed by the drowning phase, and ending up with the progressive
backfilling with sediments (Fairbridge, 1980). The origin of most modern estuaries
dates back to the rise of the sea level after the last Ice Age. The history of an es-
tuarine system after it has been established as a geomorphological entity is largely
determined by its sediment supply (Postma, 1967). Mass particulate balance is con-
trolled by the input to the estuary from rivers, the atmosphere and sea, as well as
by the output of substances to the ocean and to the bottom (Goldberg, 1978). Ac-
cumulation of sediment - even of fine-grained material- can take place due to pro-
tection from wave action and currents. Net shore-ward transport of suspended
matter is influenced by waves, tidal movement and a typical estuarine circulation,
the latter being caused by differences in specific gravity between river and sea water.
Compared with the behaviour of metals in the oceans or lakes, the estuarine
system is more complex and more dynamic due to the strong gradients in chemical
composition of the water, variable suspended matter concentrations and complex
hydrodynamic processes.
Time scales of estuarine processes vary by several orders of magnitude. The
residence time of metals of the Tamar Estuary is in the order of days; as a conse-
quence large daily changes in the relationships between the manganese concen-
\
FLUVIAL OR
UPPER .;
::~::;_!c__~~::{h§~~:~~
~l _
~ ~ sediment Tidal influence
transport onl, (tidal bores 0.
Salt - freshwater common)!
mixing ( brackish) - freshwater
zone
Fig. 112. Idealized map of a typical estuary showing three divisions, lower, middle and upper estuary;
the boundaries are transition zones that shift according to season, weather and tides (After Fairbridge,
1980)
Estuarine Circulation 213
trations and salinity are observed. On the other hand in the St. Lawrence Estuary
the residence time of the surface water is about four months whereas the bottom
waters may take several years to travel to the head of the estuary. It is evident that
these differences show up in processes governing the trace metal behaviour. Es-
tuaries are an important part of the hydrological cycle, since they determine the
amount of riverborne trace metals entering the coastal environment and ultimately
the deep ocean. Furthermore, estuaries are often subject to a large input of contam-
inants due the fact that industrial areas and cities are often located adjacent to
them. Therefore, a large amount of studies have been carried out on the fate of con-
taminants in the estuarine and coastal environment. Both subjects, their place in
the hydrological cycle and their function as recipients of waste loads will be dis-
cussed in this chapter.
6.2 Estuarine Circulation
With regard to sediment transport characteristics, four types of estuaries can be

distinguished (Fig. 113, Postma, 1980):
RIVER SEA
~?\.\.//::~·;\::~:·::·~:~:;·:;·;·,;;.:oq~{~~~:;·:::··:·':.;;:: . :.....~
35
(a)
Salt wedge
30
7 ./
35
(e)
l30
I
35
Fully mixed
Fig. 113. Schematic presenta-
tion of types of estuaries. The
dots indicate sediment con-
centration and the arrows the
net water movements over ebb
and flood. (Postma, 1980).
0-35 are %0 Salinity (S) iso-
lines. For explanation see the
text
(a) Salt wedge estuary: Most or all suspended material is fluviatile and is carried
to the sea in the low salinity surface layer and does not enter the estuarine cycle
proper. If both the tidal and wave regimes in the adjacent sea are mild, a delta may
be formed, as is the case at the mouth of the Mississippi River.
(b) Partially mixed estuaries: The landward bottom flow is sufficiently strong
to move suspended sediments up the estuary until the head of the salt intrusion is
reached. This sediment may be fluviatile material that has settled from the upper
into the lower layer, but it may also be of marine origin, depending on the concen-
tration of suspended matter in the river or in the sea. There are several examples
on the Atlantic coasts of Europe and North America.
(c) Fully mixed estuary: The suspended matter is concentrated nearshore. This
occurs also for estuaries without appreciable river flow that are tidally dominated.
(d) Negative estuaries with net inflow at the surface and outward flow near the
bottom: These may form in areas where excess evaporation (arid regions) causes
high salinities in the inner section of the estuary; silt is transported by the bottom
current.
Estuaries are sinks for sediments derived from rivers but additionally from the
marine environment. An obvious reason is that estuaries offer an effective shelter
against strong waves and currents. But, in addition, water and sediment transport
mechanisms exist which actively prevent the escape of sediments. These are the
landward transport by waves, tidal movement and the estuarine circulation pattern
(Postma, 1980).
WATER DENSITY
~ WATER FLOW
-
~ ---.. --=:;.
~
-//{/'p --
SUSPENDED - MATTER
CONCENTRATION
SUSPENDED - MATTER
- - -.....-~
TRANSPORT
- -71/ / ........ \ \
t t
Fig. 114. Main features of water and sediment move-
RIVER OCEAN ment in a stratified estuary (Meade, 1972)
Estuarine Circulation 215
The estuarine circulation is especially important in understanding processes af-

fecting trace metals and therefore, it will be described in more detail. Fig. 114 shows
the main features of water and sediment movement in a stratified estuary.
The freshwater discharge generates a residual seaward flow in the upper layer.
The seawater which is entrained from the lower layer by this flow is provided by
a residual landward flow along the bottom. The particles transported by the river
are subjected to gravitational settling and settle during horizontal transport. Here
they are taken up by the residual landward flow along the bottom. The suspended
matter concentration near the bottom is generally greater than near the surface and
this causes a residual landward sediment transport in the transition region between
salt and freshwater. Accumulation of sediment occurs until a state of (dynamic)
equilibrium is reached between sediment supply along the bottom, removal of sus-
pended matter from the lower to the upper layer by mixing, seaward transport in
the upper layer and sinking of suspended matter from the upper layer back to the
lower layer. The maximum concentration of suspended matter of the water appears
to occur at the tip of the saltwater wedge in the estuary (Fig. 115). The turbidity
maxima may extend into the freshwater tidal area (Postma, 1967; Meade, 1972).
The recirculation of mud gives rise to longer particulate residence times for the
suspended matter than in the water: water from the river with its dissolved com-
ponents is in fact flowing through the turbidity maximum whereas some propor-
tion of the particles are returned within the maximum.
Particulate material in estuaries originates from numerous sources (Goldberg,
1978):
(a) The oceanic source of particulate matter is characterized by biogenic
skeletons of diatoms, coccoliths and foraminifera as well as by clay minerals having
Suspended
Matter
•
Distance up Estuary
-0
10 c
til
<II
~
QI 0
-O.&.
.~ l-
S o~
Go.
- QI
<II
~
til
0 0.
100 80 60 40 20
Distance Above River Mouth
(K ilometers )
Fig. lIS. Example of the non-conservative behaviour of suspended matter in estuaries and the forma-
tion of a turbidity maximum at the fresh-sea water interface (Meade, 1972)
specific properties of material originating from coastal sources due to marine ero-
SIOn;
(b) The fluvial source includes materials eroded from the catchment area, oxy-
hydrates and clay minerals from weathering reactions, organic remains from
vascular plants or as humic matter;
(c) Airborne anthropogenic particulate matter constitutes an important source
locally because of the proximity of industries and urban settlements to most of the
world's major estuaries;
(d) Organic and inorganic flocculations in suspension are indicative of estuar-
ine sources as are certain authigenic minerals such as iron-phosphates and
manganese hydroxides.
While this source classification is based on modes of transport of particulate
matter, it is essential that material from anthropogenic sources be treated separate-
ly (Goldberg, 1978). This group includes metals, slag particles, tailings, fly-ash, in-
organic pigments, building materials, radionuclides, sewage and other waste par-
ticles. In "undersaturated" estuaries, most of the organic matter, whether imported
or produced in situ, is buried and preserved (or, at least is only partially decom-
posed), whereas, in "saturated" estuaries much of the organic matter is largely de-
composed within the water column.
6.3 Conservative and Non-Conservative Behaviour
When riverwater mixes with seawater a large number of physical and chemical pro-
cesses take place which affect the distribution of trace metals over the particulate
and dissolved phase and hence the composition of the deposited sediments.
If trace metals behave conservatively in estuaries both their particulate and dis-
solved concentrations can be calculated from the mixing ratio of marine to fluvial
components provided that the composition of the end-member remains constant
over the flushing time of the water (Loder and Reichard, 1981). Deviations from
the theoretical linear mixing curve point to processes other than simple mixing af-
fecting the trace metals (Fig. 116).
Mathematical relationships for mixing curves have been derived by Boyle et al.
(1974).
For dissolved trace metals the chlorinity or the chlorosity are more satisfactory
indices than salinity, because they are easily determined with a high degree of ac-
curacy by titration and there is little or no evidence that the halide ions show any
nonconservative behaviour during estuarine mixing (Aston, 1978). The difference
in oxygen isotopic composition of river- and seawater was first suggested by Boyle
et al. (1974) as a useful tracer for the mixing of water masses in estuaries. This
method was applied by Martin and Letolle (1979) for estuaries in France, Zaire and
India. The results show that with this method it may be possible to distinguish be-
tween more than one freshwater source during estuarine mixing. It should be
noted, however, than some rivers may exhibit seasonal changes in their oxygen
isotopic composition; the Rhine River for instance is fed mainly by rainwater dur-
Behaviour of Particulate Trace Metals during Estuarine Mixing 217
Fig. 116. Theoretical relationship between the compo- ,

sition of estuarine water and chlorinity; end-members " ..................
constant over the flushing time of the estuary
\, "',,<Addition
\, ", Theoretical
-..
c \, / . dilution line
.2 ,, ,
l!!
'E '"
CoO Removal"""""
=
C
c.J
"
'"
Conservative index of mixing
ing winter, however in spring and summer it is fed by meltwater whose isotopic
composition is different from rainwater, causing seasonal cycles in the oxygen
isotopic composition of the water (Mook, 1970).
In most studies, information on the behaviour of trace metals has been derived
from the mixing curve depicting the relationship between dissolved constituents.
In principle however, these observations should be confirmed by analysis of the
particulate components (e.g. losses from the dissolved phase should show up as ele-
vated levels in the particulate concentrations). However, the salinity cannot be
used to determine the mixing ratio of marine to fluvial sediments (Fig. 114 and Fig.
115), and due to a lack of suitable tracers for particulates in estuaries, this approach
has seldom been applied (Salomons and Mook, 1977; Eisma et ai., 1978; Salomons
and Eysink, 1981).
6.4 Behaviour of Particulate Trace Metals During Estuarine Mixing
Knowledge of mixing ratios of marine to fluvial material in the suspended matter,

deposited sediments and in dredged material is essential for an understanding of
the transport processes as well as for making a balance of sediments and particulate
metals in the estuarine environment.
Studies using radioactive or activable tracers provide answers to the movement
of the sediments over only relatively short time periods. More useful for long-term
transport studies are natural tracers. Several natural tracers (e.g. natural differ-
ences in composition between two or more sediments sources) are available for
tracing argillaceous sediments:
- differences in mineralogy,
- differences in chemical composition, and
- differences in the isotopic composition.
Table 63. Natural tracers for estuarine sediment transport studies
Tracer Application Reference
Mineralogy
Calcite/dolomite ratio Rhine, Ems Estuary Salomons (1975)
Heavy minerals Yaquine Bay, Oregon Byrne and Kulm (1967)
Clay mineralogy Estuaries US East Coast Hathaway (1972)
Gulf of Mexico Holmes (1982)
Elemental composition
Strontium content of carbonate Rhine, Ems Estuary Salomons (1975)
fraction Biogenic/terrigenous
material deep-sea sediments Parra et al. (1981)
Boron content Freshwater-marine sediments Harder (1970)
Trace elements in quartz Provenance studies sedimentary Dennen (1967)
rocks and sands Herrera and Heurtebise (1974)
Fe/Ti and Fe/Zn ratios Chesapeake Bay particulates Eaton et al. (1980)
B, Cr, Ga, Ni, V Marine and freshwater muds Shimp et al. (1969)
CS,Eu,La, Ta, Th, Yb North Sea, ScheIdt Estuary Salomons et aI. (1978);
Salomons (1978)
Silicones New York Bight Pellenbarg (1979)
Barium (from drilling mud) Gulf of Mexico Holmes (1982)
Isotopic composition
Organic matter ScheIdt, Ems, Rhine Estuary Salomons and Mook (1981)
St. Lawrence Estuary Tan and Strain (1979)
Estuaries of the Gulf of Mexico Schultz and Calder (1976)
Gironde Estuary Fontugne and Jouanneau
(1981)
Carbonates Rhine, Ems, Scheidt Estuary Salomons (1975); Salomons
and Mook (1977);
Salomons and Eysink (1981)
Clay minerals Rhine Estuary Salomons et aI. (1975)
Strontium isotopic composition Rio de la Plata Biscaye (1972)
of carbonate free sediment
Quartz Sands Savin and Epstein (1970)
A summary of potentially useful tracers for estuarine sediment transport stud-

ies is shown in Table 63.
The first two classes oftnlcers refer, in most cases, to the differences in the over-
all composition of the sediments, whereas with the isotope methods it is possible
to trace the individual components of the sediments. Although large differences in
concentration may be observed between marine and fluvial end-members their use
as a tracer is not always warranted. A difference in compositon may be used as a
tracer provided that it shows conservative behaviour, i.e. the amount of tracer per
unit weight of sediment in a specific source (river or sea) is not subject to variations
in time, either during transport or after deposition (Salomons et ai., 1978).
These conditions should be specified for each case individually. For instance
cadmium in the river Rhine shows a large increase in its concentrations over the
last 25 years (Fig. 87); this increa~e in time (although the differences in concen-
Behaviour of Particulate Trace Metals during Estuarine Mixing 219
trations between riverine and marine sediments are large) precludes its use as a
tracer for Rhine sediments. However, in an unpolluted estuary, provided that the
other criteria of conservative behaviour are met, it may be useful as a tracer.
During transport differential settling/flocculation of minerals may take place.
This differential segregation is important for some estuaries and delta systems
(Edzwald and O'Melia, 1975; Gibbs, 1977). From a study in lateral variations of
clay mineral assemblages in modem and ancient sediments (Parham, 1966) it was
found that kaolinite settles first followed by illite, chlorite, attapulgite and sepi-
olite. Thus, in estuaries and deltas with differential settling processes, the mineral-
ogy of the sediments cannot be used as a tracer. Also if certain elements are associ-
ated with these particular clay fractions, they also cannot be used for tracer studies.
Although Gibbs (1977) found some evidence for selective transport of clay min-
erals from the Amazon along a distance of ca 1400 km along the north coast of
South America, the observed compositional change is small as compared with the
compositional difference between Amazon mud and Orinoco mud so that the clay
mineral composition could be used as an indicator for sediment sources in the
Orinoco Estuary (Eisma et aI., 1978).
If deposited sediments are used for transport studies, the tracer should also
show conservative behaviour after depositon. Notably iron, manganese and phos-
phorus are subject to large diagenetic changes in their concentrations, which results
in enrichment in the surface layer of the sediments. Therefore, care should be taken
in sampling deposited sediments for transport studies.
In carrying out transport studies it should be known if the conclusions based
on one tracer may be extrapolated to the whole sediments; for instance heavy min-
erals which, due to their high specific gravity, behave hydrodynamically differently
from the main mass of the sediment. Therefore conclusions based on heavy mineral
studies, or conclusions based on elements which are known to be concentrated in
heavy minerals, may not be extrapolated to the origin of the sediment as a whole.
The best tracers in our opinion are tracers which provide answers regarding the
origin of the individual minerals making up the sediments. Into this category be-
long the calcite/dolomite ratio, the Sr-content of the carbonates and the isotopic
composition of the carbonates, which give direct answers to the origin of the car-
bonate fraction. In a similar way the isotopic compositon of the clay minerals, or-
ganic matter and quartz (although no estuarine studies have been carried out on
the quartz fraction) gives answers to the origin of the sedimentary components.
Results on the mixing of marine and fluvial particulates in estuaries, as deter-
mined with the aid of natural tracers, are shown in Fig. 117.
Fig. 117 shows that the ratio of marine to fluvial mud in suspended matter is
not a simple function of salinity. The relationship shows three distinct regions. At
low salinities the percentage of fluvial mud decreases relatively quickly to about
70%0 and stays more or less constant between 5 and 15%0 salinity. The amount of
fluvial mud decreases again with salinities of 150/00 and higher. This second de-
crease coincides with a broadening of the estuary.
U sing the mixing ratio determined with the natural tracer techniques it is shown
that the metal concentrations in the sediments from the rivers Rhine and Ems could
be mainly explained by a mixing of marine and fluvial sediments (Salomons and
Mook, 1977). However, the calculated values were slightly lower than the mea-
100
0~
'C 75
:::I
E
iQ
.; 50
:S
t 25
0
0 5 10 15 20 25
--+ 5 (%0)
Fig. 117. Relationship between the percentage of fluvial matter in suspended matter from the Scheidt
estuary and salinity (Salomons and Eysink, 1981)
Table 64. The calculated and observed trace metal concentrations at

Leerort (Ems Estuary, Western Germany) and in the Haringvliet (Rhine
Estuary, the Netherlands). Salomons and Mook (1977)
Metal Concentration (J.lg/g)
Leerort Haringvliet
Calculated Measured Calculated Measured
Cadmium 0.7 0.8 5.0 5.0

Chromium 86 97 195 224
Copper 17.1 22.6 82 99
Nickel 28 33.3 25.8 30.8
Lead 49 58.6 177 213
Zinc 196 220 675 870
sured concentrations, indicating the occurrence of removal processes for the dis-
solved trace metals (Table 64).
Apart from their use for the interpretation of trace metal data in estuaries,
natural tracers have great importance for the determination of the origin of
dredged material. A study in the Rotterdam harbour showed that the major mass
of the dredged material originates from the North Sea (Salomons and Eysink,
1981 ).
6.5 Iron and Manganese
Compared with other trace metals, the behaviour of iron and manganese has been
rather well studied and it is possible to depict a more or less complete picture of
the processes affecting their fate in the estuarine environment.
Iron and Manganese 221
There is at present a considerable amount of field data showing that large scale
rapid removal of iron from riverwater (Fig. 122) is a general phenomenon (Shol-
kovitz, 1976; Boyle et aI., 1977; Moore et aI., 1979). Laboratory experiments using
the batch technique (Sholkovitz, 1976; Boyle et aI., 1977; Sholkovitz, 1978) as well
as experiments conducted in an estuarine mixing simulator (Bale and Morris, 1981)
confirmed the field observations. Ultra-filtration and ultra-centrifugation ex-
periments showed that iron exists as colloids stabilized by organic matter (Boyle
et aI., 1977; Moore et aI., 1979). In the Beaulieu Estuary 90% of the iron is associ-
ated with the nominal molecular weight fraction < 10 5 (Moore et aI., 1979). Sea-
water is able to neutralise the negatively charged iron-bearing colloids allowing
flocculation (Sholkovitz, 1976; Boyle et aI., 1977; Sholkovitz, 1978; Sholkovitz and
Copland, 1981). The removal of filtrable iron during estuarine mixing should not
be interpreted to mean removal from estuarine water parcels (Mayer, 1982). Lab-
oratory experiments corroborated by field measurements showed that in three
Maine (USA) estuaries neither gravity nor suspended sediments were very effective
in removing the flocculated iron from suspension, and a significant portion of the
flocculated riverine iron may escape to shelf waters (Mayer, 1982). If this non-sett-
ling of flocculated material is a general phenomenon then also trace metals re-
moved by flocculation (Sholkovitz and Copland, 1981) might remain in suspen-
sion.
Duinker and co-workers (1978; 1980; 1982a; 1982b) gave strong evidence for
the presence of two different fractions of suspended matter in estuaries. At low sus-
pended matter concentrations, a fraction with high concentrations of Cd, Zn, Cu,
Pb, Al and organic carbon was found, and a second fraction at higher suspended
matter concentrations with lower metal concentrations. However, the iron concen-
trations in the first fraction are lower than in the second one. These fractions had
different settling properties as well as being subject to different particle sorting
mechanisms within the estuary.
Manganese shows non-conservative behaviour in most estuaries with positive
deviations from the theoretical mixing curve at low salinities (Fig. 122) and nega-
tive deviations (removal) at higher salinities. In a few cases conservative behaviour
has been observed (Holliday and Liss, 1976; Moore et aI., 1979).
The deposited sediments play an essential role in biogeochemical cycling of
manganese in estuaries (Elderfield and Hepworth, 1975; Graham et aI., 1976;
Evans et aI., 1977; Sanders, 1978; Duinker et aI., 1979; Morris and Bale, 1979;
Knox et aI., 1981). As discussed in Chap. 3.2.3 a release of manganese from the par-
ticles takes place rather rapidly after deposition. Consolidation of the freshly de-
posited sediments, diffusion, bioturbation and erosion cause a release to the sur-
face waters. Although reprecipitation takes place in the oxidised surface, part of
the dissolved Mn(II) escapes to the surface waters due to its slow oxidation rate.
Oxidation rates of manganese(II) determined in the laboratory predict removal
rates in the order of hundreds of years in seawater (Morgan, 1964) in the absence
of particulates and weeks to months in the presence of iron oxides (Sung and Mor-
gan, 1981). However, the removal observed in near shore areas is in the order of
a few days (Graham et aI., 1976; Emerson et aI., 1979; Wollastet aI., 1979; Emerson
et aI., 1982). The rate of removal is enhanced by the action of bacteria (Wollast
et aI., 1979; Emerson et aI., 1982) which might explain the discrepancies between
abiotic laboratory experiments and the field situation.
l:3
N
RIVER
,REelPlTATION SEAWARD TRANS P ORT EXPORT
INPUT 111
;;:--;:"\",",":::: ";::):\:,':({)~;/;::}":"::":;;#\:~:\::\
" ."",
SEAWARD TRANSPORT
I----~I?~{\"I-I------1 LANDWARD TRANSPORT
V~~:.~:L l~
;~ "i{
DIFFUSION OUT
OF SEDIMENT a;::
~
e:..
'"
5"
m
~
t:
I"
~"
'"I"
8-
(j
o
~
e.
~
a'
t:l
3
Fig. 1I8. Schematic model of the recycling of manganese in the St. Lawrence Estuary (Sundby et aI., 1981) "
~
Trace Metals in Estuaries: Field Investigations 223
Morris et al. (1982) studied the rate of oxidation under estuarine conditions for
the Tamar Estuary and showed that the first rate constant increases with increasing
suspended matter concentration and temperature. An increase in chlorinity caused
a decrease in the rate constant. These data suggest that the release from the sedi-
ments may be more significant at high salinities than that at the head of the estuary,
due to the lower rate constant. The conservative behaviour of manganese in the
Beaulieu Estuary (Moore et aI., 1979) may be due to the low suspended matter con-
centrations (Morris et aI., 1982).
The manganese released from the bottom deposits is transported with the land-
ward flowing bottom current to the head of the estuary. During transport part of
it is converted to particulate manganese; also erosion of the bottom deposits (Mn-
enriched surface layers) may contribute manganese-rich particles to the landward
bottom flow (Sundby et aI., 1981). In the St.Lawrence Estuary a progressive in-
crease of dissolved and particulate manganese is observed in the bottom waters in
the landward direction. This "broom effect" as it is called by Sundby et ai. (1981)
causes seaward sediments to be a source of manganese for the head of the estuary.
Some of the landward transported manganese may be lost by vertical transport and
entrainment in the seaward moving surface layer (Fig. 118). This net landward
transport in the St. Lawrence Estuary is in the same order of magnitude as the an-
nual river input (Sundby et aI., 1981).
Recycling of manganese between the upper and lower estuary has also been ob-
served for the Rhine and ScheIdt estuaries (Duinker et aI., 1979) and the Newport
River Estuary (Evans et aI., 1977).
Particulate matter transported in the landward direction is subject to a decreas-
ing pH-gradient (Mook and Koene, 1975). The decrease in the pH causes a release
of manganese from the suspended matter, causing an increase in the dissolved frac-
tion at low salinities.
Although desorption from fluvial suspended matter may be a further source of
dissolved manganese at low salinities, calculation for the Rhine Estuary showed
that this desorption alone was insufficient to explain the high concentrations ob-
served.
The magnitude of these sources, and the intensity of removal processes result
in the observed deviations from the theoretical mixing curve at low salinities.
Results thus far obtained on the behaviour of manganese in estuaries show that
it is controlled by a complex interplay of hydrodynamic and kinetic processes in
which sediments play an important role as a source of additional dissolved (and
also particulate) manganese.
6.6 Trace Metals in Estuaries: Field Investigations
In the past there has been controversy regarding the interpretation of the seaward
decrease in metal concentrations in estuarine sediments. Such a decrease can be ex-
plained by a mobilization of trace metals from the sediments or by a mixing of ma-
rine (low metal concentrations) and fluvial sediments (high metal concentrations).
This controversy was mainly based on the interpretation of trace metals in the well
studied Rhine Estuary in the Netherlands. For historical reasons it might be useful
to discuss briefly the fundamental differences and discrepancies between the vari-
ous investigations. The conclusions of de Groot and co-workers (de Groot, 1966;
de Groot et aI., 1971; de Groot and Allersma, 1975) who favoured mobilization
processes, were based on a natural tracer study to distinguish between marine and
fluvial sediments. To determine the origin of sediments in the Rhine Estuary
manganese concentrations in the uppermost part (oxidised layer) of the deposited
sediments was used as a natural tracer. This study (de Groot, 1964) showed large
differences in manganese concentrations between fluvial and marine sediments,
and also that the concentrations of manganese in the sediments from the Rhine Es-
tuary were equal to those of the river Rhine. The conclusion, at that time, seemed
to indicate that the sediments in the Rhine estuary originated from the river Rhine
only. Later studies on the concentrations of copper, mercury, cadmium, zinc, lead,
nickel and organic matter showed a decrease in trace metal and organic matter con-
centrations in the seaward direction. Moreover the CjN ratio of the organic matter
also changed and the decrease in metal concentrations could be correlated with the
order of relative stabilities of metal chelates (Irving and Williams, 1948). The sea-
ward decrease in metal concentrations in the estuarine sediments therefore was in-
terpreted as a mobilization caused by a decay of the organic matter, the decompo-
sition products of the organic matter providing ligands for solubilization of par-
ticulate trace metals.
On the other hand, after studying the Columbia River Estuary Bothner and
Carpenter (1972) and Forstner and Muller (1974), basing their observations on the
distribution of heavy metals in the clay fraction of sediments of the Elbe River tidal
area, were the first to point out that the simplest explanation for the decrease is
the mixing of highly polluted river-derived material with less contaminated marine-
derived sediment particles. Forstner and Muller (1974) suggested that a similar
process might also be able to explain the observed decrease in metal concentrations
in the Rhine Estuary. Similar mixing processes have also been found for the Savan-
nah River Estuary (Goldberg et aI., 1979).
However, the studies discussed in the preceding section showed that manganese
does not behave conservatively in estuaries. Moreover after deposition, diagenetic
recycling takes place, leading to increased manganese concentrations in the oxi-
dized surface layer. Therefore manganese does not fulfill two criteria for its use as
a natural tracer. As a result low manganese marine sediments transported into the
estuary may acquire high manganese concentrations in the oxidized upper layer
ressembling fluvial deposits. In fact, natural tracers studies based on a large range
of different techniques have shown that indeed a mixing of marine and fluvial sed-
iments takes place in the Rhine Estuary (Salomons, 1974; Salomons, 1975;
Salomons et aI., 1975). Extensive studies on the behaviour of dissolved and particu-
late trace metals in the Rhine estuary by Duinker and co-workers found no evi-
dence for mobilization processes; on the contrary they observed an extensive re-
moval of dissolved trace metals in the Rhine Estuary (Fig. 119).
Although the controversy on the interpretation of the Rhine data is resolved
in favour of the mixing process with additional removal processes, the results of
studies on estuarine trace metal behaviour over the last 10 years have shown that
Fig. 119. Dissolved Mn, Zn, Cu and Cd concentrations and ~

salinity in surface waters of the Rhine Estuary (Duinker and
Nolting, 1977)
20
Zn
10 l ..._'-.-....._---- ,119/1
Ol+-------~------~--
Cu
,119/ 1
3 :.
04-~~~..=·=-:·~"'~--.~~::::==;=~
Cd
,119/ 1
Fig. 120. (A) Metal concentrations and isotopic composition
of the carbonates in suspended matter from the Scheidt Estu-
ary. (B) Metal concentrations and isotopic composition of
the carbonates in deposited sediments from the Scheidt 10 20
Estuary (Salomons and Eysink, 1981) T salinity %0 S
fi:\ Suspended Matter

1000
'0____ v::y cf13 0
-2.00
.,..
---------___ _ Zn
III
"- 800 .\-_ ----0 --------__ •. Cd
Pb C
-1.50
--------:\
III
.,.=---------. ,\0"
::I. l( 20 III
--. -0 In
800 -1.00 \0
i . Z
i
~
II:
400 o -0.50
Z
200
.- :, :-=- '~~ o
o l------r-r-------------------------~--------------_r~~~.~====:;~.~J +~
.." : r
--
c c 'i .c 1: c
o
o ..a.
oM
o •
CI
• ! c
Ii
.!!
Z'C
J! -
:I! ;:
c
1000 -2.00
III
"-
III
::I.
800
800
C
III
In
-1.50
...,
\0
i 400
200
i
o
-..•-.
c
a.
'i
o
CI
c
C
the situation is extremely complex and that "remobilization", "removal" and

