elements and their compounds in the environment occurence analysis and biological relevance

Elements and Their Compounds
in the Environment
Edited by
E. Merian (†), M. Anke, M. Ihnat and
M. Stoeppler

Elements and their Compounds in the Environment. 2nd Edition.
Edited by E. Merian, M. Anke, M. Ihnat, M. Stoeppler
Copyright  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30459-2


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Elements and Their Compounds
in the Environment
Occurrence, Analysis and Biological Relevance
2nd, completely revised and enlarged edition

Edited by
E. Merian (†), M. Anke, M. Ihnat and M. Stoeppler


Editors:
Manfred Anke
Am Steiger 12
07743 Jena
Germany
Milan Ihnat
Pacific Agri-Food Research Centre
Agriculture and Agri-Food Canada
Summerland, BC V0H IZ0
Canada

Markus Stoeppler
Mariengartenstrasse 1a,
52428 Jülich
Germany

This book was carefully produced. Nevertheless,
editors, authors and publisher do not warrant the
information contained therein to be free of
errors. Readers are advised to keep in mind that
statements, data illustrations, procedural details
or other items may inadvertently be inaccurate.
Library of Congress Card No: applied for
British Library Cataloging-in-Publication Data:
A catalogue record for this book is available from
the British Library.
Bibliographic information published by
Die Deutsche Bibliothek
Die Deutsche Bibliothek lists this publication
in the Deutsche Nationalbibliografie; detailed
bibliographic data is available in the Internet at
<>.

 2004 WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim
All rights reserved (including those of translation
into other languages). No part of this book may
be reproducted in any form – by photoprinting,
microfilm, or any other means – nor transmitted
or translated into machine language without
written permission from the publishers. Registered names, trademarks, etc. used in this book,

even when not specifically marked as such, are
not to be considered unprotected by law.
Printed in the Federal Republic of Germany
Printed on acid-free paper.
Composition, Printing and Bookbinding:
Konrad Triltsch,
Print und digitale Medien GmbH
Ochsenfurt-Hohestadt
ISBN

3-527-30459-2


XXXI

Editorial Board
Prof. Dr. Dr. Marika Geldmacher
von Mallinckrodt
Schlehenstraße 29
91056 Erlangen
Germany

Prof. Dr. med. H. W. Schlipköter
Auf’m Hennekamp 50
40225 Düsseldorf
Germany

Prof. Dr. Robert F. M. Herber
Tollenslaan 16
03723 DH Bilthoven

The Netherlands

Dr. Mathias Seifert
Hauptverband der gewerbl.
Berufsgenossenschaft BGAG
Kưnigsbrücker Landstre 2
01109 Dresden
Germany

B.Sc. Peter J. Jenks
Newhaven House
Junction Road
Alderbury
Wiltshire SP5 3AZ
United Kingdom

Dr. F. William Sunderman, Jr
270 Barnes Road
Whiting, VT 05778-4411
USA

Elements and their Compounds in the Environment. 2nd Edition.
Edited by E. Merian, M. Anke, M. Ihnat, M. Stoeppler
Copyright  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30459-2


V

Preface

This book is the third in an unique line of
handbooks, initiated in the early 1980s by
Ernest Merian in cooperation with several
of his colleagues leading in 1984 to a first
book – Metalle in der Umwelt – published
by Verlag Chemie. The design of the book,
which became fondly known as the
’MERIAN’, was from the beginning highly
appreciated for its clear organization excellently and interdisciplinary covering the
broad range from general information,
basic elemental data, industrial uses, environmental distribution to biological and
medicinal aspects. Since many readers
from various scientific branches could benefit from it, an updated and extended English
edition titled Metals and Their Compounds
in the Environment followed relatively
quickly in 1991. It was not unexpected that
this edition sold very well over many years
until it went out-of-print in 2001.
Ernest Merian passed away in 1995 at the
age of 75 while traveling to one of his many
scientific conferences, but already realized
at that time the great success and admiration his work and particularly the voluminous English edition had received worldwide. The book is frequently quoted in the
literature as it has been accepted as a
major multielement source handbook.
Progress, in the intervening years, in
many scientific areas called for an update

rather than a simple reprint of the book
and the publisher was seeking for someone
or some group who that might be willing to

produce a new edition. Dr. Steffen Pauly, in
charge of the section of WILEY-VCH
responsible for a possible update of the
‘MERIAN’, participated in April 1997 in
the 7th International Symposium on Biological and Environmental Reference Materials
(BERM-7) in Antwerp, Belgium. BERM-7
was co-organized by Dr. Markus Stoeppler,
who took part as an author in the German
Edition of the ‘MERIAN’ and as an author
and a member of the scientific advisory
board for the English Edition as well. Thus
it was natural that Dr. Pauly asked Dr.
Stoeppler his opinion about an update. Fortunately there were two other colleagues at
the symposium, Prof. Manfred Anke, Germany, and Dr. Milan Ihnat, Canada, both
very experienced as authors and editors of
scientific publications and also knowledgeable with the subjects treated in the
MERIAN. All three have in addition a long
history of co-operation.
Thus at Antwerp general agreement was
reached for a co-editorship of Anke, Ihnat
and Stoeppler, followed by action by the
publisher to ask former members of the
Editorial Advisory Board and a few new
ones for participation and by the editors to
discuss a preliminary outline for the con-

