class="bi x0 y0 w1 h1"
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 Compoun ds

the British Library.
Bibliographic information published by
Die Deutsche Bibliothek
Die Deutsche Bibliothek lists this publication
in the Deutsche Nationalbibliografie; detailed
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 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. Regis-
tered 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
Editorial Board
Prof. Dr. Dr. Marika Geldmacher
von Mallinckrodt
Schlehenstraße 29
91056 Erlangen

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 excel-
lently and interdisciplinary covering the
broad range from general information,
basic elemental data, industrial uses, envi-
ronmental distribution to biological and
medicinal aspects. Since many readers
from various scientific branches could bene-
fit 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 admira-
tion his work and particularly the volumi-
nous English edition had received world-
wide. The book is frequently quoted in the
literature as it has been accepted as a

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
V
tent of the book. In the course of the pre-
liminary 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 strength-
ened and the basis of the literature sources
increased if not only metals and some met-
alloids 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

ters “Effects of Elements in the Food
Chain and on Human Health” and ranges
from “Essential and Toxic Effects of Ele-
ments on Microorganisms” to “Ecogenet-
ics”. Here several chapters are new or
newly written due to the somewhat changed
general concept with more emphasis on ele-
ment essentiality.
The second volume contains Part III cov-
ering all metallic elements, with some chap-
ters carefully updated and/or extended and
others new (as e.g. Mercury and the Plati-
num-Group Elements) from the Alkali
Metals to Zirconium in 44 chapters of vary-
ing length due to the elements’ individual
essential, eco-chemical and eco-toxicologi-
cal relevance. The chapter following organi-
zation, in order to maintain comparability
with the 1
st
edition and among chapters,
consists of seven sections with some free-
dom 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 Com-
pounds, Uses, Waste Products and

tions), some general tabulated information,
and an Index.
The editors wish to thank all contributing
authors for their careful work and for com-
pliance 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 con-
trol 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 encourage-
ment in the planning and realizing this
book and his continuous involvement in
all editorial matter concerning the publish-
er’s part. We are highly indebted to Dr. Wal-
traud Wüst at WILEY-VCH for her invalua-
ble help in all technical and organizational
matter concerning manuscripts, corrections
and daily advice. Without her active sup-
port, hard work, friendly attitude, and
always good ideas, the often critical dead-
lines would never have been so successfully

Hans Puxbaum and Andreas Limbeck
2.1 Introduction 17
2.2 Sources of Metal Compounds in the Atmosphere 17
2.3 Atmospheric Occurrence 20
2.4 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
IX
2.5 Chemical Speciation 25
2.6 Deposition (see also Part I, Chapter 3) 28
2.7 Historical Trends 31
2.8 Atmospheric Aerosol Sampling and Analysis (for Biomonitoring, see Part I,
Chapter 12) 33
2.8.1 Sampling of Airborne Particles with Not Classifying Methods 33
2.8.2 Sampling with Classifying Methods 34
2.8.3 Special Sampling Techniques 34
2.8.4 Diffusion Controlled Separation of Aerosols 34
2.8.5 Bulk Analysis of the Elements 34
2.8.6 Compound-pecific Analysis 35
2.8.7 Single Particle Analysis and Surface Characterization of Airborne Particles 35
2.9 Source Analysis 36
3 Deposition of Acids, Elements, and their Compounds 47
H. J. Fiedler
3.1 Introduction 47
3.2 Types of Atmospheric Deposition 47
3.2.1 Dry Deposition 48
3.2.2 Occult Deposition 48
3.2.3 Wet and Bulk Deposition 48