"mixing" are not cases of "either ... or". "Not only ... but also ... " more appropri-
ately characterizes a differentiated view of individual metals and their differences
in behaviour in the sediments and in the suspended matter. This conclusion was
especially borne out by a study of both dissolved and particulate trace metals in
the ScheIdt estuary (Salomons and Eysink, 1981; Kerdyk and Salomons, 1981).
To determine the mixing ratio of marine to fluvial sediments and marine to
fluvial suspended matter, the stable isotopic composition of the carbonates was
used as a tracer. The results for the bottom deposits showed that they did not re-
flect the concentrations of trace metals in the suspended matter (Fig. 120).
The isotopic composition of the carbonate fraction and the metal concen-
trations in the suspended matter show a continuous change in the seaward direc-
tion, reflecting the increasing proportion of marine sediments. However, those in
the deposited sediments show an erratic behaviour. High values for the b_13C (car-
bonate), indicating a high proportion of marine mud (and associated low metal
concentrations), are found at two localities in the estuary. In general the metal con-
centrations correlate with the isotopic composition of the carbonates, showing the
existence of mixing processes. The two localities, with high percentages of marine
mud, probably reflect earlier introductions of marine mud into the estuary, prob-
ably as a result of low runoff or storms, which are known in the Rhine Estuary to
introduce large quantities of marine mud into the estuary .
Large differences in the behaviour of individual trace metals were observed
from a study of24 elements in the suspended matter.
All possible types of trace metal behaviour (removal, addition, conservative)
were observed. Positive deviations from the mixing curve (addition processes) are
found for iron and phosphorus, but additionally for V, As, Eu, Tb and Mn. Con-
servative mixing was observed for Yb, Ta, Rb, Th, Cs, Hg and Cr. The elements
Co, Pb, Zn, Cu, Sb, Cd and Ni on the other hand showed negative deviations from
the mixing curve, indicating transfer of these elements to the estuarine waters. Dis-
solved trace elements determined during the same cruise (Duinker, personal com-
munication) also showed mobilization processes for Zn, Cd and Pb. A study car-
ried out in 1979 (Kerdyk and Salomons, 1981) confirmed the existence of large
scale mobilization processes (Fig. 122).
The behaviour of heavy metals in the ScheIdt Estuary is different from that in
the Rhine. Although in both cases mixing processes determine heavy metal concen-
trations in the sediments and in the suspended matter, we have in the ScheIdt Es-
tuary mainly remobilization processes superimposed on it whereas in the Rhine Es-
tuary removal processes dominate (compare Fig. 119, Fig. 121 and Fig. 122). Part
of these differences may be due to the anoxic conditions in the fluvial estuary of
the river ScheIdt. During transport in the oxic middle and lower estuary, trace
metal compounds in the suspended matter, stable under anoxic conditions, are
transformed to metal compounds unstable under oxic conditions. This may, as in
the case of dumping of anoxic dredged material in the North Sea, result in a release
of trace metals from the suspended matter, especially if the rate of decomposition
is higher than the rate of formation of new compounds stable under oxic con-
ditions. Moreover the released trace metals may become complexed with chloride
and/or ligands from the decomposing organic matter in the water column, in this
2.0r-----------------, 500
400
•
:c"- 1.5 •
:c"- •
•
I&. IlL
300
1.0
i 0.5
i 200 .e\
. ..
"10
• ,,-•
i .Il
0 0
0 50 100 0 50 100
~ % marine mud ~ % marine mud
100 40
:c"- 30
..
u
C
"-
i
i i
20·
•
10
.-=-\ -:r.a
20 • • • fII •
0 o~------~------~
0 50 100 o 50 100
2.0 20r-----------------~
C
1.5 :c"- 15
"-
III
"
.. ,
U
Z
i
1.0
i 0.5
0 o L:-----...I--....;.;.....;;.• .;::-:...z.~
0 50 100 o 50 100
Fig. 121. The relationship between trace element to aluminium ratio and the percentage marine mud
(determined with stable isotopes) in suspended matter from the ScheIdt Estuary. The straight line is the
theoretical mixing curve connecting the marine and fluvial end-members (Salomons and Eysink, 1981)
30 • 6 1.0 Cd
• Ilgll
•
,".... .
~,. ....,
• I. \ • •• •
•
,,~
•
15 { '( 3 0·5
••
• ,,_,e.
.,/:-. ~':.
I •• ..\.
,. • I.
I.· , -.. ../v...
1.. ., -\
~'.
~/····
...
.. \\
00 12 24 00 ~ ~ °0~----~~~----~24~-
%oSalinity %oSalinity %oSalinity
20 • ••• 0.50 0.50 rI

• Ni Mn Fe
,,-...' . 119/1 mgll I mgtl
\.
"..•
Il····~
\
• I~~\ ,
I
I•
I
.
Ie
",.
\
10
~
0.25 " 0.25
. ,..
-
\
\ ~
.~ •I
\
.'f i..
.
\
..
\ I
,
••-"
\
\
•
,\~
0
•~;e.;~ ••
00 12 24 0 12 24 00 12 24
%0 Salinity %0 Salinity %0 Salinity
Fig. 122. Relationship between dissolved trace metals and salinity in the ScheIdt Estuary (Kerdyk and
Salomons,1981)
way preventing their uptake or precipitations on the suspended matter. This release
of trace metals from anoxic sediments suspended in seawater, has also been ob-
served in laboratory studies (Salomons et aI., 1982).
Mobilization of cadmium has also been observed in the Weser Estuary in
Northern Germany (Calmano et aI., in press). Relatively high values of dissolved
Cd occur at Weser River km 80 (downstream from Bremen) at a salinity of appro x-
imately 60/00. Fig. 123 shows the distribution coefficient Kd of cadmium (Kd means
J.lg metal/g particulate matter: J.lg metal/ml solution) as a function of salinity; the
lower the Kd the higher is the dissolved fraction of cadmium. A decrease of the Kd
in the salinity ranges between 1%0 and about 6%0 suggests intensive mobilization
of Cd from riverine particles on the estuary mixing zone. The increase of Kd-values
in the outer estuary and in the marine zone can be interpreted by dilution of less
contaminated sea-water or by re-adsorption of Cd in the oxygen rich sea-water.
Mobilization processes such as in the example of the lower estuary do not neces-
sarily take place to the same extent under natural (uncontaminated) conditions.
Possibly the occurrence of freshly adsorbed Cd-inputs - in the Weser Estuary from
Cd Cd
,ug/' 80
•
0.4 km1Oi~ 90 5 ~
i •___ •
0.2 .", 4 '-.......- -
: ~IL. 3
r
a o0• 10 20 %.s 30 b 0 10 20 %.s 30
Fig. 123. Cadmium mobilization in the Weser Estuary (Calmano et aI., in press). (a) Cd-concentrations
(Jlg/I) vs. salinity (Ian = distance from Bremen) (b) Cd-distribution between particulate matter and so-
lution as a function of salinity Kd = distribution coefficient (Jlg Cd/g particulate matter: Jlg Cd/ml so-
lution)
waste water in the Bremen and Nordenham areas and from dredged spoil, which
is regularly dumped near the lower Weser River km 80 where the maximum for dis-
solved Cd was observed - are the reason of this phenomenon, which may establish
detrimental effects on the aquatic biota in such area.
It should be pointed out that observations on the behaviour oftrace metals for
one estuary cannot be extrapolated to other estuaries, since chemical and hydro-
dynamic processes may differ to a large extent. For instance in the Scheidt Estuary
a removal of arsenic is observed (probably associated with the removal of iron),
however, studies in several rivers in the southeastern United States (Waslenchuk
and Windom, 1978) showed that it is largely unreactive in the estuarine environ-
ment. Complexes were found between arsenic and low molecular weight dissolved
organic matter. Unlike high molecular weight organic matter, the low molecular
weight organic fractions (and associated As) passed conservatively through the es-
tuaries they studied.
In the same estuaries a complicated pattern for the behaviour of copper was
observed (Windom et aI., 1983). Results for the Savannah River Estuary are pre-
sented in Fig. 124A.
Deviations from the conservative mixing behaviour are found at both high and
low salinities, which implies a release from particles and/or bottom sediments. In
the Ogeechee Estuary (Fig. 124 B) a similar positive deviation at low salinities and
an even more pronounced at higher salinities was observed. Release of copper at
low salinities was more pronounced during times of high river discharge. Mixing
experiments showed that it was not associated with a release from bottom sedi-
ments. It was thought that the high release is caused by a higher amount of ex-
changeable copper on particles and colloids during these periods.
The increase of copper during periods of low discharge could be explained by
release from bottom sediments. During these periods the residence time of the wa-
ter is longer and release from bottom sediments would be expected to have a
greater influence on dissolved concentrations (Windom et aI., 1983). The influence
of discharge on the behaviour of copper has also been observed by Eaton (1979).
He observed removal of copper in the San Francisco Bay during periods oflow dis-
charge but an essentially conservative behaviour during high discharge periods.
I Savanna" Estuary
-
15
..... 10 ~
01 E
C c
~~- ~~ II 0
o ...::o~-~--II---'"
- _
....... .,,
CT, 5
.'':.7
~
A
O+---~----r----r----r---'----'----'-~O
1000
Ogeechee Estuary I 15
10 ~
500
ic
5
B
O+---~----r----r----r---,----,----~-LO
o 5 10 15 20 25 30 35
Salinity %0
Fig. 124. A. Dissolved copper in the Savannah Estuary during January 1979 (e) and June 1980 (0). The
dashed lines give only the general trend of the mixing curve B. Dissolved copper in the Ogeechee Estuary
during April (e) and may (0),1979 (Windom et aI., 1983)
The removal was observed in the turbidity zone, which comprises 30% phyto-
plankton during summer. Calculations showed that this removal of soluble copper
was caused by biological uptake. Eaton (1979) also observed that at high salinities
the copper concentrations are above the theoretical mixing values, which he could
attribute to anthropogenic sources; a release from sediments could be ruled out.
Direct observations in the field on the influence of pore waters on the compo-
sition of surface waters have been reported for the Wadden Sea area (The Nether-
lands). Studies carried out by Duinker and co-workers during severe wind con-
ditions showed strong maxima in the dissolved copper and zinc concentrations
during periods of maximum current velocities. No such maxima were observed
during a period of extremely calm weather (Duinker et aI., 1974). The results show
that under extreme conditions pore waters are able to supply the overlying waters
with large amounts of dissolved metals. It appeared that the suspended matter can
immediately take up part of the dissolved copper and zinc released by the intersti-
tial waters.
Gendron et al. (1982) found evidence for different release mechanisms for co-
balt and cadmium near the sediment-water interface. The hydroxylamine ex-
-..
a.
.:
125
-..
a.
125
!.. 100 .
.:
~
:;
......
S
.....
S
.=
';
...
75
-..
.=
co
Zn
...
;it. "#.
Cu
lit
-..
S S
..
Cd
.2
S
-..
50
-.
co co Ni
z
z
25 25
J 0
A
,
10
,
20
,
30
0
0
B
10 20 30
Surface salinity (%,) Surface salinity( "")
Fig. 125. A The net outflow of dissolved and particulate iron and manganese and suspended matter as
a function of salinity at various sections in the Gulf of St. Lawrence. B Net outflow of total Zn, Cu,
Cd, Co and Ni as a function of salinity at various sections in the Gulf of St. Lawrence (Redrawn after
Yeats and Bewers, 1982)
tractable fraction of the sediment surface layer in the St. Lawrence Estuary
(Laurentian Trough) was enriched in cobalt but depleted in cadmium relative to
the subsurface sediment. The concentrations of dissolved cobalt in this surface
layer were negligible while the highest cadmium concentrations were observed in
this layer. The profiles for cobalt resemble those for manganese and iron suggesting
a release in the reduced zone and reprecipitation in the surface layer. On the other
hand, cadmium appears to be released in the surface, probably as a result of
aerobic degradation of the organic matter. Concentration gradients showed that
the upward flux of cadmium across the sediment-water interface is an order of
magnitude higher than the downward flux into the sediment. This indicates that
the cadmium released near the sediment-water interface is efficiently recycled back
into the water column (Gendron et aI., 1982). Also high concentration of hydroxyl-
amine extractable zinc and copper were observed and high concentrations of these
metals in the pore waters of the surface layer (Vale et aI., 1982). Zinc and copper
are probably released from a labile phase. Part of the metals are turned back into
water column, whereas another part is adsorbed on the abundant iron and
manganese oxides in the surface layer (Vale et aI., 1982).
A balance for the St. Lawrence Estuary in Canada and the Gulf of St. Lawrence
was constructed taking into account the inflow of freshwater and the inflow of sea-
water into the Gulf (Bewers and Yeats, 1979; Yeats and Bewers, 1982). The net out-
flow of trace metals in % of the freshwater input is presented in Figs. 125 A and
125B.
The influence of the turbidity maximum is clearly shown in the high suspended
matter concentrations at Pte. aux Orignaux. Also an increased outflow of nickel
and particulate iron and dissolved manganese is observed. In the estuary and in the
nearshore area an extensive removal of particulate matter (99%) and particulate
iron and manganese takes place (> 97%). The removal of Ni, Co, Cu, Zn and Cd
varies between 25 and 50%.
The behaviour of copper, nickel and cadmium in the Amazon plume was stud-
ied by Boyle et al. (1982). Both field data and laboratory mixing experiments
showed conservative behaviour for copper and nickel, However, field data from
an earlier cruise in 1974 indicated a 25% removal of copper, probably by biological
processes. Some indications for desorption of cadmium were observed at low
salinities.
In the Gironde Estuary (France) extensive metal mobilization processes have
been recognised (Martin et aI., 1971; Jouanneau, 1982). The Gironde Estuary is
characterized by a turbidity maximum in which suspended matter concentrations
may reach values of several gil. The total mean mass of suspended sediment in the
turbidity maximum is 4.4 x 10 6 tons, which corresponds to a two year supply of
the river (Jouanneau, 1979). The position of the turbidity maximum depends on
hydrological conditions. The estuarine water masses and the suspended matter
move towards the sea during ebb and toward the estuary during flood. So, after
each trip in the open ocean, an important part of estuarine waters and suspended
matter comes back into the estuary. A minor part may reach the line of no return
and escapes from the estuary (Jouanneau and Latouche, 1982). Only when floods
coincide with high spring tides does a large expulsion of estuarine water masses and
suspended matter escape to the ocean.
Compared with the fluvial suspended matter, the concentrations of metals in
the lower estuary are much lower (Table 65).
Since oceanic sources are minor, the low concentrations in the estuary mouth
can not be explained by admixtures of low metal containing marine sediments as
is the case for a number of other European estuaries. The decrease in metal con-
Table 65. Average metal concentrations (l975~ 1976) in suspended matter

(in Ilg/g) from the Gironde Estuary (Jouanneau and Latouche, 1981)
Zn Cu Pb Ni
Fluvial estuary 900 50 300 35

Central estuary 250 20 50 35
Estuary mouth 220 20 50 25
Trace Metals in Estuaries: Laboratory Investigations and Simulations 233
exchangeable + easily
reducible phase
800 ZINC
[ill]] organic phase
§ moderately reducible phase
rn
800
-
."
...
"-
." residual phase
o
i
10km
400
200
0
II
'0
..
:I
".o
II
II II
II:
II
..i ID
Fig. 126. Changes in the mode of occurrence of zinc in suspended matter from the Gironde Estuary
(Jouanneau, 1982)
centrations in the suspended matter correlates with a decrease in organically bound

trace metalfraction, this is evident for zinc (Fig. 126).
In fact a strong correlation is observed between seasonal cycles in zinc and in
particulate organic matter (Etcheber et aI., 1981). It seems likely that the decrease
in trace metal concentrations is related to the decrease in particulate organic car-
bon.
In the upper estuary, the metal impoverished sediments from the turbidity
zone mix with the fluvial suspended matter, causing a decrease in metal concen-
trations. The decrease in this part of the estuary should not be interpreted as a mo-
bilization process, since the sediments have already lost their metals in the lower
part of the estuary (Jouanneau et aI., 1983).
6.7 Trace Metals in Estuaries: Laboratory Investigations

and Simulations
The various field investigations have shown that a large number of processes gov-
ern the behaviour of dissolved trace metals in estuaries causing deviations from the
theoretical mixing curve. The more important processes are summarized in Table
66.
A number of processes have been studied in more detail in the laboratory. The
most simple experiments are those in which the two end-members (river- and sea-
water) are mixed in various proportions to obtain the salinity gradient in the estu-
ary (e.g. the influence of bottom sediments is cancelled out). Duinker and Nolting
(1978) mixed river water from the river Rhine with its suspended matter with fil-
Table 66. Summary of processes which cause deviations from the theoretical mixins curve between
dissolved trace metals and chlorinity
A. Change in the composition of the end-members

B. Flocculation of colloids
C. Release and/or uptake of dissolved trace metals by bottom sediments
D. Degradation of organic matter and subsequent release or solubilization of trace metals
E. Biological uptake of trace metals
F. Changes in adsorption/desorption equilibria due to:
* Changes in pH
* Changes in salinity
* Changes in turbidity
* Formation of new particulate matter
tered seawater. Their results showed conservative mixing for Cd, Cu, Cr, Fe and
Mn over a one hour period. However, Weijden v.d. et aI. (1977) showed that con-
siderable mobilization takes place when suspended matter from the river Rhine is
suspended in distilled water and mixed with artificial seawater. However, both ex-
periments did not give the expected removal of dissolved trace metals, as was ob-
served in the field. Other mixing experiments have been carried out with Ogeechee
water and seawater (Windom et aI., 1983), in this experiment the conditions ob-
served in the field (e.g. release of copper at low salinities) could be reproduced.
Flocculation processes and their effect on the removal trace metals have been stud-
ied in detail by Sholkovitz and co-workers (Sholkovitz, 1976; 1978; Sholkovitz and
Copland, 1981). Their experiments were carried out with filtered organic rich
waters from the river Luce in Scotland, which has higher concentrations of organic
matter than "average" rivers but has counterparts in the world including the Rio
Negro and the Zaire (Sholkovitz and Copland, 1981). Rapid flocculation of humic
substances is observed in their mixing experiments. The rate of removal of trace
metals varies to a considerable extent: iron was removed by 95%, copper and nick-
el by 40%, cobalt by 10% and cadmium by only 5%. Their experiments show that
for some rivers and some trace metals, flocculation may be an important process
for the removal of dissolved trace metals from solution.
A number of studies have adressed adsorption/desorption processes occur-
ring in estuaries with laboratory experiments (Salomons, 1980; Bourg, 1983; Mill-
ward and Moore, 1982). Processes which affect adsorption/desorption phenomena
under estuarine conditions are:
- oxidation either of organic particles containing trace metals or oxidation of
metal sulfides and the surface desorption of trace metals caused by a high dilu-
tion ratio (Rohatgi and Chen, 1976);
- the chlorinity increase, which affects a competition between chloride ions and
particulates for complexation of the dissolved metals;
- the changes in turbidity (turbidity maximum) which offers additional sites for
adsorption;
- the changes in pH (Mook and Koene, 1975, Fig. 127) which affect adsorption-
desorption processes significantly (Chap. 2.5);
- the formation of new particulate matter (e.g. iron and manganese hydroxides)
as well as the release of dissolved organic matter from the pore waters;
- the flocculation of dissolved organic matter and the fact that estuarine particles
change their surface properties, which are consistent with the formation of a
macromolecular film (Neihof and Loeb, 1974; Loeb and Neihof, 1977; Hunter
and Liss, 1979; 1982) may also affect their adsorption properties.
In a number of studies with radioactive cadmium and zinc the influence of pH,
turbidity, chlorinity and the formation of new particulate matter was studied by
Salomons (1980). Additional studies with a number of different particles and nat-
ural sediments were conducted by Bourg (1983). Millward and Moore (1982) stud-
ied the adsorption of trace metals on iron hydroxides on estuarine conditions.
Some results ofSalomons (1980) are presented in Fig. 127.
The simultaneous influence of chlorinity and pH on the adsorption is shown
in Fig. 127 A. With an increase in chlorinity the amount of metal which adsorbs on-
to the suspended matter decreases; however an increase in pH causes more adsorp-
tion. Especially for cadmium an increase in chlorinity causes at all pH values a
drastic decrease in the adsorption. Also the adsorption of zinc and cadmium on
freshly precipitated manganese shows the strong influence chlorinity (Fig. 127 B).
Fig. 127 C shows the important effect of suspended matter concentrations on the
adsorption. With an increase in suspended matter concentrations, as occurs in the
turbidity maximum, the suspended matter can effectively compete with chloride
ions for complexation of trace metals. Based on these studies the following picture
of adsorption-desorption processes can be drawn: With increasing chlorinity the
amount of metal which adsorbs to the suspended matter decreases, especially for
cadmium the influence of chlorinity is drastic at all pH values. The influence of
chlorinity on the adsorption of zinc is much smaller. Similar behaviour is observed
for the adsorption on hydrous manganese oxides. The influence of chlorinity on
adsorption on suspended matter is constant for chlorinities between 5 and 200/00,
whereas for cadmium the adsorption decreases still further (Fig. 127 C).
The results indicate that if the pH and the suspended matter concentration in
the river are equal to that in the estuary, no additional adsorption of dissolved cad-
mium will take place on the suspended matter, even a desorption may be found (if
the adsorption process is reversible) from the riverine particles. However, the situ-
ation is completely different if a turbidity maximum is found in the estuary. Since
the residence time of the particles in the estuary is higher than in the water, the
riverwater is in fact flowing through the turbidity maximum. If the turbidity maxi-
mum extends into the freshwater tidal area (Fig. 115), the river water with its dis-
solved trace metals encounters already an increase in suspended matter concentra-
tion in the river system. Due to the increase in turbidity, the dissolved metal con-
centrations decrease to reach a new equilibrium with the suspended matter. When
the remaining dissolved trace metals enter the estuarine system, the chloride ions
compete with the particulate matter for their complexation. Depending on hydro-
dynamic conditions (relation between suspended matter concentrations and
chlorinity), the decrease in adsorption may be cancelled out by increases in sus-
pended matter concentration. It is possible to define a zone of enhanced adsorption
in the estuary: a zone in which the adsorption is larger compared with the river up-
CADMIUM ZINC
100% 100%
75 o pH 8.5
• pH 8.0
• pH 7.5
50 ' pH 7.0
,
A 15 20 5 10 15 20
ii
;
---. %. CI ---. %. CI
E 100%
100% /;;;;-o-~r-
"e /A5W
."""
/ow
o
75 • 75
'i
'# = Artificial River Water
.5
I:
/ ASW = Artificial Sea Water
a...
~
o /
II
-: B 10 100 10 100
-.. mall Mn ---. mall Mn
100%
1 0_ ===================05000
01500
\\\~-05000 mall -------------------0500
~
suspended
o matter ------------------_0200
.~.'.o.
o
-------------------0100
o 0-
_ --
_ - --------- 0 500
----=::0200 -------------------050
o '-0 100 OL-__ ~ ____ _____ L_ _ _ _
~ ~
C 0 5 10 15 20 50
---. %. CI -.. %.CI
Fig. 127 A-C. Adsorption of Cd (5 Ilg/l) and zinc (50 Ilg/l) on sediment from the river Rhine. A Influence
of chlorinity and pH. B Adsorption of cadmium and zinc on hydrous manganese hydroxides in artificial
riverwater and artificial seawater. C Influence of chlorinity and suspended matter concentration on the
adsorption of cadmium and zinc
stream from the turbidity maximum (Salomons, 1980). To show these effects more
clearly, we have superimposed on Fig. 127 C the adsorption caused by a hypotheti-
cal turbidity maximum (Fig.128A). The adsorption of cadmium up to about 5%0
chlorinity is larger compared with the river upstream from the turbidity maximum.
If the turbidity maximum extends into the freshwater zone, a removal of dissolved
metals already takes place in the freshwater tidal area of an estuary. Even more
adsorption can be predicted if the estuarine circulation pattern is taken into ac-
count: the "broom-effect" carries suspended particles sedimented from the surface
layer in the landward direction (Fig. 128).
RIVER ESTUARY
75 F-----------~~--; 5000
mgll
50
1500
25
500
L______L-________~~~~~;;~~;;~~~~200
I 5 10 15
100
20 50
I .. : ~ ~CI
,OIl
zone of
- -
A enhenced ed.orption
-
R
I S
--
V E
E A
R
t
sediment flux of Mn, Fe, doc to s~rface water
B
Fig. 128. A Adsorption (heavy line) caused by a hypothetical turbidity maximum in an estuary. B The
estuarine circulation pattern and adsorption processes
Added to this flux of suspended matter is the manganese released from pore
waters and the erosion of the surface layer additionally provides Mn-enriched par-
ticles (Sundby et aI., 1981). In this way the landward transported suspended matter
acquires a higher adsorption potential. In the lower estuary, the chlorinity is less
and hence less competition of chloride ions for complexation of dissolved trace
metals (e.g. the suspended matter has entered the zone of enhanced adsorption).
In this way even more fluvial dissolved trace metals may be removed from solution.
In fact the estuarine circulation pattern and the bottom sediments generate a highly
adsorbant filter system in the estuary. It should be noted however, that the decrease
in pH encountered by the landward flowing particles may counteract some of the
before mentioned processes causing an increase in adsorption. Both Fig. 127 A and
the results from Millward and Moore (1982) show the importance of pH on ad-
sorption under estuarine conditions. Whether desorption of the trace metals out-
side the zone of enhanced adsorption will take place depends on the reversibility
of the adsorption processes. Results from Salomons (1980) and Kharkar et al.
(1968) show that only partial desorption may take place with increase in chlorinity.
Both Hodgson (1960) and Salomons (1980) found that with increase in time, the
metals become more strongly attached to the sediments and are less prone to de-
sorption. This shows that not only hydrodynamic conditions determine the ad-
sorption process but also the desorption process (a high residence time causes a
stronger binding of the metals to the sedimentary particles).
In laboratory experiments, a number of these processes can be isolated out and
therefore, studied in more detail. However, a drawback remains that the estuarine
system is extremely complex and particularly that the time scale of processes is dif-
ficult to simulate. Moreover, during storage the properties of sediments and sur-
face waters used for the experiments change in ways which might have affected the
results. On the other hand, controlled experiments with pure compounds and ar-
tificial estuarine water, are difficult to extrapolate to the field and may yield only
answers of purely physico-chemical interest. However, in most cases the qualitative
results can be extrapolated to the field situation.
During the past decade enclosures have been used to study geochemical pro-
cesses affecting contaminants in lake and ocean environments. Important studies
have been carried out in the enclosures of CEPEX (Controlled Ecosystem Pollu-
tion Experiment) at Saanich Inlet, British Columbia, Canada and Loch Ewe, Scot-
land and the outdoor tanks of the Marine Ecosystem USA (Santschi, 1982) The
mesocosm approach for studying geochemical processes lies between the complex
and highly variable natural world and the tightly controlled but less naturallabo-
ratory systems (Santschi, 1982). Relevant for the estuarine and coastal environ-
ment are the experiments conducted in the MERL (Marine Ecosystem Research
Laboratory) mesocosms, which were designed to simulate nearshore conditions.
The MERL experiments included both the pelagic and benthic system. The ecosys-
tems used consisted of outdoor fiberglass tanks, 5.5 m high and 1.8 m in diameter,
containing 13 m 3 of water and a 30 cm layer of silty-clay sediments. The water col-
umn is cyclically mixed to simulate tidal currents, turbulence and the sediment re-
suspension regime in the Narrangansett Bay (Amdurer et aI., 1982, 1983). A total
of 23 elements were added in radioactive form to the microcosm and their removal
measured both in summer and in winter. These list of elements included Th, for
which extensive data of oceanic measurements are available. Their purpose, there-
fore was, to establish a relationship between the removal behaviour ofTh and that
of other trace metals, in order to use Th in the ocean to predict the rates of removal
of other trace metals. The elements studied could be classified in four general
groups on the basis of their half removal times from the water column and chemical
forms (Table 67).
The differences in removal between the winter and summer period are remark-
able. Three mechanisms were studied in detail to explain the seasonal differences
in removal rate [Santschi et al. (1982)]:
- the filtering of suspended particles and associated trace elements by organisms
such as zooplankton or benthic suspension feeders;
- aggregation of particles followed by faster settling;
- impaction of particles i.e. convection or advection and entrainment of particles
into the laminar sublayer, and/or adsorption of trace elements at the sediment-
water interface.
To study the effect of organisms, zooplankton was caged and allowed to feed
on surrounding water and suspended sediments (Adler at aI., 1981). The zoo plank-
Table 67. Comparison of seasonal removal behaviour and distribution coefficients of different groups
of elements in the microcosm tanks. (Santschi et aI., 1982)
Group of elements Half removal times Distribution

