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METAL IONSIN LIFE SCIENCES

edited by

Astrid Sigel,(1) Helmut Sigel,(1) and Roland K. O. Sigel(2)

(1) Department of ChemistryInorganic ChemistryUniversity of BaselSpitalstrasse 51CH-4056 Basel, Switzerland

(2) Institute of Inorganic ChemistryUniversity of ZürichWinterthurerstrasse 190CH-8057 Zürich, Switzerland

VOLUME 2

Nickel and Its Surprising Impactin Nature


VOLUME 2



edited by

Astrid Sigel,(1) Helmut Sigel,(1) and Roland K. O. Sigel(2)

(1) Department of ChemistryInorganic ChemistryUniversity of BaselSpitalstrasse 51CH-4056 Basel, Switzerland

(2) Institute of Inorganic ChemistryUniversity of ZürichWinterthurerstrasse 190CH-8057 Zürich, Switzerland

VOLUME 2


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Library of Congress Cataloging-in-Publication DataNickel and its surprising impact in nature/edited by Astrid Sigel, Helmut Sigel, Roland K. O. Sigel. p. ; cm. – (Metal ions in life sciences ; v. 2) Includes bibliographical references and index. ISBN-13: 978-0-470-01671-8 (cloth : alk. paper) ISBN-10: 0-470-01671-X (cloth : alk. paper) 1. Nickel in the body. 2. Nickel enzymes. 3. Nickel toxicity. I. Sigel, Astrid. II. Sigel, Helmut. III. Sigel, Roland K. O. IV. Series. [DNLM: 1. Nickel–metabolism. 2. Environmental Exposure. 3. Nickel–adverse effects. QU 130 N6323 2006] QP535.N6N53 2006 615.9’25625–dc22 2006022828

British Library Cataloguing in Publication DataA catalogue record for this book is available from the British LibraryISBN 978-0-470-01671-8

Typeset in 10/12pt Times by Thomson Digital, IndiaPrinted and bound in Spain by Grafos S.A. BarcelonaThis book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production.The fi gure on the dustcover is Figure 15 of Chapter 4 by Roland K.O. Sigel and Helmut Sigel.

www.wiley.com

Historical Development and Perspectivesof the Series

Metal Ions in Life Sciences

It is an old wisdom that metals are indispensable for life. Indeed, several of them, such as sodium, potassium, and calcium, are easily discovered in living matter. However, the role of metals and their impact on life remained largely hidden until inorganic chemistry and coordination chemistry experienced a pronounced revival in the 1950s. The experimental and theoretical tools created in this period and their application to biochemical problems led to the development of the fi eld or discipline now known as Bioinorganic Chemistry, Inorganic Biochemistry, or more recently also often addressed as Biological Inorganic Chemistry.

By 1970 Bioinorganic Chemistry was established and further promoted by the book series Metal Ions in Biological Systems founded in 1973 (edited by H.S., who was soon joined by A.S.) and published by Marcel Dekker, Inc., New York, for more than 30 years. After this company ceased to be a family endeavor and its acquisition by another company, we decided, after having edited 44 volumes of the MIBS series (the last two together with R.K.O.S.) to launch a new and broader minded series to cover today’s needs in the Life Sciences. Therefore, the Sigels’ new series is entitled

Metal Ions in Life Sciencesand we are happy to join forces in this new endeavor with a most experienced publisher in the Sciences, John Wiley & Sons, Ltd, Chichester, UK.

The development of Biological Inorganic Chemistry during the past 40 years was and still is driven by several factors; among these are: (i) the attempts to reveal the interplay between metal ions and peptides, nucleotides, hormones or vitamins, etc.; (ii) the efforts regarding the understanding of accumulation, trans-port, metabolism and toxicity of metal ions; (iii) the development and applica-tion of metal-based drugs; (iv) biomimetic syntheses with the aim to understand biological processes as well as to create effi cient catalysts; (v) the determination of high-resolution structures of proteins, nucleic acids, and other biomolecules;

vi PERSPECTIVES OF THE SERIES

(vi) the utilization of powerful spectroscopic tools allowing studies of structures and dynamics; and (vii), more recently, the widespread use of macromolecular engineering to create new biologically relevant structures at will. All this and more is and will be refl ected in the volumes of the series Metal Ions in Life Sciences.

The importance of metal ions to the vital functions of living organisms, hence, to their health and well-being, is nowadays well accepted. However, in spite of all the progress made, we are still only on the brink of understanding these processes. Therefore, the series Metal Ions in Life Sciences will endeavor to link coordination chemistry and biochemistry in their widest sense. Despite the evident expectation that a great deal of future outstanding discoveries will be made in the interdis-ciplinary areas of science, there are still ‘language’ barriers between the histori-cally separate spheres of chemistry, biology, medicine, and physics. Thus, it is one of the aims of this series to catalyze mutual ‘understanding’.