H. J. Fiedler
4.1 Nonetals 67
4.1.1 Nitrogen 67
4.1.2 Phosphorus 70
4.1.3 Sulfur 71
4.1.4 Chlorine 73
4.2 Metals 73
4.2.1 Exchangeable Bases 73
4.2.2 Sodium 75
4.2.3 Potassium 75
4.2.4 Magnesium 77
4.2.5 Calcium 77
5 Trace Elements and Compounds in Soil 79
Alina Kabata-endias and Wieslaw Sadurski
5.1 Introduction 79
5.2 Trace Elements in Soil 79
5.2.1 Origin, Forms, and Compounds 80
5.2.2 Background Ranges 83
5.3 Weathering 83
5.3.1 Dissolution and Sorption 85
5.3.2 Soil Solution 86
5.3.3 Speciation (see also Part II, Chapter 3) 87
5.4 Soil-lant Transfer 90
5.5 Contamination 91
5.5.1 In-situ Methods 93
5.5.2 Non-in-situ Methods 94
5.6 Environmental Quality Criteria 94
5.7 Final Remarks 96
Contents XI
6 Transfer of Macro, Trace and Ultratrace Elements in the Food Chain 101

7.3 Metal Complex Formation 132
7.3.1 Labile Complexes 132
7.3.2 Inert Complexes 132
7.4 Hard and Soft Acceptors and Donors 133
7.5 Bioavailability of Metals 135
7.5.1 Metal Uptake into the Organism 136
7.5.2 Accumulation of Elements 138
7.6 Aquatic Food Chain 140
7.6.1 Concentration Factors 141
ContentsXII
7.6.2 Trophic Levels 142
7.6.3 Biomagnification 143
8 Elements and Compounds in Sediments 149
Ulrich Förstner and Wim Salomons
8.1 Introduction 149
8.2 Remobilization of Metals from Polluted Sediments 149
8.2.1 Acidity 150
8.2.2 Salinity 151
8.2.3 Complexing Agents 151
8.2.4 Oxidation/Reduction Processes 151
8.3 Sediment Management Strategies: Remedial Options 153
8.3.1 In-itu Remediation using Geochemical Engineering Methods 154
8.3.2 Natural Attenuation on Floodplain Sediments 155
8.3.3 Subaqueous Depot and Capping 157
8.4 Managing Contaminated Sediments: A Holistic Approach 158
9 Elements and Compounds in Waste Materials 163
Ulrich Förstner
9.1 Introduction 163
9.2 Waste Composition and Impact on Adjacent Media 164
9.2.1 Household Waste and Industrial Waste 164

10.1 Introduction 199
10.2 Treatment of Contaminated Industrial Sites 199
10.2.1 Solidification/Stabilization 201
10.2.1.1 Cement 202
10.2.1.2 Glass 203
10.2.1.3 The pozzolanic effect 203
10.2.1.4 Lime 203
10.2.2 Washing and Electrochemical Methods 203
10.2.2.1 Electrochemical Remediation 205
10.3 Natural Attenuation 205
10.3.1 General Description 205
10.3.2 Natural Attenuation Mechanisms 206
10.3.3 Natural Attenuation Concepts 207
10.3.3.1 Pollutant Degradation Concept 207
10.3.3.2 Immobilization Concept 208
10.3.4 Potential of Application 211
11 Elements and Their Compounds in Indoor Environments 215
Pat E. Rasmussen
11.1 Introduction 215
11.2 Composition of Indoor Dust 216
11.2.1 Element Speciation 217
11.2.2 Particle Size 217
11.3 Measurement of Elements in Indoor Environments 218
11.3.1 Vacuum Methods 218
11.3.2 Dust and Metal Deposition Techniques 220
11.3.3 Surface Wipe Techniques 221
11.3.4 Indoor Air Sampling 221
11.4 Relationships between Indoor and Outdoor Environments 224
11.4.1 Outdoor Sources 224
ContentsXIV