Elements and their Compounds in the Environment. 2nd Edition.
Edited by E. Merian, M. Anke, M. Ihnat, M. Stoeppler
Copyright  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30459-2

VI

Preface

tent of the book. In the course of the preliminary planning phase, including the six
members of the Editorial Advisory Board
(three former and three new), it was jointly
decided that the comprehensive character of
the book could be significantly strengthened and the basis of the literature sources
increased if not only metals and some metalloids previously covered, but also several
other metals and nonmetals that play
important roles in industry, environment,
medicine, nutrition and biota, namely
alkali metals, alkaline earths, nitrogen,
sulfur, phosphorus and the halogens, were
to be included as separate chapters. This
was finally accepted by the publisher with
a slightly changed title influencing the
length of the whole text, the organization
of the introductory and the analytical part
as well. Subsequently the final working
phase started in 2002.
This updated and significantly extended
2nd edition of the ’MERIAN’ is a tribute to
Ernest Merian and therefore also bears his
name in the editorial lineup as the book
constitutes a continuation and some broadening of his initial comprehensive concept
that was not significantly changed by his

successors. This book, presented in three
volumes, includes 81 chapters written by
83 experts from 20 countries around the
world, based on the available international
literature on approximately 1700 text
pages. As the authors came from very different research areas it was thus unavoidable
that their main interest often influences
the style, content and general focus of individual chapters.
The first volume is composed of two
parts. Part I deals with Element Distribution in the Environment and consists of
twelve chapters ranging from “Composition
of the Earth’s Upper Crust, Natural Cycles of
Elements, Natural Resources” to “From the
Biological System of the Elements to Bio-

monitoring”. Part II discusses in ten chapters “Effects of Elements in the Food
Chain and on Human Health” and ranges
from “Essential and Toxic Effects of Elements on Microorganisms” to “Ecogenetics”. Here several chapters are new or
newly written due to the somewhat changed
general concept with more emphasis on element essentiality.
The second volume contains Part III covering all metallic elements, with some chapters carefully updated and/or extended and
others new (as e.g. Mercury and the Platinum-Group Elements) from the Alkali
Metals to Zirconium in 44 chapters of varying length due to the elements’ individual
essential, eco-chemical and eco-toxicological relevance. The chapter following organization, in order to maintain comparability
with the 1st edition and among chapters,
consists of seven sections with some freedom for the authors to add and organize
subsections individually: 1) Introduction,
2) Physical and Chemical Properties and
Analytical Methods (the latter mainly as a
subsection with more details for elements

for which chemical speciation is essential),
3) Sources, Production, Important Compounds, Uses, Waste Products and
Recycling, 4) Distribution in the Environment, in Foods and Living Organisms,
5) Uptake, Absorption, Transport and Distribution, Metabolism and Elimination in
Plants, Animals and Humans, 6) Effects
(beneficial and/or adverse) on Plants, Animals and Humans, 7) Hazard Evaluation
and Limiting Concentrations, 8) Complete
References using the Harvard (Name and
Date) System. The reference citation
system, regrettably not continuously found
in the 1st edition, has been, as far as possible, followed in this edition for the benefit
of our readers.
The third volume contains Part IV with
some important metalloids and nonmetals


Preface

from Boron to Tellurium and all Halogens;
Part V deals with three chapters: Standards
and Regulations Regarding Metals and
Their Compounds, Analytical Chemistry of
Element Determination (Non Nuclear and
Nuclear) and Analytical Chemistry of Speciation (Principles, Main methods). The latter
is a new contribution by an expert in this
area in order to emphasize the increasing
importance of speciation for clarification
of many elemental actions. Part VI contains
additional information in a Glossary (Acronyms, Abbreviations, Symbols and definitions), some general tabulated information,
and an Index.

The editors wish to thank all contributing
authors for their careful work and for compliance with the general editorial concepts,
and publisher and their colleagues in the
editorial advisory board for their always
quick and very helpful discussions and
expert advice. We thank in particular Prof.
Dr. Marika Geldmacher von Mallinckrodt,
Prof. Dr. Robert F.M. Herber and Dr.
Mathias Seifert for very effective support

in the final phase of urgent manuscript control during proof reading, and Dipl.-Ing.
Karl-Heinz Schaller, for his steady advice
when detailed information on actual
national and international limit values was
required. Our thanks go also to Dr. Steffen
Pauly at WILEY-VCH for his encouragement in the planning and realizing this
book and his continuous involvement in
all editorial matter concerning the publisher’s part. We are highly indebted to Dr. Waltraud Wüst at WILEY-VCH for her invaluable help in all technical and organizational
matter concerning manuscripts, corrections
and daily advice. Without her active support, hard work, friendly attitude, and
always good ideas, the often critical deadlines would never have been so successfully
reached. The support of Institutional libraries and staff therein for assistance with literature verification and acquisition is gratefully acknowledged. Finally we are indebted
to our families for their support and understanding during this time-consuming
undertaking.