(days) coefficients
Winter Summer Winter Summer
A. Particle reactive
Fe, Hg, Sn, Cr (III), Pb, Po, Th, Pa, Pu, Am, Be 10- 20 2- 3 (3-8) WS (0.5-2)10 5
B. Recyclable
Mn,Co 30- 50 5- 30 (1-5)J03 (0.6-1)J03
C. Biologically active
Zn, Cd, Se, As 60-100 10- 50 102_10 3 102 -10 3
D. Quasi conservative
Ba, Ra, Cs, Sb 150-600 80-150 10-102 10-102
ton filtered 5-8% of the suspended particles in the tank per day (however, the re-
moval time of trace metals from the tanks is a rapid 2-3 days in summer). Calcu-
lations showed that less than 4% of the total element transport from the water col-
umn occurred via fecal pellets. The removal and aggregation of particles was stud-
ied with microspheres. The settling velocity of these spheres in settling cylinders
was equal to that predicted by Stokes law. However, in the microcosms, the disap-
pearance from the water column was between 8 (15 ~m particles) to 100 times (3
~m particles) faster than predicted by the settling cylinders or Stokes law (Santschi
et aI., 1982). They concluded that some benthic processes play an important role
in the removal of particles and their associated trace metals.
The experiments also showed that the standing stock of particles in the water
is replaced 8 times a day by resuspension and deposition, while in winter only every
two days.
To determine the effect of benthic processes, the sedimentation in sediment
traps was compared to the total removal from the microcosm, and indicated by the
factor R, which is the rate of removal through sedimentation in the traps divided
by the total removal. A ratio of 1 implies that the removal can be accounted for
by settling of particles, which was indeed the case for microcosms with low benthic
activity. However, in tanks with active benthos (summer) the ratio was less than
1 for particle active trace metals. A comparison between the total filtering capacity
of organisms in the microcosm (mainly originating from the activity of benthic or-
ganisms) and the rate of removal of the micro spheres showed that benthic activity
could account for the removal of particles from the water column. The results show
that the most important mechanisms for the removal of trace metals from the water
phase is the resuspension of bottom sediments by tidal action providing ample sur-
face area for adsorption. This is followed by a fast removal by the activity of ben-
thic organisms. Since the benthic processes are efficient in removal of trace metals,
it was concluded that as the depth of the water column decreases the removal of
chemicals from the water to the sediments will accelerate (Adler et aI., 1982).
A different approach to study the behaviour of trace metals in estuaries was

used by Etcheber et al. (1980). They marked a quantity of sediment with two ra-
dioactive tracers: hafnium and zinc. Hafnium is solidly fixed to the particulate mat-
ter regardless of physical and chemical conditions as was shown by laboratory ex-
periments, on the other hand zinc is subject to mobilization processes in the Giron-
de Estuary (see section 6.6). A labelled quantity of the sediment was introduced up-
stream in the Gironde estuary. During transport the ratio of Zn/Hf decreased from
an intitial value of 0.7 to 0.07 and 0.05 in the bottom sediments of the lower estuary
after a three months period which was lower than the 0.2 ratio in the suspended
sediments. The experiment confirmed the field observation on the mobilization of
zinc in the Gironde Estuary (see Fig. 126).
6.8 Environmental Impact Studies
The contamination of coastal areas including estuaries and marginal seas can gen-
erally be attributed to one of the following causes (Weichart, 1973): (i) direct input
of effiuents from industries and communities situated near the coast, (ii) effiuents
from communities via sewer outfalls, (iii) dumping of waste from ships, (iv) soluble
and suspended load from rivers, (v) atmospheric fallout, (vi) waste derived from
the extraction of raw materials from the sea and (vii) pollution by the shipping in-
dustry. Terms such as "resiliency", "carrying ability" and "assimilative capacity"
denote the capacity of estuaries to receive a certain amount of waste material be-
fore this use of the system begins to affect other uses adversely (U.S. EPA, 1977).
This requires thresholds of water quality to be maintained (Goldberg, 1979). Es-
tuarine ecosystems are less resilient and may be seriously vulnerable to toxic ma-
terials which are not inherent in the genetic history of the biota, especially if they
are highly persistent in the estuary. The assimilative capacity for persistent toxic
substances which may repeatedly cycle in estuarine processes is very low. The re-
covery capacity of estuaries has been observed in a few investigations of benthic
macrofauna invertebrates. However, similar studies on meiofauna - which proba-
bly respond more rapidly to environmental changes than benthic organisms - and
sediments are scarce. However, the following should be noted in respect to the few
that are available:
Decontamination of sediments is in general a slow process but it is accelerated
by the presence of burrowing benthic organisms; the recovery of the bottom strata
is mainly due to the deposition of unpolluted sediments with a subsequent embed-
ding of the contaminated sediment cover (Cato et aI., 1980). Among the various
problems with heavy metals in coastal waters of Japan the catastrophic pollution
in the Minamata Bay and surrounding area of the Yatsushiro Sea still cause con-
siderable concern because of the long-term effects of methylmercury compounds,
even if there is a significant decrease of mercury concentration in bed sediments
with increasing distance from the effiuent discharge point (Fig. 129).
Calculations from Goldberg (1972) on a global basis indicate that approx. 140
million tons of wastes are annually dumped by ships into the sea. Furthermore, ap-
prox. 15 million tons of industrial particulates will reach the sea via atmospheric
United States Estuaries and Coastal Areas 241
Fig. 129. Decrease in mercury con- 1000

centrations in bed sediments with
500
increasing distance from the Mini-
mata Bay (Kudo et aI., 1980) .
';
"E 200
a.
.s-
..
100
III
c 50
III
E
:; 20
III
UI
10
"III
III
c 5
c
0
.."c.
:; 2
1
III
C)
c 0.5
0
U
01
Z 0.2
0.1 •
0.05~~__~~-L__~__- L__~_·__•__~__~
•
0.1 0.2 0.5 1 2 5 10 20 50 100
Distance from Sources (Km)
emissions. Although there is no accurate data available, it is assumed that wastes

from input of rivers are discharged to the same extent, or even more, than direct
dumping occurs. However, since the dumped wastes tend to concentrate more in
certain areas, they pose more immediate problems with regard to the effects on or-
ganic life than do the more diffuse influences from the atmosphere and also (in
most cases) from the river discharges. In some areas, as described below, planned
or municipal waste dumps often surpass the deposits caused by natural sedimen-
tation in quantity and quality of waste materials. Gross (1972) has stated that
waste-solid disposal by coastal cities modifies shorelines and covers adjacent ocean
bottom with characteristic deposits on a scale large enough to be geologically sig-
nificant; the activities change sediment distribution and dislocate sediment-trans-
port processes in estuaries and along the coast. The input of dredged material in
the North Sea is twice the annual mud budget of this area (Salomons and Eysink,
1981).
6.8.1 United States Estuaries and Coastal Areas
Aside from large construction projects or land reclamation activities, dredging and
disposal of dredged materials are among the most important activities affecting es-
tuaries and the coastal oceans near industrial centres (Gross, 1978). In the United
Table 68. Discharge and composition of various wastes dumped into coastal waters near New York
and their probable impact on these waters. (From Gross et aI., 1971)
Waste solids Discharge Composition Environmental effect

106
tons/year
Dredged wastes 49 Silicate sediment (85-95%) Shoaling of waterways, turbidity

("dredged spoils") mixed with various carbon- of waters, oxygen demand,
rich wastes (5-15%) release of materials
Sewage sludges 0.19 Silicate sediment (45%) Bacteria, viruses released, oxygen
Organic wastes (55%) demand,
Industrial wastes (?%) Floating materials, dissolved
constituents
Coal ash 0.9 Silicates, quartz, mullite glass Turbidity, shoaling adsorption
Waste chemicals
Liquids Variable Toxic constituents, oxygen
Solids Variable demand, turbidity
Table 69. The best estimates for the flux of trace metals to the New York Bight Apex. Flux in
10 2 tons/yr (Krom et aI., 1981)
Cu Pb Zn Cd
Total dredge spoil material dumped at site 12 9 0.24

Dredge spoils lost from dumpsite 7 5 0.14
Sewage sludge 4-8 1-35 2-9
Atmospheric input (Min) 1 1 0.02
Atmospheric input (Max) 1.5 5 5 0.04
States, about 2 x 10 8 m 3 are dredged each year from existing channels (mainte-
nance dredging) and about 6 x 10 7 m 3 are dredged during construction of new fa-
cilities (new work) at an annual cost of$ 150,000,000 (1970).
To visualize the volume of the dumping of waste from New York City (about
8.6 million tons) one must imagine that if the annual discharge of these waste solids
were spread uniformly over Manhattan, it would form a layer 13 cm thick each
year (Goldberg, 1976).
About 76 per cent of the wastes dumped in the New York Bight in the 1960s
was dredged wastes, fine-grained materials (for example, ash) and small stones
(Table 68; Gross et aI., 1971). After waste solids, rubble from building construction
and demolition is the second largest source; a third major type of waste dumped
in the New York Bight is sewage sludge from municipal sewage treatment plants.
In an area of New York Bight, including the Hudson Gulf Valley, approximately
60 km 2 , sediments contained Cu, Cr, Pb and Zn concentrations ten times higher
than normal values, whereas a larger area encompassing some 170 km 2 was shown
to contain a five-fold increase (Carmody et aI., 1973). These areas correspond to
the sewage sludge and dredge spoil disposal areas, respectively. In Table 69 the best
United States Estuaries and Coastal Areas 243
estimates of the contributions of sewage sludge, dredge spoils and atmospheric

transport of several metals are summarized for New York Bight Apex region
(Krom et aI., 1981). These estimates suggest that sewage sludge may be the most
important source quantitatively though all three sources have a total flux which
is of a similar order of magnitude (10 2 tons/yr). The trace metal flux by dredge
spoil dumping though large probably remains localized within a pile at the dump-
site whereas the entire amount of both the sewage and atmospheric inputs is avail-
able for homogenization and deposition throughout the New York Bight Apex
(Krom et aI., 1981).
Coal ash has been dumped in amounts averaging about 0.1 million tons per
year between 1960 and 1969, but because of the reduction in the use of coal for fuel
and increased use of ash for various purposes, less coal ash is expected to be dum-
ped in the New York Bight in the future. Among the various industrial wastes dis-
charged at sea having substantial solid concentrations, the largest quantities are de-
rived from titanium-pigment processes. These residues of extracted titanium ores
suspended in dilute iron-rich sulfuric acid total approx. 3.5 million m 3 /yr, 10% of
which is solid content by weight.
The second largest source area of waste materials on the Atlantic coast is the
Chesapeake Bay region. A pronounced population concentration centres in the
vicinity of the city of Baltimore, and, as a consequence, the human influence on
pollution of the northern part of the bay is most strongly felt in the Patapsco Sub-
estuary of Baltimore Harbour. Of the 3.05 x 10 8 tons/yr of total wastewater dis-
charge from sewage treatment plants to the Chesapeake Bay, 2 x 10 8 tons flow into
Baltimore Harbour. Helz (1976) calculated that minimum percentages of anthro-
pogenic waste materials are 3 to 6 per cent solids on a dry weight basis.
Dredging activities are particularly important in these processes as, for ex-
ample, dredged material constitutes approx. 80% by weight of all substances that
are dumped into the oceans off the United States (U.S. Army Corps of Engineers,
1977). The possibility that metals can be released during dredging operations is
high and should be kept in mind. The input from municipal waste water is in the
same order of magnitude as by natural weathering processes.
Along the U.S. west coast, the sewage discharges into the Southern California's
marine region are probably among the most remarkable examples of environmen-
tal contamination. Combined annual mass emission rates of Southern California's
five largest municipal effluents have been calculated annually to be approximately
0.9 million tons of suspended particulates containing 1,500 tons of zinc, 650 tons
of chromium, 520 tons of copper, 200 tons of lead, 50 tons of cadmium, 25 tons
of silver and 2-3 tons of mercury; about two-thirds of these masses reach the sea
via Hyperions Joint Water Pollution Control Plant near Los Angeles (Schafer,
1976). Sediment investigations around Hyperion's 7-mile outfall performed by
Schafer and Bascom (1976) indicate strong enrichment of trace elements; near the
outfall the cadmium content of the sediment is as much as 300 times higher than
in the less contaminated sediments some distance away. Respective enrichment
factors are found to be 140 for mercury, 85 for lead, 80 for copper, 60 for silver,
and 15 for nickel and chromium.
Sediment investigations from the Southern California coastal region also indi-
cate characteristic influences from atmospheric pollution. Chow et al. (1973) dem-
onstrated from their isotope ratios that the lead accumulations in sediment cores
from Baja California are probably derived from lead additives such as are present
in the type of gasoline sold in Southern California. It has been estimated that on
an annual basis, 180 tons of lead are deposited into the zone of California by at-
mospheric fallout, 200 are discharged through municipal waste effluents and 90
tons come from storm and river runoff.
Investigations of Christensen et al. (1978) on vertical profiles of heavy metals
in sediment cores from the tidal flats of Newport Bay, California, a very shallow
estuary located in Orange Country, 60 km southeast of Los Angeles, showed clear-
ly oscillating patterns in that maximum concentration of a metal, such as lead, is
associated by maximum grain size. It is suggested that material is carried by large
storms since there is a characteristic cause-effect relationship between patterns of
grain size/heavy metal concentrations and those of rainfall. Galloway (1979) stud-
ied the marine discharge of wastewater in the coastal area of Southern California.
Less than 10% of the metals injected from the outfall were present in the contami-
nated marine sediments of the study area. The remaining 90% are either dissolved
out of the waste solids suspended in seawater or transported out of the area by cur-
rents while still associated with the particulate matter (Galloway, 1979). He extra-
polated these data (Southern California with about 1% of the industrial world
population) to global discharge of waste into the marine environment (Table 70).
In the southern part of Puget Sound (Wash.) smokestack emissions from Ta-
coma Cu-smelter have resulted in significant accumulations of As, Sb, Cu, Pb and
Zn. Atmospheric input to Puget Sound was calculated by Schell and Nevissi (1977)
as approximately 450 tons/yr of zinc; the respective values for the inputs from Met-
ro's West Point Sewage Plant were 29 tons/yr Cu, 9 tons/yr Pb and 56 tons/yr Zn.
At the waste outfall from a mercury cell chloralkali plant in Bellingham Bay
(northern Puget Sound), an estimated 5-10 kg of mercury were discharged daily
between 1965 and 1970 (Bothner and Carpenter, 1974).
Table 70. Comparison between artificial and natural rates of global

metal injection into the oceans and atmosphere (10 3 metric tons/yr)
(Galloway, 1979)
Input from Input from Natural

Municipal combustion" weathering b
Waste water
Cd 3 36
Cr 55 1.5 50
Cu 42 2.1 250
Pb 15 3.6 110
Ni 17 3.7 11
Ag 2.3 0.07 II
Zn 100 7 720
a Bertine and Goldberg, 1971

b Turekian, 1971
Mediterranean Sea 245
6.8.2 Mediterranean Sea
The pollution problems in the Mediterranean Sea are chiefly due to the high quan-
tity of domestic sewage and the virtually total absence of control on toxic com-
ponents. Among the rivers entering the Mediterranean, the Rhone, Po and Tiber
discharge by far the highest contaminant load, which originates from both indus-
trial and municipal inputs (Naeve, 1974). Characteristic increases of mercury con-
centrations have been reported from the French and Italian coast, e.g. the Gulf of
Lion (Aubert et al., 1974), the Ligurian coast and the Gulf of Genoa (Renzoni et
al., 1974), and from the industrial centres ofCagliary (Sardinia) and Naples (Shep-
pard and Bellamy, 1974). The 1975-review of Bernhard on heavy metals and
chlorinated hydrocarbons in the Mediterranean notes several areas of elevated
metal contents in the water phase (Table 71): The higher copper concentrations in
the coastal waters near Cadiz, for example, are affected by the Huelva copper
mines, so anthropogenic Cu pollution is superimposed on a geochemical Cu anom-
aly (Establier, 1969). Data from the Ligurian Sea and Tuscan coast by Capelli et
al. (1976), Frache et al. (1976) and Bernhard et al. (1977) show elevated concen-
trations of cadmium, copper, zinc and nickel in the harbour areas. Bernhard et al.
(1977) found that in the outer and inner harbour of La Spezia the ratios between
particulate and ionic species of zinc vary considerably, probably due to anthropo-
Table 71. Metal concentrations in the coastal waters of the Mediterranean Sea (after Bernhard, 1978).
Values in Ilg/1 (range in parenthesis)
Sampling sites Cadmium Copper Zinc Nickel Mercury Ref
Gulf of Cadiz 5.2 (a)

(2.6-8.6)
San Remo to 0.1 2.4 1.7 (b)
Livorno* (0.1-D.28) (0.8-4.0) (0.6-5.7)
Imperia to 0.07 1.43 0.99 (c)
Livorno** «0.5-D.6) (0.71-2.43) (0.35-2.93)
Gulf of La Spezia IO.S (d)
(6.S-IS)
Ventimiglia O.lS 3.S (e)
to Anzio (0.00S-D.4S) (0.13-3.6)
Trieste to Ravenna 13.6 (f)
(1.4-36.4)
Plonim to Nin 0.12 1.2 13.8 (g)
(Adriatic) (0.05-6.9) (0.2-3.6) (1.5-36S)
Saronikos Gulf 3.0 20 (h)
Rosh Hanigra 0.94 3.7 38.3 3.3 0.06 (i)
to Haifa (0.6-2.9) (0.8-36.2) (1.0-2S7) (2.O-S.4) (0.01-0.18)
* Mainly in ports ** 4-20 km offshore

Ref: (a) Establier (1969) (f) Grancini et al. (197 S)
(b) Capelli et al. (1976) (g) Bubic et al. (1977)
(c) Frache et al. (1976) (h) Papadopolou (1972)
(d) Bernhard et al. (1977) (i) Roth and Hornung (1977)
(e) Niirnberg et al. (1977a; 1977b)
genic input from the shipbuilding industry and the town of La Spezia. The lower
values of cadmium (0.005 Ilg/1), copper (0.13 Ilg/1) and lead (0.018 Ilg/1) of the
study of Niirnberg et ai. (1977) may be considered as local background data in rel-
atively unpolluted waters. The influence of an anthropogenic Hg source was stud-
ied south of Livorno in seawater and biota along the coast of Tuscany by Renzoni
et ai. (1973); near the outfall (1 km south) they observed relatively high values of
around 0.2 Ilg/1 Hg, but at about 10 km south and north of the outfall the Hg con-
centration was already below its detection limit of 0.02 Ilg/1 (Bernhard, 1978). The
Adriatic Sea is particularly susceptible to pollution, especially that from the indus-
trial centres in the northern part of the region. Neave (1974) noted 76 wastewater
effluents from industrial plants in Venice; thus the concentration of certain heavy
metals, e.g. mercury, in water and edible organisms lies at or even slightly above
the acceptable safety levels. Data of Grancini et ai. (1975; 1976) from the northern
Italian Adriatic coast from Triest to Ravenna indicate significantly higher values
of silver, cobalt, antimony and zinc compared to the data from open-sea water
samples; similar findings on sediment samples (Grancini et aI., 1975) suggest that
this increase is related to the waste input from rivers. Significant anthropogenic ef-
fects, mainly for zinc concentrations, were found in the Kvarner region (Rijeka)
of the Yugoslavian Adriatic Sea (Branica et aI., 197; Bubic et aI., 1977), the Saroni-
kos Gulf (Athens) in Greece (Papadopolou, 1972) and in the surface waters along
the Israel coastline from Rosh Hanigra to Haifa; in the latter area high metal values
could be attributed to the run-off of the River Qishon, which is heavily polluted
by industrial discharges, and the River Na'amon polluted by agricultural and do-
mestic wastes (Roth and Hornung, 1977).
6.8.3 Western Europe
In western Europe there are five areas of particularly high amounts of waste dis-
posal: Clyde Sea (Liverpool Bay), Thames Estuary, Rhine-Waal/Meuse/Scheldt
estuaries, the German Bight and the Baltic Sea. During the last decade, many stud-
ies have been performed with regard to metal pollution, of which only a few can
be mentioned here.
Sewage sludge from the city of Glasgow and adjoining areas is dumped into a
restric area of the Firth of Clyde, at a rate of I x 10 6 tons per year (Mackay et aI.,
1972). Metal analysis from bottom sediments indicate characteristic enrichment of
mercury, lead zinc and copper. From a summary of the heavy metal input to the
Clyde Sea given by Topping (lit. cit. Cam bray et aI., 1975), it is evident that rain-
water plays a significant role with regard to the input of cadmium, copper, zinc and
in particular, lead (Table 72).
Considerably higher amounts of metals are discharged with sewage materials
into Liverpool Bay than into the Firth of Clyde disposal site; it must be noted, how-
ever, that the Liverpool discharges are distributed over a larger area. Even higher
amounts of metals have been dumped with the sludge from the London sewage
works (Shelton, 1971).
Contaminants enter the North Sea mostly from rivers and the atmosphere, as
well as from direct discharges. According to recent mass-balance evaluations by
Western Europe 247
Table 72. Annual quantities of metal (in tons/year) discharged

into the Clyde Sea from the most important anthropogenic
sources "sewage sludge" and "rainwater". (Topping, lit. cit.
Cambray et aI., 1975)
Sewage sludge Rainwater
Cadmium 0.25 1.7

Copper 25 50
Lead 25 60
Zinc 60 250
Table 73. Enrichment factors· of contaminant metals in sediments from different environments in
the Elbe, Weser, and Ems and North Sea. (Schoer et aI., 1982) n = number of samples
River area Environment n Cadmium Copper Lead Nickel Zinc
Elbe River Fluvial (3) 6 2 6 2 4

Estuarine (6) 9 2 9 1 4
Marine (3) 5 1 6 1 2
Weser River Fluvial (5) 22 2 10 3 7
Estuarine (2) 7 1 3 2 3
Marine (7) 10 2 6 3
Ems River Marine (7) 4 1 5 2
German Bight (North Sea) (5) 4 2 8 2
a Metal in sample/metal in background material x Sc in sample/Sc in background material (average

shale or shallow water sediments)
Eisma (1981) approx. 4.5 X 10 6 tons/yr of suspended matter is contributed by rivers

(Rhine/Meuse: 1.70; Ems: 0.07; Weser: 0.95; Elbe 0.86; Thames + Humber:
1.47 x 106 tons/yr dry weight), and approx. 1.6 x 106 tons of particulate matter is
annually deposited from atmospheric sources into the Noth Sea. The annual depo-
sition of sediments in the estuaries of the North Sea is estimated to approx.
1.8 x 106 tons. Data on the concentrations of contaminants in suspended matter
and bottom deposits indicate that offshore Zn, eu and Pb in particulate form are
predominantly accumulated in the areas where suspended matter is deposited; only
small amounts are yearly incorporated in the offshore sandy deposits (Eisma,
1981). Sediment studies from the German Bight (southeastern North Sea) have
shown significant increases of heavy metals, such as mercury, cadmium, lead, zinc,
chromium and copper (Gad ow and Schafer, 1973, 1974; Forstner and Reineck,
1974; Dominik et aI., 1978; Forstner and Patchineelam, 1981).
In Table 73 (after Schoer et aI., 1982) enrichment factors for selected metals
were evaluated from sediment samples from different environments in the south-
eastern North Sea. The relatively strong enrichment of lead and cadmium in the
samples from the outer part of the German Bight (North Sea) is mainly caused by
dumping of waste material, but atmospheric influences will also contribute to the
increase of these metals in the sediments.
Table 74. Input routes of heavy metals to the North Sea. (From Norton, 1982)
Input route Copper Zinc Lead Chro- Cad- Nickel Mer-

mium mium cury
t/a t/a t/a t/a t/a t/a t/a
Atmosphere 3,450 10,750 4,500 720 530 1,650 6

Rivers 1,950 13,840 2,430 1,820 280 1,620 30
Direct discharge 310 5,570 560 210 20 310 6
Dumping:
Sewage sludge 160 610 140 90 10 60 2
Other waste 60 130 110 40 10
Total 5,930 30,900 7,740 2,880 840 3,650 44
Table 75. Major river inputs of heavy metals to the North Sea. (Norton, 1982)
Copper Zinc Lead Chromium Cadmium Nickel

% % % % % %
Total contribution 33 45 31 63 34 44
from rivers
Rhine/Meuse 16 25 14 32 11 18
Elbe 5 6 5 9 6 7
Thames 1 1 1 2 4 3
ScheIdt 2 2 2 1 1 3
Humber 1 1 1 2 2 2
Other rivers 8 10 8 18 10 11
The North Sea is surrounded by one of the most industrialised areas in the
world. As a consequence it receives large contaminant loads, including heavy
metals. Norton (1982) recently summarised the available information on major in-
put routes of heavy metals to the North Sea (Table 74).
There are very significant atmospheric inputs for cadmium (63% of the total
Cd-load to the North Sea), lead and copper (58%), nickel (45%), zinc (35%), chro-
mium (25%) and mercury (14%). Of the major river inputs (Table 75 lists the per-
centage of the riverine metal inputs from total metal load to the North Sea) the
Rhine/Meuse system is by far the biggest contributor, followed by the rivers Elbe
and Thames.
However, estuaries, artificial lakes created in the lower courses of the rivers,
sedimentation on river flood plains and dredging activities cause a retention of
trace metals (Fig. 130). The data for the rivers Rhine and Meuse, in whose lower
courses large civil engineering activities have been carried out since 1900, have par-
ticularly to be corrected for this retention to determine the actual input to the
North Sea. Salomons and Eysink (1981) made a first balance study of metal trans-
port by these two rivers. Apart from transport to the North Sea by the estuarine
pathway, two additional pathways have to be considered:
Western Europe 249
2900 11
NORTH SEA
I
10
I
21
9600
Fig. 130. Particulate metal transport (tons/a) and dredging activities (106 m 3/a) in Belgium, The
Netherlands and Germany
Freshwater basins
The closing of river mouths (Haringvliet, 1970, see Fig. 130) and coastal lagoons
(Usselmeer, 1932) has created large freshwater basins in which the river water be-
fore it enters the marine environment, is subject to hydrodynamic and geochemical
processes causing a retention of both dissolved and particulate metals (see also
Chap. 5.4.4).
Harbours and navigation channels

The construction of the world's largest port in the Rhine Estuary (Rotterdam) has
favoured the sedimentation of suspended matter and its associated heavy metals.
Dredged material from this harbour is partly dumped on land (and thus per-
manently removed from the aquatic system) and partly in the North Sea. In order
to determine the fate of riverborne material, the proportion of marine to fluvial
sediments in the dredged material was determined with natural tracers (Salomons
and Eysink, 1981, see also Chap. 6.4). The balance on the fate of trace metals trans-
ported by the river Rhine in the direction of the North Sea (Table 76) was based
on trace metals transported by the rivers Rhine and Meuse, as measured at the Ger-
man-Dutch and Belgium-Dutch border respectively, discharges in the Netherlands
(Santema, 1980), studies carried out in the Haringvliet and Usselmeer (Salomons
and Mook, 1980; Salomons and Eysink, 1981; Salomons, 1981), dredging data ob-
tained from the Municipality of Rotterdam (corrected for the mount of marine sed-
iments) and metal analysis of the dredged material (Salomons, unpublished data).
Table 76. Tentative metal balance for the rivers Rhine and Meuse
Cu Ni Zn Pb Cd Cr MeT
tons/a
Input
Meuse+ Rhine from 1,215 886 11,051 1,707 195 2,463 16,517
Belgium and Germany
Discharge in the 130 130 1,700 380 27 530 19,414
Netherlands
Accumulation in the Netherlands (ill % of the discharge by Rhille+ Meuse)

Freshwater basins 43 24 48 49 51 45 47
(Ijsselmeer +
Haringviet)
Dreged Material 15 6 11 14 11 16 12
(landfill areas)
Output to the North Sea

Sluices in freshwater 9 26 9 7 9 6 9
basins
Dumping in the 5 3 4 6 3 7 4
North Sea
Not accounted for (direct transport through the estuary, sedimentation on river flo;;d plains, dredging
in small distributaries etc)
28 41 28 24 26 26 28
All data are based on 1977-1978, except for the input of trace metals in the Dutch
part of the rivers, which are for 1975.
The data show that more than 50% of the total metal transported by these two
rivers accumulates in its lower courses and is removed as part of the dredged ma-
terial to landfill sites. Similarly the data given for the other rivers in Table 76 have
to be corrected for retention in their lower courses and estuaries. The actual con-
tribution of rivers to the metal load of the North Sea is probably therefore less than
shown in Table 76, and the relative importance of the atmospheric contribution
much higher.
6.8.4 Environmental Impact of Metals in Biota
In general, estuaries contain more living organisms than any other part of seas and
oceans and their chemistries are correspondingly more influenced by these or-
ganisms than other marine zones (Wolfe, 1980). A complex of periodically chang-
ing parameters limit colonization to a restricted number of organism species with
a wide range of ecological adaptations (Day, 1951). While the magnitude and rel-
ative importance of the input from benthic and planktonic plants will depend upon
a variety of factors, e.g. topography and hydrology - accordingly varying mark-
edly from one estuary to the next - it is clear that a substantial proportion of prod-
ucts of plant growth will enter the estuarine sediments which are known to be im-
Environmental Impact of Metals in Biota 251
Table 77. Cadmium concentrations in water, seaweeds and shore animals of four collecting stations
on the southern side of Severn Estuary and Bristol Channel. (Butterworth et aI., 1972)
Collecting Distance from Seawater Fucus Patella Thais

point Avonmouth I!g Cd/I mgCd/kg mgCd/kg mgCd/kg
Portishead 4km 5.8 220 550

Brean 25km 2.0 50 200 425
Minehead 60km 1.0 20 50 270
Lynmouth 80km 0.5 30 50 65
portant sites for many reactions involving the degradation of organic material and
the regeneration of inorganic forms (Goldberg, 1978). The fate of toxic metals, and
hence the capacity of the estuary to receive them, is mostly linked to the fine-
grained organic-rich sediments which may be concentrated, deposited, resus-
pended or distributed by physical processes; and since such sediment is an attrac-
tive food source for many bottom-dwelling organisms, it is clearly useful to study
how bioturbation affects metal concentrations and inventories in estuarine sedi-
ments (Goldberg, 1979). Exemplary investigations performed by Butterworth et al.
(1972) in the Severn Estuary are chosen to demonstrate the effects of contamina-
tion on the concentrations of metals in aquatic organisms. Coastal waters border-
ing the southern shore of the Bristol Channel have been shown to contain abnor-
mal amounts of cadmium, zinc and lead, which are probably introduced from the
Bristol area via the River Avon. In the water samples, the effects of the pollution
have been traced as far away as Hartland Quay, some 150 km to the west from
A vonmouth into the Bristol Channel. Table 77 indicates that the contamination in
the water (by cadmium, similar effects have been observed for zinc) is obviously
transmitted to the living material inhabiting this shore - at relatively low levels in
seaweed Fucus (the producer), at higher levels in the limpet Patella (a primary con-
sumer) and greatest concentrations in the whelk Thais (the secondary consumer of
contaminated organisms). Although this type of bio-amplification of metals at
higher trophic levels has generally not been confirmed, there is clear evidence that
the highest concentrations, both in the water and in the biological material, occur
near the source of pollution and that the metal content in the estuary decreases
towards the open sea.
In a study on more than 100 sites in over 30 estuaries in south-west England
and South Wales (Bryan et aI., 1980) three burrowing species, the polycheate
Nereis diversicolor and the deposit-feeding bivalves Scrobicularia plana and Ma-
coma balthica have been evaluated as indicators of the availability of metals in es-
tuarine sediments. Scrobicularia is the best accumulator of metals; it exchanges
metals slowly and appears to be a good indicator of changes in chronic contami-
nation. Most of the metals lie in the digestive gland and therefore this organ can
be taken for a general survey without analyzing the whole soft parts; studies on the
influence of size and season on metal levels show that sampling animals of 4 cm
shell length in the autumn or early spring is the most reliable method of comparing
different sites. When Scrobicularia was absent, Macoma balthica (1.5 cm) was used
wherever possible. The polycheate Nereis diversicolor was analysed at almost every
site and proved a useful indicator for Ag, Cd, Cu, and Hg, although not Zn which
it regulates. The data show that for six of the metals, the highest concentrations
in sediment occur in estuaries where the organisms are clearly also contaminated.
However, contaminated organisms have also been found in areas where the sedi-
ments are not so obviously contaminated. It has been suggested by Bryan et ai.
(1980) that chemical factors, e.g. the availability of particle associated metals, are
usually most important and that information on the chemistry of the sediments
from different estuaries will be useful because:
1. It may help to predict whether the properties of sediments in a particular
estuary are favourable or not for the introduction of metallic wastes and
2. it may indicate ways of controlling the composition of wastes so that the avail-
ability of metallic components is inhibited rather than promoted.
Although there are only few data available at present, it has been shown, for
example, that the biological availabilities of sediment-bound lead and arsenic to
Scrobicularia are strongly influenced by the level of readily extractable Fe in the
sediment, lower concentrations of Pb and As being found in animals from sedi-
ments high in Fe (Luoma and Bryan, 1978; Langston, 1981).
The reactivity of metal compound, as evaluated, for example by sequential
chemical extraction procedures (Chap. 2.3.2), also gives indications on possible re-
mobilization effects in the estuarine mixing zone.
The Western ScheIdt, where an extensive mobilization of cadmium from the
sediments and suspended matter takes place (Fig. 122), reflects this geochemical
process in the metal uptake by bivalves (Fig. 131). In fact, the relationship between
cadmium accumulation and salinity is similar to the dissolved cadmium-salinity re-
lationship shown in Fig. 122. Cadmium levels in Mytilus edulis in the Ems-Dollard
Estuary and in the mouthing area of the Rhine Estuary are much lower and are
similar to values observed in the North Sea. This reflects the extensive removal of
dissolved cadmium during estuarine mixing in the Rhine and Ems Estuaries
(Chap. 6.6).
It has been noted by Bryan et ai. (1980) that because different organism species
have different affinities for metals and absorb them from different sources, it seems
unlikely that any organism will come to be regarded as a universal indicator of
metallic contamination. Any reasonable monitoring programme should be in-
volved in an analysis of several species (e.g., seaweed, filter-feeding bivalve and a
deposit-feeding bivalve) to try to assess contamination in different forms.
An important limitation on the use of some suggested biological indicators in
estuaries is their inability to penetrate into the less saline areas where contamina-
tion is often greatest (Bryan et aI., 1980): In the lower reaches of an estuary, the
seaweed Fucus vesiculosus, the filter-feeders Mytilus edulis and Cerastoderma edule,
and the deposit-feeders Scrobicularia plana and Macoma balthica may all be pres-
ent, together with species of the herbivores Patella and Littorina; in the less saline
parts of an estuary the choice of species becomes more limited and will include, in
addition to Fucus, Scrobicularia and Macoma, the polycheate Nereis diversicolor.
A detailed study on metal uptake by marsh vegetation in two contrasting areas
in the Netherlands was carried out in the Eastern ScheIdt a coastal lagoon under
the influence of the North Sea and without local pollution and the Western ScheIdt
Environmental Impact of Metals in Biota 253
Mytilus edulis L , summer 1980
4 Cd conc. , IIg g -1
ash - free dry weight
3
i A B
2 10 Western - Scheidt Estuary