It is our hope that Metal Ions in Life Sciences proves a stimulus for new activi-ties in the fascinating ‘fi eld’ of Biological Inorganic Chemistry. If so, it will well serve its purpose and be a rewarding result for the efforts spent by the authors.

Astrid Sigel, Helmut Sigel Roland K. O. SigelDepartment of Chemistry Institute of Inorganic ChemistryInorganic Chemistry University of ZürichUniversity of Basel CH-8057 ZürichCH-4056 Basel SwitzerlandSwitzerland October 2005

Preface to Volume 2Nickel and Its Surprising Impact in Nature

This volume is solely devoted to the vibrant research area surrounding nickel and its complexes and their role in Nature. The book opens with the biogeochemis-try of this element and its release into the environment, which occurs from both natural and anthropogenic sources, whereby atmospheric distribution plays an important role. In the second chapter the impact of nickel on the metabolism of cyanobacteria and eukaryotic plants including defi ciency and toxicity is consid-ered, as is the application of nickel hyperaccumulator plants for phytomining and phytoremediation.

Complex formation of nickel(II/III) with amino acids and peptides as well as of nickel(II) with sugar residues, nucleobases, phosphates, nucleosides, and nucleic acids is summarized in Chapters 3 and 4, respectively, by also taking into account intramolecular equilibria and comparisons with related metal ions.

Bioinspired nickel coordination chemistry has fl ourished in recent years and the resulting synthetic models for the active sites of nickel-containing enzymes are reviewed in Chapter 5. In fact, each of the well-established biological nickel sites is rather unique with respect to its structure and function. Hence, the following eight chapters are individually devoted to the various nickel enzymes which catalyze rather diverse reactions. For example, urease reduces the half life of urea in water from about 3.6 years to a few microseconds, whereas nickel-iron hydrogenases catalyze the heterolytic conversion of dihydrogen into protons and electrons and vice versa. Next, methyl-coenzyme M reductase and its nickel corphin coenzyme F430 in methanogenic archaea are described in detail as are acetyl-coenzyme A synthases and nickel-containing carbon monoxide dehydro-genases. These critical reviews are followed by in-depth considerations on nickel superoxide dismutase, and the nickel-dependent glyoxalase I enzymes. The role of nickel in acireductone dioxygenase and the properties of the nickel-regulated peptidyl-prolyl cis/trans isomerase SlyD are discussed next.

viii PREFACE TO VOLUME 2

Nickel is toxic to cells and therefore the synthesis of nickel enzymes requires carefully controlled nickel-processing mechanisms that range from selective transport of nickel into the cells to productive insertion of nickel into the correct apoproteins. This demanding task is the focus of Chapter 14 which is devoted to the chaperones of nickel metabolism.

The primary colonization and long-term survival of Helicobacter pylori in the hostile gastric niche and the role of nickel in this environmental adaptation is covered in detail in Chapter 15.

Nickel is widely employed in modern industry in conjunction with other metals for the production of alloys for coins, jewellery, and stainless steel; it is also used for plating, battery production, as a catalyst, etc. Workers are exposed to nickel at all stages of the processing of nickel-containing products through air, water or skin contacts. For example, the exposure to airborne nickel-containing particles has long been known to cause acute respiratory symptoms ranging from mild irritation and infl ammation of the respiratory system to bronchitis, asthma, and pulmonary fi brosis and edema. Another well-known adverse effect is allergic contact dermatitis. The indicated health problems caused by nickel exposure are mediated by an active change in the expression of genes that control infl amma-tion, the response to stress, cell proliferation or cell death. All this and more is covered in Chapter 16. However, the most serious health effects beyond nickel toxicity relate to carcinogenesis; these concerns represent an area of considerable research activity today as is evident from the terminating chapter of Nickel and Its Surprising Impact in Nature.

Astrid SigelHelmut Sigel

Roland K. O. Sigel

Contents

HISTORICAL DEVELOPMENT AND PERSPECTIVESOF THE SERIES v

PREFACE TO VOLUME 2 viiCONTRIBUTORS TO VOLUME 2 xviiTITLES OF VOLUMES 1–44 IN THE

METAL IONS IN BIOLOGICAL SYSTEMS SERIES xxiCONTENTS OF VOLUMES IN THE

METAL IONS IN LIFE SCIENCES SERIES xxiii

1 BIOGEOCHEMISTRY OF NICKEL ANDITS RELEASE INTO THE ENVIRONMENT 1

Tiina M. Nieminen, Liisa Ukonmaanaho, Nicole Rausch,and William Shotyk

1. Introduction 22. Chemistry of Nickel 23. Ancient and Modern Uses of Nickel 64. Sources of Atmospheric Nickel 65. Deposition and Fate of Atmospheric Nickel 76. Historical Records of Nickel Deposition 147. Bioavailability and Mobility of Nickel in Soils 178. Summary and Conclusions 21

