Table Of ContentU. Forstner· G.T.w. Wittmann
Metal Pollution in the
Aquatic Environment
With Contributions by
F. Prosi and J. H. van Lierde
Foreword by Edward D. Goldberg
With 102 Figures and 94 Tables
Springer-Verlag
Berlin Heidelberg New York 1979
Professor Dr. ULRICH FORSTNER
Institut fUr Sedimentforschung
UniversiUit Heidelberg
1m Neuenheimer Fe1d 236
6900 Heidelberg IjFRG
Dr. GOTTFRIED T. W. WITTMANN
Department of Chemistry
University of Pretoria
Pretoria 0002jSouth Africa
ISBN-13: 978-3-642-96513-5 e-ISBN-13: 978-3-642-96511-1
DOl: 10.1007/978-3-642-96511-1
Library of Congress Cataloging in Publication Data. Forstner, Ulrich. Metal pollution
in the aquatic environment. Bibliography: p. Includes index. 1. Heavy metals
Environmental aspects. 2. Water - Pollution. I. Wittmann, Gottfried, 1929-. joint author.
II. Title. TD427.H45F62.553'.7. 79-11122.
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© by Springer-Verlag Berlin Heidelberg 1979
Softcover reprint of the hardcover I st edition 1979
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Cover design: Dietrich Bogumil, Weinheim.
Foreword
Aquatic chemistry is becoming both a rewarding and substantial area of
inquiry and is drawing many prominent scientists to its fold. Its literature
has changed from a compilation of compositional tables to studies of the
chemical reactions occurring within the aquatic environments. But more
than this is the recognition that human society in part is determining the
nature of aquatic systems. Since rivers deliver to the world ocean most of
its dissolved and particulate components, the interactions of these two sets
of waters determine the vitality of our coastal waters. This significant vol
ume provides not only an introduction to the dynamics of aquatic chem
istries but also identifies those materials that jeopardize the resources of
both the marine and fluvial domains. Its very title provides its emphasis
but clearly not its breadth in considering natural processes.
The book will be of great value to those environmental scientists who
are dedicated to keeping the resources of the hydrosphere renewable. As
the size of the world population becomes larger in the near future and as
the uses of materials and energy show parallel increases, the rivers and
oceans must be considered as a resource to accept some of the wastes of
society. The ability of these waters and the sediments below them to
accommodate wastes must be assessed continually.
The key questions relate to the capacities of aqueous systems to carry
one or more pollutants. These may be based upon impacts on public health,
the communities of organisms, navigation, recreation, aesthetics, or econ
omics of aquatic environments. Of concern is the amount of material that
the water body can carry before the impact becomes unacceptable. The
amount, essentially determined by a titration of the pollutant with the
water body, becomes evident at an endpoint. One of the goals of environ
mental managers is the identification of these endpoints.
Perhaps the most extensive set of endpoints evolves from the entries
of radionuclides into the oceans from facilities of the nuclear fuel cycle.
Human health is to be protected from the consumption of artificial radio
activities in fish, shellfish, or edible ~lgae or through exposure to radiation
on beaches. The acceptable amounts of radionuclides in natural waters are
related to potential damage to the human body from exposure to ionizing
radiation. The endpoints are found in the levels in organisms or beach solids.
Sometimes a catastrophe initiates a concern about a pollutant. The
Minimata Bay episode identified methyl mercury as a contaminant in the
marine system which could endanger human health. Endpoints for this
material are found in methyl mercury levels of commercial fish.
VI Foreword
The impact of DDT, a biocide, upon nontarget organisms, such as fish
eating birds, could have provided endpoints for its entry into natural waters.
Its ingestion results in egg-shell thinning, and populations decline as a result
of reproductive failures in the birds. Either of these phenomena might
have been translated into an endpoint.
In this volume we have background information for managing our
environment. Whether we seek endpoints for metal pollutant loads or merely
understanding of natural phenomena, the relevant concepts are to be
found herein.
Edward D. Goldberg
Scripps Institution of Oceanography
Preface
This work represents an attempt by the authors to compile and evaluate
the present state of affairs with regard to heavy metal pollution in streams,
lakes and near-shore marine areas. The considerable interest in, and appre
hension about the role and fate of heavy metals in aquatic systems, as dis
played by scientists and authoritative bodies, is warranted on the grounds of
several disasters which are related to mercury and cadmium poisoning. How
ever, in order to determine the degree of heavy metal enrichment it is essen
tial to establish suitable norms and criteria.