8 Cd
initial Atlantic cone.
6 0 ....... ---,°
"' Aug:80
4 • 0 "' \
2 Jan~\\
o I I I I 'I
days 102560 102560 days 10 15 20 25 30 35
Ems - Dollard South - Holland _ _ salinity. %0
North - Sea North - Holland Western - Scheidt
Fig. 131. A Uptake of cadmium by Mytilus edulis in the North Sea compared with the Rhine Estuary,
the Ems Estuary and the Scheidt Estuary. B Cadmium uptake in the Scheidt Estuary as a function of
salinity (De Kock, 1982)
which is influenced by the River ScheIdt (Beeftink et aI., 1982). Cadmium concen-
tration in Salicornia (which is consumed as a vegetable by the local people) in the
Eastern ScheIdt was 0.19 mg/kg (dry weight), whereas in the Western ScheIdt
values up to 2.2 mg/kg, well above the maximum for vegetables) were observed.
Calculations on fluxes of trace metals in salt marshes have been made by Wolfe
(1975) for an ecosystem from the Newport River on the basis of several assump-
tions about trophic structure and flow efficiency within the system: (1) each con-
sumption step involves an assimilation efficiency of 0.2 with un assimilated 0.8 be-
ing returned to the detrital compartment as faeces; (2) the zooplankton population
regenerates itself on average 18 times per year; (3) biological half-life of Zn in zoo-
plankton is 7.6 days; (4) the macrofauna compartment regenerates with a mean
production/standing crop ratio of 2.0/yr; (5) an average of 2 trophic interactions
is effected on all Zn consumed by the macrofauna compartment; (6) biological
half-life of Zn in macrofauna is 300 days; (7) all detrital Zn, whether originating
directly from phytoplankton and S. alterniflora or from previously cycled fecal
matter, is assimilated by the microbiota and meiofauna with a net efficiency of
40% prior to becoming available to consumers.
The results show that the amount of zinc cycled annually through the trophic
structure is approximately 16 times greater than that entering the estuary from the
watershed. If most of the un assimilated Zn from the detrital compartment is re-
turned to the water column, the biological zinc cycle would very nearly represent
a closed system. These findings suggest that neither of the very large reservoirs of
potentially available zinc, i.e. the sediments and the ocean, is directly involved in
the rapid biological cycle, and furthermore, that biologically available zinc in es-
tuarine waters represents a different compartment than that involved in the sedi-
ment-water equilibrium. Wolfe (1975) notes that the major complexities involved
in progressing from this static "annual budget" concept to a dynamic model of the
flow of trace metals through the estuarine ecosystem arise because physico-chemi-
cal speciation of the metal itself must be superimposed upon food chain transfers.
Again, therefore, it becomes evident that the question of chemical reactivity of a
specific metal in both dissolved and particulate form is decisive for its adsorption,
excretion, and storage in an organism.
6.9 Estuaries as Sinks for Trace Metals?
Estuaries are the interface between the continents and the oceans, and with regard
to the movement of trace metals along the hydrological cycle, the question arises
how efficient are the estuaries and the coastal zones in trapping the particulate and
dissolved metals. This question is especially important for assessing the input of
trace metals from natural and anthropogenic sources into the world oceans. Few
detailed balance studies have been carried out to answer this question. Turekian
(1977) considered the fate ofPb-21O in estuaries and showed that its residence time
in Long Island Sound is in the order of days before it is trapped by particles and
incorporated in the sediments. His observations on lead and related elements lead
him to the following conclusion: "The estuarine trace metal cycle is mainly self-
contained: release and deposition occur virtually entirely within the system" (Ture-
kian, 1977). Only very little leakage of particulate heavy metals to the deep sea will
occur. Only low-density particles of extremely fine-grained particles can escape this
process and may provide a mechanism of supply of metals to the ocean.
Lal (1977) calculated that for particles to be effectively transported to the open
ocean, they should have diameters less than 5 ~m. Also the observation of Mayer
(1982) (see Chap. 6.5) indicated that only very finely grained material escape the
estuarine circulation pattern. This fraction of the suspended matter may be similar
to the "non-settling" suspended matter fraction discussed by Duinker and co-
workers (see Chap. 6.5).
Although these more or less semi-quantitative studies indicate that estuaries are
an efficient trap for riverborne material, few balance studies have been carried out.
Metal balance studies have been reported for two West-European estuaries: the
Gironde and the Scheidt Estuary, and for the St. Lawrence Estuary. Results for the
Gironde and Scheidt Estuary are presented in Table 78 and Table 79. Results for
other estuaries show retentions between these two extremes (see Tables 78 and 79).
The metal balance for the Gironde estuary (Table 78) clearly shows that it acts
as a metal mobilizing system. Metals entering in particulate form are leaving the
estuary mainly in dissolved form. Retention in % of the input for Zn, Cu, Pb and
Ni are 17,3,13 and 17, respectively.
Balances and flux calculations have been made for the Scheldt Estuary (Kerdijk
and Salomons, 1982; Wollast and Peters, 1978) The outflow of trace metals from
the estuary, in % of the inflow from the river are presented in Table 79.
The results of both investigations show that relatively large amounts of trace
metals are held back in the estuary. The differences, considering the fact that dif-
ferent surveys have been conducted, are rather small. Interesting is the fact that
nickel is far less removed from the system than other trace metals, this small reten-
Estuaries as Sinks for Trace Metals? 255
Table 78. Mean annual metal balance for the Gironde Estuary (Jouanneau, 1982). In tons/year
Metals Inflow Outflow
Dissolved Particula te Dissolved Particulate
Zinc 202 1,528 1,211 230

Copper 82 148 202 22
Lead 61 371 326 48
Nickel 114 96 141 34
Table 79. Metal balances for the Scheidt estuary (tons/y) (Kerdijk and
Salomons, 1982)
Inflow Outflow Outflow in %

of inflow
Zinc 1,271 (1,420) III (320) 9 (23)

Copper 311 (253) 33 (63) 11 (25)
Lead 353 (300) 26 (22) 7 (7)
Cadmium 48 5 10
Nickel 128 53 41
The values in brackets refer to the flux calculations by Wollast and Peters (1978)
tion for nickel was also found for the rivers Rhine and Meuse (Table 76). Similar
behaviour has also been found for other estuaries (Klinkhammer, 1983). The con-
trasting results for the Gironde and Scheidt Estuary may serve to illustrate the
large difference in efficiency observed in the estuarine trap for trace metals.
Also a large amount of metals transported by the rivers Rhine and Meuse in
the direction of the North Sea does not enter the marine environment. However,
in this case the retention is mainly caused by civil engineering activities (Salomons,
1981), such as the creation of freshwater basins, the construction of the Rotterdam
harbour (increased siltation) and estuarine and freshwater processes causing a re-
moval of dissolved trace metals (Table 76). Yeats and Bewers (1982) who studied
the St. Lawrence Estuary and the Gulf of St. Lawrence, used the results from this
large estuary and marginal sea as a model to obtain information on the magnitude
of exchanges between the freshwater and deep marine environments. They could
use the Gulf of St. Lawrence as a world model because it has many characteristics
that are similar to those of a section of continental shelf. The area of the Gulf is
about 250,000 km 2 with water depths comparable to those on the adjacent con-
tinental shelf. Fig. 125 shows that SPM and the associated particulate metals are
removed more rapidly outside the high energetic estuarine zone. Most of the dis-
solved trace metals are removed within the estuarine region of the system (Yeats
and Bewers, 1982). Yeats and Bewers (1982) recently made a generic model of trace
metal transport through the coastal zone. They compared the discharge ofparticu-
late and dissolved metals by rivers, with the average sedimentation in the coastal
Table SO. Results of the generic coastal zone model of Yeats and Bewers (1982). The retention in the
coastal zone refers to the % of the inititially settling river borne particulate flux which remains in
the coastal zone
Com- Global River Net effiux Retention Pelagic sediment concentration

ponent discharge from the in the coast-
flux coastal zone al zone Predicted Observed
kgJy kg/y % gJkg g/kg
SPM 1.8 x 10 13 1.0 X 10 12

Fe 9.2 x 1011 5.5 X 10 10 99.8 5.3% 5.8%b 8.0%"
Mn 2.2 x 10 10 7.9 X 109 69 5,600 4,000c 12,500 d

Co 3.0 X 10 8 7.8 X 10 7 79 61 38 c 116 d
Ni 1.5 x 10 9 2.3 X 10 8 92 180 72 c 293 d
Cu 2.5 X 10 9 5.8 X 10 8 66 410 130 c 540 d
Zn 5.4 x 109 2.8 X 10 9 54 1,900 130 C
Cd 3.0 x 10 7 1.3 X 10 7 69 8.5 0.5'
" Value for sedimentary rocks

b Average pelagic clay after Rosier and Lange (1972)
c Atlantic pelagic sediments after Chester and Aston (1976)
d Pacific pelagic sediments after Chester and Aston (1976)
, Average oceanic sediments after Simpson (1981)
COASTAL PELAGIC
:
. ________ jE~~~_S_~:~~:~_____________________________lr:T~~~~~~_~~::c
COASTAL ZONE : PELAGIC
: :OCEAN
RIVER DISSOLVED :I
,
I •
'
I :
PARTICULATE i 1.0xlU12!
1.8xlU13
SETTLING'(95% /
OF PARTICULATE
INPUT) ,:
,,
,,
,
l--------I:;::~.. fAji..------------- ---------------I;,;-,"'-----J

Fig. 132. Generic coastal zone model illustrated with particulate matter fluxes in kg· a-I (Yeats and
Bewers, 1982)
and its mean metal contents with the composition of ocean sediments. The results
are presented in Table 80.
The transport of particulate matter within their generic coastal model is shown
in Fig. 132.
An interesting facet of this model is the differences in composition between
riverborne particulate matter and nearshore sediments. The concentrations of al-
uminium and iron are equal, however, the concentrations of Mn, Co, Cu, Zn and
Estuaries as Sinks for Trace Metals? 257
Cd are lower. This shows that some additional mechanism of metal transport from
the coastal zone to the deep-ocean must exist in order to maintain these low metal
concentrations. The percentage of metals which are redistributed (expressed as %
of the initial particulate metal sedimentation flux in the coastal zone) is given in
Table 80. Processes which may cause this redistribution are: size sorting of river-
borne particulates, diagenetic release to the water column and eventual reassoci-
ation with fine suspended particles. This is one of the major routes for the redis-
tribution of manganese but in the case of this metal and especially for others, size
sorting of suspended particles during transport through the coastal zone must also
be important (Bewers, 1982, personal communication). These results show that the
input of riverborne trace metals to the deep-ocean is determined not only by pro-
cesses in the estuaries, but by additional processes during transport in the coastal
zone, and by release of trace metals from coastal sediments.
The observed variability in the behaviour of trace metals in various estuaries
may be due to a number of reasons. These processes are operating on different time
scales, the adsorption processes in estuaries on a rather rapid time scale, the iron
precipitation being more rapid than the manganese oxidation. Also the flux varies
to a large extent. The results from the behaviour of copper in Eastern U.S. estuaries
(see Fig. 124), show that the flux from the sediments is rather constant and shows
up when the riverborne flux of copper is low. It seems highly likely that these dif-
ferences in fluxes and time scales obscure some processes in estuaries. Some of the
variability in trace metals in estuaries may be due to differences in time frame, hy-
drodynamic conditions, biological activity, sediment influence etc. Unfortunately,
at this moment it does not appear to be possible to depict a general description of
trace metal behaviour in estuaries. More field studies, jointly carried out with lab-
oratory and/or mesocosm studies on a number of contrasting estuaries are needed.
7.1 Introduction
The oceans are the last part of the hydrological cycle and here trace metals are re-
moved from the hydrological cycle and incorporated in the sediments. There they
spend several hundred million of years before taking part in the next hydrological
cycle.
Roughly three sources contribute to the input of trace metals in the world
oceans:
- rivers
- the atmosphere
- hydrothermal inputs from active ridges.
It should be remembered that the river inputs are retained to a large extent in
the estuaries and in the coastal zone (see Table 80). The atmospheric inputs, which
are less known than the fluvial inputs, have been discussed in Chapter 4, especially
with regard to the complex processes at the sea-air interface and the origin of the
oceanic aerosol. Little information is available on the influence of active ridges on
the supply of trace elements to the world oceans. The available data will be dis-
cussed in this chapter.
Removal of trace metals includes the settling of the particulate phases and the
incorporation of dissolved metals in biological tissues and their adsorption on par-
ticulate matter; furthermore manganese nodules may playa role in the removal of
trace elements from the oceans.
The reactivity of elements in the ocean varies to a large extent. In Fig. 133, the
mean oceanic residence time is shown together with current estimates on element
concentrations and some characteristic time scales for oceanic processes. The mean
oceanic residence time varies over several orders of magnitude between elements.
For major elements like sodium, the oceanic residence time is near to the age of
oceanic sediments, whereas for some trace elements the residence time is shorter
than one oceanic stirring time, showing their low reactivity in the marine environ-
ment.
The processes affecting trace metals in the oceans can be schematised with box
models (Broecker, 1974; Lerman, 1979). A four box model which includes the sed-
iments is shown in Fig. 134. (It is possible to include a fifth box: the air-sea inter-
face. However, the processes occurring in this box have already been discussed in
Chapter 4.)
Introduction 259
Ocanlc Water Sediment

stirring residence residence
time time time
I
I Time In yeers I
1p3 10 4 1 10 5 10 6 10 7 10 8
I I ~I~
I I I
: I Ca SM9 I Major
I I K:
I ------~-----~----E-----Jl---~r- ---
I
-4
.. 10 I N
I lSI F LI Sr :
- I I I
~ I I P Rt I Minor
! -----~-----l~!-~ Mo --------1- ---

i AI I zn I As NI U I
§
-6 TI
Trace
10 r- Fe - - -M--;: Cu -Cr-~~-V---s~------ :
-~-Cd -rSb-Ga-c;,-w ------------1-
Pb lAg KgI Au I
LalThSnI I
I Cs I I
Ca IGd Er I I
-12
10 IPr Ho I I Ultra-trace
I Eu I I
I: I
I I I
Fig. 133. Concentrations and mean oceanic residence time of elements in the ocean together with some
characteristic time scales of oceanic processes (Whitfield, 1982)
Atmosphere
Rive rs
~
Dissolved
-• Particulate
... ::
..
:-(Bi ota)
Surface layer
Dow nwelling:
, Upwelling;
:
--
Selliing
particulate
... ..
.. -_. Deep layer
•
: Sedi ment -water
interlace
Net
sedimentation Sediments
Fig. 134. Four box model of the ocean
1. The Surface Mixed Layer

This box receives trace metals from a number of sources:
- the riverine input (see Chapter 5.3 )
- the atmospheric input (see Chapter 4)
- input from upwelling water.
The rate of upwelling is about 4 m/yr, which is 40 times the water discharge of
the rivers (0.1 m/yr). For metals which have higher concentrations in the deep wa-
ter compared with the surface water, upwelling is a major source. In the surface
layer biological processes take place which result in the formation of particulate
matter. Trace metals are incorporated in the particulate matter and/or are ad-
sorbed on it.
Metals are removed from the surface layer by the sinking particles and through
downwelling of water.
2. The Deep Layer

This layer is subject to a continuous passing through of particulate matter, causing
adsorption of some trace metals on it. On the other hand, part of the biogenic par-
ticulate matter decomposes releasing trace metals. Since the oceanic stirring time
is about 1600 years and the residence time of the large particulates only days to
weeks and those of the small particles about 50-100 years, the particles continu-
ously provide the deep layer with trace metals whereas for some trace metals
scavenging takes place. This situation is different from that in an estuary, where
the residence time of suspended matter is higher compared with the water masses,
causing a continuous scavenging of the dissolved metals; in the oceans the water
masses may be considered as stationary.
3. The Sediment-Water Interface

The composition of particulate matter recovered or sampled in sediment traps
above the ocean floor differs from that of the sediments (see Chap. 7.3). In partic-
ular the organic matter concentrations in the sediment traps are higher. This shows
that at the sediment-water interface important degradation processes are taking
place which possibly result in the release of trace metals. In addition the diffusion
of trace metals in the pore waters of ocean sediments (enhanced by bioturbation
and consolidation) provides the overlying surface waters with some trace metals.
The occurrence of nepheloid layers, the region of increased suspended matter near
the seabed, on the other hand, provides large surface areas for adsorption and may
promote the removal of trace metals.
4. The Ocean Sediment

The ocean sediments are the ultimate sink for the trace metals in the hydrological
cycle. In the sediments solid phase transformations take place which affect the
mode of occurrence of the trace metals in them.
Vertical and Horizontal Distribution of Trace Metals 261
Fig. 135. Schematic diagram of the lat- Wind-mixed

eral movement of watermasses in the layer
ocean
Deep ocean
Pac if ic Indian Atlantic
This four box model of the ocean is a simplification of processes occurring in

the vertical. The processes in the polar areas are different due to absence of a well-
defined surface layer and less biological activity than midlatitude areas. Also the
lateral movement of water is not taken into account (Fig. 135). The Pacific receives
relatively large amounts of water from the Atlantic. As a consequence the deep
waters in the Pacific are older, and hence have been subject to a large passing
through of particulate matter and as a consequence have higher nutrient levels; also
the carbonate compensation depth (see 7.4.1) differs between the Atlantic and the
Pacific.
7.2 Vertical and Horizontal Distribution of Trace Metals
Since the mid-seventies important advances have been made in solving the prob-
lems associated with sampling, storage and analysis of trace metals at the low levels
occurring in the oceans due to the pioneering work of C. Patterson at the California
Institute of Technology (Goldberg, 1981).
The amount of reliable data on the metal distribution in the oceans is still
limited and the present discussion gives merely a state-of-the-art overview of the
available knowledge in a field in which rapid advances are being made.
Metal distribution in the Pacific Ocean, which has been studied by independent
groups, is the best known at present. Profiles of cadmium, zinc, copper, nickel to-
gether with those for the nutrients phosphates, nitrate and silicate are presented in
Fig. 136.
All four metals studied (cadmium, zinc, copper and nickel) are depleted in the
surface layers, as are the nutrients nitrate, silicate and phosphate.
A comparison of the cadmium profile with those for the nutrients shows a
strong resemblance. In fact a high correlation is observed between phosphate and
cadmium (Boyle et ai., 1976; Bruland et ai., 1978; Bruland, 1980). The linear cor-
relation can be explained by a removal of cadmium from the surface waters by or-
ganisms. The organic tissue carrier is regenerated in the thermocline, releasing cad-
mium and the labile nutrients. Also a good correlation is observed between the Cd/
Ca concentration in recent benthic foraminifera and the phosphate concentrations
in bottom waters (Hester and Boyle, 1982). This relationship can be utilized to re-
construct chemical variations in the oceans from fossils in deep-sea sediment cores.
The profile of zinc shows a regeneration at greater depths, as is also the case
with silicate. A good linear correlation is observed between zinc and silicate, show-
.. to
PHOSPHATE (I/mol/kg) NITRATE (I/mol/kg) CADMIUM (nmol/kg)
..
SILICATE (I/mol/kg)
00 2.0 3.0 o.a to
. ..
00 10 20 30 40 40 80 120 160 00 0.2 0.4 0.6 t2
~
01'.
.. .
..
_2 2
e2 .. e 2
E
::I: e: '"
i"
:
:I:
.... :I:
.... ....
Il. .... Il. Il.
::;3
UJ UJ UJ
03 03 03
0
4 4 4 4
5 5 5 5
..
COPPER (nmol/kg) ZINC ("rimol/kg) NICKEL (nmol/kg)
00 1 2 3 4 5 00 2 4 6 8 10 00 2 4 6 8 10 12
e2 e: 2 e2
: :I:
~
:I:
.... ....
Il.
:I:
....
Il. W Il.
~ 3 03 ~ 3
4 4 4
5 5 5
Fig. 136. Metal concentrations along profiles in the central gyre of the Pacific Ocean (Bruland, 1980)
ing that the release of zinc is associated with the regeneration of hard skeletal ma-
terial.
The profile of nickel is similar to the one reported by Sclater et al. (1976). In
the upper 800 m it appears to be similar to phosphate (Bruland, 1980), while at
greater depths it exhibits a maximum similar to silicate. Nickel appears to undergo
both a shallow and deep water regeneration cycle.
The profile for copper differs from those for the other three metals; it shows
a surface minimum, but the copper concentration increases with depth. Similar ob-
servations have been made by Boyle et al. (1977). The curves are interpreted as the
result of vertical advection of bottom waters high in copper and diffusive mixing
with overlying intermediate waters. Results on copper in pore water show that
oceanic sediments are able to provide the overlying bottom waters with copper
(Klinkhammer, 1980) (see Chap. 7.4.3.1). The curvature of the copper profile im-
plies scavenging in deep and intermediate waters. Similar scavenging might also
take place for Cd, Zn and Ni. However, their distributions are strongly influenced
by the internal biogeochemical cycles, which makes it difficult to observe these re-
moval processes (Bruland, 1980).
The horizontal distribution of trace metals in the surface waters of the Pacific
(Bruland, 1980; Boyle et ai., 1981) and in the Atlantic (Boyle et ai., 1981) shows
large differences in concentrations. The lowest concentrations of Cd, Ni and Cu
were observed in non-upwelling open-ocean areas; metal concentrations are high
in cold nutrient-rich waters (Boyle et ai., 1981). The distinctly higher copper con-
centrations in the coastal waters north of the Gulf of Panama and in shelf waters
north of the Gulf Stream may be caused by copper remobilised from mildly reduc-
ing shelf sediments (Boyle et ai., 1981). As an example of horizontal variations in
the Pacific data for a transect from Hawaii to Monterey, California are presented
in Fig. 136. Although for Cu, Ni, Zn and Cd a large removal is found in the surface
layers a large part is regenerated in the deep water or at the sediment-water inter-
face (Cu) and returned to the water masses and through upwelling entering the sur-
face layer again. Comparatively little loss occurs to the sediments during each stir-
ring time. This means that the metals can participate in the vertical redistribution
processes under steady state conditions for a long time, requiring only small exter-
nal inputs to the water column, just sufficient to balance losses to the sediments
(Schaule and Patterson, 1981).
Crecelius (1982) calculated the input from the atmosphere and by upwelling in-
to a 100 m thick surface layer for an open ocean area remote from river inputs and
land masses. Some results are presented in Table 81.
Although these calculations give only order of magnitude estimates on the flux-
es, they clearly show the important contribution of the atmosphere for the elements
Pb and Zn, and the importance of upwelling for Ni, Cr, Cu and Co. It should be
noted, however, that the ocean at present is not in a steady state. The concen-
Table 81. Mean concentrations in the surface (0-100 m) and subsurface layer, the input and output
from the surface layer and the % contribution of the atmosphere to the total input to the surface layer
(Crecelius, 1982)
Metal Mean metal Flux % input

concentrations atmosphere
Up Down Atmo- to total
Surface Subsurface welling welling sphere input
ng!1 ng/I mgm- 2 yr- 1 mgm- 2 yr- 1 mgm- 2 yr- 1 %
Mn 165 55 0.28 0.85 0.22 44

Pb 30 10 0.05 0.15 1.3 96
Zn 7 70 0.35 0.035 1.3 79
Cu 80 130 0.65 0.40 0.28 30
Ni 140 180 0.90 0.70 0.076 8
Cr 200 150 0.75 1.0 0.10 12
Cd 1 10 0.050 0.0050 0.050 50
Co 10 10 0.050 0.050 0.018 26
Fig.137. Depth profile for lead in the Atlantic and the