Jena, Germany
Summerland, British Columbia, Canada
Jülich, Germany

Manfred Anke

Milan Ihnat
Markus Stoeppler

2003 December

VII


IX

Contents
Preface V
Overview XXI
List of Contributors
Editoral Board

XXIV

XXXI

1

Part I

Element Distribution in the Environment

1

The Composition of Earth’s Upper Crust, Natural Cycles of Elements, Natural
Resources 3

Karl Hans Wedepohl

1.1
1.2
1.3

Formation of the Earth’s Crust 3
Alteration of the Earth’s Crust 4
Average Abundance of 25 Elements in Sedimentary, Magmatic and Metamorphic Rock Species 7
Concentration and Transport of 25 Elements in Natural Waters 8
Average Abundance of 25 Metals in Natural Raw Materials 10
Natural Resources 12
Concluding Remarks 14

1.4
1.5
1.6
1.7
2

Chemical Compounds in the Atmosphere
Hans Puxbaum and Andreas Limbeck

2.1
2.2
2.3
2.4

Introduction 17
Sources of Metal Compounds in the Atmosphere 17

Atmospheric Occurrence 20
Size Distributions of Atmospheric Particles and Trace Metals 22

Elements and their Compounds in the Environment. 2nd Edition.
Edited by E. Merian, M. Anke, M. Ihnat, M. Stoeppler
Copyright  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30459-2

17


X

Contents

2.5
2.6
2.7
2.8
2.8.1
2.8.2
2.8.3
2.8.4
2.8.5
2.8.6
2.8.7
2.9

Chemical Speciation 25
Deposition (see also Part I, Chapter 3) 28

Historical Trends 31
Atmospheric Aerosol Sampling and Analysis (for Biomonitoring, see Part I,
Chapter 12) 33
Sampling of Airborne Particles with Not Classifying Methods 33
Sampling with Classifying Methods 34
Special Sampling Techniques 34
Diffusion Controlled Separation of Aerosols 34
Bulk Analysis of the Elements 34
Compound-pecific Analysis 35
Single Particle Analysis and Surface Characterization of Airborne Particles 35
Source Analysis 36

3

Deposition of Acids, Elements, and their Compounds
H. J. Fiedler

3.1
3.2
3.2.1
3.2.2
3.2.3
3.3
3.3.1
3.4
3.4.1
3.4.1.1
3.4.1.2
3.4.2
3.4.2.1

3.4.2.2
3.4.3
3.4.4
3.5
3.5.1
3.5.1.1
3.5.1.2
3.5.1.3
3.5.2
3.5.2.1
3.5.3
3.5.3.1

Introduction 47
Types of Atmospheric Deposition 47
Dry Deposition 48
Occult Deposition 48
Wet and Bulk Deposition 48
Methods for Measuring Atmospheric Deposition in Forests 49
Throughfall 49
Deposition of Elements and their Compounds 50
Dust Deposition 50
Natural Dusts 50
Industrial Dusts, Deposition of Heavy Metals 50
Deposition of Acid Pollutants 51
Sulfur Deposition 52
Nitrogen Deposition 53
Deposition of Alkalizing Substances and Basic (Base) Cations 54
Deposition of Sea-alt Particles and Chloride Deposition 55
Deposition and Forest Ecosystems 55

Site and Stand Dependence 55
Elevation 55
Soils 55
Forest stands 56
Forest Decline 57
Effects of pollutant combinations 57
Critical Levels and Loads 57
Critical levels of sulfur 58

47


Contents

3.5.3.2
3.5.3.3
3.5.3.4
3.5.3.5
3.5.3.6
3.5.3.7
3.5.4

Critical loads 58
Critical load of nitrogen 59
Consequences of an increased nitrogen deposition 59
Critical load of sulfur 60
Consequences of an increased sulfur deposition 60
Critical load of acids; long-term effects of acid deposition and acid formation on
terrestrial ecosystems 60
Change with Time 62

4

Macro Elements in Soil
H. J. Fiedler

4.1
4.1.1
4.1.2
4.1.3
4.1.4
4.2
4.2.1
4.2.2
4.2.3
4.2.4
4.2.5

Nonetals 67
Nitrogen 67
Phosphorus 70
Sulfur 71
Chlorine 73
Metals 73
Exchangeable Bases
Sodium 75
Potassium 75
Magnesium 77
Calcium 77

5

Trace Elements and Compounds in Soil 79
Alina Kabata-endias and Wieslaw Sadurski

5.1
5.2
5.2.1
5.2.2
5.3
5.3.1
5.3.2
5.3.3
5.4
5.5
5.5.1
5.5.2
5.6
5.7

Introduction 79
Trace Elements in Soil 79
Origin, Forms, and Compounds 80
Background Ranges 83
Weathering 83
Dissolution and Sorption 85
Soil Solution 86
Speciation (see also Part II, Chapter 3) 87
Soil-lant Transfer 90
Contamination 91