1.1.2.2 Rule Number 2 (Usefulness rule) 260
1.1.2.3 Rule Number 3 (Toxicity rule) 261
1.2 Biology of the Periodic System of the Elements 261
1.2.1 Main Groups Containing Major Bioelements and some Trace Elements 261
1.2.1.1 Group IA (H, Li, Na, K, Rb, Cs, Fr) 261
1.2.1.2 Group IIA (Be, Mg, Ca, Sr, Ba, Ra) 261
1.2.1.3 Group IIIA (B, Al, Ga, In, Tl) 262
Contents XV
1.2.1.4 Group IVA (C, Si, Ge, Sn, Pb) 262
1.2.1.5 Group VA (N, P, As, Sb,Bi) 263
1.2.1.6 Group VIA (O, S, Se, Te, Po) 263
1.2.1.7 Group VIIA (F, Cl, Br, I, At) 263
1.2.2 Transition Metals 264
1.2.2.1 Group VB (V, Nb, Ta) 264
1.2.2.2 Group VIB (Cr , Mo, W) 264
1.2.2.3 Group VIIB (Mn, Tc, Re) 265
1.2.2.4 Group VIIIB1 (Fe, Ru, Os) 266
1.2.2.5 Group VIIIB2 (Co, Rh, Ir) 266
1.2.2.6 Group VIIIB3 (Ni, Pd, Pt) 267
1.2.2.7 Group IB (Cu, Ag, Au) 268
1.2.2.8 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
2.2 Functions of Nutrient Elements in Higher Plants 279
2.2.1 Principles of Substance Formation 279
2.2.2 Special Effects of Beneficial Elements 288
2.2.3 Visual Symptoms as Consequences of Nutritional Disorders 291

3.2.3.3 Silicon 321
3.2.3.4 Arsenic 322
3.2.3.5 Cadmium 323
3.2.3.6 Lithium 325
3.2.3.7 Boron 326
3.2.3.8 Lead 327
3.2.3.9 Vanadium 327
3.2.3.10 Tungsten 327
3.2.3.11 Bromine 328
3.2.3.12 Aluminum 328
3.2.3.13 Rubidium 329
3.2.3.14 Titanium 330
3.3 Summary 330
4 Essential and Toxic Effects of Macro, Trace, and Ultratrace Elements in the
Nutrition of Man 343
Manfred K. Anke
4.1 Introduction 343
4.2 Macro elements 343
4.2.1 Normative Requirements and Recommendations for Intake 344
4.2.2 Macro element Intake of Adults with Mixed and Ovolactovegetarian Diets 344
4.2.3 Macro element Concentration of the Dry Matter Consumed 346
4.2.4 Macro element Intake per kg Body Weight of Humans 346
4.2.5 Fecal Excretion and Apparent Absorption of Macro elements 347
4.2.6 Macro element Intake Measured by the Duplicate Portion Technique and the
Basket Method 348
4.2.7 Intake of Macro elements Through Animal and Vegetable Foodstuffs and Bev-
erages 348
4.3 Trace Elements 349
Contents XVII
4.3.1 Normative Requirements and Recommendations for Intake 349

5.3.1.2 Dental Alloys 372
5.3.2 Wear Particles 372
5.3.3 Ceramics 373
5.3.3.1 Sintered Ceramics 373
5.3.3.2 Bioceramics as Bone Substitutes 373
5.3.3.3 Carbon Materials 374
5.3.4 Tissular Reactions 375
5.3.5 Inflammatory Reactions 376
5.3.6 Immunologic Reactions 376
ContentsXVIII
5.3.6.1 Sensitization and Allergy 376
5.3.6.2 Alloys for Surgical Implants 377
5.3.6.3 Dental Alloys 377
5.3.7 Induction of Cancer 378
5.4 In-vitro Toxicity Assessment 379
5.4.1 Cell Viability 379
5.4.1.1 Liability of Tests 380
5.4.1.2 Influence of Metals on Cell Survival 381
5.4.2 Inflammatory Response 381
5.4.2.1 Liability of Test 381
5.4.2.2 Influence of Metals on the Inflammatory Response 383
6 Metallothioneins 391
Bartolome Ribas
6.1 Introduction 391
6.2 Physicohemical Characteristics 392
6.3 Biological Implications of MT 395
6.3.1 MT Analogues 395
6.3.2 MT Complex with Methotrexate 395
6.3.3 MT and Anemia 396
6.3.4 MT and Endocrine Pancreas 396