,...._......:o:....._=r:-_--=r....-....;4:r0:.. . . :;O Pacific (Schaule and Patterson, 1983)
2
DEPTH
(km)
5 Fig. 138. Cadmium, zinc and copper profiles in the Atlantic

and in the Pacific (Bruland and Franks, 1983)
T
Copper (nM-kg- 1 )
.
Cadmium (nM-kg- 1 ) Zinc (nM-kg- 1 )
o 0.2 0.4 0.6 0.8 1.0 0 2.0 4.0 6.0 8.0 0 1.0 2.0 3.0 4.0 5.0
o~ '."6
~
J
• P • ~
500 0
• 0
• 0
•
0
• 0
• 0
•
1000 0 • 0 • o •
1500 0
• 0
• o.
!
-
.I:.
Q,
CD
Q
2000 0
North Atlantic
0
North •
Pacific
0
North Atlantic
0
•
North
Pacific
Northo
Atlantic
0
•
North
Pacific
2500
• • •
3000 0
•
0
• 0
•
3500
• • •
4000 • • •
trations in the deep layers still partly reflect the pre-industrial period. Especially
for lead (and possible for cadmium) the anthropogenic inputs to the surface layer
have to be considered. Undoubtedly, this type of calculation will be refined in the
future when more data become available.
Schaule and Patterson (1981) compared the natural flux of lead to sediments
in the central North Pacific with present-day fluxes. The natural flux varied be-
tween 1.2 and 7.5 ng/cm 2 /yr with a mean value of about 3 ng/cm 2 /yr, whereas the
presentday flux to the surface waters was estimated to be 68 ng/cm 2 /yr, which is
a 10 fold increase. Due to larger industrial emissions in North America than in Asia
the fluxes in the Atlantic are even higher (170-330 ng/cm 2 /yr) (Schaule and Patter-
son, 1983).
The high atmospheric input of atmospheric lead in the surface waters of
the oceans is reflected in the depth profiles for both the Atlantic and the Pacific
(Fig. 137).
A notable feature of Fig. 137 is the difference in lead concentrations between
the Atlantic and the Pacific, those in the Atlantic being significantly higher. This
is not the case for all trace metals. In the Pacific the concentrations of Cd, Cu, Zn
(Bruland and Franks, 1983) exhibit 2 to 4-fold increases. Examples of these differ-
ences are shown in Fig. 138.
This observation can be explained by the continuous supply of some trace
metals from degrading organic particles to deep waters along the trajectory of the
watermasses (e.g. the deep waters of the Pacific are derived partly from the Atlan-
tic), in a way similar to that for the nutrients (Broecker, 1974). Since the residence
time of the trace metals (except lead) is much longer than the stirring time of the
ocean, this leads to a continuous build-up of metal concentrations. The residence
time of lead, however, 100-150 years for the Northwestern Atlantic and 80 years
for the Northeast Pacific (Schaule and Patterson, 1983), is much lower than the
transit time of the deep water masses, and no build-up occurs.
As a consequence the concentrations in these waters are increasing in response
to large increases of lead input (see Fig. 55) during the past decades. The longer
residence time in the Atlantic causes a slower response than in the Pacific, and have
certainly not reached steady state (Schaule and Patterson, 1983). In the surface
waters, the residence time of lead is about 2 years and steady conditions prevail,
so that the present larger industrial lead input flux to the North Atlantic compared
to that in the North Pacific is recorded directly as higher concentrations in its sur-
face waters.
A few other elements also exhibit pronounced maxima in the surface layers.
This is especially true for cobalt and manganese, and in particular in profiles taken
close to the continent; this reflects riverine inputs (Landing and Bruland, 1980;
Martin and Knauer, 1980; Schaule and Patterson, 1981; Knauer and Martin,
1982). The influence of riverine inputs on the distribution of manganese is also
shown by their increase in surface water concentrations close to the continents in
transects from the open ocean to the continent (Schaule and Patterson, 1981) and
by the correlation between salinity and cobalt concentrations (Knauer et aI., 1982).
Lead concentrations on the other hand (and also 21O-Pb) decrease (Fig. 139).
This removal oflead on the continental shelves is probably associated with the
increased biological activity and elevated loads of organic and inorganic particles.
Turekian (1977) showed that very little lead escapes the estuaries and coastal areas.
Li et aI. (1981) studied seasonal cycles of 210-Pb concentrations in waters of the
New York Bight. They found that the pathway of phytoplankton-zooplankton-fe-
cal pellets is not important for the removal of 21O-Pb in the shelf, but in the slope
areas. Also during winter periods they observed a regeneration of 21O-Pb from the
sediments and a transport back to the surface waters. The most likely overall re-
moval of 21O-Pb from the shelf surface water is adsorption onto suspended parti-
cles and subsequent settling to the bottom.
120 400 40 20 Fig. 139. Metal concentrations in

surface waters in a transect from
Hawaii to Monterey (California)
DI
.>t (Schaule and Patterson, 1981)
90 300 30 015
DI
0
DI
.... .>t
"-
.>t "- DI
"- DI E c
g' 60 ~200
DI
20 %10 ~
C C .c
:E Q.
::i Z 0
() 30 100 10 ~ 5
o o
111315 171820212325
HAWAII MONTEREY
BAY
A number of studies have been carried out in the Arctic Ocean and surrounding
areas (Moore, 1981; Rahn, 1981; Campbell and Yeats, 1982; Heggie, 1982). In po-
lar areas no surface depletion is observed; on the contrary, in most cases concen-
trations in surface waters are higher than in deep waters. The copper profiles ob-
served by Campbell and Yeats (1982) and by Heggie (1982) show, like the profiles
from mid-latitudes, an increase in copper concentrations with depth, indicating
that also in these areas the bottom sediments are a significant source for copper.
Campbell and Yeats (1982) found that the concentrations in sea ice and glacier
ice are higher than those for surface waters from the same area. They concluded
that the spatial and vertical variation in trace metal concentrations is determined
by the high metal concentrations in the inflowing waters. Rahn (1981) made a bal-
ance calculation for the Arctic Ocean, which showed that for aluminium,
manganese, cadmium and lead the riverine inputs were comparable to either the
surface or below-surface oceanic inputs. Except for lead the atmospheric inputs are
much lower than either the riverine or oceanic inputs.
7.3 Particulates and Metal Behaviour
Particulates form the conveyer belt by which dissolved metals are ultimately trans-
ported to the sediments. With regard to the interaction between particulates and
metals four depth zones can be recognised in the oceans (Lal, 1980):
- fluvial and aeolian input in surface waters and biological fixation in the euphotic
zone (0-100 m),
- grazing by zooplankton, fragmentation and oxidation in the top 1 km level,
- sinking of particulates through the water column with associated in-situ biolog-
ical, physical and chemical changes, and
- dissolution of particulates and particulate-water exchange occurring at the
ocean-sediment interface.
Particulates and Metal Behaviour 267
The total mass of suspended matter in the ocean is estimated at 10 16 grams

(Lal, 1977). In the surface waters the concentrations of particulates vary between
100 and SOO I1g/1 and depend mainly on biological activity. The deep and interme-
diate waters, which represent 90% of the ocean volume, contain 10--20 I1g/l. Close
to the bottom, the concentrations increase (nepheloid layer), owing to resuspension
of bottom sediments (Chesselet, 1979). The known particles in the oceans can be
classified in fine particulate matter (FPM) and coarse particulate matter (CPM)
(Lal, 1980). The fine particulate matter is composed of particles < 10 11m, the size
distribution is log normal down to 0.2 11m size (Lambert et al., 1981). The coarse
particulate matter is composed of biological and fecal matter. The mean residence
time of the fine particles in a 4 km water column is SO--100 year, whereas the large
particles (SO-SOO 11m) remain in the water column for only a few weeks or days.
Although the large particles account for only 10% of the mass in suspension they
constitute 90% of the mass of sediments at any particular time. Small particles ac-
count for the other 10% although they represent 90% of the standing stock
(Chesselet, 1979). The large aggregates are extremely difficult to study, because the
number of aggregates present (less than 10 grains per litre) are overwhelmed by the
small particles (10 5-10 6 grains/I) (Chesselet, 1979). The large particles are respon-
sible for a fast flux of trace metals to the sediments, a fact which was discovered
by the occurrence of radionuclide from nuclear bomb testing in deep ocean sedi-
ments. The falling particles release their labile nutrients and part of the metals;
however, the long residence time of the small particles and their large surface area
is responsible for the removal of some trace metals from the deep waters.
Adsorption processes in the oceans have been discussed in detail by Balistrieri
et al. (1981) (see Chap.2.S). For some trace elements there is an equilibrium be-
tween dissolved and particulate forms (Bacon and Anderson, 1982), but not irre-
versible uptake on particulate surfaces. Bacon and Anderson (1982) used available
data on residence time and the ratio of dissolved to particulate forms for Mn, Cu,
Pb, Th and Pa to show that the removal of all five metals may be controlled by
a single population of particles having a residence time of about S-1O years in the
water column.
However, the main population of particles in the ocean have a diameter less
than 2 11m (McCave, 1975; Lambert et al., 1981) with a residence time between SO
and 100 years. There is more evidence for this apparent discrepancy between the
residence time of the particles and the residence time of trace metals as well as the
flux of aluminium silicates to the ocean:
- The removal of SS- Fe, 234-Th, 210-Pb and 239-Pu is consistent with particles of
3-S 11m radius (Lal, 1980), which have settling velocities an order of magnitude
larger than that for FPM and two to three orders smaller than that for CPM.
- The settling rate of alumino silicate to the ocean bottom is much higher than that
calculated from aluminium concentrations in suspended particles and from their
settling velocity (Lambert et al., 1981).
To explain this type of discrepancy, Lal (1980) proposed a "piggy-back" mech-
anism. The large particles, mainly biogenic in origin, have a coating whereby once
they impact on other particles they adhere to them strongly. The impacted "small"
particle is then transported downward with a velocity slightly in excess of the larger
Total mass Organic carbon Carbonate Lithogenic

flux flux flux particle flux
1689
...
°I'~'E
an ....
en
E
18 33
~
726
64
"E
(33)
21
(4a)
876
6)
12 2 4 6 8 10 12 12 2 4 6 8 10 12 12 2 4 6 8 10 12 12 2 4 6 8 10 12
Month in 1980
Fig. 140. Total mass flux, organic carbon, carbonate and lithogenic particle flux at three different depths
in the Panama Basin (Honjo, 1982b)
impacting particle until the sticky layer degrades. The process happens repeatedly
for a particle of micron size so that the effective sinking velocity is that of the larger
impacting particle (Lal, 1980).
Recent experiments using sediment traps have given convincing evidence for
such a kind of mechanism. Result from sediment trap experiments in the Panama
Basin are presented in Fig. 140.
Fluxes are high in the months March and July corresponding to high carbon
fixation in the surface waters (March) and high zooplankton biomass in May-July.
Large differences in the lithogenic particle fluxes are observed between the traps
at 1890 m, 2590 m and 3560 m. A large fraction of these excess lithogenic particles
did not originate from surface waters (Honjo et aI., 1982a). Fine lithogenic parti-
cles are probably resuspended from the slope and lateralIy transported to the sta-
tion by the westerly undercurrent (Honjo, 1982a). The coccolithophorid Muscus
probably plays a major role in the vertical transport of these lithogenic particles
by scavenging and agglutinating them while they are settling through the water col-
umn (Honjo, 1982b), the sinking speed of the aggregates being accelerated due to
Marine Sedimentary Facies 269
the addition of heavier lithogenic particles. These factors would give rise to the
higher lithogenic flux in deeper traps, particularly during the period in which a
large quantity of Muscus is available.
In this way certain anthropogenic metal additions to the oceans, those which
are not redissolved during settling, are able to influence the composition of oceanic
bottom sediments on a relatively short time scale.
7.4 Composition of Oceanic Sediments
Marine sediments are highly variable in origin and composition. Terrestrial inputs,
marine-biogenous formations and hydrothermal discharge have made their im-
prints on the sedimentary components. Thus, the sedimentary sequence can reflect
the variations of wind directions, seasonal changes of river discharges and of pri-
mary production in the euphotic zones of the sea as well as variations of volcanic
activity in the rift areas (Soutar and Crill, 1977; Deuser and Ross, 1980; Campo
et aI., 1982). Marine deposits consist of debris from erosion processes on the con-
tinents - mainly quartz, feldspars, clay minerals and detrital carbonates, shells and
organic matter derived from biogenous processes, pumice from volcanic events and
cosmic spherules (Seibold and Berger, 1982).
The process of rock formation, which starts with sedimentation or resedimen-
tation, is governed by the intensity of diagenetic processes such as compaction, re-
crystallization, cementation and especially the rate of sedimentation. Sedimenta-
tion at the continental slopes occurs at a rate of 100 mm/l000 yr and 1-20 mm/
1000 yr in the deep-sea. This represents an average continental erosion rate of 60
mm/l000 yr (Seibold, 1975). Generally it can be determined that in the North At-
lantic, a relatively young ocean surrounded by various landmasses, substantial
amounts of weathering products are contributed by rivers. In the equatorial
Pacific, an oceanic region relatively isolated from land, however, internal effects
such as the composition of volcanoclastic materials combined with biological pro-
ductivity, and sea water chemistry are dominant (Davies and Gorsline, 1976).
Therefore, the general term "ocean sediment" should be specified according to the
particular situation with respect to the various inputs and processes.
7.4.1 Marine Sedimentary Facies
Whereas the sediments of the shelf zone and the continental slope consist chiefly
ofland-derived detritus (terrigenous sediments), pelagic sediments, ooze or pelagic
ooze are made up mainly of organic skeletal remains of micro-organisms. Red
brown clays are either derived from land or originate from local input of volcanic
material. A differentiation of the biogenous deposits is usually made according to
the major groups of micro-organisms in the open ocean (Reineck and Singh, 1979):
(i) Globigerina ooze is made up mainly of tests of various planktonic foramini-
fera, especially of Globigerina; additional platelets of coccoliths, radiolarian shells,
diatom parts and pteropods are also abundant.
(ii) Radiolarian ooze is typical of the equatorial areas and is characterized by

the high content of radiolarian shells, usually more than 50%; inorganic com-
ponents are the same as for red clay.
(iii) Diatom ooze is made up of 50% or more diatom frustules, this material
is typical for high latitudes and some continental margins (Berger, 1974).
(iv) Pteropod ooze is made up largely of aragonitic pteropod shells. There is
also abundant planktonic foraminifera in this sedimentary facies. Pteropod ooze
is present on the slopes of the mid-Atlantic Ridge, the slopes of the Bahama Plat-
form and the slopes of the Bermuda Pedestal.
Sediment composition on the sea floor is controlled by the composition of the

source material (fluvial, aeolean and hydrothermal inputs) and by biological pro-
ductivity. Since the organic oozes are particularly important for the non-volcano-
genic distribution of trace metals these processes should be described in terms of
(1) supply of biogenous material and (2) dissolution of organic debris in the water
column (Kennett, 1982).
(1) Primary production depends on sunlight and nutrient supply. Thus in the
photic zone, large areas are relatively low in nutrients, since they are used up by
phytoplankton. On the other hand, nutrients are transported to intermediate water
depths as dead organisms; however, the permanent thermocline existing between
nutrient-poor surface waters and nutrientrich intermediate depths prevents re-
plenishment of the upper zone by nutrients. Only if the thermocline is indistinct -
in areas of upwelling or oceanic divergence - do high rates of ooze formation take
place.
Upwelling along the equator brings cold nutrient-rich water to the surface and
makes the eastern equatorial Pacific one of the most biologically productive re-
gions of the world. A high standing crop of zooplankton results in a zone of thick
sediment accumulation. Near the equator itself, the sediments are highly cal-
careous, but north and south of it belts of siliceous sediment are observable.
Beyond the boundaries of the high productivity zone, non-fossiliferous pelagic
clays accumulate. In the eastern part of the region the zone of calcareous sediment
accumulation extends north and south over the shallow region of the East Pacific
Rise and its associated ridges (Fig. 141).
(2) The distribution of the sediment type is dependent not only on productivity
but also on the different solubilities of silica and carbonate in the oceans as
schematically presented in Fig. 142 (Kennett, 1982). Since the oceans are under-
saturated with respect to silica, the dissolution of biogenous silica is initiated im-
mediately upon the death of the organisms. It has been estimated that only approx.
4% of the skeletal silica formed in the oceans survives to reach the sea floor (Heath,
1974), while further dissolution takes place after deposition (Berger, 1974). Pre-
servation of siliceous shells appears to be better in sediments rich in organic matter
(Berger, 1970); their association with fecal pellets is a significant mechanism.
Surface ocean waters are supersaturated with respect to carbonate; therefore
calcareous sediments accumulate quickly in shallow seas. However, dissolution of
carbonate commences at depths greater than a few hundred meters, preferentially
at the sediment/water interface and not in the water column. The depth at which
the rates of supply and dissolution of carbonate are equal is termed the carbonate
~
po
::l.
i'I
C/l
(1)
P.
~.
::s
S
~
'11
O.
(1)
'"
::~~~ Clay or no deposil .:: .' Calcareous Ooze ~ Siliceous Ooze D Shelf and Slope Deposils BDeep Sea Muds ~~ Glacial Debris
IV
-..J
Fig. 141. Distribution of principal types of sediment on the floors of the ocean (Berger, 1974)
RADIOLARIA FORAMNFERA
O~~~~~~~~~~----------------I°
VIRTUALLY NO 2
DISSOLUTION IN
TRANSIT
3
o Incre.slng dissolution Incre.slng dissolution
Fig. 142. Dissolution profiles of siliceous and calcareous material compared. (after Berger, 1970 from
Kenneth, 1982). Silica reflects biological fertility of surface waters, whereas carbonate biogenic sedi-
ments generally are an expression of the preservation of calcium carbonate at depth
compensation depth (CCD). The "CCD" tends to be depressed under the equator-
ial high productivity belt but occurs at lesser depths in highly productive ocean
margins. The latter effect is a result of an abundance of organic matter which leads
to the development of carbon dioxide-rich, and hence corrosive, bottom water. An-
other level similar to the CCD which can be charted to describe dissolution pat-
terns is the lysocline - a contour following the boundary zone between well- and
poorly-preserved foraminifera assemblages (Seibold and Berger, 1982). The rate of
carbonate dissolution increases at the lysocline, being approx. 3600 m in depth in
the tropical Pacific.
Residual red-brown clay dominates at lower organic productivities within
deep-sea basins. The median diameter of this material is in the clay size range
« 2 !lm). Clay minerals and other resistant mineral residues derived from land are the
main constituents together with volcanic ash. The red clay of the South Pacific is
mainly made up of authigenic clay minerals, produced by in situ alteration of vol-
canic material (Reineck and Singh, 1979). The accumulation rate of calcareous ma-
terial ranges from 10 to 20 mm/lOOO years, that for siliceous material from
4-5 mm/lOOO years, whereas the rate of deposition of pelagic clays in the Pacific is
about 2 mm/lOOO years (Van Andel et aI., cited in Davies and Gorsline, 1976).
7.4.2 Metal Concentrations
Facies differentiation is also reflected in the metal contents of sediments (Table 82

shows examples of typical marine sediments).
As expected, the composition of near-shore sediments is determined by the
chemistry of river-derived material and hence by the petrology of the contributing
catchment area. In this context, it is the terrigenous silicate minerals that determine
the content of the minor elements. This is especially true for rapidly accumulating
Metal Concentrations 273
Table 82. Metal concentrations in typical marine sediments
Fe Mn Cu Ni Co Zn
% % Ilg/g Ilg/g Ilg/g Ilg/g
Nearshore mud (I) 6.99 0.09 48 55 13 95

Volcanoclastic mud (2) 10.45 0.41 441 83 96 347
Red-brown pelagic clay (3) 6.50 0.67 250 225 74 165
Fe/Mn concretions (4) 15.61 16.17 2,561 4,888 2,987 710
Siliceous ooze (2) 3.33 0.30 394 138 54 171
Deep-sea carbonate (5) 0.90 0.10 30 30 7 35
(I) Wedepohl (1960), (2) Forstner and Stoffes (1981), (3) Chester and Aston (1976), (4) Cronan (1976),
(5) Turekian and Wedepohl (1961)
sediments, whereby vanatlOns in minor elements are governed primarily by

changes in terrigenous supply as well as distance from the source area - by dilution
with silica and carbonates (Price, 1976). Data in Table 82 show that the dilution
effect of the carbonates is significantly greater than that of siliceous material and
strongest for cobalt, iron and nickel. The other clastic component affecting element
contents in deep-sea sediments is the input of volcanoclastic material; also in this
case it is the local lithological composition that plays the greatest role.
Trace elements in deep-sea sediments can be divided into two broad groups accord-
ing to their accumulation patterns (Chester and Aston, 1976):
1. Those which have similar abundances in nearshore muds and deep-sea clays
(e.g. chromium and vanadium) and
2. those which are enriched in Atlantic deep-sea clays relative to nearshore muds
and which are even more enriched in Pacific Fe/Mn concretions (examples are
Mn, Ni, Co, Cu and Pb).
In the following sections we shall discuss the origin of these "excess" trace ele-
ment concentrations. Before doing this a number of methodological aspects will
be treated with respect to the geochemical-analytical differentiation of the various
sources of trace metals in deep-sea sediments. According to their geochemical
source two groups of metal components can be distinguished in pelagic sediments;
one portion - often designated as "lithogenous" - consists of detrital minerals de-
rived from the continents by aeolean or fluvial inputs, but can also contain vol-
canogenic debris, e.g. from the submarine weathering and erosion of exposed
basaltic rocks; the "hydrogenous" fraction, on the other hand, is so named because
of its origin from the water phase, by sorption, precipitation or from diagenetic
reactions. It should be noted, however, that part of these "hydrogenous" metal in-
puts may well have been formed during the transport of particulate matter from
rivers via estuaries to the ocean, i.e. by flocculation and aggregation in the estuar-
ine mixing zone, by deposition of organic and inorganic "coatings" on detrital
grains during all stages of sediment transport, and finally by various processes of
transformation during the settling in the oceanic water body. In addition there is
still confusion about the position of hydrothermal deposits which are increasingly
recognized as characteristic metal accumulations on or near actively spreading

mid-ocean ridges (Francheteau et aI., 1979); their chemical nature seems to be more
related to hydrogenous formations than to lithogenous material (Cronan et aI.,
1982).
There may exist some differences in the stability of these components. The "hy-
drogenous" material is generally more easily affected by chemical changes. How-
ever, caution should be shown when extrapolating the data, e.g., of extraction stud-
ies to a definite distinction of the source of a particular metal accumulation.
Differentiation of "hydrogenous" and "lithogenous" forms of metals in pelagic
sediments by chemical leaching procedures (Chap. 2.6) has been attempted since
the early days of manganese nodules research. Chemical extraction with ethylene-
diamine-tetra acetic acid (EDTA), dilute hydrochloric and acetic acid was used by
Goldberg and Arrhenius (1958) and Arrhenius and Korkish (1959) to determine
the distribution of elements in detrital igneous minerals and authigenic phases
(mainly the oxide minerals and microcrystalline apatite) in pelagic sediments.
Chester and Hughes (1967) introduced a combined acid-reducing agent of 1 M hy-
droxylamine hydrochloride and 25% (v/v) acetic acid for the separation of ferro-
manganese minerals, carbonate minerals and adsorbed trace elements from marine
deposits. The latter technique has been used widely on marine sediment samples,
e.g. from the North Atlantic (Chester and Messiha-Hanna, 1970; Horowitz, 1974;
Horowitz and Cronan, 1976), the North Pacific (Chester and Hughes, 1969) and
the East Pacific (Sayles et aI., 1975). Examples from the North Atlantic show that
the hydrogenous character of trace metals decreases in the order Mn> Co > Cu >
Ni>Cr> V>Fe. It is evident that the supply of V, Cr and Ni is governed largely
by the input of detrital material from the continent. Chester and Messiha-Hanna
(1970) have shown from the geographical distribution of nickel that (i) in areas
close to the continent, 50% of the Ni has a lithogenous origin, (ii) in "intermediate
areas, between 25% and 50% and (iii) in mid-ocean areas> 25% of the Ni is held
in the lithogenous fractions of the sediment. A similar order can be found for the
hydrogenous components in the North Pacific (Chester and Hughes, 1969) al-
though there Mn, Cu and Ni are enriched in the hydrogenous phases. The reason
for this may be that less detrital material has been deposited in these areas, leading
to a general rise in the levels of most metals. Significantly enriched in Mn, Co and
Ni occur in the hydrogenous phases of the sediments from the Bauer Deep in the
East Pacific (Sayles et aI., 1975). The adsorption and incorporation of metals from
seawater in the micronodules or on the Fe and Mn oxide colloids best explain the
element relations for Fe, Mn, Cu, Zn and Ni in the oxide fraction of the sediment.
The correlation between the acid-reducing solubilized elements are significantly
positive for Mn and Fe. The minor metals Cu, Zn and Ni likewise correlate well
with Mn; Co also shows a positive correlation with Mn at the sediment-water in-
terface and under oxidizing conditions (Sayles et aI., 1975). Extraction experiments
by Forstner and Stoffers (1981) using a five step sequence on different types of
Pacific pelagic sediments confirm these findings. Approximately 30% ofthe metals
in the volcanoclastic sediment is associated with the HCI soluble (moderately redu-
cible) fraction. In other sedimentary facies (red-brown clays, siliceous ooze, marly
sediments and nanno-foram ooze), a distinct difference is indicated between the
elements Fe, Cu and Zn on the one hand and Mn, Ni and Co on the other: the for-
Metal Enrichment in Deep-Sea Sediments 275
mer group contains characteristically higher percentages of HCI-soluble as-

sociations (20-40%) compared to the elements in the latter group (5-20%). For
the micronodules the respective percentages of moderately reducible phases are 70-
80% for Fe, Cu and Zn and 20-45% for Mn, Ni and Co. Whereas the percentages
of Ni and Co indicate a significant increase in the easily reducible extractant com-
pared to the HCI treatment for the above-mentioned sedimentary facies, the same
is not valid for the micronodule samples. One possible explanation for this effect
is the mechanism of recrystallization of minerals in the nodule material, which
probably affects a lower leachability of the less acidic, easily reducing agent than
is the case for the amorphous oxides and hydroxides in the red-brown clays,
siliceous and foraminiferous oozes. There is a general decrease of the residual
bonding, i.e. of the acidic leachability, of Cu in all cores investigated and of Mn,
Ni, Zn, Co and Fe in many examples with core depth. This could suggest that dia-
genetic processes affect chemical associations of transition elements subsequent to
deposition.
7.4.3 Metal Enrichment in Deep-Sea Sediments
Elevated concentrations of metals are mainly observed in areas of low sedimenta-

tion rates, i.e. where brown pelagic clays accumulate at less than 1 mm, up to about
2.5 mm per 1000 years. Because iron and manganese tend to be the principal metal
constituents, these deposits have been designated deep-sea iron deposits, ferrugen-
ous sediments or ferromanganese sediments. Several mechanisms have been pro-
posed to explain the formation of iron-manganese deposits (and their constituent
metal enrichments) on the sea floor (Bonatti et aI., 1972; Elderfield, 1976; Chester
and Aston, 1976; Meylan et aI., 1981):
1. hydrogenous - slow precipitation of metals from seawater;
2. diagenetic - remobilization of metals from the underlying sediment column;
3. hydrothermal - transportation of metals out of underlying sediment or base-
ment rock by volcanically heated fluid;
4. halmyrolitic -low temperature leaching of basaltic pyroclastics by seawater.
With regard to the occurrence of hydrogenous metal accumulations (i), there
are two principal non-volcanic theories: the "differential transport" theory (Ture-
kian, 1967), which favours the idea that trace metal enrichment occurs mainly from
river particulate matter, and the "trace element veil" theory (Wedepohl, 1960),
which attributes the observed enrichments to precipitation of a metal-rich hydro-
genous phase from seawater. The latter theory is supported by comparative data
of the manganese/trace element ratios of the hydrogenous fractions of marine sed-
iments with those of manganese nodules (Elderfield, 1972).
Biological transfer of metals seems to play an important role in the accumula-
tion of elements in pelagic sediments. Bostrom et al. (1974) considered some of the
more general implications of simulating the composition of pelagic sediments from
admixtures of various "end-members", such as seawater, the marine biomass (see
Chap. 7.3), continental crust, oceanic crust and active ridge sources. Despite the
obvious limitations of such models, these researchers concluded that the elemental
composition of many deep-sea sediments can largely be described in terms of ad-

mixtures of various proportions of continental crust (shale) and the marine bio-
mass. It should be noted, however, that the biomass-associated trace elements do
not necessarily originate from the same source (Chester and Aston, 1976). For ex-
ample, although the marine biomass incorporates continentally-derived and authi-
genic solids by filter-feeding, plankton can also remove dissolved trace elements di-
rectly from seawater. Therefore, for such elements the marine biomass acts as an
intermediate transport mechanism, whereas the elements themselves have seawater
origin as opposed to a continental one.
The enrichment of metals in deep-sea sediments that may attain exploitable
levels can be due to two main effects (see Gundlach and Marchig, 1981):
(1) Submarine exhalative, i.e. "hydrothermal" formations bound to recent tec-
tonic faulting. The biggest and the only one of economic value is situated in the
Red Sea (rift valley); smaller deposits have been found near the Galapagos Islands
(Galapagos Rise; Corliss et aI., 1979; Edmond, 1980) and the Gulf of California
(East Pacific Rise: Cyamex Scientific Team, 1979; Rise Project Group, 1980). In
each of these cases, sulfides were the original phase precipitated, although they may
have undergone partial oxidation later.
(2) Product of diagenesis and repeated redeposition of siliceous sediments,
mainly of radiolarian oozes. These deposits contain metals as oxides or in silicates.
The more advanced diagenesis is the higher is the content of the autochthonous
group of elements - compounds formed in the same place as they are sedimented
(La and Y in apatite; Cu and Ni in Mn oxide, barite) - compared to the "terrig-
enous" elements, which are fixed in compounds resistant to terrestrial weathering
and in clay minerals, e.g. Pb, Fe, V, AI, Ti and Cr.
7.4.3.1 Diagenetic Metal Enrichment-Manganese Nodules