In-situ Methods 93
Non-in-situ Methods 94
Environmental Quality Criteria 94
Final Remarks 96

67

73

XI


XII

Contents

6

Transfer of Macro, Trace and Ultratrace Elements in the Food Chain 101
Manfred K. Anke

6.1
6.2
6.2.1
6.2.2

Introduction 101
Terrestrial Indicator Plants of the Elemental Load 102
The Element Content of Several Plant Species on the Same Site 103
Influence of Geological Origin of the Site on the Macro, Trace and Ultratrace

Element Contents of Indicator Plants 106
Influence of Plant Age on the Macro, Trace and Ultratrace Element Contents of
Plants 107
The Element Contents of Plant Stems, Leaves, and Flowers 109
Influence of Geological Origin of Soil on Macro, Trace and Ultratrace Contents
of the Terrestrial Food Chain 111
Influence of Pollution on the Terrestrial Food Chain 112
Cadmium 113
Chromium 115
Nickel 116
Strontium 118
The Influence of Conventional and Ecological (Organic) Farming 119
Macro, Trace and Ultratrace Elements in Foodstuffs 120
Conclusions 122

6.2.3
6.2.4
6.3
6.4
6.4.1
6.4.2
6.4.3
6.4.4
6.5
6.6
6.7
7

Elements and Elemental Compounds in Waters and the Aquatic Food
Chain 127

Biserka Raspor

7.1
7.1.1
7.1.1.1
7.1.1.2
7.1.1.3
7.1.1.4
7.1.1.5
7.2
7.3
7.3.1
7.3.2
7.4
7.5
7.5.1
7.5.2
7.6
7.6.1

Introduction 127
Periodic Table of the Elements 127
Metals 128
Nonmetals 128
Metalloids 129
Ionic Metal Compounds 129
Covalent Metal Compounds 129
Hydration of Ions 130
Metal Complex Formation 132
Labile Complexes 132

Inert Complexes 132
Hard and Soft Acceptors and Donors 133
Bioavailability of Metals 135
Metal Uptake into the Organism 136
Accumulation of Elements 138
Aquatic Food Chain 140
Concentration Factors 141


Contents

7.6.2
7.6.3

Trophic Levels 142
Biomagnification 143

8

Elements and Compounds in Sediments 149
Ulrich Förstner and Wim Salomons

8.1
8.2
8.2.1
8.2.2
8.2.3
8.2.4
8.3
8.3.1

8.3.2
8.3.3
8.4

Introduction 149
Remobilization of Metals from Polluted Sediments 149
Acidity 150
Salinity 151
Complexing Agents 151
Oxidation/Reduction Processes 151
Sediment Management Strategies: Remedial Options 153
In-itu Remediation using Geochemical Engineering Methods 154
Natural Attenuation on Floodplain Sediments 155
Subaqueous Depot and Capping 157
Managing Contaminated Sediments: A Holistic Approach 158

9

Elements and Compounds in Waste Materials 163
Ulrich Förstner

9.1
9.2
9.2.1
9.2.2
9.2.3
9.3
9.3.1
9.3.2
9.3.2.1

9.3.2.2
9.3.2.3
9.3.2.4
9.3.3
9.3.3.1
9.3.3.2
9.4
9.4.1
9.4.2
9.4.3
9.5
9.5.1
9.5.2

Introduction 163
Waste Composition and Impact on Adjacent Media 164
Household Waste and Industrial Waste 164
Mining Waste 166
Impact on Adjacent Media 167
Waste Treatment 168
Chemical-hysical Treatment of Industrial Waste 168
Waste Incineration 169
Slags and Ashes 170
Fly Ash Post-reatment 170
Smelting Processes 171
Treatment of Wastewater from Waste Incineration Facilities (WIF) 172
Stabilization of Wastes 173
Stabilizing Additives 173
Storage Minerals 174
Metals in Landfills 175

Metals in “Reactor” Landfills 175
Metals and Final Storage Quality 178
Geochemical Engineering Concept for Landfills 180
Prognostic Tools for Metal Release from Wastes 181
Factors Influencing Release of Metals from Solid Waste Materials 181
Test Procedures 182

XIII


XIV

Contents

9.5.2.1
9.5.3
9.6
9.6.1
9.6.2
9.6.3
9.6.4
9.6.5

Development and Harmonization of Leaching Test Procedures 182
Lysimeter Test on MSWI Residues 184
Material Management: Recycling of Metals 185
Avoidance as the Primary Task of Pollution Control Technology 185
Waste Avoidance during Mining and Smelting 186
Recycling of Industrial Waste 189
Limitations and Potentials of Metal Recycling 190

Regional Material Management: An Example – Metal Balances 191

10

Elements and Compounds on Abandoned Industrial Sites
Ulrich Förstner and Joachim Gerth