8.5.1.2 Systemic Effects 421
8.5.1.3 Chronic Clinical Effects of Metal Toxicity 422
8.5.2 Pathways of Chronic Exposure 422
8.5.2.1 Chronic Indoor Exposure 422
8.5.2.2 Chronic Environmental Exposure 423
8.5.2.3 Chronic Occupational Exposure 423
8.5.2.4 Chronic Iatrogenic Exposure 424
8.5.2.5 Transplacental Transfer 424
8.6 Guidelines and Exposure Limits 424
8.6.1 Guidelines for Drinking Water Quality 424
8.6.2 Air Quality Guidelines 424
8.6.3 Acceptable Daily Intake (ADI) 424
8.6.4 Reference Values and Human Biological Monitoring Values for Environmental
Toxins 425
8.6.5 Occupational Exposure Limits 426
8.6.5.1 Threshold Limit Values (TLV) 426
8.6.5.2 Maximum Allowable Concentration (MAC) 427
8.6.5.3 Other Terms for Occupational Exposure Limits 427
8.6.6 Biological Monitoring and Biological Limits 428
8.6.6.1 BEI Values 428
8.6.6.2 BAT Values 429
9 Mutagenicity 433
Erich Gebhart
9.1 Introduction 433
9.2 Mutagenicity 434
9.2.1 Reactions of Metals with Nucleic Acids and Proteins 434
9.2.2 Induction of Molecular (Point) Mutations 437
9.2.3 Induction of Chromosome and Genome Mutations 439
9.2.4 Modulating Effects 442
9.3 Carcinogenicity 443

1 Alkali Metals 479
1.1 Lithium 479
Ulrich Schäfer
1.1.1 Introduction 479
1.1.2 Physical and Chemical Properties and Analytical Methods 480
1.1.2.1 Physical and Chemical Properties 480
1.1.2.2 Analytical Methods 481
1.1.3 Sources, Production, Important Compounds, Uses, Waste Products and Recy-
cling 481
1.1.4 Distribution in the Environment, in Foods, and in Living Organisms 485
1.1.5 Uptake, Absorption and Elimination in Plants, Animals, and Humans 487
1.1.6 Effects on Plants, Animals, and Humans 488
1.1.7 Hazard Evaluation and Limiting Concentrations 491
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
IX
1.2.1 Introduction 497
1.2.2 Physical and Chemical Properties, and Analytical Methods 498
1.2.2.1 Physical and Chemical Properties 498
1.2.2.2 Analytical Methods 498
1.2.3 Sources, Production, Important Compounds, and Uses 498
1.2.4 Distribution in the Environment, in Foods, and in Living Organisms 499
1.2.4.1 Distribution in the Environment 499
1.2.4.2 Flora 500
1.2.4.3 Fauna 501
1.2.4.4 Foods and Beverages 502

ContentsX
1.3.5.3 Transport and Distribution 534
1.3.5.4 Excretion 535
1.3.6 Effects on Plants, Animals, and Humans 536
1.3.6.1 Effects on Plants 536
1.3.6.2 Effects on Animals and Man 537
1.3.6.3 Toxicity in Animals and Man 541
1.3.7 Hazard Evaluation and Limiting Concentration 542
1.4 Rubidium 547
Manfred K. Anke and Ljubomir Angelov
1.4.1 Introduction 547
1.4.2 Physical and Chemical Properties, and Analytical Methods 547
1.4.3 Sources, Production, Important Compounds, Uses, Waste Products, and
Recycling 548
1.4.4 Distribution in the Environment, in Foods and Living Organisms 549
1.4.4.1 Distribution in the Environment 549
1.4.4.2 Flora 549
1.4.4.3 Vegetable Food 551
1.4.4.4 Fauna 551
1.4.4.5 Animal Food 552
1.4.4.6 Beverages 553
1.4.5 Uptake, Absorption, Transport and Distribution, Metabolism and Elimination
in Animal and Man 553
1.4.5.1 Intake 553
1.4.5.2 Absorption, Transportation, and Distribution 555
1.4.5.3 Metabolism, Excretion, Apparent Absorption Rate, and Balance 556
1.4.6 Effects on Plants, Animals, and Humans 556
1.4.6.1 Flora, Essentiality, and Toxicity 556
1.4.6.2 Essentiality in Animals and Man 557
1.4.6.3 Pharmacological Effects and Toxicity in Animals and Man. 559