Abbreviations 21References 22

x CONTENTS

2 NICKEL IN THE ENVIRONMENT AND ITS ROLEIN THE METABOLISM OF PLANTSAND CYANOBACTERIA 31

Hendrik Küpper and Peter M. H. Kroneck

1. Introduction 322. Nickel as a Micronutrient for Plants and Cyanobacteria 373. Nickel as an Environmental Pollutant and Its Effects on Plants 404. Nickel Hyperaccumulation 485. Outlook 53

Acknowledgments 54Abbreviations 54References 55

3 NICKEL ION COMPLEXES OF AMINO ACIDSAND PEPTIDES 63

Teresa Kowalik-Jankowska, Henryk Kozlowski, Etelka Farkas,and Imre Sóvágó

1. Introduction 642. Complexes of Amino Acids and Derivatives 663. Complexes of Peptides and Related Ligands 764. Formation of Nickel(II) Complexes under Biological

Conditions: Model Calculations in Multicomponent Systems 945. Conclusions 96


4 COMPLEX FORMATION OF NICKEL(II) AND RELATED METAL IONS WITH SUGAR RESIDUES, NUCLEOBASES, PHOSPHATES, NUCLEOTIDES, AND NUCLEIC ACIDS 109

Roland K. O. Sigel and Helmut Sigel

1. Introduction 1102. Nickel(II)–Sugar Interactions 1123. Interactions of Nickel(II) with Nucleobase Residues 1184. Complexes of Nickel(II) with Phosphates 1285. Nickel(II) Complexes of Nucleotides 1316. Complexes of Some Less Common Nucleotides 1447. Complexes of Some Nucleotide Derivatives and Analogs 1498. Mixed Ligand Complexes Containing a Nucleotide 1599. Nickel(II) Binding in Nucleic Acids 165

10. Concluding Remarks 168

CONTENTS xi

Acknowledgments 169Abbreviations and Defi nitions 169References 172

5 SYNTHETIC MODELS FOR THE ACTIVE SITESOF NICKEL-CONTAINING ENZYMES 181

Jarl Ivar van der Vlugt and Franc Meyer

1. Introduction 1812. Models for Cofactor F430 1823. Models for Sulfur-Rich Nickel Sites 1914. Models for the Urease Active Site 2145. Models for Acireductone Reductase 2296. Concluding Remarks 230


6 UREASE: RECENT INSIGHTS ON THE ROLE OF NICKEL 241Stefano Ciurli

1. Introduction: Urease and Its Biological Signifi cance 2422. The Biochemistry of Urease 2433. Structural Studies on Bacterial Ureases 2444. The Structure-Based Mechanism of Urease 2675. Conclusions 273


7 NICKEL IRON HYDROGENASES 279Wolfgang Lubitz, Maurice van Gastel, and Wolfgang Gärtner

1. Introduction to Hydrogenases 2802. Biochemistry and Molecular Biology 2833. Crystallization and X-Ray Structure Analysis 2914. Spectroscopic Investigations 2955. Electrochemistry 3066. Hydrogenase Function and the Catalytic Cycle 3097. Conclusions and Outlook 312


xii CONTENTS

8 METHYL-COENZYME M REDUCTASEAND ITS NICKEL CORPHIN COENZYME F430

IN METHANOGENIC ARCHAEA 323Bernhard Jaun and Rudolf K. Thauer

1. Introduction 3242. Structure and Properties of Coenzyme F430 3283. Molecular Properties of Methyl-Coenzyme M Reductase 3354. Catalytic Properties of Methyl-Coenzyme M Reductase 345


9 ACETYL-COENZYME A SYNTHASESAND NICKEL-CONTAINING CARBON MONOXIDE DEHYDROGENASES 357

Paul A. Lindahl and David E. Graham

1. Introduction 3582. Structure and Function of Carbon Monoxide Dehydrogenases 3613. Sequence Analysis and Phylogeny of Carbon Monoxide

Dehydrogenases 3694. Acetyl-Coenzyme A Synthases/Carbon Monoxide

Dehydrogenases 3735. Sequence Analysis and Phylogeny of the α Subunit 3816. Corrinoid Iron-Sulfur Proteins 3827. Acetyl-Coenzyme A Decarbonylase/Synthases 3848. Physiological Roles and Evolution of Acetyl-Coenzyme A

Synthase/Carbon Monoxide Dehydrogenase Proteins 3869. Origins and Evolution of ACDS, ACS/CODH,

and CODH Complexes 392Acknowledgments 393Abbreviations 394Appendices 395References 411