10.1
10.2
10.2.1
10.2.1.1
10.2.1.2
10.2.1.3
10.2.1.4
10.2.2
10.2.2.1
10.3
10.3.1
10.3.2
10.3.3
10.3.3.1
10.3.3.2
10.3.4

Introduction 199
Treatment of Contaminated Industrial Sites 199
Solidification/Stabilization 201
Cement 202
Glass 203
The pozzolanic effect 203

Lime 203
Washing and Electrochemical Methods 203
Electrochemical Remediation 205
Natural Attenuation 205
General Description 205
Natural Attenuation Mechanisms 206
Natural Attenuation Concepts 207
Pollutant Degradation Concept 207
Immobilization Concept 208
Potential of Application 211

11

Elements and Their Compounds in Indoor Environments
Pat E. Rasmussen

11.1
11.2
11.2.1
11.2.2
11.3
11.3.1
11.3.2
11.3.3
11.3.4
11.4
11.4.1

Introduction 215
Composition of Indoor Dust 216

Element Speciation 217
Particle Size 217
Measurement of Elements in Indoor Environments 218
Vacuum Methods 218
Dust and Metal Deposition Techniques 220
Surface Wipe Techniques 221
Indoor Air Sampling 221
Relationships between Indoor and Outdoor Environments 224
Outdoor Sources 224

199

215


Contents

11.4.2
11.5
11.5.1
11.5.2
11.5.3
11.5.4
11.6

Element Enrichment in the Indoor Environment 225
Sources of Elements in the Indoor Environment 226
House Characteristics 227
Mode of Cooking 227
Activities of Residents 228

Consumer Products 228
Bioavailability of Metals in the Indoor Environment 229

12

From the Biological System of the Elements to Biomonitoring
Bernd Markert, Stefan Fraenzle and Annette Fomin

12.1
12.2
12.3
12.4
12.4.1
12.4.2
12.4.3
12.4.4
12.4.5
12.5
12.5.1
12.5.2
12.5.3

Introduction 235
From the Biological System of the Elements towards Biomonitoring 236
Definitions 238
Comparison of Instrumental Measurement: Bioindicators/biomonitors and
Harmonization/Quality Control 241
Instruments and Bioindicators 241
Precision and Accuracy 242
Calibration 243

Harmonization 244
An Example of Effect Biomonitoring 245
Integrative Biomonitoring 246
The Multi-markered Bioindicator Concept (MMBC) 247
Environmental Specimen Banks 248
Time- and Site Integration 250

Part II

Effects of Elements in the Food Chain and on Human Health

1

Essential and Toxic Effects of Elements on Microorganisms
Dietrich H. Nies

1.1
1.1.1
1.1.2
1.1.2.1
1.1.2.2
1.1.2.3
1.2
1.2.1
1.2.1.1
1.2.1.2
1.2.1.3

Introduction 257
Bioelements 257

Parameters Defining the Biological Impact of a Chemical Element 257
Rule Number 1 (Availability rule) 257
Rule Number 2 (Usefulness rule) 260
Rule Number 3 (Toxicity rule) 261
Biology of the Periodic System of the Elements 261
Main Groups Containing Major Bioelements and some Trace Elements 261
Group IA (H, Li, Na, K, Rb, Cs, Fr) 261
Group IIA (Be, Mg, Ca, Sr, Ba, Ra) 261
Group IIIA (B, Al, Ga, In, Tl) 262

235

255

257

XV


XVI

Contents

1.2.1.4
1.2.1.5
1.2.1.6
1.2.1.7
1.2.2
1.2.2.1
1.2.2.2

1.2.2.3
1.2.2.4
1.2.2.5
1.2.2.6
1.2.2.7
1.2.2.8

Group IVA (C, Si, Ge, Sn, Pb) 262
Group VA (N, P, As, Sb, Bi) 263
Group VIA (O, S, Se, Te, Po) 263
Group VIIA (F, Cl, Br, I, At) 263
Transition Metals 264
Group VB (V, Nb, Ta) 264
Group VIB (Cr, Mo, W) 264
Group VIIB (Mn, Tc, Re) 265
Group VIIIB1 (Fe, Ru, Os) 266
Group VIIIB2 (Co, Rh, Ir) 266
Group VIIIB3 (Ni, Pd, Pt) 267
Group IB (Cu, Ag, Au) 268
Group IIB (Zn, Cd, Hg) 269

2

Essential and Toxic Effects of Macro-Trace and Ultratrace Elements for Higher
Plants, Interactions and Requirement 277
Günther Schilling

2.1

Chemical Elements in Higher Plants and Their Classification in Nutritional

Science 277
Functions of Nutrient Elements in Higher Plants 279
Principles of Substance Formation 279
Special Effects of Beneficial Elements 288
Visual Symptoms as Consequences of Nutritional Disorders 291
Mechanisms of Toxicity in Higher Plants 295
Requirement of Mineral Nutrient Elements and its Estimation for Crops 297

2.2
2.2.1
2.2.2
2.2.3
2.3
2.4
3

Essential and Toxic Effects of Macro, Trace, and Ultratrace Elements in the
Nutrition of Animals 305
Manfred K. Anke