In their book, Schwermetalle in Flilssen und Seen als Ausdruck der
Umweltverschmutzung (Springer-Verlag Berlin/Heidelberg/New York,
1974), Ulrich Forstner and German MUller adopted a geochemical and
sedimentological approach for assessing heavy metal pollution in aquatic
systems. The practice of separating the chemically active fine-grained sediment
fraction and subsequent analysis of the metal content thereof has proved
to serve as a reliable pollution indicator. Further basic research as well as
the interest displayed by colleagues in the above mentioned book, and in
several papers published by the present authors, both jointly and individually,
have been incentives to compile this work.
Although an evalutation of different analytical techniques-especially
in connection with water analysis-lies beyond the scope of this study, we
hope to have stimulated further research relating to heavy metal pollution.
In particular, attention is drawn to hitherto unresolved problems-such as
those associated with chemical speciation, the availability and toxicolog
ical properties of different species, the uptake mechanisms of metals by
organisms, and the remobilization of heavy metals from sediments.
We wish to record our appreciation for such special information which
was graciously made available to us by unnamed colleagues and which
would otherwise have been well-nigh unobtainable. In particular, we are
specially indebted to Dr. Prosi for the chapter on bio-accumulation of metals
and for the assistance of Mr. J. H. van Lierde on the subject of water purifi
cation. We further gratefully acknowledge the support of those colleagues
with whom we have had fruitful discussions and who have been ofinvalu-
able assistance to us, especially the efforts of Professor German MUller,
Bernhard Schaule and Dr. S. R. Patchineelam. Both latter colleagues, as well as
Dr. I. Thornton (Imperial College, London) and Dr. U. Schottler (Dortmund)
kindly also gave access to some of their unpublished information. Further
more, our appreciation includes the contributions of J. Broadbridge,
VIII Preface
S. Knapton, and D. Godfrey for typing and translation assistance as well as
of U. Kastner for his technical drawings.
Finally, we gratefully acknowledge the continued financial support of
our research projects by various organizations, in particular the German
Research Society, the Universities of Reidelberg and Pretoria and the South
African Water Research Commission.
Rei del berg/Pretoria U. Forstner
May, 1979 G. T. W. Wittmann
Contents
Chapter A
Introduction
Aquatic Ecosystems .............................. .
2 Pollutants in Water ............................... .
Chapter B
Toxic Metals (G. Wittmann) 3
Metals ........................................ 3
1.1 Classification of the Elements 3
1.2 Classification of Metals .......................... 6
1.3 Trace Metal Species in Aquatic Systems ............... 7
2 Trace Metals and Organic Life ......................... 8
2.1 Trace Elements Essential to Human Life .............. 9
2.2 Deficiency and Oversupply ....................... 11
2.3 Metal Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
2.4 Health Hazard Due to Certain Trace Elements .. . . . . . . . .. 14
2.5 Accumulation of Toxic Substances in the Aquatic Food
Chain ..................................... 17
2.6 Catastrophic Episodes of Metal Poisonings ............. 18
2.6.1 Mercury Poisoning .. . . . . . . . . . . . . . . . . . . . . . .. 18
2.6.2 Cadmium POisoning ........................ 21
2.6.3 Lead Poisoning ........................... 23
2.6.4 Copper POisoning. . . . . . . . . . . . . . . . . . . . . . . . .. 24
2.6.5 Chromium POisoning ....................... 25
3 Water Quality Criteria: Standards ...................... 26
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 26
3.2 Criteria Development ........................... 26
3.3 Water Quality Criteria . . . . . . . . . . . . . . . . . . . . . . . . . .. 29
4 The Sources of Metal Pollution. . . . . . . . . . . . . . . . . . . . . . .. 30
4.1 Geologic Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31
4.2 Mining Effluents .............................. 33
4.3 Industrial Effluents ............................ 38
x
Contents
4.4 Domestic Effluents and Urban Stormwater Runoff ....... 43
4.4.1 Domestic Effluents ........................ 43
4.4.2 Urban Storm Water Runoff ................... 44
4.4.3 Spoil Heaps ............................. 47
4.5 Metal Inputs from Rural Areas ..................... 48
4.6 Atmospheric Sources ........................... 49
4.7 Special Sources ............................... 55
4.8 Multi-Source Effects . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