Diagenetic processes in which Mn oxides - and to a lesser extent Fe-oxyhydrates
- with their associated elements can be dissolved under the effect of minor redox
gradients originate from the decay and oxidation of organic matter (Emerson et
aI., 1980), leading to a manifold increase in Mn, Fe, Cu, Ni and Zn contents in ma-
rine interstitial water (Hartmann and Miiller, 1979; Klinkhammer, 1980).
Data of the pore water distribution of other characteristic metals, copper and
nickel, in pelagic sediment cores are given in Fig. 143 (after Klinkhammer, 1980).
In the upper, oxygenated zone, where N0 3 -concentrations reach a maximum, cop-
per concentrations are higher than in bottom pore water. This Cu-maximum is
maintained by oxidation of labile organics and is estimated to provide approx.
100% of the total flux of dissolved Cu to the deep ocean waters. On the other hand,
since the concentrations of Ni and Mn in the oxygenated zone are essentially the
same as in the bottom water, benthic fluxes of Ni and Mn from these sediments
are insignificant. The Mn oxidation zones lies between 5 and 20 cm; estimates of
Mn and O 2 fluxes to this zone suggest that the flux of O 2 is more than sufficient
to oxidize the upward diffusing manganese.
The strong nickel concentration gradient drives a flux of nickel into the
manganese oxidation zone; the authigenic oxide produced in the Mn oxidation
zone has a NijMn ratio similar to nodules and metalliferrous sediments (see Chap.
NO;,jI! Mn,jlmol/kg Fe,jlmol/kg CU,nmol/kg Nl,nmol/kg
0 20 250 500
0
E
U
II
I
II
II
20 I
...%
II. I
II I I
I
I
I
I I
I
W 40 I I I I I
0 I I I
I
80
Fig.143. Pore water distribution of nitrate, manganese, iron, copper and nickel (Klinkhammer, 1980)
A.
E.
Fig. 144. Fluxes of manganese and copper in northeast equatorial Pacific Ocean (Callender and Bowser,
1980)
7.4). The graphs in Fig. 144 show fluxes of manganese and copper in typical sed-
iments from the northeastern equatorial Pacific Ocean, as estimated by Callender
and Bowser (1980): Manganese is transported to and deposited in pelagic sediment
associated with terrigenous particles, whereas the input of copper is predominantly
regulated by biogenic phases such as organic matter, skeletal calcium carbonate,
or silica. During diagenesis there is a minimal transport of manganese from sedi-
ment to overlying water; dissolution of biogenic materials releases copper, which
is, in part, incorporated into micro nodules actively growing in surficial sediments
and, in part lost to the overlying water column by diffusive transport. The decreas-
ing ratios of manganese nodules to sediment accumulation rates of manganese in
the order of "pelagic clay" < "siliceous pelagic clay" < "siliceous ooze" evidently
represent a gradient of increasing diagenesis from pelagic clay to siliceous ooze.
With regard to the copper data, the most important aspect is that both sediment
accumulation and associated nodule accumulation flux rates are very small in com-
parison to diagenetic flux rates (Callender and Bowser, 1980). Experimental data
of Hartmann (1979) and Pfeiffer et al. (1982) have shown that with weak chemical
reduction, elements such as Mn, Ni and Co were preferentially leached from metal-
liferous sediments and nodules; the same elements revealed a typical deficiency in
yellow coloured zones of red-brown pelagic clay (Hartmann, 1979). The incon-
sistency which shows copper to be present in high concentrations, but barely mo-
bilized by diagenetic reduction has not been completely and satisfactory explained.
According to Ruppert (1980) Cu- and Zn-ferrites possibly occur in or on cells of
planktonic organisms that remain stable after transport to the ocean bottom and
after decomposition of the organic parts. Halbach et al. (1979) found copper and
zinc in Pacific Ocean sediment to be concentrated in small particles « I /lm),
whereas Ni and Mn are generally associated with "micronodules", which can be
considered as the reservoir of metals to be incorporated into the manganese nod-
ules.
The characteristic form in which autochthonous, diagenetic metal accumu-
lations occur is Mn nodules (Cronan, 1976). An estimated 1.5.10 12 tons of
manganese nodules are on the Pacific Ocean floor alone, and they are estimated
to be forming at an annual rate of about 10 6 tons (Mero, 1979). Averaging about
4 cm in diameter, these manganese nodules contain as much as 2.5 percent copper,
2.0 percent nickel, 0.2 percent cobalt and 35 percent manganese respectively. Such
concentrations would be considered high-grade ores if found on land. Because of
the large horizontal extent of the deposits, the nodules are a potential source of
many important industrial metals. (Preliminary work suggests that physical and
smelting methods of separation are not the best and that chemical techniques -
leaching with either hydrogen sulfide or hydrogen chloride and separation in ion-
exchange processes - hold the most promise; cost estimates of such a process are
about 8-15 US Dollars per ton of nodules; Ross, 1978).
Manganese nodules are particularly abundant -locally covering as much as 75
percent or more of the sea floor - in a broad area between about 6° Nand 20° N
extending from approx. 120° W to 160° E in the Pacific Ocean, where the sedimen-
tation rates are lower than in the equatorial zone to the south. The abundance and
spatial density of nodules in the Atlantic Ocean is lower than in the Pacific; rela-
tively high concentrations occur in the areas of clay deposition between the abyssal
plains bordering the continents and the Mid-Atlantic Ridge. An important factor
for the distribution of nodules or incrustations is the rate of accumulation of their
associated sediments. Generally high sedimentation rates are thought to inhibit
nodule growth, perhaps by burying potential nuclei - or even the nodules them-
selves (Cronan, 1976). On the other hand, nodule growth can also be increased by
higher sedimentation rates if these contribute to an increased diagenetic remobil-
ization of manganese, which is followed by an upward migration of this metal and
its reprecipitation at the sediment-water interface, such as has been observed in the
area of Baja California (Cronan and Tooms, 1969).
In the discussion on the origin of the metals in the manganese nodules the
iron:manganese ratio plays an important role (Seibold and Berger, 1982). These
authors have noted that the Mn/Fe ratio is greater in the Pacific than in the Atlan-
tic and that the content of trace elements in Pacific nodules is, on the average,
about twice that of Atlantic ones. The Mn/Fe ratio obviously increases with the
degree of oxidation and with depth. High manganese content appears to be fa-
voured by both high biogenous sediment supply and low rates of accumulation;
under these conditions, presumably, the carrier material dissolves but leaves be-
hind its content of trace elements.
Four major types of nodules can be distinguished (Mero, 1965; Glasby and
Read,1976):
A-type, iron rich nodules found in the South Pacific are thought to have formed
by the preferential depositions of iron from a water mass moving towards Tahiti;
B-type, manganese-rich nodules found mainly in or near the Gulf of California.
These nodules are generally depleted in Cu, Ni and Co probably due to the rapid
formation, which provides insufficient time for the incorporation of trace metals
onto the manganese-rich colloids;
C-type, copper- and nickel-rich nodules found in the central parts of the Pacific
farthest from land and thought to reflect the importance of biological activity par-
ticularly associated with the high-productivity zone of the equatorial divergence;
D-type, cobalt-rich nodules on topographic highs in the central parts of the
Pacific, which are characterized by highly oxidizing environments.
A very strong enrichment of metals in manganese nodules is demonstrated by
Tl, Mo, Co (more than lOO-fold compared with crustal abundances), Ag, Ir, Pb,
Ni, Cu, Bi Wand Cd (30-100-fold enrichment), whereas other elements (e.g. Ca,
AI, Si and Cu) are more or less strongly "diluted" (Table 83; after Cronan, 1976).
The specific enrichment mechanisms have been discussed by Li (1982); using
R-mode factor analysis, most of the elements in abyssal ferromanganese nodules
and associated pelagic sediment would fall in one of the three major phases: "alu-
mino-silicates", "Fe-oxides" or "Mn-oxides".
These data have also been recalculated in terms of enrichment factors (Fig.
145). The enrichment factor, E, is defined here as the average concentration ratio
Table 83. Enrichment of elements in Pacific ferro-manganese concretions relative to crustal abundances
(data from Cronan, 1976)
> 100 50-100 30-50 <1
Element EF Element EF Element EF Element EF
Thallium 287 Silver 86 Copper 47 Chromium 0.14

Molybdenum 275 Iridium 71 Bismuth 47 Silicon 0.31
Manganese 170 Lead 69 Tungsten 40 Aluminium 0.38
Cobalt 119 Nickel 65 Cadmium 40 Calcium 0.61
3~--------------------------------------------------'
Ti
OSe W
• 500
2
--- -- -.- ....
Mn
.Co
-:
NI
•
-
~
·Ag
- - - •- - • - ·Sb
~
- - - - - - -?Ir
?
- - -OBi- -
~O
100
50
.-w« 1
CI
___
BOO P 0 Ti
OV)(
S~_ - - 0 - --0- ~~~N~ _ ~ _ :~"tJ~
Fe 0
In
S~ L~ Nd J ~o Lu
_______
oHg
10._
5 w
«
o
...I M9)( )( Ca Pd)( U Yb )(Au 3
o A A
Si~S~c
A Ga Ba
________________________________________ ~
2
Be AI AK
ANa 0.5
ACr
• Manganese oxide phase
o Iron oxide phase
-1 ... Aluminosillcate 0.1
X More than one phase
- Atomic number .....

Fig. 145. Enrichment factors of elements in the global average ferromanganese nodules relative to the
global average pelagic clays (roughly in increasing order of atomic numbers) (Li, 1982)
of element C i and the normalizing element Al (CdC N ) in ferrromanganese nodules

(world average nodules) compared to this ratio in the associated pelagic sediments
(using the world average pelagic clays as reference material) (Li, 1982). Fig. 145
shows that the E's of Mn, Co, Ni, Cu, Mo and Sb (Mn oxide group); of Fe, Ti,
Zr, Hf, Th, U, P, Y, As, B, S, V, Ge, Nb, Pd, Hg and rare earth elements (Fe oxide
group); and of AI, Si, K and Rb (alumino-silicate group) are similar, confirming
the data of the earlier R-mode factor analysis. (For discussion of several special
developments see Li, 1982).
Some of the characteristics of the enrichment behaviour of trace metals - espe-
cially those of the Mn oxide group elements - can be a result of the various min-
eralogical species ofMn oxides. X-ray diffraction data from a large number of nod-
ules indicate at least two distinct manganese phases; one with a strong 9.7 A line
(10 A manganite; Mn2+ -Mn 4 + -oxide with substituting cations such as Ba, Ca
and Mn; todorokite) and the other with a broad band near 2.44 A (!5-MnO z). The
7.14 A (7 A manganite = birnessite with substitution by Na and Ca) occurs infre-
quently (Cronan, 1976). Structural disorder and degree of oxidation increase from
the 10 A manganite through 7 A manganite to the !5-MnO z.Due to its lower rate
of oxidation, todorokite may be more likely to form in the less oxidizing marine
environments, such as in the continental margin sediments, whereas !5-Mn0 2 is
particularly abundant on the highly oxidized tops of the seamounts. Deep water
pelagic sediment may have intermediate redox potentials and nodules may contain
a mixture of todorokite and !5-Mn0 2 . The findings of Cronan and Tooms (1969)
indicating that Ni and Cu are enriched in nodules rich in todorokite and that those
nodules containing MnO z as their principal mineral phase are enriched in Co and
Pb have been interpreted according to the data of Buser (1959), Goldberg (1961),
Burns (1965), Burns and Fiirstenau (1966), Burns (1976), and Moorby and Cronan
(1981) to imply that divalent manganese in the disordered layer of 10 A manganite
(todorokite) might be replaceable by other ions. These mechanisms lead to a stable
phase containing Ni, Cu, Zn and other divalent ions, whereas the general associ-
ation of Co and Pb with b-Mn0 2 -rich nodules may result from the replacement of
Mn 4 + in b-Mn0 2 by Co3+ and Pb 4 + or their substitution for Fe3+ in the iron ox-
ide phases of the nodules, such as FeOOH. Recently evidence has been given for
a non-hydrogenous origin of some of the manganese crusts. "Hydrothermal
manganese deposits" from the Galapagos Rift (Malahoff et aI., 1982) and from the
south-west Pacific Island Arc (Cronan et aI., 1982) characteristically consist of
well-crystalline birnessite, as well as todorokite (whereas normal hydrogenous
ferromanganese oxide encrustations consist mainly of b-Mn0 2 or amorphous
ferromanganese oxides). Elements Cu, Ni, Co and Zn are generally lower than
their concentrations in hydrogenous Fe/Mn-oxides.
7.4.3.2 Metal Enrichment from Hydrothermal Inputs

Hydrothermal metal transfer processes include both the effects of geothermal heat
sources and chemical interactions (Elderfield, 1976). Although the chemistry of
these processes is unknown there are indications that cold groundwater from the
sea floor is percolating through submarine rift systems (Rona and Lowell, 1981);
the intruding water reacts with hot basalt or ophiolite at temperatures of about
300°C and is released from the sediment in the form of "vents" and "hot springs"
(MacDonald, 1982). During these reactions the seawater composition changes
from slightly alkaline to slightly acidic solutions enriched in sodium, calcium and
chloride (Hekinian et aI., 1980).
Experimental data for seawater-basalt interaction at 300°C and 500 bars from
Seyfried and Bischoff (1981) suggest that it is mainly the removal of magnesium
which generates the acidity for maintaining heavy metals in solution; apparently
seawater chlorinity is not capable of ~nhancing heavy metal solubility by chloride
complexing in the these reactions. According to these authors seafloor heavy-metal
deposits can result from (a) seawater-basalt interaction at moderate temperature
( ~ 300°C) and high effective water/ rock ratios, or (b) at relatively high temper-
atures (~400 0c) and low « 10) water-rock ratios. Hydrothermal metal enrich-
ment of deep-sea sediments may be syngenetic involving settling of exhalative pre-
cipitates, or epigenetic, involving infiltration by hydrothermal fluids, possibly ac-
companied by baking. Syngenetic activity may be focused on hydrothermal vents,
and epigenetic activity may occur primarily at intrusive sills (Meylan et aI., 1981).
Massive ore-grade zinc, copper and iron sulfide deposits - syngenetic for-
mations - have been found at the axis of the East Pacific Rise (Francheteau et aI.,
1979; Spiess et aI., 1980). Hydrothermal vents jet out water at 380 ° ± 30°C; the
hottest waters issue from mineralised chimneys and are blackened by sulfide pre-
cipitates; cooler springs ("Galapogos" -type vents) are clear to milky and support
exotic benthic communities of giant tube worms, clams, and crabs. The black vent
water precipitates consist primarily of pyrrhotite in hexagonal platelets, plus
pyrite, sphalerite and Cu-Fe-sulfides. Mineral and geochemical analysis (Hekinian
et aI., 1980) showed two main types of intimately associated products: a polymetal-
lic sulfide-rich material composed of pyrite and marcasite in association, zinc-rich
phases, and copper-rich compounds, and an iron-rich and hydroxide material com-
posed largely of goethite and limonite. Whereas the polymetallic sulfides are be-
lieved to have been formed by rapid cooling at the sea floor-seawater interface,
many of the hydrous iron oxides observed - forming large portions of the specimen
collected - result from low-temperature alteration of pre-existing sulfide phases.
Silicate phases such as opaline silica, iron-silicon clay, and trace amounts of mica
and zeolite are encountered in both types of autochthonous products. The discov-
ery of these deposits provides a new focus for deep-sea exploration, leading to new
assessments of the concentration of metals in the upper layers of the oceanic rust.
Following the earlier deposition of iron silicates and polymetallic sulfide (Red
Sea, Galapagos Rift) the last phases of a hydrothermal fractionation sequence
seems to be the formation of very Mn-rich deposits poor in Cu, Ni and Co, as was
recognised by Cronan et aI. (1982) in the south-west Pacific Island Arc; it is clear
therefore that in addition to mid-ocean ridges, modem island arcs must also be tar-
gets in future exploration for potentially exploitable submarine massive sulfide de-
posits. Recent data of Edmond et aI. (1982) show that ridge crest hydrothermal ac-
tivity is pervasive and chemically relatively uniform and that the fluxes of the vari-
ous elements injected into (or removed from) the ocean are substantial when com-
pared with fluvial transport. The dispersal of this effluent is controlled by the glo-
bal oceanic circulation at mid-depths. Hotspring organisms that have motile ben-
thic larvae also control the dispersal of elements.
A characteristic example of metal accumulations resulting from geothermal ac-
tivity - the chemistry of the brines is determined by the sediment or rock through
which water percolates - are the Red Sea deposits. Ridge crest accumulations of
the Red Sea were found in 1883 by the British vessel "Discoverer". In some
"deeps" of the central graben, the bottom is filled with a hot salt brine with a tem-
perature of about 60°C and a salinity of25%, seven times that of seawater (Degens
and Ross, 1969). Although the exact formation mechanisms of the Red Sea mineral
deposits is still essentially unknown, Bischoff (1969) has proposed some processes
to explain the different facies in the hot brine (Fig. 146).
Hot, metalliferous solutions may have developed from reactions of seawater
with the freshly formed basalt near the axis of an active spreading center. These
solutions may have percolated through deposits of Tertiary age, containing sever-
al-hundred-meter-thick salt and gypsum layers which abut against the newly
formed sea floor. Metals and salts have been dissolved and issued into the brine
(Seibold and Berger, 1982). These brines are probably composed of metal-chloride
and metal-bisulfide complexes of low Eh and near-neutral pH; part of the metals
precipitate upon cooling or oxidation. In the Red Sea deposits three different facies
are the major carriers of metal accumulations (Bischoff, 1969; Degens and Ross,
1976).
1. Goethite-amorphous jacies, consisting of orange to yellow beds underlying iron-
montmorillonites: Poorly crystalline goethite and amorphous limonite of vary-
ing proportions are the major components. In some areas there is a well-crys-
tallized hematite suggesting a higher temperature, perhaps due to proximity to
a vent.
(
ATLANTIS ]I DEEP SILL
CaS04 PRECIPITATES
PRECIPITATES
(OXIDATION)
~
FeJEFe m Sla020(OH)4nH20 PRECIPITATES

.?
(MIXING) (PARTICAL OXIDATION and COOLING)
,/ ~t + ~
~ Zns PRECIPITATES
COOLING, REALEASE OF
METALS FROM COMPLEXES
/ \.
"
\Ol\,:O
o
~
\, I
.~"'"
1f
~
..
I POINT OF
I BRINE DISCHARGE
II
ZnS and PbS PRECIPITATION
ALONG CRACKS and FISSURES
(COOLlNG,RELEASE OF
METALS FROM COMPLEXES)
~'*'-/
.\ I
° ~
METAL METAL-CI- METAL-HS-,COMPLEXES
LOW Eh,pH NEAR NEUTRAL T > saGc
Fig. 146. Schematic representation of some of the possible processes of mineral precipitation within the
Atlantis II Deep of the Red Sea (Bischoff, 1969)
2. Sulfide facies, a black homogenous unit and generally the deepest unit pen-
etrated. Sphalerite, with lesser amounts of chalcopyrite and pyrite make up this
unit, which is potentially the economically most valuable unit.
3. Manganite facies, containing well-crystallized manganite with occasional to-
dorokite oflocal occurrence.
In the economically most valuable of the Red Sea "deeps", the Atlantis II
Deep, which has an area measuring only 6 x 15 km, the exploitable ore minerals
in the extremely fine grained sediments are mainly sphalerite and chalcopyrite. The
minerals containing the valuable metals zinc, copper and silver can be separated
from the prevailing iron oxides and silicates by flotation methods. Due to the rel-
atively low grade of the ore, transport of the bulk mined material and processing
onshore is not feasible economically; therefore, separation has to be carried out on
bord of the mining vessel and the resulting tailings have to be disposed off nearby
(Lange et aI., 1981). According to calculations from 1980 there are 1.7 million tons
of zinc, 400,000 tons of copper and 4,000 tons of silver, apart from exploitable por-
tions of sulfur and gold. The analytical total value of the Zn, Cu- and Ag-contents
represents an actual market value of approx. 3 billion US dollars (Lange et aI.,
1981). Studies carried out since 1976 to investigate the environmental implications
of the tailings disposal indicate that the adverse effects can be minimised if the ma-
terial is discharged below 800-1000 m water depth (Lange et aI., 1981); with these
procedures the tailings can be kept away from the biologically active coastal areas,
i.e. from the coral reefs and their associated fauna.
7.5 Cycling of Trace Metals Between Continents and Oceans
The processes discussed in the preceding sections show the complex interactions
between geochemical and biological cycles, and their influence on lateral and ver-
tical distributions of trace metals in the world oceans. However, we have not yet
adressed the processes governing the absolute concentrations of metals in the
oceans (Fig. 133).
An order of magnitude estimate of these concentrations can be made by placing
the hydrological cycle in its proper geological context as has been done by Whit-
field and co-workers (Whitfield and Turner, 1979a; Whitfield, 1979; Whitfield,
1981; Martin and Whitfield, 1983). In this content the oceans are part of the four
reservoir geological system (Fig. 147).
The sedimentary material deposited in the oceans is incorporated in the endo-
genic cycle. Here it is compacted and/or subject to metamorphic processes and
forms new continental material (after uplift). The residence time of the elements
on the continents is relatively short and sedimentary material will have been re-
cycled through the oceans ten or a dozen times; sedimentary rocks took on "mod-
em" characteristics implying that also the composition of the ocean has been con-
stant over the same period to the same extent (Garrels and Mackenzie, 1972). So-
lution of the differential equations describing the four reservoir model at steady
state suggest that there is a relationship between the mean oceanic residence time
and the partition function Ky defined as:
K/SW) = Y(concentration in seawater)/Y(concentration in crustal rock)
This partition function describes the efficiency with which seawater extracts ele-
ments from crustal rocks. The relationship is found to hold good for nearly 60 ele-
Crustal rock River water 1---1 Sea water
Sediment
Fig.147. The oceans as part of a four-re-
servoir system (Whitfield, 1981).
Cycling of Trace Metals Between Continents and Oceans 285
1o.-------------------------------------------------------------------------,
CI
•
Na
8
•
Rb,U
• Ca
6
•co •
F. tl.MO
LU,Tm
v• • :~
. / . P Au Sa
.N
EU,Tb E',Vb I Ga C . .'/.Ni' Hg •

~• 41.. -?CO
4 O\ . . . . S, .Sa •
Sc Sn. ·Sb
Pre T~I ......... Zn
La,Nd,Sm - . Gd Ti •
.z.
AI. F.... Pb Cu
./ e .Mn •
·Ce
~L8----------_~6-------------~4-----------~2~------~0~---------~2---------~4
Log Ky (SW)
4.-----------------------------------------------,
'.
2
.
-.........C
N ............
o -.........
R-"""'"
:.M~~
As .U ,
i -2 •
.Sb
lAg
Hg
.Cd
-.........
~
... '-... "-... PI w ·Bi
Ge,Ni .Zn
-.........
-.........
~ '-...... • TI • • V "-...
CI
~U Si Cr "-...
.3 -4 ~
•
·Co : ...... Ta Hf '-......
~n. G~Pb Be ~I Tm,Lu ............
-......... • Nb Mn. E Ybl OY ........
Ti .Zr r, Ho La,Nd,Sm,Eu,Gd
-6 .Fe '-...
.AI
SCI
Y
Tb~pr -.........
-......... Ce.
"-...
'-...... B
-8~----------~------------~----------~----------~
2 4 6
Q yO
Fig. 148. A Correlation between mean oceanic residence time (ry) and the partition coefficient of ele-
ments between crustal rocks and seawater. B Correlation between the electro negativity function (Qyo)
and the partition coefficient (Whitfield, 1981)
ments (Fig. 148 A), providing strong circumstantial evidence for the steady state
ocean (Whitfield, 1981).
For the removal of elements in his model, Whitfield used the approach of
Schindler (1975), which assumes that the initial removal takes place by adsorption
at the surface of oxygen dominated mineral lattices followed by incorporation into
the crystal structure. Elements which bound strongly to the solid phase (e.g. those
which have a high electro negativity function for the element in question and for
oxygen) should therefore have small partition coefficients. In fact such a correla-
tion is indeed observed (Whitfield and Turner, 1979): Fig. 148A, B shows that the
partition coefficients of the elements in the main sequence (e.g. trace metals) are
controlled by their solid state chemistry (Whitfield, 1981). These correlations also
imply a series of simple relationships between the mean oceanic residence time and
the electronegativity function.
With this approach, by taking the electronegativity function and the present
flux of dissolved components discharged into the oceans from the world rivers, it
was possible to calculate a sea water composition that is correct to within an order
of magnitude for more than 40 elements (Fig. 149).
This shows that the composition of the world ocean is controlled by relatively
simple geochemical processes. Furthermore the oceans have been in a steady state
equilibrium with crustal rocks for about 2 billion years. However, for some trace
elements, this equilibrium state is no longer in existence due to large anthropogenic
additions of elements such as lead into the hydrological cycle.
7r-------------------------------------~~
'0 2
~
;;
u
iii
.2
,. 0
1>-•
.2'" -2
-4
-4 -2 o 2 4 6 7
log Ysw (observed)
Fig. 149. The calculated and observed concentrations of elements in the oceans (Whitfield, 1979)
8 Summary and Outlook
In the preceding six chapters an overview of recent developments of trace metal be-
haviour on the earth's surface has been given. Hydrological cycles have been used
as a convenient framework, which enable the various interactions ofbiogeochemi-
cal factors in an integrated system - both natural as well as effected by man's im-
pact to be presented.
In retrospect it seems that the single most important development over the last
decade was the recognition of the manifold problems associated with trace metal
analysis and especially with sampling. The partial solution of these difficulties has
resulted in an increasing number of reliable data on metal concentrations in rivers,
lakes, estuaries, and, in particular, in the world's oceans. In addition, data have
been obtained on metal concentrations in biological materials and increasingly on
metal concentrations in the atmosphere. These basic data are essential for an
understanding of the processes affecting trace metal distribution in the hydrologi-
cal cycle and for elucidating the sources, transport, and fate of man-made dis-
charges of trace metals, as well as the results of other human pertubations on the
natural cycling of trace metals, such as eutrophication, discharge of complexing
agents, and acid rain.
There are still several open questions connected with sampling and analysis,
and in some respect with the interpretation of the data. One major question is stiII
the position of colloidal metal species in water samples. Many difficulties are as-
sociated with the discrimination of dissolved and particulate metal concentrations
by filtration, centrifugation, etc. Moreover it has become evident that total metal
concentrations in surface waters, as they are being measured on a large scale by
several agencies, have at most only a monitoring character and bear little relevance
to the ecotoxicological impact on the aquatic environment.
Both the ecotoxicological impact and geochemical processes are determined by
the physicochemical forms of the metals (speciation). Several approaches are pres-
ently being carried out to study the speciation of metals. Only one class of metals
can be measured directly, e.g. the organo-metal compounds like methyl-mercury
and similar compounds. Several elegant analytical methods have been developed
in this respect. However, for the majority of the heavy metal species in surface
waters, it is necessary to rely on operational defined metal speciation schemes. Sev-
eral are in use. However, a good link with metal speciation in the field and bioac-
cumulation has been reported only in a few cases. A complicating factor in finding
this link is the labile nature of the metal species which causes changes in the spe-
ciation after sampling. In the field of particulate metal speciation the several ap-
proaches have resulted in the proposition of a "recommended" speciation scheme.
However, in the field of dissolved metal speciation a large number of schemes are
in use with different approaches (e.g. ASV, filtration, etc.) and no single scheme
of a more general nature has appeared; undoubtedly in the near future one will
have to reach some kind of mutual agreement on a simple scheme which would
make it possible to compare the results of different investigators.
Speciation is not only important for a study ofbioavailability, in addition it de-
termines geochemical processes as well. The adsorption of metals on model com-
pounds is rather well studied, and the application of the results and approaches to
the "real world" have recently started. Although research and understanding in
this field are increasing, they are hampered by the limited knowledge of the adsorp-
tive species and the exact nature of the surface of the particulates in the water.
Much more research is needed to understand the removal of trace metals from sur-
face waters and their incorporation in the sediments. This also holds true for the
reverse process: the circumstances which cause a remobilization of the trace metals.
The importance of sediments in the aquatic system is now well recognized.
Since sediments, in contrast to the dissolved metals, reflect the condition of the wa-
ter body over longer periods of time, information can be obtained on the current
condition of a water system as well as on the historical development of certain hy-
drological and chemical parameters. Sediment data are playing an important role
within the framework of environmental forensic investigations, particularly in
those cases in which a short-term or past pollution event is not or only insufficient-
ly traceable from water analysis. Furthermore, sediments are increasingly recog-
nized as a pollutant proper and as a carrier and possible source of contaminants
in aquatic systems. Metals temporarily immobilized on the suspended matter and
in bottom sediments of aquatic systems may be released, for example, as a result
of physicochemical changes, such as the lowering of the pH, increased salinity, an
alteration in the redox conditions, and an increased input of organic chela tors. It
seems, therefore, that for effective strategies in pollution control, more attention
has to be paid to the dynamic nature of metal distribution, and, in particular, to
the relative stabilities of the metal pollutants within interim storage sites. It is quite
probable that in the assessment of the availabilities of metals for biological inter-
action, the concept of relative mobility is more relevant than that of accumulation.
The former includes knowledge of the concentrations, the fluxes, as well as the spe-
cies of the metals - both actual and potential- in the environment.
Within the hydrological cycle the atmospheric trace metals playa central role.
They are able to influence all geochemical compartments of the hydrological cycle
on very short time scales. The importance of atmospheric trace metals has been rec-
ognized over the last 10 years, which reflects in the increased research in this field
especially with regard to the association with acid rain. Both pollutants (acidity
and metals) combined have a greater impact on aquatic and terrestrial ecosystems
than either of them alone. Research will have to be carried out on processes at the
interface between atmosphere and surface water to determine the fate of the metal
input from the atmosphere, and, at the interface between atmosphere and vegeta-
tion (e.g. the processes of metal uptake at leaf surfaces). Furthermore acid precip-
itation may enhance metal uptake by vegetation. This is an area in which further
research is necessary.
The great variety in soils in drainage areas of rivers, the variety in industries
and the variability in the hydrological regime of a river make the processes affect-
Summary and Outlook 289
ing metal concentrations in rivers extremely complicated. Often no steady state be-
tween dissolved and particulates exists. Periods of deposition of contaminated sed-
iments are intermittent with periods of high discharge resulting in erosion of the
contaminated sediments. In addition discharges of other chemicals (NT A, chloride
and phosphates) effect metal behaviour in a complicated pattern. The same is true
for lakes fed by rivers. For some lakes the atmosphere may be an important addi-
tional source of metals. In lakes, metal research is still hampered by a lack of good
data. Only recently data have become available, which show a strong link between
the carbon cycle in the lake and trace metal behaviour. In lakes subject to acidic
input and lying in areas devoid of carbonate rocks, the pH decrease causes an in-
crease in metal concentrations. In deep lakes both the links of metals with the car-
bon cycle and with the redox cycle have to be taken into account. The link with
the redox cycle is complicated and needs further research. On the whole, trace
metal behaviour in lakes and rivers appears to be less well studied than trace metal
behaviour in oceans. Further research is strongly needed since lakes are major eco-
logical units and, compared with other ecological units in the hydrological cycle,
more subject to the stress imposed by man.
Intensive research has been carried out over the last decade on the processes
occurring at the interface between the continents and the oceans (e.g. the estuaries).
The nature of the processes has been subject to large shifts in the common census.
Earlier investigations favoured mobilization, later on removal was favoured,
whereas nowadays it is recognised that the processes are highly complicated. In the
same estuary mobilization of one element may occur whilst for other elements re-
moval takes place. Trace metal concentrations are highly influenced by hydro-
dynamic processes, causing mixing of marine and fluvial sediments, and the exis-
tence of turbidity maxima, the latter favouring adsorption processes. Due to com-
bination of chemical and physical processes it has not yet been possible to present
a general theory on the processes affecting both particulate and dissolved metal
concentrations in estuaries. This also makes it difficult to predict the fate of dis-
charges of chemicals in estuaries and in the near shore environment.
The strong impetus on trace metal analysis, resulting in the many new dis-
coveries over the last 10-15 years, has been borne out by studies on the metal be-
haviour in the oceans. A number of good profiles of trace metal concentrations in
both major oceans, the Pacific and the Atlantic, have been obtained, and also data
for arctic areas have been reported. The profiles show a strong link, as in lakes,
with the carbon cycle in the surface waters. The deeper layers show release from
and scavenging by particulates as well as the release from bottom sediments. The
extent of these different processes is element-specific. In remote areas of the oceans,
the atmosphere is a major source of trace metals, isotope analysis oflead even mak-
ing it possible to identify their sources. The further development of theories on the
interactions between particles and metals as well as man's influence on metal con-
centrations in the oceans will continue to form major research areas.
Metal pollution of surface waters, which caused considerable public concern
during the 1970's, seems to have passed its climax in critical cases partly as a result
of recent improvements of waste water treatment, partly as the result of the partial
replacement of metals in several applications, and as a result of the general effects
of the slowdown in industrial activity. However, problems with metal pollutants
still exist both on a local and regional scale: Waters oflarge areas in southern Scan-
dinavia and in eastern North America are severely endangered by the combined
effects of air-borne pollutants and acidity. Increasing quantities of dredged ma-
terials and waste deposits represent long-term reservoirs for the release of metals
possibly involving detrimental effects for the quality of both ground water and ag-
ricultural products.
Since the general objective in pollution control is containment, processes in-
volving dispersion should be restricted. Examples of the latter, which generally
seem to be increasing, include high-temperature emissions from fossil fuel burning,
smelting and from the cement production. Acid precipitation multiplies the effects
of the influences of high temperature emissions on a regional scale. The introduc-
tion of synthetic chelators, such as nitrilotriacetic acid (to replace phosphates in
detergents), elevated salinities (due to salt discharges) and the change of the redox
conditions, all interfere with natural removal processes and may mobilize metals
from the sediments. The knowledge of the chemical interactions of metals in the
hydrological cycle can therefore, in a practical sense, be used to establish counter-
measures against the mobility of metals at critical sites, e.g. predominantly at the
sources of metal release, such as coal-burning power plants, smelters and electro-
plating works; acid mine drainage; at waste dumps, both on land and in the sea;
at sites where sewage sludge is applied as fertilizer; and casually in the water supply
system at enhanced corrosion.
Modelling of the processes affecting trace metals is becoming increasingly im-
portant, however there is still a lack of thermodynamic and kinetic data. Neverthe-
less, modelling is extremely useful in predicting trends under changing environ-
mental conditions.
The environmental impact assessment of trace metals is still subject to intensive
research. Results up to now show that total metal concentrations have only a moni-
toring function and cannot be used to assess their ecotoxicological impact. The
same holds for the classification of sediments by pollution indices. As has already
been stressed sediments are part of a dynamic system. Contaminated sediments in
high pH environments have a different ecotoxicological impact than the same sed-
iments in a low pH environment. Also, in the selection of dumping sites for metal-
contaminated wastes the dynamic approach should be used in contrast to a strict
classification scheme. At present, environmental impact can only be assessed on a
case by case study, and extrapolation of the results from one study area to other
areas should be carried out with extreme caution.
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Subject Index
Abundance principle 83 mineralogy 106 f.