3.1
3.1.1
3.1.2
3.1.3
3.1.4
3.1.5
3.1.6
3.1.7
3.1.8
3.2

3.2.1
3.2.2

Introduction 305
Essentiality and Toxicity 305
Groups of Mineral Elements 306
The Identification of Essential Mineral Elements 307
Requirement and Recommendations of Mineral Elements 308
Pharmacological Levels of Essential Elements 308
Interactions of Mineral Elements 309
Toxic Levels of Mineral Elements 310
Ecogenetics 312
Essentiality and Toxicity of Mineral Elements 312
Macro Elements 312
Essentiality and Toxicity of Trace Elements (see Table 3.3) 314


Contents

3.2.2.1
3.2.2.2
3.2.2.3
3.2.2.4
3.2.2.5
3.2.2.6
3.2.2.7
3.2.2.8
3.2.2.9
3.2.3
3.2.3.1

3.2.3.2
3.2.3.3
3.2.3.4
3.2.3.5
3.2.3.6
3.2.3.7
3.2.3.8
3.2.3.9
3.2.3.10
3.2.3.11
3.2.3.12
3.2.3.13
3.2.3.14
3.3

Iron 314
Iodine 314
Copper 314
Manganese 316
Zinc 316
Cobalt 316
Molybdenum 316
Selenium 317
Nickel 317
Essentiality and Toxicity of Ultratrace Elements (see Table 3.4)
Fluorine 318
Chromium 321
Silicon 321
Arsenic 322
Cadmium 323

Lithium 325
Boron 326
Lead 327
Vanadium 327
Tungsten 327
Bromine 328
Aluminum 328
Rubidium 329
Titanium 330
Summary 330

4

Essential and Toxic Effects of Macro, Trace, and Ultratrace Elements in the
Nutrition of Man 343
Manfred K. Anke

4.1
4.2
4.2.1
4.2.2
4.2.3
4.2.4
4.2.5
4.2.6

Introduction 343
Macro elements 343
Normative Requirements and Recommendations for Intake 344
Macro element Intake of Adults with Mixed and Ovolactovegetarian Diets 344

Macro element Concentration of the Dry Matter Consumed 346
Macro element Intake per kg Body Weight of Humans 346
Fecal Excretion and Apparent Absorption of Macro elements 347
Macro element Intake Measured by the Duplicate Portion Technique and the
Basket Method 348
Intake of Macro elements Through Animal and Vegetable Foodstuffs and Beverages 348
Trace Elements 349

4.2.7
4.3

318

XVII


XVIII

Contents

4.3.1
4.3.2
4.3.3
4.3.4
4.3.5
4.3.6
4.3.7
4.4
4.4.1
4.4.2

4.4.3
4.4.4
4.4.5
4.4.6
4.4.7
4.5

Normative Requirements and Recommendations for Intake 349
Trace Element Intake of Adults with Mixed and Ovolactovegetarian Diets 350
Trace Element Concentration of the Dry Matter Consumed 352
Trace Element Intake of Humans per kg Body Weight 352
Fecal Excretion and Apparent Absorption of Trace Elements 353
Trace Element Intake Measured by the Duplicate Portion Technique and the
Basket Method 354
Intake of Trace Elements Through Animal and Vegetarian Foodstuffs and
Beverages 354
Ultratrace Elements 355
Normative Requirements and Recommendations for Intake 355
Ultratrace Element Intake of Adults with Mixed and Ovolactovegetarian
Diets 356
Ultratrace Element Concentration of the Dry Matter Consumed 357
Ultratrace Element Intake per kg Body Weight 358
Fecal Excretion and Apparent Absorption of Ultratrace Elements 359
Ultratrace Element Intake Measured by the Duplicate Portion Technique and
the Basket Method 360
Intake of Ultratrace Elements Through Animal and Vegetable Foodstuffs and
Beverages 361
Summary 361

5

Metal and Ceramic Implants 369
Hartmut F. Hildebrand

5.1
5.2
5.2.1
5.2.2
5.2.3
5.3
5.3.1
5.3.1.1
5.3.1.2
5.3.2
5.3.3
5.3.3.1
5.3.3.2
5.3.3.3
5.3.4
5.3.5
5.3.6

Introduction 369
Alloys 369
Alloys Used for Surgical Implants 370
Dental Alloys 370
Metals Used for Biomedical Alloys 371
Risks: the State of the Art 371
Ion Release 371
Alloys for Surgical Implants 371

Dental Alloys 372
Wear Particles 372
Ceramics 373
Sintered Ceramics 373
Bioceramics as Bone Substitutes 373
Carbon Materials 374
Tissular Reactions 375
Inflammatory Reactions 376
Immunologic Reactions 376


Contents

5.3.6.1
5.3.6.2
5.3.6.3
5.3.7
5.4
5.4.1
5.4.1.1
5.4.1.2
5.4.2
5.4.2.1
5.4.2.2

Sensitization and Allergy 376
Alloys for Surgical Implants 377
Dental Alloys 377
Induction of Cancer 378
In-vitro Toxicity Assessment 379