5 Metal Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
5.1 Media of Pollution Assessment ..................... 62
5.2 Sampling and Analytic Methods .................... 68
5.2.1 Sampling ............................... 68
5.2.2 Analytic Methods ......................... 68
ChapterC
Metal Concentrations in River, Lake, and Ocean Waters (U. Forstner) 71
Distribution of Major Ions . . . . . . . . . . . . . . . . . . . . . . . . . .. 71
1.1 Natural Salt Concentrations . . . . . . . . . . . . . . . . . . . . . .. 71
1.2 Man-Made Contamination ........................ 73
2 Chemical Conditions for Trace Metals in Natural Waters ....... 73
2.1 Chc.mical Speciation in Freshwater and Seawater ......... 75
2.1.1 Analysis of Trace Metal Speciation .............. 75
2.1.2 Freshwater/Seawater Model . . . . . . . . . . . . . . . . . .. 78
2.2 Redox Conditions in Natural Waters ................. 79
3 Trace Metals in Seawater . . . . . . . . . . . . . . . . . . . . . . . . . . .. 82
3.1 Natural Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . .. 83
3.2 Man-Made Effects ............................. 86
3.2.1 Atmospheric Input of Metals .................. 88
3.2.2 Metal Input from Sewage Effluents .............. 89
4 Trace Metals in Inland Waters . . . . . . . . . . . . . . . . . . . . . . . .. 90
4.1 Natural Contents .............................. 90
4.2 Metal Pollution in River Water: Regional Examples ....... 93
4.2.1 Heavy Metal Pollution in United States Water Systems. 93
4.2.2 Metal Pollution in Inland and Coastal Waters of
Great Britain ........................... " 96
4.2.3 Heavy Metals in River Water of the Federal Republic
of Germany ............................. 98
4.2.4 Heavy Metals in River Water of the U.S.S.R. ....... 102
4.2.5 Heavy Metals in Waters of Japan . . . . . . . . . . . . . . .. 104
4.3 Metal Transport in Freshwater Systems ............... 104
4.3.1 Water Discharge and Metal Transport ............. 104
4.3.2 Annual Cycles of Metal Transport ............. " 107
Contents XI
Chapter D
Metal Pollution Assessment from Sediment Analysis (U. Forstner) 110
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 110
1.1 Soluble/Solid Equilibrium ........................ 110
1.2 Surface Samples and Sediment Cores . . . . . . . . . . . . . . . .. 112
2 Metal Investigations on Aquatic Sediments ................ 113
2.1 Sampling and Storage ........................... 114
2.1.1 Soils and Se dimen ts ........................ 114
2.1.2 Grab and Sore Samplers ..................... 114
2.1.3 Bottom Sediment Traps ..................... 115
2.1.4 Suspended Materials . . . . . . . . . . . . . . . . . . . . . . .. 115
2.1.5 Recovery of Pore Waters ..................... 115
2.1.6Storage ................................ 115
2.2 The Mechanical Sediment Analysis .................. 116
2.3 Mineralogical Analysis .......................... 116
2.4 Chemical Analysis of Nutrient Components (C-N-P) 117
2.4.1 Determinations of Oxidizable Matter (Organic
Carbon) by the Chromic Acid Method . . . . . . . . . . .. 117
2.4.2 Determination of Kjeldahl Nitrogen ............. 117
2.4.3 Determination of Total Phosphorus . . . . . . . . . . . . .. 117
2.5 Sediment Digestion in Metal Analysis ................ 118
2.5.1 Hydrofluoric Acid Decomposition .............. 118
2.5.2 Hydrochloric-Nitric Acid (Aqua Regia)
Decomposition or Digestion by Nitric Acid . . . . . . . .. 118
2.5.3 Lithium Metaborate Fusion (with Simultaneous
Determination of Silica) ..................... 118
2.5.4 Transfer of Solid Suspensions into Graphite
Cuvettes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 118
3 Geochemical Reconnaissance of Aquatic Sediments .......... 119
4 Grain-Size Effects ................................ 121
4.1 Grain-Size Dependencies of Trace Metal Concentrations .... 122
4.2 Reduction of Grain-Size Effects .................... 124
4.2.1 Extrapolation from Grain-Size Distribution ........ 124
4.2.2 Metal Concentrations vs Surface Area ............ 126
4.2.3 Separation of Clay/Silt and Fine Sand Fractions by
Sieving . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 126
«
4.2.4 Separation of the Pelitic Fraction 2 11m) in Settling
Tubes ................................. 127
4.2.5 Treatment with Dilute Acids (Hydrochloric Acid,
Nitric Acid) ............................. 128
4.2.6 Mineral Separation: Quartz Correction Method ...... 128
4.2.7 Comparison with "Conservative" Elements ......... 129
4.2.8 The Relative Atomic Variations of Elements ........ 130
5 Factors Controlling the Distribution of Metals in Aquatic
Sediments ..................................... 131