Accumulation 250 Mn/V ratio 129 ff.
Acetic acid 45 f., 274 nucleation 105 ff.
Acid lakes 207 f. nucleus mode 106f.
Acid-mine drainage 58 f., 9 If. oceanic 134 ff.
Acid precipitation 49, 208 f. rainoureffect 105 ff.
Acidic cation exchanger 46 f. sedimentation 109ff.
Active ridge 258,275 f. size distribution 103 ff.
Adsorption washout effect 105ff., 112f.
crystal structure 286 wet removal III f.
definition 25 ff. Aggregation 44,238 f., 267 ff., 273
dissolved complexes 32 f. Aging effects 43
equilibria 37, 176 f., 204 f. Agricultural waste 246
estuarine sediment 234 f. Air bubbles l3lff.
fractional 28 f. Alabandite (Mn-sulfide) 92 f.
humic substances 28 f. Algae
hydrolysis model 25 f. bloom 195
ion exchange model 26 effect of zinc 52 f.
ion-solvent interaction model 25 f. lakes 180
kinetic reactions 27 f., 37 metal uptake 196
lake sediment 20 If. methylation 61
metal oxides 28 ff. release of extracellular material 58 f.
multiligand system 28 f. surface chemistry 36
organic chelators 35 f. Alkalinity 204 f.
organic substances 28 ff. Aluminium
physical effects 44, 192 atmospheric particles 107 f.
reversibility 37 f., 237 Eniwetok atmosphere 136 f.
sediment characteristics 42 oxide 196f.
site energies 32 f. particulate concentrations 139 f.
specifici ty 26 f. particulate, dissolved flux 140
surface complex model 26 f. reference element 73
Advection 238 river water 160
Aerobic transpiration 86 sea surface microlayer 133 f.
Aerosols sediment 149
accumulation mode 106f. soil 149f.
Arctic and Antarctic 124ff.,127f. solubility products 145 f.
coagulation 105 ff., lliff. urban/remote air 114 f.
coarse particle mode 106 f. weathering 144ff.
collision efficiency 112 Alunite 183
condensation 105 ff. Amazon River 138ff., 150, 160, 162,219,232
continental/oceanic 131 ff. Amino acid 23
deposition velocities llOf. Ammonium
diffusional transport 110 f. acetate 40 f.
dry deposition 113 aerosols 104
graphite carbon 127 anoxic sediment 198
humidity 1l0f. pore water 98 f.
interception 110 f. Anadontagrandii 57
334 Subject Index
Anodic stripping voltammetry 13 fT., 96 methylmercury synthesis 60 f.

Antagonism 155 oxidation rate 221 f.
Antarctica 102 response to copper forms 51 f.
Antimony sulfate reduction 58 f., 97
atmospheric emissions 101 f. surface chemistry 36, 52
atmospheric particles 103, 107 f. Baja California 244,279
estuarine mixing 226 f. Baltic Sea 246
half removal time 239 f. Baltimore Harbour 243
sediment 149 Barium
soil 123f.,149f. half removal time 239 f.
urban/remote air 114 f. minerals 143
Apatite 141 natural tracer 218
Aragonite 182 f. precipitation type 6
Arctic 102 rocks 141 f.
Arctic haze 124 sediment 149
Arctic ocean 266 soil 149f.
Argillaceous rocks 148 f. solubility product 145 f.
Arsenic Barrow (Alaska) 126f.
adsorption experimen ts 28 ff. Basalt 281
association with oxides 33 f. Bauer Deep (East Pacific Ocean) 274
atmospheric missions 10 I f. Beaulieu Estuary (U.K.) 221,223
biological cycle 59 f. Bedload 65
complexation 229 Belgium 153
estuarine mixing 226 f. Bellingham Bay (Washington) 94,244
fluvial input (IJsseimeer) 190 Benthic fluxes 96
fluxes (IJsselmeer) 194 Benthic processes 239
half removal time 239f. Bentonite clay 32
lamination nodules 184 Bermuda 101
methylation 60 ff. Beryllium
minerals 143 f. half removal time 239f.
pore water 89 f., 193 f. rocks 141 f.
precipitation type 6 sediment 149
residence time in soil 152 soil 149 f.
river water 160 solubility product 145 f.
sediment 149 Binding capacity 19 f.
core 185 f. Bioamplification 25 I
history 172 f. Bioassay 22 ff., 53
soil 123 f., 149f. Bioavailability 50 ff.
solubility product 145 f. Biochemical oxygen demand (BOD) 89 f.
urban/remote air I 14 f. Biological activity 265,279
Artificial radio nuclides 78 Biological productivity 180
Assimilative capacity 240 Biomagnification 55
Atlantis II Deep (Red Sea) 282 ff. Biomass 196f.,20If.,276f.
Atmospheric fallout 240 f. Biotite 141 f.
Atmospheric input 247 f., 259 f. Bioturbation 58 f., 221 f., 260
Atmospheric particles 103 ff., 109 ff. Birkenes (Southern Norway) 121 f.
Attapulgite 219 Birnessite 183,280
Authigenic components 49 Bismuth, enrichment in nodules 279 f.
Average shale 77 Bisulfide complex 94
Avoca Estuary (Ireland) 81 f. Black Lake (Ontario) 24
Black Sea 93, 199
Bacteria Bodensee = Lake Constance 69f., \76, 182, 197
adsorption of metals 29 f. Bogs 123
anoxic water 202 Bonding strength 45
cultures in bioassay 22 f. Boron
decomposition 147f. minerals 142 f.
lakes 181 na tural tracer 218
Subject Index 335
rocks 141 f. radio tracer 235

solubility product 145 f. ratio to aluminium 227
Botlek (Netherlands) 88 f. release sediment 38
Bristol Channel 251 residence time in soil 152
Bromine retention in coastal zone 256 f.
atmospheric particles 107f. Rhine water 173 f.
urban/remote air 114 f. river particulates 162
Broom effect 223,236 river water 160
Brownian diffusion 133 sea surface micro layer 133 f.
Bubble flotation 133 seaweed 251
sediment 73,149
Cadmium background 77 f.
adsorption 25 f., 27 f., 29 f. core 210f.
algae 192 enrichment factor 80
Atlantic Ocean profile 264 history 712 f.
atmospheric deposition 99 f., 101 f., 118 f., water interface 230
198,263 f. sedimentary flux 189
atmospheric particles 107 f. sewage sludge 158 f.
benthic fluxes 96 shellfish 155
coastal flux 242 f. soil 123f.,149f.
coastal water 245 solid speciation 41 f., 49 f.
complexes 33 f. solubility 6, 145 f.
desorption experiments 39 f. sorption
dissolved species 16 f. experiments 28 f
dredged material 95,158 organic matter 37
Eniwetok atmosphere 136 f. oxides 31 f., 37
enrichment in nodules 279 f. speciation IJsselmeer 193
enrichment phases 49 speciation river sediment 168 ff.
estuarine mixing 225,228, 231,234 speciation urban air 108 f.
fluvial input (IJsselmeer) 190 sulfide complex 93 f.
flux in lake sediment 187 f., 194 f. suspended sediment 176
foliar leaching 119 f. technogenic migration 79 f.
forest ecosystem 121 f. thermodynamic data 9
global fluxes 3 thiosulfate complexes 32
grass shrimp 52 f. toxicity to bacteria 61
half removal time 239f. uptake by clams/shellfish 53, 54
hydroxy carbonate 14 urban/remote air 114 f.
index of geoaccumulation 170 f. voltammetry 14f.
industrial effluents 94 f., 174 Cagliary (Sardinia) 245
input North Sea 248 f. Calcareous ooze 271
ion-selective electrode 22 Calcite 183
kidney 155f. Calcite/dolomite ratio 219
lake sediment 190 Calcium
lake water profile 197 f. aerosols \04
lambs liver 124 competing ions 32
Macoma balthica 56 precipitation type 6
marine aerosol 135 IT. residence time in soil 152
Mytilus edulis 252 solubility product 145 f.
ocean water 263 urban/remote air 114 f.
octavite, CdC0 3 9 California coast 243 f.
Pacific Ocean profile 261 f. CanopyelTect 118 f.
particulate/dissolved flux 140 Carbon
pH-redox effects 94 f. aerosols \07
plants 155 f. redox processes 86
polluted soil 155 ff. Carbonate compensation depth (CCD) 270 IT.
pore water 89 f., 95 f., 193 f. Carbonate, detrital 69
precipitation type 6 isotopic composition 225 f.
336 Subject Index
Carbonate, detrial, minerals 198,274 Rhine water 173 f.

natural tracer 218 river particulates 162
solubility 270 f. ri ver water 160
Carboxilate 24 rocks 141 f.
Carboxylic functional groups 36 sea surface micro layer 133 f.
Cationexchangecapacity(CEC) 150,155,159 sediment 149
Cayuga Basin 159 sediment
Cementation 269 background 77 f.
Centrifugation 12 core 185 f.
CEPEX (controlled ecosystem pollution history 172 f.
experiment) 238 sedimentary flux 189
Cerastoderma edule (bivalve) 252 soil 149f.
Cerium, urban/remote air 114 f. solid speciation 49 f.
Cesium solubility product 145 f.
Eniwetok atmosphere 136 f. speciation Ilsselmeer 193
half removal time 239 f. speciation urban air 108 f.
leaching experiments 40 technologic migration 79 f.
minerals 142 f. voltammetry 14f.
reference element 73 f. urban/remote air 114f.
rocks 141 f. Chronic contamination 251 f.
sediment 149 Clay minerals 69, 150f., 215, 269
soil 149f. natural tracer 218
solubility product 145 f. weathering 144 ff.
urban/remote air 114f. Climate 147f.,152
Chalcopyrite 147,283 Clyde Sea 246
Chapel Hill Lake 24 CfN ratio 224
Charcoal 18 Coagulation 32
Charleston (West Virginia) 107 Coal 102
Chemical defense system 55 Coal ash 242 f.
Chemisorption 25 f. Coal-fired power plants 117
Chesapeake Bay 218,243 Coastal sedimentation 256
China dust 131 Coastal zone model 255 f.
Chloralkali plant 185,244 Coatings 36f., 147, 167,273
Chlorine, urban/remote air 114 f. Cobalt
Chlorinity 24, 52, 216 f., 234 f. association with oxides 33 f.
Chlorite 219 atmospheric input to ocean 263 f.
Chlorocomplexes 32 atmospheric particles 108 f.
Chromite 147 carbonate shells 56
Chromium Eniwetok atmosphere 136 f.
adsorption 28 IT. enrichment in nodules 279 f.
algae 192 estuarine mixing 226 f.
atmospheric emission 101 f., 136f. forest ecosystem 121 f.
atmospheric input to ocean 263 f. half removal time 239 f.
atmospheric particles 107 f. humic acids 37
estuarine mixing 226 f., 234 lacustrine nodules 184
fluvial input (Ilsselmeer) 190 leaching experiment (metalliferous sediment)
fluxes (IJ sselmeer) 194 f. 278f.
forest ecosystem 121 f. M acoma balthica 56
half removal time 239 f. marine sediment 273 f.
hydroxide complex 93 f. minerals 142f.
industrial discharge 174 ocean water 263
input North Sea 248 f. oceanic profiles 265 f.
lake sediment 190 particulate/dissolved flux 140
minerals 142 f. precipitation type 6
ocean water 263 retention in coastal zone 256 f.
pore water 89, 193 f. rocks 141 f.
ratio to aluminium 227 sediment 149
Subject Index 337
sediment enrichment in nodules 279 f.

background 77 f enrichment phase 49
core 21Of. equilibrium calculation 8 f.
enrichment factor 80 estuarine mixing 225 ff., 228-230, 234
history 172 f. fluvial input (Usselmeer) 190
interface 230 fluxes in lakes 187f.,194f.
soil 149f. forest ecosystem 121 f.
solid speciation 208 f. glycinate complex 35
solubility product 145 f. humate complex 37 f., 93 f., 152
speciation urban air 108 f. hydroxylamine extract 231
sulfide 182 index of geoaccumulaton 170 f.
urban/remote air 114 f. input North Sea 248 f.
voltammetry 14f. ion-selective electrode 22
water profile (Black Sea) 199 f. lacustrine nodules 184
Coccolith 215, 269 f. lake sediment 190
Cohesion 64 lake water 20 I f.
Colloids 14,64,98,274 manganese oxide 280 f.
coagulation 32 marine sediment 273 f.
destabilization 32 mass-balance (Gironde Estuary) 255
estuary 221, 229 minerals 142f.
flocculation 234 mobilization by NTA 177 f.
Colonization 250 ocean water 261 f., 263 f., 265f.
Colorado River 159 ore 209
Columbia River estuary 224 particulate/dissolved flux 140
Combustion 244 polycheates 55
Compaction 269 pore water 89 f., 95 f., 276 f.
Competition 237 precipitation type 6
Complexation 18ff.,61, 153, 176f. residence time in soil 152
Complexing capacity 19 f., 2lf., 23 retention in coastal zone 256 f.
Condensation nuclei 103 f., 106 Rhine water 173 f.
Conditional formation constants 20 f. river particulates 162
Congo River 138, 150 river water 160
Conservative elements 75 f. sand filter 96
Consolidation 66,260 sea surface microlayer 133 f.
Continental shelf 265,269 sediment 73, 149
Convection 238 background 77 f.
Copper core 185f.,188f.,210f.
adsorption enrichment factor 80
bacteria 29 f. flux 189
experiments 28 ff. history 172 f.
quartz 26 soil 123f.,149f.
algae 192 solid speciation 4lf., 49 f.
Arctic aerosols 127 solubility product 145 f.
association with oxides 33 f. sorption
Atlantic Ocean profile 264 of NTA-complex 34f.
atmosphere 99 f. on organic matter 37
atmospheric emissions 10 I f. on oxides 37
atmospheric input 102, 198,263 f. speciation Usselmeer 193
benthic fluxes 96 speciation river sediment 169 f.
chelating ability 98 speciation urban air 108 f.
chemical defence system 55 sulfide 182
coastal flux 242 f. technologic migration 79 f.
coastal water 245 toxicity (bacteria) 51 f., 61
complexing capacity 20 uptake by Daphnia 53
dissolved species 16 f. urban/remote air 114 f.
dump leachate 8 voltammetry 14f.
Eniwetok atmosphere 136 f. waste and water 174
338 Subject Index
Copper, water profile, Black Sea 199 f. Electronegativity 26,284 ff.

Bodensee 197 f. Electrostatic interactions 26,33
Coprecipitation 25 f., 44 Elliptio complanata 57
Coral reef 284 Ems River estuary (Germany/Netherlands)
Cornish estuaries 164 73 f., 75, 168 f., 218 f., 247
Corpus Christi Bay 94 f. Endogenic cycle 284
Corrosion 272 Eniwetok Atoll 101, 108, 135 f.
Cosmic spherules 269 Entrainment 222
Coulombic attraction 34 Epigenetic deposit 281
Crustal weathering 10 1 f. Epilimnion 180f., 197,201 f.
Equilibrium calculations 8 f.
Daphnia magna 53 Erosion 68, 138, 221 f.
Dating of sediment cores 79 Esthwaite Water (U.K.) 201
Decomposition 196 Estuary
Decontamination 240 circulation 213ff.
Deep-sea carbonate 273 f. compartment 253 f.
Deep-sea Fe/Mn-nodules 50 dynamic model 253
Deforestation 68 ecosystem 251 ff.
Degradation 260 equilibrium 235
Delaware River estuary 95, 159 flushing time 216 f.
Delta 214 half removal time 239 f.
Denitrification 86, 203 hydrodynamic condition 238
Density variation 199 laboratory studies 233 ff.
Denudation 139 metal balance 232
Deposit feeder 51 metal cycles 254 ff.
Detoxification 53 f., 55 metal mobilization 240
Detritus 269 mixing 216ff., 221
Detroit River 71 f. pollution 240 ff.
Diagenesis 36,39, 86ff., 138, 150, 182, 192f., residence time 238 f.
219,276 suspended matter 221
Dialysis 12f., 2lf., 85 f. types 213f.
Diatoms 78, 215, 269 f. Euphotic zone 266
Differentiated settling 219 Europium, reference element 73 f.
"Differential transport" theory 275 Euxenic sediment 198
Digestive physiology 55 Evaporation 214
Dilute acid 153 Exchanger resin 48
Diorite 141 f. Exogenic cycle 138
Dissolved gases 198 Exposure time 155
Dissolved organic carbon (DOC) 23 f., 89 f., 97 Extraction procedure 48 f.
Dissolved organic matter (DOM) 44
Distribution coefficient 228 Factor analysis 279 f.
Dithionite-citrate buffer 46 f., 48 Fecal pellets 239,265 f., 270 f.
Dolomite 182 f. Feldspar 269
Down-welling 263 Ferrites 278
Dredged material 48,49,68f., 155, 158f., 187, Ferromanganese minerals 274
220,226,229,241 f., 249 f. Filter feeder 51
Dreissena polymorpha 195 f. Filtering particles 238 f.
Dry deposition 109 ff., 204 Filtration 12
DTPA(chelatingagent) 56,58,153 Firth of Clyde 246 f.
Dumping 240f.,247f. Flocculation 44,216,219,273
Flood plains 66 f., 164
East African Rift zone 182, 198 Fluidmud 65
East Pacific Rise 270, 281 Flushing effect 164
Economic recession 116 Fluvialmud 219f.
Eddy diffusion 202 Fluxes 3 f.
EDT A (chelating agent) 22,45,56,58,274 anoxic environment 199 f.
Elbe River estuary (Germany) 75,81,224,247 carbonate in ocean 268 f.
Subject Index 339
dissolved component 286 Hematite (Fe-oxide) 50, 92 f.

dredge spoil 243 Histidine 22
nodule accumulation 278 f. Hornblende 141 f.
organic carbon in ocean 268 f. Hot salt brine 282
particulate/dissolved 140 Hotspring 28lf.
Fly ash 102, 216 Hovvatn (Norway) 208 f.
Foliarleading 117 Hudson River 159,242 f.
Food uptake 52f. Humber River (U.K.) 248
Foraminifera 215,261 Humic acid
Foraminiferous ooze 264 complexes 152
Forensic investigation 63 copper complexation 5 I
Forest fires 99, 103 f. effect on Fe-oxidation 90 f.
Fran90is River (Quebec) 168 flocculation 234 f.
Fucus sp., seaweed 81,252 grain size distribution 69 f.
Fulvic acid 36 f. metal sorption 37 f.
soil 151
Gabbro 141 ff. sorption in seawater 32
Galapagos Islands 276f., 282 Huntite(Mg-carbonate) 182
Ganges River 150 Hydrochloric acid 45 f., 72, 274
Garnet 147 Hydrogen peroxide 41,48
Gases 85 Hydrogen sulfide 97 f., 198
Genesee River 72 Hydrothermal deposits 273 f.
German Bight (Southeastern North Sea) 75, Hydroxylamine buffer 40 f.
246 Hypolimnion 180f., 196,201 f.
Germanium, organic material 152
Geochemical modelling 7 Ichi River (Japan) 156f.
Geographical variability 161 Igneous minerals 274
Gironde Estuary (France) 38,218 f., 240, 254 f. Igneous rock 73, 141 f.
Glacial debris 271 Usselmeer 20,189,205
Glauberite 183 Ussel River (Netherlands) 169 f.
Glauconite (Fe-silicate) 92 f. Illite 219
Glo bigerina ooze 269 f. Ilmenite 147
Goethite (Fe-oxyhydrate) 50,92 f., 183,282 Index
Gold, minerals 143 bioproduction, in ecological risk 83 f.
Grain size 150, 166 f. dissolved transport (DTI) 161 f.
Grand Lake (Ontario) 184 ecological risk 82 ff.
Granite 141 ff. geoaccumulation 80 f., 170 f.
Granodiorite 141 f. pollution load 81 f.
Gravitational settling 133 pollution (0.5 M-HCI) 82
Greigite (Fe-sulfide) 92 f. relative pollution potential 79
Groundwater 158, 173 technophility 79 f.
Growth rate 184 Indium, urban/remote air 114 f.
Gulf of Cadiz (Spain) 245f. Interstitial water = pore water 48,85 f., 176
Gulf of California 276 f., 279 Iodine, urban/remote air I 14 f.
GulfofGenoa 245 Ion-dipole, interaction 25
Gulf of La Spezia (Italy) 245 f. Ion-exchange 25 f.
GulfofMexico 24,218 Ion-exclusion, chromatography 12
Gulf Stream 263 Ion-selective electrode 2 I f., 53
Guyana 66 Ionic potential 145 f.
Gypsum 183 Ionic radius 141 f.
Ionicstrength 19f.,32
Hafnium, radiotracer 240 Iridium, enrichment in nodules 279 f.
Halmyrolisis 275 Iron
Halocline 199 atmospheric particles 107 f.
Halogenated hydrocarbons 78 crusts 146
Hamburg Harbour 8 I dissolved species 16 f.
Heavy minerals 147,218 Eniwetok atmosphere 136f.
340 Subject Index
Iron Lagoon 66
estuarine mlXlng 220 ff., 226, 228, 23 I f., 234 Lake Alpnach (Switzerland) 23 f., 196
fluxes (IJsselmeer) 194 f. Lake Baldegg (Switzerland) 20 I
forest ecosystem 121 f. Lake Bonneville (Nevada) 180
grain size effect 166 f. Lake Erie 71 f., 73, 185 f., 187 f., 189
half removal time 239 f. Lake Geneva 38, 218 f., 240, 254 f.
humic acids 37 Lake Huron 71 f., 189
lacustrine nodules 184 LakeMichigan 71f.,93, 159, 160, 167, 184,
lake water 201 f. 230f.
marine sediment 273 f. Lake Oneida 184
minerals 143 Lake Ontario 24,71 f., 184, 189
organic complex 93 f. Lake Ramsey (Ontario) 208 f.
oxidized layer 97 Lake Superior 71 f.
particulate concentrations 139 f. Lake Wavy (Ontario) 208f.
particulate/dissolved fluxes 140 Lake Windermere (U.K.) 189
pore water 89 f., 95 f., 193 f., 276 f. Lake Zurich (Switzerland) 78
ratio to aluminium 227 Lakes
redox processes 86 atmospheric input 203 ff.
reference element 73 f. current 179
retention in coastal zone 256 f. grain size effects 182
river particulates 162 size 179
river water 160 systems 179 f.
sea surface micro layer 133 f. temperal variation 179 f., 196f.
sediments 72,73, 149 vertical flux 198
background 77 f. Langtjern (Norway) 208 f.
enrichment 80, 93 f. Lead
soil 149f. adsorption experiments 28 ff.
solid speciation 49 f. quartz 26
solubility product 145 f. algae 192
speciation in river sediment 169 f. Atlantic Ocean profile 264
technologic migration 79 f. atmospheric emission 101 f.
urban/remote air I 14 f. atmospheric input 99 f., 103, 118 f., 198,
waste material 72 203 f., 263 f.
weathering 144ff. atmospheric particles 107 f.
Iron oxyhydrate automotive emission 100 f., 117
adsorption edges 28 coastal flux 242 f.
chemical extraction 45 f., 49 ff. dissolved species 16 f.
coatings 43 dry deposition 136 f.
concretions 181 f., 183,235,273 f. Eniwetok atmosphere 136 f.
core profiles 89 ff. enrichment in nodules 279 f.
forms 36f.,48 enrichment phases 49
grain size distribution 69 f. estuarine mixing 225 f., 231
kinetics of transformation 90 f. fluxes, estuary 255
precipitation type 6 lake sediment 187 f.
sorption in seawater 32 forest ecosystem 121 f.
Iron phosphate 216 half removal time 239f.
Irrigation 68 history IOOf.
Isotopic composition 225 humate complexes 152
Isotopic measurements 79 hydroxy carbonate 14
Itai-itai disease 156 f. index of geoaccumulation 170 f.
Jinzu River (Japan) 156 f. input North Sea 248 f.
Jungfrau Mount (Switzerland) 113 f. lake sediment 190
lake water 206
Kansas River 159 lambs liver 124
Kaolinite 147 marine aerosol 135 ff.
Kinetic fractionation 17 methylation 60 ff.
Klebsiella aerogennes (bacteria) 61 minerals 142 ff.
Subject Index 341
ocean water 263, 265 f. residence time in soil 152

Pb-210 isotope 79, 128 f., 254 rocks 141 f.
pore water 95 f. solubility product 145 f.
precipitation type 6 urban/remote air 114 f.
release from sediment 38 Magnetite 147
residence time in soil 152 Main River (W.-Germany) 80,164,171
Rhine water 173 f. Maine (USA) 159
river particula tes 162 Malta 153
river water 160 Manganese
Scrobicularia plana 57 algae 192
sea surface microla yer \3 3 f. atmospheric emissions 10 I f.
sediment 73,149 atmospheric input 118 f., 263 f.
background 77 f. atmospheric particles 107f.
core 188f.,210f. chloride complex 93 f.
enrichment factor 80 crusts 146
flux 189 Eniwetok atmosphere 136 f.
history 172 f. enrichment in nodules 279 f.
smelting 100 f. estuarine mixing 220 ff., 225 f., 228, 231
soil 123f.,149f. Fe-sulfide 95 f.
solid speciation 4lf.,169f. fluxes (IJ sselmeer) 194 f.
solubility product 145 f. foliarleading 119 f.
sorption on organic matter 37 forest ecosystem 121 f.
sorption on oxides 37 half removal time 239 f.
speciation urban air 108 f. humic acids 37
sulfide 93 f., 182 lacustrine nodules 184
technologic migration 79 f. lake water 20 I f.
urban/remote air 114 f. leaching experiments 40, 278 f.
voltammetry 14 f. marine sediment 273 f.
water profile (Bodensee) 197 f. minerals 142f.
Leakage 254 ocean water 263, 265 f.
Ligand 18 ff. oceanic nodules 278 ff.
Ligurian Sea (Italy) 245 f. oxidation rate 221 f.
Lime 209 oxide phases 280 f.
Limonite (Fe-oxyhydrate) 282 oxidized layer 97
Lippe River (W.-Germany) 172 particulate concentrations 139 f.
Lithium particulate, dissolved flux 140
minerals 142f. pore water 89f.,95f.,193f.,237,276f.
sediment 149 precipitation in estuaries 235 f.
solubility product 145 f. precipitation type 6
soil 149f. recycling 223
Littorina 252 red is solution 20 I f.
Liverpool Bay 246 redox processes 86
Loch Fyne (Scotland) 95 relation to Mn-54 40 f.
Lough Neagh (N.-Ireland) 187,189 release from sediment 203,232
Lysocline 272 retention in coastal zone 256 f.
river particulates 162
Maasmond (Netherlands) 88 f. river water 160
Mackinawite (Fe-sulfide) 50,92 f. rocks 141 f.
Macoma balthica (bivalve) 54 f., 251 f. sea surface micro layer 133 f.
Macrofauna 253 sediment 73, 149
Magadiite (Na-silicate) 147 background 77 f.
Magdalena River 150, 169 f. enrichment 93 f.
Mage\a Creek (Australia) 24 profiles 92 f.
Magmatic differentiation 141 f. soil 149 f.
Magnesite 182 solid speciation 49 f., 69 f.
Magnesium chloride, cation exchange 46 f. solubility product 145 f.
competing ions 32 speciation urban air 108 f.
342 Subject Index
Manganese, technologic migration 79 f. atmospheric fallout 187

urban/remote air 114f. average shale 149
voItamrnetry 14 f. background river water 160
waste material 72 basic oxides 48
water profile (Black Sea) 199 f. binding ligand 20
Manganese oxide bioavailability of complexes 53 IT.
chemical extraction 45 f. biological transfer 275
coatings 43 biological uptake (mechanisms) 50 IT.
complexing capacity 22 bisulfide complexes 282
forms 36f. carbonates 145
reduction 86 f. chemical extraction 46 IT.
sorption in seawater 32 chloro-complexes 47
Manganite (Mn-oxide) 280,283 coastal water (Mediterranean Sea) 245 f.
Marcasite (Fe-sulfide) 91 f., 282 deep-sea clay 149
Marine atmosphere 107 IT. diagenetic release 257
Marl 199 dissolved input to sea 256
Maruyama River (Japan) 156 f. distribution coefficient (estuary) 239 f.
Mass-balance for North Sea 246 f. dredged material 173
Mass median diameter (MMD) 107f., 136 enrichment factor 102 f., 247, 274 IT., 279 f.
Meiofauna 253 equilibrium condition 19 f.
Mekong River 150 exchangeable ions 45 f.
Melbourne (Australia) 95 f. fish 204
Melimex experiment 24 flux in lake sediment 189
Mercury flux in New York Bight 242 f.
atmospheric emission 101 f., 103 flux in ocean 263 f.
atmospheric particles 108 f. fluxes in forest floor 119 ff.
biological cycle 59 f. fluxes in salt marsh 253
coastal water 245 free ion 19 f.
estuarine mixing 226 f. freshwater Fe/Mn-nodule 184 f.
fluxes 94, 194 glacier 266
half removed time 239f. heavy minerals 147
index of geoaccumulation 170 f. hydroxides 145
input North Sea 248 f. input to deep-ocean 257
lake sediment 190 kidney 158
methylation 60 IT. lake sediment 183 f.
precipitation type 6 lakes 179 ff.
ratio to aluminium 227 ligand ratio 35
river water 160, 173 f. limestone 149
sediment 73,149 marine sediments 273 f.
background 77 f. mass-balance calculation 173 f., 174f., 194 f.,
core 185f., 188 f. 249f.
enrichment factor 80 mean crust 149
flux 189 mean sediment 149
history 172 f. Mississippi water 160
soil 149f. mobility 82
solubility product 145 f natural flux to sediment 264
sulfide complex 93 f. ocean water 263 f.
technologic migration 79 f. oceanic particulates 266 ff.
urban/remote air 114 f. organic complexes 19 ff.
MERL (marine ecosystem research laboratory) organic solids 184 f.
238 f. particulate transport 249
Metallic waste 252 phosphates 9,184
Metallogenium (bacterium) 60 reactivity in ocean 258 ff.
Metals remobilization 223 f., 244
accumulation in soil 121 removal in estuary 238 f.
aqueous speciation 10 IT. removal from lake water 195
association with humic acids 95 f. residence time in lake water 195
Subject Index 343
retention in coastal zone 254 f., 256 Minnesota lakes 204 f.