Cell Viability 379
Liability of Tests 380
Influence of Metals on Cell Survival 381
Inflammatory Response 381
Liability of Test 381
Influence of Metals on the Inflammatory Response

6

Metallothioneins 391
Bartolome Ribas

6.1
6.2
6.3
6.3.1
6.3.2
6.3.3
6.3.4
6.4
6.5

Introduction 391
Physicohemical Characteristics 392
Biological Implications of MT 395
MT Analogues 395
MT Complex with Methotrexate 395
MT and Anemia 396
MT and Endocrine Pancreas 396
MT and Tolerance to Ionizing Radiation 396

Clinical and Pathologic Involvement of MT 397

7

Influence of Metals on DNA
Zeno Garban

7.1
7.2
7.2.1
7.2.2
7.3
7.3.1
7.3.2
7.3.3
7.4

Overview on Metals and DNA Interaction 401
Steric Parameters of the DNA Macromolecule 401
Steric Parameters depending on Residual Nucleotides 403
Steric Parameters depending on Nucleobase Pairs 404
Interaction of DNA with Divalent Metal Ions 405
Interaction with Alkaline-arth Biometals 406
Interaction with Transition Biometals 406
Interaction with Toxic Transition Metals 407
Peculiarities of the SAR of DNA-M2+ Adducts 407

8

Acute and Chronic Toxicity of Metals and Metal Compounds for Man

Marika Geldmacher-Mallinckrodt and Karl-einz Schaller

8.1
8.2

Introduction 415
Mechanisms Responsible for Toxic Effects of Metals 415

383

401

415

XIX


XX

Contents

8.3
8.4
8.4.1
8.4.2
8.4.3
8.4.4
8.5
8.5.1
8.5.1.1

8.5.1.2
8.5.1.3
8.5.2
8.5.2.1
8.5.2.2
8.5.2.3
8.5.2.4
8.5.2.5
8.6
8.6.1
8.6.2
8.6.3
8.6.4
8.6.5
8.6.5.1
8.6.5.2
8.6.5.3
8.6.6
8.6.6.1
8.6.6.2

Role of Speciation and Way of Uptake 417
Acute Toxicity 417
General 417
Uptake and Distribution 418
Quantitative Assessment of Acute Toxicity of Individual Metal Compounds 418
Symptoms of Acute Metal Poisoning 420
Chronic Toxicity 420
General 420
Local Effects 421

Systemic Effects 421
Chronic Clinical Effects of Metal Toxicity 422
Pathways of Chronic Exposure 422
Chronic Indoor Exposure 422
Chronic Environmental Exposure 423
Chronic Occupational Exposure 423
Chronic Iatrogenic Exposure 424
Transplacental Transfer 424
Guidelines and Exposure Limits 424
Guidelines for Drinking Water Quality 424
Air Quality Guidelines 424
Acceptable Daily Intake (ADI) 424
Reference Values and Human Biological Monitoring Values for Environmental
Toxins 425
Occupational Exposure Limits 426
Threshold Limit Values (TLV) 426
Maximum Allowable Concentration (MAC) 427
Other Terms for Occupational Exposure Limits 427
Biological Monitoring and Biological Limits 428
BEI Values 428
BAT Values 429

9

Mutagenicity 433
Erich Gebhart

9.1
9.2
9.2.1

9.2.2
9.2.3
9.2.4
9.3

Introduction 433
Mutagenicity 434
Reactions of Metals with Nucleic Acids and Proteins 434
Induction of Molecular (Point) Mutations 437
Induction of Chromosome and Genome Mutations 439
Modulating Effects 442
Carcinogenicity 443


Contents

9.3.1
9.3.2
9.4
9.5

Genetic and Cellular Mechanisms
Animal Models 446
Teratogenicity 448
Concluding Remarks 449

445

10

Ecogenetics 459
Marika Geldmacher Mallinckrodt

10.1
10.2
10.3
10.4
10.4.1
10.4.2
10.4.3
10.4.3
10.4.3.1
10.4.3.2
10.4.3.3
10.4.3.4
10.4.3.5
10.4.3.6
10.4.3.7
10.4.3.8

Introduction 459
Bacteria 459
Plants 461
Mammals 463
Mice 463
Rats 464
Dogs 464
Humans 465
Arsenic (see also Part IV, Chapter 6) 465
Calcium (see also Part III, Chapter 2.3) 466

Copper (see also Part III, Chapter 8.1) 466
Iron (see also Part III, Chapter 13.1) 468
Lead (see also Part III, Chapter 15) 469
Magnesium (see also Part III, Chapter 2.2) 469
Molybdenum (see also Part III, Chapter 18) 470
Zinc (see also Part III, Chapter 29) 470