10 NICKEL SUPEROXIDE DISMUTASE 417Peter A. Bryngelson and Michael J. Maroney

1. Introduction 4182. Molecular Biology 4223. Structural Biology 4264. Mechanism 429

CONTENTS xiii

5. Conclusions 438Acknowledgments 438Abbreviations and Defi nitions 439References 439

11 BIOCHEMISTRY OF THE NICKEL-DEPENDENT GLYOXALASE I ENZYMES 445

Nicole Sukdeo, Elisabeth Daub, and John F. Honek

1. Introduction 4462. Biochemical Investigations of Glyoxalase I 4503. Biophysical and Mechanistic Studies of Glyoxalase I 4534. Glyoxalase I Genes and Protein Sequence Comparisons 4605. Glyoxalase I as a Member of the βαβββ Superfamily

of Proteins 4636. Other Aspects of Glyoxalase I 4647. Conclusions 465


12 NICKEL IN ACIREDUCTONE DIOXYGENASE 473Thomas C. Pochapsky, Tingting Ju, Marina Dang, Rachel Beaulieu,Gina M. Pagani, and Bo OuYang

1. Introduction 4742. The Methionine Salvage Pathway 4753. One Protein, Two Enzymes: Acireductone Dioxygenase from

Klebsiella oxytoca 4774. Homologs of Acireductone Dioxygenase from

Other Organisms 4815. Known Acireductone Dioxygenase Structures 4836. Spectroscopic Probes of Acireductone Dioxygenase Enzyme

Active Sites 4867. Enzymatic Studies of Acireductone Dioxygenase 4898. Mechanistic Considerations: What is the Role of Ni(II) in

Acireductone Dioxygenase Activity? 4909. Structurally and Functionally Related Enzymes 493

10. Future Directions 495Acknowledgments 497Abbreviations 497References 498

xiv CONTENTS

13 THE NICKEL-REGULATED PEPTIDYL PROLYLCIS/TRANS ISOMERASE SlyD 501

Frank Erdmann and Gunter Fischer

1. Introduction 5022. SlyD Belongs to the Peptidyl Prolyl cis/trans Isomerases 5033. Insights into the Biological Role of SlyD 5134. Conclusions 515

Abbreviations and Defi nitions 515References 516

14 CHAPERONES OF NICKEL METABOLISM 519Soledad Quiroz, Jong K. Kim, Scott B. Mulrooney,and Robert P. Hausinger

1. Introduction to Nickel Metabolism 5202. Nickel Metallochaperones 5303. Molecular Chaperones Involved in Nickel Metabolism 5344. Conclusions and Remaining Questions 538


15 THE ROLE OF NICKEL IN ENVIRONMENTALADAPTATION OF THE GASTRIC PATHOGEN HELICOBACTER PYLORI 545

Florian D. Ernst, Arnoud H. M. van Vliet, Manfred Kist, Johannes G. Kusters, and Stefan Bereswill

1. Introduction 5462. Nickel Enzymes and Environmental Adaptation 5543. Nickel Uptake Systems 5604. Mechanisms of Nickel Regulation 5625. Protection of Nickel Metabolism 5666. Metal Metabolism as Drug Target: Therapeutic Considerations 5687. Conclusions 570


16 NICKEL-DEPENDENT GENE EXPRESSION 581Konstantin Salnikow and Kazimierz S. Kasprzak

1. Introduction 5822. Genetic and Epigenetic Changes in Nickel-Exposed Cells 585

CONTENTS xv

3. Alteration of Gene Expression Following Nickel-InducedLung Injury 587

4. Nickel-Induced Allergy and Gene Expression 5925. Nickel-Induced Expression of Erythropoietin 5926. Alteration of Transcription Factors and Signaling Pathways 5937. Changes in Gene Expression and Nickel Carcinogenesis 6078. Conclusions 608


17 NICKEL TOXICITY AND CARCINOGENESIS 619Kazimierz S. Kasprzak and Konstantin Salnikow

1. Introduction 6212. An Overview of Nickel Toxicity 6213. Nickel-Induced Carcinogenesis 6384. Conclusion 645


SUBJECT INDEX 661

Contributors

Numbers in parentheses indicate the pages on which the authors’ contributions begin.

Rachel Beaulieu Departments of Chemistry and Biochemistry, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454-9110, USA (473)

Stefan Bereswill Charité - University Medicine Berlin, Institute for Micro-biology and Hygiene, Campus Charité Mitte, Dorotheenstrasse 96, D-10117 Berlin, Germany, �[email protected]� (545)

Peter A. Bryngelson Department of Chemistry, 701 Lederle Graduate Research Tower, University of Massachusetts, 710 North Pleasant Street, Amherst, MA 01003-9336, USA, �[email protected]� (417)

Stefano Ciurli Laboratory of Bioinorganic Chemistry, Department of Agro-Environmental Science and Technology, University of Bologna, Viale Giuseppe Fanin 40, I-40127 Bologna, Italy, �[email protected]� (241)

Marina Dang Departments of Chemistry and Biochemistry, Brandeis Univer-sity, MS 015, 415 South Street, Waltham, MA 02454-9110, USA (473)

Elisabeth Daub Department of Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada, �[email protected]� (445)

Frank Erdmann Max-Planck Research Unit for Enzymology of Protein Fold-ing, Weinbergweg 22, D-06120 Halle, Germany,�[email protected]� (501)

Florian D. Ernst Department of Gastroenterology and Hepatology, Erasmus MC - University Medical Center, Rotterdam, The Netherlands (545)