Rhine water 160 Minnesota River 12
river fluxes 140 Mississippi River 24, 138ff., 160, 162, 167,214
river input North Sea 248 f. Mobile Bay, Alabama 94
river sediment 164 ff. Molecular sieve 25
river suspension 149 Molecular weight fraction 13
rocks 140 ff. Molybdenum
rural/remote air 114 f. atmospheric emission 10 1 f.
sandstone 149 atmospheric particles 108 f.
sea ice 266 enrichment in nodules 279 f.
seasonal removal in estuaries 239 f. minerals 143
seasonal variability in river particulates 163 organic material 152
sediment core 185f., 187,244 precipitation type 6
sedimentary flux 185 rocks 141 f.
shallow water sediment 149 sediment 149
shipping industry 187 soil 149f.
soil 140ff., 149, 150ff. urban/remote air 114f.
speciation river sediment 167 ff. Monazite 141
sulfides 9,48, 9lf., 98,145 Montmorillonite 38,147,282
suspended matter 192 Mould Bay (Canada) 130 f.
toxic species 22 f., 55, 82 Muscus (coccolittophorid) 268
uptake by Anadonta grandii 57 Mytilus edilus 53
uptake by Elliptio complanata 57
uptake by leaf surface 119 ff. Nanno-foram ooze 274
uptake by Nuphar variegatum 57 Nantucket sound 23
Metals in air Naples (Italy) 245
anomalously enriched elements (AEE) 125 ff. Narragansett Bay, R.1. 95, 133,238
Arctic and Antarctic 125 ff. Natural organic matter (NOM) 197
enrichment factor 101 f. Natural tracer 217 ff., 224, 249
environmental impact I 16ff. Navigation 68
indicator elements 126 ff. Nearshore mud 273 f.
industrial mission 116 NeckarRiver(W.-Germany) 80,I64f.
long-range transport 121 ff. Nepheloid layer 260,267
long-term trends 115 f. Nereis diversicolor (polychaete) 57,251 f.
mobilization factor 101 ff. Neuse River (USA) 159
relative solubility 107, 117 f. New England lakes 207 f.
residence time 99,106 New York bight 218 f., 242f.
seasonal changes 115 f., 126f. Newark Bay (N.Y.) 95
terrestrial ecosystem 117 ff. Newport River estuary N.C. 72,223,253
volcanism 125 f. Niagara River 72
Metamorphic rocks 14lf. Nickel
Methane fermentation 86 algae 192
Methylation 58 f., 60 ff. association with oxides 33 f.
Meuse River 157f., 168f., 195f.,248f. atmospheric input 99 f., 101 f., 263 f.
Microbial degradation 12 a tmospheric particles 108 f.
Microbiota 253 benthic fluxes 96
Microcosm 239 f. coastal water 245
Microenvironment 35 enrichment in nodules 279 f.
Micronodules 274,278 f. estuarine mixing 226 f., 228
Micronutrients 153 Fe-sulfide 95 f.
Mid-Atlantic ridge 278 fluxes (IJsselmeer) 194
Migration 146f. forest ecosystem 121 f.
Minamata Bay 240 f. humic acids 37
Mine waste 164, 168 industrial discharge 174
Mineral deposits 205 input North Sea 248 f.
Mineral exploration 165 lacustrine nodules 184
Mineralization 63,165 lake sediment 190
344 Subject Index
Nickel, manganese oxide 280 f. geologic time 258 f.

marine sediment 273 f., 278 f. hydrogenous material 274 f.
mass-balance estuary 255 hydrothermal input 258, 281 ff.
minerals 142f. labile nutrients 267
ocean water 261 f., 263 f., 265 f. lithogenous material 274 f.
ore 209 particle flux 267 ff.
particulate/dissolved flux 140 redox gradient 276 f.
pore water 89f.,95f.,276f. regeneration cycle 261 f.
precipitation type 6 residence time 284 ff.
ratio to aluminium 227 stirring time 258 ff., 265 f.
remobilization 177 f., 210 wind-mixed layer 261
residence time in soil 152 Offshore deposits 247
retention in coastal zone 256 f. Ogeechee River estuary 230 f., 234
river water 160,190 Olivine 14If.
rocks 141 f. Opaline silica 71, 182, 282
sea surface micro layer 133 f. Ophiolite 281
sediment 149, 177f.,210 Organic complexes 14, 56 f.
background 77 f. Organic debris 270
core 185f. Organic film 39,43
enrichment factor 80 Organic matter 64, 198,224,226
flux 189 early diagenesis 92 ff.
history 172 f. natural tracer 218
soil 123 f., 149 f. ocean 265f.
solubility product 145 f. oxidation 234
sorption on oxides 34 f., 37 soil 154f.
speciation lake sediment 208 f. Organic solvents 46 f., 48
speciation river sediment 169 f. Organic surfaces 36 ff.
speciation urban air 108 f. Organism
technologic migration 79 f. aerobic heterotrophs 86
urban/remote air 114f. benthic 211, 240, 250
voltammetry 14f. bottom-dwelling 251
Nitrate consumers 51
anoxic sediment 198,203 deni trifiers 86
Pacific Ocean profile 261 f. fermentors 86
pore water 276f. filtering capacity 239 f.
reduction 86 generic history 240
Nitricacid 41 growth rate 22 f.
Nitrilotriaceticacid (NTA) 34 f., 51, 176f. indication 250 f., 252 f.
Nitrogen metal uptake 50 ff.
redox process 86 methane bacteria 86
sediment 73 planktonic plant 250
Nodule diameter 278 producers 51
Fe/Mn-ratio 279 relation to sediment 54 f.
growth 278 relation to water depth 239 f.
Nontronite 183 seasonal effect 251
Normalizing element 280 size 251
Norra Barken Lake (Sweden) 83 f. sulfate reducers 86
North Sea 173, 218f., 241, 246ff. test 22f.
Northwest Territories (Canada) 206 Orinoco River 150,169f.
Nucleation 45,93 f. Osaka Bay (Japan) 167
Nuphar variegatum 57 Oswego River (N.Y.) 72
Nutrient 270 Ottawa River 169f.
Oxalate buffer 41
Ocean Oxidation
advection 262 by metallogenium 60
biogenic material 277 potential 6
box-model 260 f. by thiobacillus ferrooxidans 60
SUbject Index 345
Oxygen estuary 230

fluxes in ocean 276 methylation 61
isotope 217 "Piggy-back" mechanism 267 f.
redox processes 86 Pigment 216
Placer deposits 147
Pacific Island Arc 281 f. Plagioclase (feldspar) 141 f.
Pacific Mn-nodules 279 f. Plankton 276
Palaemonetes pugio (grass shrimp) 53 Plant growth 250
Panama Basin 268 Plant root 56
Parana River 150 Plant species 155
Particles Plating industry 174
biogenic 260 Po River (Italy) 245 f.
concentration 2 Polder 157
removal 239 f. Pollen 184
transport 255 f. Pollution
Partition coefficient 285 Mediterranean Sea 245 ff.
Patella 252 U.S. coast 241 ff.
Pelagic organism 211 Western Europe 246 ff.
Pelagic sediment 49,277 f. Polycyclic aromatic hydrocarbons (PAH) 78
Peptides 36 Polyelectrolyte 36
Perch Lake (Ontario) 184 Polymerizlftion 44
Permeability 66 Polysaccharides 61
Pesticides 173 Polysulfide complexes 94
pH Pore water 53, 192 f., 230, 235
adsorption 179,204 f., 234, 235 f., 237 f. Porosity 66
algal bloom 191 Potassium
atmospheric deposition 118 f. sediment 73
carbonate production 192 solubility product 145 f.
chlorinity 235 ff. urban/remote air 114 f.
dredged material 158 Precipitates 6 f., 44, 47
estuary 223 Pseudofaeces 58
lakes 180 f., 199, 206 ff. Psilomelane (Mn-oxide) 183
leaching experiments 47,49 Pteropods 269 f.
microzone 36 Puget Sound (Washington) 244
modification by organisms 58 f. Pumice 269
NTA 179 Pyrite (Fe-sulfide) 50,58,91 f., 93 f., 147, 182,
river water 160 281
seasonal cycle 191 Pyroxene 141 f.
soil 151 f., 154f. Pyrrhotite 281
Phenolic groups 36
Phosphorus Quartz 69,71,141 f., 269
association with oxides 33 f.
atmospheric particles 107f. Radiolaria 269 f.
estuarine mixing 226 f. Radionuclide 216
grain size distribution 69 Radiotracer 18
lakes 182, 184, 194 f. Rare earths minerals 142 f.
minerals 143 Reaction principle 141 f.
ocean profile 261 f. Readsorption 47
oxidized layer 97 Reassociation 257
pore water 89 f., 193 f. Recovery capacity 240
ratio to aluminium 227 Recrystallization 269
sediment 73,149,198 Red brown clay 269 f., 273 f.
core 188 f. Red Sea 276 ff., 282
enrichment 93 f. Redox conversion 58
soil 149f.,154f. Redox potential
Phytoplankton dredged material 158
biochemical cycle 20 I f. lake water 200
346 Subject Index
Redox potential, manganese release 211 Scheidt River estuary 168 f., 218 f., 226,229,
processes 86 ff. 248 f., 252, 254 f.
Redox titration 90 Scrobicularia plana (bivalve) 54,251 f.
Reducible phases 49 ff. Sea surface micro layer 132 ff.
Residence time Searles Lake (California) 180
estuary 212 f., 254 Seasaltspray 99, 103 f., 13 If.
ocean 258 ff., 265 f., 267 f.
soil 152 Seasonal effets
Residual fraction 49 f. estuary 216f.
river transport 138
Resiliency 240
Reverse-phase liquid chromatography 13 Seaweed 251
Reverse weathering 146 f. Sediment
Rhine River 20,69 f., 157 f., 160 f., 163, 168 f., accumulation (estuary) 215
170ff.,179,216f.,246,255 background 76 ff., 82
Rhine River estuary 218f., 223 f., 226 chemical phases 46 ff.
Rhizome 57 compaction 65
Rhodochrosite (Mn-carbonate) 87 ff., 92 ff., 183 composition 63 ff.
Rhone River (France) 40 f., 245 f. concentration factor 83
Rio Grande 167 core profile 73 f., 77, 78 ff., 88 f., 165,209,
Rio de la Plata 218 f. 244,247
River discharge 138 dating 79,102
River pollution 170 ff. distribution 67 ff.
River Qishon (Israel) 246 dynamics 65
Rotterdam Harbour 157 f., 170 f., 173,220,249, early diagenesis 85 ff.
255 effect of NT A 177 f.
Rubidium enrichment (deep-sea) 274 ff.
atmosphere 136 f. environmental impact 79 ff.
minerals 142f. environments 86 f.
reference element 73 f. fluxes in lakes 180
rocks 141 f. grain size 69 ff.
Ruhr River (W.-Germany) 81,171, 174ff., hydraulic conditions 66 f.
177f. marin nearshore 272 f.
mobile fraction 72 f.
oceanic 269 ff.
SaaleRiver(GDR) 159 organic matter 64 f.
Saanich Inlet (B.C.) 22 f., 95 f. pH 204
Saddle River (N. Y.) 166 f. pore waters 85 ff.
Sahara dust 131 release 223
Salicornia 253 residence time 259 f.
Salicylic acid 36 f. transport 65 ff., 173
Salinity 219 f. uptake of metal 234
gradient Black Sea 199 ff.
Sedimentary rocks 148 ff.
metal uptake 57
Sedimentation rate 2,185,272
reference element 73 f.
Segregation 219
sorption 38 f.
Selectivity 20
Sampling 12,165,261 Selenium
San Francisco Bay 38,41,55 f., 229 f. atmospheric emission 101 f.
Sand filter 49 atmospheric particles 108 f.
Sargasso Sea 23 half removal time 239 f.
Saronikos Gulf (Greece) 245f. minerals 143
Savannah River estuary 224,230 organic material 152
Scandium precipitation type 6
Eniwetok atmosphere 136 f. residence time in soil 152
reference element 73 f. sediment 149
sediment 149 soil 149 f.
soil 149 f. urban/remote air 114 f.
urban, remote air 114f. Sepiolite 219
Subject Index 347
Sequential extraction 37,49ff., 107, 167f., kinetic approach IS

208 f., 274 f. river sediment 167 ff.
Severn estuary 251 sea surface micro layer 134
Sewage sludge 49, 158f., 167, 187,216,240, solid matter 44 ff.
242f. Specific surface area 69
Shale 148, 199 Sphalerite (Zn-sulfide) 281,283
Shoreline erosion 187 Spores 184
Siderite (Fe-carbonate) 89 f., 183 Spring tide 232
Siderophores 62 St. Clair River 7 I f.
Siliceous ooze 270 f., 273 f., 277 f. St. Lawrence estuary 139f., 147, 160, 162,213,
Silicon 223,23 I f., 254 f.
association with oxide 33 f. St. Louis (USA) 106 f.
atmospheric particles 107f. Stable isotope 226 f.
lacustrine nodules 184 Standard extraction 168 f.
natural tracer 218 Storage 261
ocean profile 261 f. Storm runoff 164,226
pore water 89 f. Stratified lake 199 f.
sediment 73,149 Stratosphere 99
soil 149f. Strontium
weathering 144f. natural traccer 2 I 8
Silver precipitation type 6
adsorption experiments 28 ff. sediment 149
atmospheric emission 101 f. soil 149f.
atmospheric particles 108 f. solubility product 145 f.
enrichment in nodules 279 f. Submarine exhalative deposit 276 f.
minerals 143f. Sudbury lakes 208 f.
precipitation type 6 Sulfate
sediment 149 aerosols 104
soil 149f. pore water 89 f.
solid speciation 49 f. reduction 86
solubility 145 f. Sulfide 199 f.
Size fractionation I I ff. deposits 281 f.
Skeletal material 262 ore 144f.
Slope 265,269 oxidation 86, 234
Smelting 209,244 sediment 73, 182
Sodium Surface charge 33 ff.
residence time 152 Surface coatings 64
sediment 73 Surface microlayer 189,204
solubility product 145 f. Suspended load 138
urban/remote air I 14 f. Suspended matter
Sodium hydroxide, extraction 48 estuary 214f.,235ff.
Sodium pyrophosphate, extraction 48 non-settling fraction 254
Soil ocean 266 ff.
acid rain 204 residence time 267 f.
erosion 136 f. retention in coastal zone 256 f.
fertility 45 seasonal variation 269 f.
pollution 155 ff. size distribution 257,267
profiles 147 f. transport 70
residence time 152 trapping 254
Solid waste material 44 Susquehanna River 164
Soiling forest (W.-Germany) 117,119ff. Swedish lakes 205
Solubility 8 f., 145 f. Synergism ISS
South Pole 102, 113 f. Syngenetic deposit 281
Southern California basin 95
Speciation Tailings 2 I 6,283
algal toxicity 15 Tamar estuary (U.K.) 212,223
aqueous 9f.,15ff. Tectonic uplift 138
348 Subject Index
Tellurium 143 rocks 141 f.

Terrigenous mud 277 f. sediment 149
Thallium soil 149 f.
enrichment in nodules 279 f. solubility 145 f.
rocks 141 f. Urban atmosphere 107f.
Thames River estuary 161, 246, 248 Urbanization 167
Thermaikos Gulf (Greece) 72 ff. UV -radiation 16, 18,23
Thermocline 261, 270
Thiobacillus ferrooxidans (bacterium) 60 Valence reduction 56
Thorium Vanadium
Eniwetok atmosphere 136 f. atmospheric input 101 f., 103, 126ff., 136f.
half removal time 239 f. atmospheric particles 108f.
reference element 73 f. estuarine mixing 226 f.
removal 238 humate complexes 152
rocks 141 f. marine aerosol 135 f.
Tiber River (Italy) 245 minerals 142f.
Tidal flat 66 organic material 152
Tidal movement 214 f. precipitation type 6
Tin rocks 141 f.
atmospheric emission 101 f. sea surface microlayer 133 f.
atmospheric particles 108 f. sediment 149,189
half removal time 239 f. soil 149f.
methylation 60 IT. solubility 145 f.
minerals 143 urban/remote air 114 f.
rocks 141 f. Van der Waals forces 25 f.
sediment 149 Variability of data 165
soil 149f. Varmslandssjon Lake (Sweden) 83 f.
solubility 145 f. Vegetation 99, 103 f.
voltammetry 14f. Vent (sea floor) 281 f.
Titanite 141 Vivianite (Fe-phosphate) 50,92 f.
Titanium Volcanic eruption 99,103f.
rocks 141 f. Volcanoclastics 269 f., 273 f.
sediment 73 Voltammetric techniques 13 ff., 21 f.
solubility 145 f.
Waalhaven (Netherlands) 88 f.
urban/remote air 114f.
Wadden Sea 230
Titration 19
Walker Branch Watershed (Tenn.) 117 ff.
Todorokite (Mn-oxide) 183,280
Waste disposal 241 f.
Tokyo Bay 167
Water density (estuary) 214f.
"Trace element veil" theory 275
Wave 214
Troposphere 99
Weathering 138, l44ff., 244 f., 273, 276
Tungsten
Weser River estuary (W.-Germany) 75,228 f.,
enrichment in nodules 279 f.
247
minerals 142f.
Windblown dust 99, 103 f.
sediment 149
Witwatersrand (S. Africa) 160
soil 149 f.
Woronora River (Australia, New South Wales)
Turbidity 234f.
95f.
maximum 215 f., 232, 235 f.
Wraymires, Lake District, U.K. 113
Tuscan Coast (Italy) 245 f.
Yamaska River (Quebec) 168
Ultra-centrifugation 221 Yaquine Bay (Oregon) 218
Ultra-filtration 12,221 Yarra River (Australia) 16
Upland disposal 158 YatsushiroSea(Japan) 240f.
Upwelling 259 f., 263, 270 Ystwyth River (Wales) 164
Uranium
minerals 143 Zaire River 169 f.
organic material 152 Zeolite 147
precipitation type 6 Zero point of charge (ZPC) 38
Subject Index 349
Zinc precipitation type 6

algae 52 f., 192 radio tracer 240
Arctic aerosols 127 residence time in soil 152
association with oxides 33 f. retention in coastal zone 256 f.
atmospheric emission 99 f., 10 1 f., 136 f. river particulates 162
atmospheric input 103, 118, 198,203 f., 263 f. river water 160, 173 f.
atmospheric particles 107f. sand filter 96
carbonate 7 sea surface micro layer 133 f.
coastal flux 242 f., 248 f. seasonal cycle 191
coastal water 225 f., 245 sediment 72ff.,149
dissolved species 16 f. background 77 f.
enrichment phases 49 core 185f., 188f., 21Of.
estuarine mixing 225,228,231,253 enrichment factor 80
estuarine water 225 f., 230 flux 189
fluvial input (Usselmeer) 190 history 172 f.
fluxes in lakes 187 f., 194 f. shellfish 57
foliar leaching 119 f. soil 149 f.
forest ecosystem 121 f. solid speciation 49 f., 208 f.
grain size effect 166 f. solubility 6, 145 f.
half removal time 239f. sorption experiments 28 ff., 39 f.
humic acids 37 f. sorption organic matter 37
hydroxide 7 sorption oxide-surfaces 31 f.
hydroxylamine extract 231 speciation sediment 169 f.
index of geoaccumulation 170 f. speciation urban air 108 f.
lacustrine nodules 184 speciation water 193
lake sediment 190,206 f. sulfide 7,95 f.
lake water 199f., 20 If. , 206 suspended matter 233
marine aerosol 135 ff. technologic migration 79 f.
marine sediment 273 f. uptake biogenic carbonates 57
mass-balance estuary 255 urban/remote air 114 f.
minerals 142ff. voltammetry 14f.
mobilization 177 f., 207 waste material 72,174
ocean water 261 f., 263 f. Zircon 141
particulate concentration 139 f. Zoo benthos 180
particulate/dissolved flux 140 Zooplankton 238 f., 265, 266 f.
pore water 96, 276 f. Zuidersee = Usselmeer 170 f.
U. Forstner, G. T. W. Wittmann
Metal Pollution in the

Aquatic Environment
With contributions by F. Prosi, J. H. van Lierde,
Foreword by E. D. Goldberg
2nd revised edition. 1981. 102 figures, 94 tables.
XVIII, 486 pages
ISBN 3-540-10724-X
Contents: Introduction. - Toxic Metals. - Metal Concentra-

tions in River, Lake, and Ocean Waters. - Metal Pollution
Assessment from Sediment Analysis. - Metal Transfer Bet-
ween Solid and Aqueous Phases. - Heavy Metals in Aquatic
Organisms. - Trace Metals in Water Purification Processes.
- Concluding Remarks. - Appendix. - References. - Sub-
ject Index.
The continued demand for Metal Pollution in the Aquatic

Invironment, combined with rapid advances in this field,
have necessitated the preparation of this new edition which
includes coverage of all important developments made since
1978.
From the reviews:

"This is an impressive and useful compilation of a large
amount of data on heavy metals in the natural environment.
The book contains nearly 500 pages and 70 of these are
taken up by the references, of which the majority were pub-
lished in the last ten years. I found the book lucidly
written and on the whole easily readable ...
In conclusion this is a very valuable book that has been well
produced. It will be, as I expect, consulted regularly by
many scientists interested in the contamination of the natu-
ral environment by metals ... " Hydrobi%gia
" ... the authors present what is probably the first successful
compilation on a world-wide basis, including a critical
inventory and evaluation of the prevailing investigations in
water, sediments and organisms ....
Springer-Verlag The book contains an extensive list of references (ca. 2000),
is well written in a lively and critical style ....
Berlin ... the book is more than a necessary inventory; it should
Heidelbeg stimulate further research and be helpful in solving prob-
New York lems. I highly recommend this book to everyone involved in
aquatic trace metal research, whether biologist, chemist or
Tokyo geologist." Marine Chemistry
S.A.Gerlach
Marine Pollution
Diagnosis and Therapy
Translated from the German by R. Youngblood,

S. Messele-Wieser
1981. 91 figures. VIII, 218 pages
ISBN 3-540-10940-4
Contents: Introduction. - Domestic Effiuents. - In-

dustrial Effiuents. - Pollution of the Sea by Ships. -
Oil Pollution. - Radioactivity. - General Problems of
Harmful Substances in the Sea. - Global Contamina-
tion of the Oceans by Heavy Metals. - Global Pollu-
tion of the Oceans with Chlorinated Hydrocarbons. -
Laws Against the Pollution of the Oceans. - Diagnosis
and Therapy. - References. - Subject Index.
The increasing awareness of marine pollution on the

part of the scientific community and the public at
large has brought with it the need for a reliable over-
view of the problems involved. In an effort to meet
this need, the author of this book has combined his
own vast experience as a marine biologist with a criti-
cal evaluation of the ever-increasing literature in a
work which highlights those long-term effects and
dangerous materials most threatening on a global
scale.
Wide-ranging in scope, Marine Pollution covers

household and industrial wastes, ocean dumping, the
effects of oil and radioactivity, the influence of toxic
materials on geochemical and biochemical processes,
and the dangers of wide-spread pollution by heavy
metals and organic substances. This English transla-
Springer-Verlag tion of the highly acclaimed German original has been
Berlin revised and expanded to keep pace with the rapid
Heidelberg process of research in the field. A particularly large
number of changes were made in the chapter on oil
New York pollution, and new chapters on waste heat and
Tokyo radioactivity in the ocean have been added.

Metals in The Hydro Cycle

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Metals in The Hydro Cycle

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wim.salomons@home.

With 149 Figures

Delft Hydraulics Laboratory

Professor Dr. ULRICH FORSTNER

ISBN-13: 978-3-642-69327-4 e-1SBN-13: 978-3-642-69325-0

Metals in the hydrological cycle represent a very broad subject

2 Interactions with Ligands, Particulate Matter and Organisms

3 Sediments and the Transport of Metals

3.7 Early Diagenesis of Trace Metal Compounds in Sediments 85

4 Metals in the Atmosphere

5 Metals in Continental Waters

5.1 Introduction . . . . . . . . . . . . 138

5.3.2 Dissolved and Solid Transport. 161

6 Metals in Estuaries and Coastal Environments

6.1 Introduction . . . . . . . . . . . . . . 212

7 Metals in the Ocean

7.1 Introduction . . . 258

7.4 Composition of Oceanic Sediments 269

8 Summary and Qutlook 287

Subject Index 333

Fig. I. Movement of trace metals

Advective velocity (cm/sec)

Fig. 3. Particulate concentrations in the hydrological cycle. (Kranck, 1980)

o Fluxes 103 to/Jahr

2.2 Metal Ions in Aquatic Systems

Table 1. A Calculated speciation of metals in model seawater at pH 8.2. B Calculated speciation of

A Model seawater pH 8.2

* = Indicates calculated abundance < 1%

An example of a modelling approach for the prediction of dissolved copper

10-2'---'--'--'--............-'--'--'--'--'--'--' pH 8 . K. va luf! of CuD 1 - 19.9 [no !:quilibrium with atmosphere)

- analytical techniques of separating dissolved organic compounds in classes,

2.3 Speciation of Dissolved Metals

'0 IS SOL VE O' 0.4 51' 'PARTICULATE'

SPECIATION -------I -a1fec¥ve --1

2.3.1 Physical Separation

Method Range References

Filtration 0.015-12 ~lm Van den Meent et al. (1982)

Fig. 9. The distribution of iron, cop-

2.3.2 ASV -Labile Species

is proportional to the concentrations in the original solution. Metals which can be

ELECTROCHEMICALL Y ACTIVE ELECTROCHEMICALL Y INACTIVE

LABILE NON - LABILE

ORGANIC COMPLEXES ----+---..,.·ORGANIC COMPLEXES

By chemical treatment of the solution, e.g. lowering of the pH and destruction

2.3.3 Ion-Exchange Methods

2.3.4 Speciation Schemes

1 Acidify 1 Acidify 1 Add Chelex 1 Dialyse

TOT. SOLUBLE TM'S

B ASVor very labile traction ~ Slowly labile traction

CD Very + moderately labile tractions • Inert traction

A kinetic fractionation scheme has been developed by Figura and McDuffie

2.4 Interaction with Ligands

Where L t is the total concentration of ligand capable of binding M and is equal

Generally L t is referred to as the metal complexing capacity. To calculate the con-

ow.~~~~ ______ ~ ______ ~

o 20 40 60 1.1 1.2 1.3 14 15 t6

Substitution of equation 5 in 4 gives a Langmuir adsorption isotherm:

x= [ML] =(BC. *K. [Mn+])j(l +*K[Mn+]) (6)

not require preconcentration that may disturb the natural equilibrium

Method Description References

Water Complexing Conditional Method and References

variations apparently reflect the differences in molecular structure of the organic

2.5 Interaction with Particulate Matter

ow.~~~~ ~ ~

x= [ML] =(BC. K. [Mn+])j(l +K[Mn+]) (6)