XXI


IX

Contents
Preface V
Overview XXIX
List of Contributors
Editoral Board

XXXV

XLII

477

Part III

Metals and their Compounds

1

Alkali Metals 479

1.1

Lithium 479
Ulrich Schäfer

1.1.1

Introduction 479

1.1.2
1.1.2.1
1.1.2.2
1.1.3

Physical and Chemical Properties and Analytical Methods 480
Physical and Chemical Properties 480
Analytical Methods 481
Sources, Production, Important Compounds, Uses, Waste Products and Recycling 481
Distribution in the Environment, in Foods, and in Living Organisms 485
Uptake, Absorption and Elimination in Plants, Animals, and Humans 487
Effects on Plants, Animals, and Humans 488
Hazard Evaluation and Limiting Concentrations 491

1.1.4
1.1.5
1.1.6
1.1.7
1.2

Sodium 497
Manfred K. Anke

Elements and their Compounds in the Environment. 2nd Edition.
Edited by E. Merian, M. Anke, M. Ihnat, M. Stoeppler
Copyright  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30459-2


X

Contents

1.2.1
1.2.2
1.2.2.1
1.2.2.2
1.2.3
1.2.4
1.2.4.1
1.2.4.2
1.2.4.3
1.2.4.4
1.2.5
1.2.5.1
1.2.5.2
1.2.5.3
1.2.6
1.2.6.1

1.2.6.2
1.2.6.3
1.2.7

Introduction 497
Physical and Chemical Properties, and Analytical Methods 498
Physical and Chemical Properties 498
Analytical Methods 498
Sources, Production, Important Compounds, and Uses 498
Distribution in the Environment, in Foods, and in Living Organisms 499
Distribution in the Environment 499
Flora 500
Fauna 501
Foods and Beverages 502
Uptake, Absorption, Transport and Distribution, Metabolism and Elimination
in Animals and Man 503
Intake 503
Absorption, Transportation, and Distribution 505
Excretion, Apparent Absorption Rate, and Balance 507
Effects on Plants, Animals, and Humans 508
Essentiality and Toxicity for Plants 508
Essentiality and Toxicity for Animals 509
Essentiality and Toxicity for Man 512
Hazard Evaluation and Limiting Concentrations 515

1.3

Potassium 521
Manfred K. Anke

1.3.1
1.3.2
1.3.2.1
1.3.2.2
1.3.3

Introduction 521
Physical and Chemical Properties and Analytical Methods 522
Physical and Chemical Properties 522
Analytical Methods 522
Sources, Production, Important Compounds, Uses, Waste Products, and Recycling 523
Sources and Production 523
Important Compounds and Uses 524
Waste Products and Recycling 524
Distribution in the Environment, in Food and in Living Organisms 524
Rocks, Soil, and Water 524
Flora 525
Fauna 527
Food 529
Intake, Absorption, Transport and Distribution, Metabolism and Elimination 532
Intake 532
Absorption 534

1.3.3.1
1.3.3.2
1.3.3.3
1.3.4
1.3.4.1
1.3.4.2
1.3.4.3

1.3.4.4
1.3.5
1.3.5.1
1.3.5.2


Contents

1.3.5.3
1.3.5.4
1.3.6
1.3.6.1
1.3.6.2
1.3.6.3
1.3.7

Transport and Distribution 534
Excretion 535
Effects on Plants, Animals, and Humans 536
Effects on Plants 536
Effects on Animals and Man 537
Toxicity in Animals and Man 541
Hazard Evaluation and Limiting Concentration 542

1.4

Rubidium 547
Manfred K. Anke and Ljubomir Angelov

1.4.1

1.4.2
1.4.3

Introduction 547
Physical and Chemical Properties, and Analytical Methods 547
Sources, Production, Important Compounds, Uses, Waste Products, and
Recycling 548
Distribution in the Environment, in Foods and Living Organisms 549
Distribution in the Environment 549
Flora 549
Vegetable Food 551
Fauna 551
Animal Food 552
Beverages 553
Uptake, Absorption, Transport and Distribution, Metabolism and Elimination
in Animal and Man 553
Intake 553
Absorption, Transportation, and Distribution 555
Metabolism, Excretion, Apparent Absorption Rate, and Balance 556
Effects on Plants, Animals, and Humans 556
Flora, Essentiality, and Toxicity 556
Essentiality in Animals and Man 557
Pharmacological Effects and Toxicity in Animals and Man. 559
Hazard Evaluation and Limiting Concentrations 560

1.4.4
1.4.4.1
1.4.4.2
1.4.4.3
1.4.4.4

1.4.4.5
1.4.4.6
1.4.5
1.4.5.1
1.4.5.2
1.4.5.3
1.4.6
1.4.6.1
1.4.6.2
1.4.6.3
1.4.7
1.5

Cesium 565
H. Hecht

1.5.1
1.5.2
1.5.3
1.5.4
1.5.5

Introduction 565
Physical and Chemical Properties, and Analytical Methods 565
Sources, Production, Important Compounds, and Uses 566
Distribution in Environment and Foods 566
Uptake, Absorption, Transport and Distribution, Metabolism and Elimination
in Plants, Animals and Humans 567
Effects on Plants, Animals, and Humans 568

1.5.6

XI