Etelka Farkas Inorganic and Analytical Chemistry Department, University of Debrecen, Egyetem ter. 1, P.O. Box 21, H-4010 Debrecen, Hungary,�efarkas@delfi n.klte.hu� (63)

Gunter Fischer Max-Planck Research Unit for Enzymology of Protein Folding, Weinbergweg 22, D-06120 Halle, Germany, �fi [email protected]� (501)

Wolfgang Gärtner Max-Planck-Institute for Bioinorganic Chemistry, Stift-strasse 34-36, D-45470 Mülheim/Ruhr, Germany (279)

David E. Graham Department of Chemistry and Biochemistry, University of Texas, Austin, TX 78712, USA, �[email protected]� (357)

Robert P. Hausinger Department of Biochemistry and Molecular Biology, Cell and Molecular Biology Program, and Department of Microbiology and Molecular Genetics, Michigan State University, East Lansing, MI 48824-4320, USA, �[email protected]� (519)

John F. Honek Department of Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada, �[email protected]� (445)

Bernhard Jaun Organic Chemistry, ETHZ, ETH Hönggerberg HCI E317, CH-8093 Zürich, Switzerland, �[email protected]� (323)

Tingting Ju Departments of Chemistry and Biochemistry, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454-9110, USA (473)

Kazimierz S. Kasprzak Laboratory for Comparative Carcinogenesis, National Cancer Institute at Frederick, Bldg 538, Room 205E, Frederick, MD 21702-1201, USA, �[email protected]� (582, 619)

Jong K. Kim Cell and Molecular Biology Program, Michigan State University, East Lansing, MI 48824-4320, USA (519)

Manfred Kist Department of Microbiology and Hygiene, Institute of Medical Microbiology and Hygiene, University Hospital, Freiburg, Germany (545)

Teresa Kowalik-Jankowska Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, PL-50383 Wroclaw, Poland, �[email protected]� (63)

Henryk Kozlowski Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, PL-50383 Wroclaw, Poland, �[email protected]� (63)

xviii CONTRIBUTORS

Peter M. H. Kroneck Fachbereich Biologie, Universität Konstanz, Postfach M665, D-78457 Konstanz, Germany, �[email protected]� (31)

Hendrik Küpper Fachbereich Biologie, Universität Konstanz, Postfach M665, D-78457 Konstanz, Germany, �[email protected]� (31)

Johannes G. Kusters Department of Gastroenterology and Hepatology, Eras-mus MC-University Medical Center, Rotterdam, The Netherlands (545)

Paul A. Lindahl Department of Chemistry and of Biochemistry and Bio-physics, Texas A&M University, College Station, TX 77843-3255, USA,�[email protected]� (357)

Wolfgang Lubitz Max-Planck-Institute for Bioinorganic Chemistry, Stiftstrasse 34-36, D-45470 Mülheim/Ruhr, Germany, �[email protected]� (279)

Michael J. Maroney Department of Chemistry, 701 Lederle Graduate Re-search Tower, University of Massachusetts, 710 North Pleasant Street, Amherst, MA 01003-9336, USA, �[email protected]� (417)

Franc Meyer Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany,�[email protected]� (182)

Scott B. Mulrooney Department of Microbiology and Molecular Genetics, Michigan State University, East Lansing, MI 48824-4320, USA (519)

Tiina M. Nieminen Finnish Forest Research Institute (Metla), P. O. Box 18, FI-01301 Vantaa, Finland, �[email protected] � (1)

Bo OuYang Departments of Chemistry and Biochemistry, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454-9110, USA (473)

Gina M. Pagani Departments of Chemistry and Biochemistry, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454-9110, USA (473)

Thomas C. Pochapsky Departments of Chemistry and Biochemistry, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454-9110, USA,�[email protected]� (473)

Soledad Quiroz Department of Biochemistry and Molecular Biology, Michi-gan State University, East Lansing, MI 48824-4320, USA (519)

CONTRIBUTORS xix

Nicole Rausch Institute of Environmental Geochemistry, University of Heidelberg, Im Neuenheimer Feld 236, D-69120 Heidelberg, Germany,�[email protected]� (1)

Konstantin Salnikow Laboratory for Comparative Carcinogenesis, National Cancer Institute at Frederick, Bldg 538, Room 205E, Frederick, MD 21702-1201, USA, �[email protected]� (582, 619)

William Shotyk Institute of Environmental Geochemistry, University of Heidelberg, Im Neuenheimer Feld 236, D-69120 Heidelberg, Germany,�[email protected]� (1)

Helmut Sigel Department of Chemistry, Inorganic Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland, �[email protected]� (109)

Roland K. O. Sigel Institute of Inorganic Chemistry, University of Zürich, Room 34-F-36, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland,�[email protected]� (109)

Imre Sóvágó Inorganic and Analytical Chemistry Department, Univer-sity of Debrecen, Egyetem ter. 1, P.O. Box 21, H-4010 Debrecen, Hungary,�sovago@delfi n.klte.hu� (63)

Nicole Sukdeo Department of Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada, �[email protected]� (445)

Rudolf K. Thauer Max Planck Institute for Terrestrial Microbiology, Karl-von-Frisch-Strasse, D-35043 Marburg, Germany, �[email protected]� (323)

Liisa Ukonmaanaho Finnish Forest Research Institute (Metla), P. O. Box 18, FI-01301 Vantaa, Finland, �[email protected] � (1)

Jarl Ivar van der Vlugt Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany,�[email protected]� (182)

Maurice van Gastel Max-Planck-Institute for Bioinorganic Chemistry, Stiftstrasse 34-36, D-45470 Mülheim/Ruhr, Germany (279)

Arnoud H. M. van Vliet Department of Gastroenterology and Hepatology, Erasmus MC - University Medical Center, Rotterdam, The Netherlands (545)

xx CONTRIBUTORS

Titles of Volumes 1–44 in theMetal Ions in Biological Systems Series

edited by the SIGELsand published by Dekker/Taylor & Francis

Volume 1: Simple ComplexesVolume 2: Mixed-Ligand ComplexesVolume 3: High Molecular ComplexesVolume 4: Metal Ions as ProbesVolume 5: Reactivity of Coordination CompoundsVolume 6: Biological Action of Metal IonsVolume 7: Iron in Model and Natural CompoundsVolume 8: Nucleotides and Derivatives: Their Ligating AmbivalencyVolume 9: Amino Acids and Derivatives as Ambivalent Ligands

Volume 10: Carcinogenicity and Metal IonsVolume 11: Metal Complexes as Anticancer AgentsVolume 12: Properties of CopperVolume 13: Copper ProteinsVolume 14: Inorganic Drugs in Defi ciency and DiseaseVolume 15: Zinc and Its Role in Biology and NutritionVolume 16: Methods Involving Metal Ions and Complexes in

Clinical ChemistryVolume 17: Calcium and Its Role in BiologyVolume 18: Circulation of Metals in the EnvironmentVolume 19: Antibiotics and Their ComplexesVolume 20: Concepts on Metal Ion ToxicityVolume 21: Applications of Nuclear Magnetic Resonance to

Paramagnetic SpeciesVolume 22: ENDOR, EPR, and Electron Spin Echo for Probing

Coordination SpheresVolume 23: Nickel and Its Role in BiologyVolume 24: Aluminum and Its Role in BiologyVolume 25: Interrelations Among Metal Ions, Enzymes, and Gene Expression

Volume 26: Compendium on Magnesium and its Role in Biology, Nutrition, and Physiology

Volume 27: Electron Transfer Reactions in MetalloproteinsVolume 28: Degradation of Environmental Pollutants by Microorganisms

and Their MetalloenzymesVolume 29: Biological Properties of Metal Alkyl DerivativesVolume 30: Metalloenzymes Involving Amino Acid-Residue and

Related RadicalsVolume 31: Vanadium and Its Role for LifeVolume 32: Interactions of Metal Ions with Nucleotides, Nucleic Acids,

and Their ConstituentsVolume 33: Probing Nucleic Acids by Metal Ion Complexes of

Small MoleculesVolume 34: Mercury and Its Effects on Environment and BiologyVolume 35: Iron Transport and Storage in Microorganisms, Plants,

and AnimalsVolume 36: Interrelations Between Free Radicals and Metal Ions

in Life ProcessesVolume 37: Manganese and Its Role in Biological ProcessesVolume 38: Probing of Proteins by Metal Ions and Their

Low-Molecular-Weight ComplexesVolume 39: Molybdenum and Tungsten.

Their Roles in Biological ProcessesVolume 40: The Lanthanides and Their Interrelations with BiosystemsVolume 41: Metal Ions and Their Complexes in MedicationVolume 42: Metal Complexes in Tumor Diagnosis and as Anticancer

AgentsVolume 43: Biogeochemical Cycles of ElementsVolume 44: Biogeochemistry, Availability, and Transport of Metals

in the Environment

xxii VOLUMES IN THE MIBS SERIES

Contents of Volumes in the Metal Ions in Life Sciences Series

edited by the SIGELsand published by John Wiley & Sons, Ltd, Chichester, UK

<http://www.wiley.com/go/mils>

Volume 1: Neurodegenerative Diseases and Metal Ions

1. The Role of Metal Ions in Neurology. An IntroductionDorothea Strozyk and Ashley I. Bush

2. Protein Folding, Misfolding, and DiseaseJennifer C. Lee, Judy E. Kim, Ekaterina V. Pletneva, Jasmin Faraone-Mennella, Harry B. Gray, and Jay R. Winkler

3. Metal Ion Binding Properties of Proteins Related to NeurodegenerationHenryk Kozlowski, Marek Luczkowski, Daniela Valensin, and Gianni Valensin

4. Metallic Prions: Mining the Core of Transmissible Spongiform EncephalopathiesDavid R. Brown

5. The Role of Metal Ions in the Amyloid Precursor Protein and in Alzheimer’s DiseaseThomas A. Bayer and Gerd Multhaup

6. The Role of Iron in the Pathogenesis of Parkinson’s DiseaseManfred Gerlach, Kay L. Double, Mario E. Götz, Moussa B. H. Youdim, and Peter Riederer

7. In Vivo Assessment of Iron in Huntington’s Disease and Other Age-Related Neurodegenerative Brain DiseasesGeorge Bartzokis, Po H. Lu, Todd A. Tishler, and Susan Perlman

8. Copper-Zinc Superoxide Dismutase and Familial Amyotrophic Lateral SclerosisLisa J. Whitson and P. John Hart

9. The Malfunctioning of Copper Transport in Wilson and Menkes DiseasesBibudhendra Sarkar

10. Iron and Its Role in Neurodegenerative DiseasesRoberta J. Ward and Robert R. Crichton

11. The Chemical Interplay between Catecholamines and Metal Ions in Neurological DiseasesWolfgang Linert, Guy N. L. Jameson, Reginald F. Jameson, and Kurt A. Jellinger

12. Zinc Metalloneurochemistry: Physiology, Pathology, and ProbesChristopher J. Chang and Stephen J. Lippard

13. The Role of Aluminum in Neurotoxic and Neurodegenerative ProcessesTamás Kiss, Krisztina Gajda-Schrantz, and Paolo F. Zatta

14. Neurotoxicity of Cadmium, Lead, and MercuryHana R. Pohl, Henry G. Abadin, and John F. Risher

15. Neurodegerative Diseases and Metal Ions. A Concluding OverviewDorothea Strozyk and Ashley I. BushSubject Index

Volume 2: Nickel and Its Surprising Impact in Naturethis book

Volume 3: The Ubiquitous Roles of Cytochrome P450 Proteins(in press)

1. Diversities and Similarities of P450 Systems: An IntroductionMary A. Schuler and Stephen G. Sligar

2. Structural and Functional Mimics of Cytochromes P450Wolf-D. Woggon

3. Structures of P450 Proteins and Their Molecular PhylogenyThomas L. Poulos and Yergalem T. Meharenna

4. Aquatic P450 SpeciesMark J. Snyder

5. The Electrochemistry of Cytochrome P450 SystemsAlan M. Bond, Barry D. Fleming, and Lisandra L. Martin

6. P450 Electron Transfer ReactionsAndrew K. Udit, Stephen M. Contakes, and Harry B. Gray

7. Leakage in Cytochrome P450 Reactions in Relation to Protein Structural PropertiesChristiane Jung

8. Cytochromes P450. Structural Basis for Binding and CatalysisKonstanze von König and Ilme Schlichting

9. Beyond Heme-Thiolate Interactions. Roles of the Secondary Coordination Sphere in P450 SystemsYi Lu and Thomas D. Pfi ster

10. Interactions of Cytochrome P450 with Nitric Oxide and Related LigandsAndrew W. Munro, Kirsty J. McLean, and Hazel M. Girvan

xxiv CONTENTS OF MILS VOLUMES

11. Cytochrome P450-Catalyzed Hydroxylations and EpoxidationsRoshan Perera, Shengxi Jin, Masanori Sono, and John H. Dawson

12. Cytochrome P450 and Steroid Hormone BiosynthesisRita Bernhardt and Michael R. Waterman

13. Carbon-Carbon Bond Cleavage by P450 SystemsJames J. De Voss and Max J. Cryle

14. Design and Engineering of Cytochrome P450 SystemsStephen G. Bell, Nicola Hoskins, Christopher J. C. Whitehouse,and Luet L. Wong

15. Chemical Defence and Exploitation: Biotransformation of Xenobioticsby Cytochrome P450 EnzymesElizabeth M. J. Gillam and Dominic J. B. Hunter

16. Drug Metabolism as Catalyzed by Human Cytochrome P450 SystemsF. Peter Guengerich

17. Cytochrome P450 Enzymes: Observations from the ClinicPeggy L. CarverSubject Index

Volume 4: Biomineralization. From Nature to Application(tentative contents)

1. Crystals and Life. An IntroductionArthur Veis

2. Gene-Directed Crystal Growth Exemplifi ed by the Biomineralization of Calcium CarbonateFred H. Wilt and Christopher E. Killian

3. The Role of Enzymes in Biomineralization ProcessesIngrid M. Weiss and Frédéric Marin

4. Metal-Bacterial Interactions at Both the Planktonic Cell and Biofi lm LevelsRyan Hunter and Terry J. Beveridge

5. Biomineralization of Calcium Carbonate. The Interplay with BiosubstratesAmir Berman and Yael Levi-Kalisman

6. Sulfate-Containing BiomineralsFabienne Bosselmann and Matthias Epple

7. Oxalate BiomineralsEnrique J. Baran and Paula V. Monje

8. Structural Control, Molecular Components, and Multi-Level Regulation of Biosilifi cation in DiatomsAubrey K. Davis, Kim Thamatrakoln, and Mark Hildebrand

9. Dynamics of Biomineralization and BiodemineralizationLijun Wang and George H. Nancollas

CONTENTS OF MILS VOLUMES xxv

10. Mechanism of Mineralization of Collagen Based Connective TissueAdele J. Boskey

11. Mammalian Enamel FormationJanet Moradian-Oldak and Michael Paine

12. Heavy Metals in the Jaws of InvertebratesHelga C. Lichtenengger

13. Ferritin. Biomineralization of IronElizabeth C. Theil

14. Molecular Biology and Magnetism for Magnetic Iron Minerals in BacteriaRichard B. Frankel, Sabrina Schübbe, and Dennis Bazylinski

15. Mechanical Design of Biomineralized TissuesPeter Fratzl

16. Biominerals. Recorders of the PastDanielle Fortin and Susan Glasauer

17. Bio-Inspired Growth of Mineralized TissueDarilis Suarez and William L. Murphy

18. Biomineralization of Novel Inorganic Materials for ApplicationHelmut Cölfen and Markus Antonietti

19. Crystal Tectonics. Chemical Construction and Self-OrganizationAnnie K. PowellSubject Index

Comments and suggestions with regard to contents, topics, and such for future volumes of the series are welcome.

xxvi CONTENTS OF MILS VOLUMES

Met. Ions Life Sci. 2, 1–30 (2007)

1

Biogeochemistry of Nickel and Its Release into the Environment

Tiina M. Nieminen,1 Liisa Ukonmaanaho,1 Nicole Rausch,2 and William Shotyk2

1Finnish Forest Research Institute (Metla),FI-01301 Vantaa, Finland

<[email protected] ><[email protected] >

2Institute of Environmental Geochemistry, University of Heidelberg,D-69120 Heidelberg, Germany<[email protected]>

<[email protected]>

1. INTRODUCTION 22. CHEMISTRY OF NICKEL 2

2.1. Chemical Properties 22.2. Geological Abundance and Occurrence 42.3. Measurement of Nickel in Environmental Samples 4

3. ANCIENT AND MODERN USES OF NICKEL 64. SOURCES OF ATMOSPHERIC NICKEL 6

4.1. Natural Sources 64.2. Anthropogenic Sources 7

5. DEPOSITION AND FATE OF ATMOSPHERIC NICKEL 75.1. Air Quality and Deposition in Polluted Areas

versus Remote Areas 75.2. Regional Indicator Surveys: The Use of Mosses, Lichens, Bark 8

5.2.1. Mosses 85.2.2. Lichens 95.2.3. Bark 10

Metal Ions in Life Sciences, Volume 2 Edited by Astrid Sigel, Helmut Sigel and Roland K. O. Sigel© 2007 John Wiley & Sons, Ltd

2 NIEMINEN, SHOTYK et al.

Met. Ions Life Sci. 2, 1–30 (2007)

5.3. Nickel Concentration in Aquatic and Biotic Media 105.4. Nickel Fluxes in Forested Catchments 12

6. HISTORICAL RECORDS OF NICKEL DEPOSITION 146.1. Sediment 146.2. Peat Bog 156.3. Polar Snow and Ice 15

7. BIOAVAILABILITY AND MOBILITY OF NICKEL IN SOILS 177.1. Uptake and Translocation of Nickel by Plants 177.2. Importance of Partitioning for Bioavailability and Mobility 19

8. SUMMARY AND CONCLUSIONS 21ABBREVIATIONS 21REFERENCES 22

1. INTRODUCTION

Nickel and its compounds are released into the atmosphere from both natural and anthropogenic sources. Although Ni is an essential element to plants and many other biota, there has been much more concern about the toxicity of Ni than about Ni defi ciency. Field observations have indicated a signifi cant increase in heavy metal concentrations in agricultural and forest soils as well as in marine and in-land water sediments during the last century [1,2]. An increase is also frequently observed in remote areas thousands of kilometers away from major anthropo-genic sources due to long-range atmospheric transport, e.g., elevated Ni concen-trations have been reported from the Norwegian arctic and the Finnish Lapland region [3–5]. Nriagu and Pacyna [6] give an estimation of 24 000–87 000 tons in 1983 for the worldwide Ni emissions to the atmosphere, and for the total global release of Ni into soils (atmospheric fallout, wastes, fertilizers, sewage sludge, etc.) an estimate ranging from 106 000 to 544 000 tons per year. In this context, it is important to know the background concentrations of trace elements in uncon-taminated sites for comparison with polluted areas.

2. CHEMISTRY OF NICKEL

2.1. Chemical Properties

Nickel (Z � 28, atomic weight 58.69) belongs to Group 10 (formerly VIII) of the periodic table, the so-called iron–cobalt–nickel group of metals. As such,

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