MODERN BIOGEOCHEMISTRY MODERN BIOGEOCHEMISTRY

VLADIMIR N. BASHKIN Moscow State University, Russia

In cooperation with Robert W. Howarth, Cornell University, USA

KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: 0-306-48103-0 Print ISBN: 1-4020-0992-5

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Preface vii

CHAPTER 1: INTRODUCTION 1

1. The Basic Concepts and Approaches to the Subject 1

2. Historical Development of Biogeochemistry 5 Further Reading 10 Questions and Problems 11

CHAPTER 2: EVOLUTIONARY BIOGEOCHEMISTRY 13

1. Introduction 13

2. Origin of Elements 14

3. Earth Evolution 15 3.1 Evolution of the Lithosphere 15 3.2 Evolution of the Atmosphere 21 3.3 Evolution of the Hydrosphere 27 3.4 Prebiotic Earth and Mineral Cycling 31

4. Origin of Life 35 4.1 When Did Life Originate? 36 4.2 Primordial Soup 38 4.3 Clays and Life 42 4.4 Pyrite-Based Life Origin 43 4.5 The “Thioester World” 47

5. Evolution of Biogeochemical Cycles 50 5.1 Application of Isotopic Analysis for the Geological History of the Biogeochemical Cycles 50 5.2 Evolution of Oxygen Biogeochemical Cycle 53 5.3 Evolution of the Nitrogen Biogeochemical Cycle 54 5.4 Evolution of Carbon and Sulfur Biogeochemical Cycles 56

6. Role of Biogeochemical Cycles in Biogenic Deposition Formation 61 6.1 Formation of Biogenic Depositions from Kerogen 63 6.2 Geological and Biological Factors of Oil Composition Formation 65 Further Reading 68 Questions and Problems 69 ii

CHAPTER 3: BIOGEOCHEMICAL CYCLING OF MACROELEMENTS 73

1. Introduction to Biogeochemical Cycling of Elements 73 1.1 Biogeochemical Cycling of Macroelements in the Atmosphere 76 1.2 Biogeochemical Cycling of Macroelements in Terrestrial Aquatic Ecosystems 80 1.3 Biogeochemical Cycling of Macroelements in Soils 87

2. Biogeochemistry Cycle of Carbon 92 2.1 Turnover of Carbon in the Biosphere 95 2.2 Carbon Fluxes in Terrestrial Ecosystems 99 2.3 Comparison of Carbon Biogeochemical Processes in Terrestrial and Aquatic Ecosystems 101 2.4 Global Carbon Fluxes 106

3. Biogeochemistry Cycle of Nitrogen 109 3.1 Nitrogen Cycling Processes 110 3.2 Main Nitrogen Species 111 3.3 General Characterization of Nitrogen Biogeochemical Cycling Processes 113 3.4 Global Nitrogen Cycle 120

4. Biogeochemistry Cycle of Phosphorus 125 4.1 Phosphorus Forms in the Biosphere 125 4.2 Fluxes and Pools of Phosphorus in the Biosphere 128

5. Biogeochemistry Cycle of Sulfur 134 5.1 Sulfur in the Earth 134 5.2 Sulfur in the Biosphere 136 5.3 Global Fluxes and Pools of Sulfur 139

6. Biogeochemical Cycle of Silicon 144 6.1 Silicon in the Earth 144 6.2 Migration and Accumulation of Silicon Compounds in Soil-Water Systems 144 6.3 Biogeochemical Migration of Silicon in Arid Tropical Ecosystems 146 6.4 Biogeochemical Migration of Silicon in Wet Boreal and Tropical Ecosystems 147 6.5 The Importance of Silicon in Coastal Ecosystems 151 6.6 Global Pools and Fluxes of Silicon 151

7. Biogeochemistry Cycle of Calcium 152 7.1 Calcium in the Earth 152 7.2 Calcium Pools and Fluxes in the Biosphere 153 7.3 Solubility of Calcium Species in Natural Waters 153 iii

7.4 Overall Global Biogeochemical Fluxes of Calcium 157 Further Reading 158 Questions and Problems 158

CHAPTER 4: BIOGEOCHEMICAL CYCLING OF TRACE ELEMENTS 161

1. Biogeochemistry of Copper 161 1.1 Copper Speciation 162 1.2 Global Cycle of Copper 166

2. Biogeochemistry of Zinc 167 2.1 Zinc in Biosphere 168 2.2 Biogeochemical Fluxes of Zinc 171 2.3 Global Biogeochemical Fluxes and Pools of Zinc 173

3. Biogeochemistry of Selenium 173 3.1 Selenium in the Biosphere 174 3.2 Selenium Enriched Biogeochemical Food Webs 175 3.3 Case Studies 175 3.4 Global Selenium Cycle 184

4. Biogeochemistry of Boron 185 4.1 Boron Enriched Biogeochemical Food Webs in Arid Ecosystems 185

5. Biogeochemistry of Molybdenum 192 5.1 Mo-Enriched Biogeochemical Food Web 192 5.2 Biochemical and Physiological Response to High Content of Molybdenum in Biogeochemical Food Webs 195 Further Reading 196 Questions and Problems 196

CHAPTER 5: INTERACTIONS OF BIOGEOCHEMICAL CYCLES 199 1. Stoichiometric Aspects of Nutrient Uptake and Nutrient Limitation of Living Matter Production 199 1.1 Interactions of Biogeochemical Cycles in Terrestrial Ecosystems 201 1.2 Eutrophication of Natural Waters 204 2. Stoichiometric Aspects of Nutrient Recycling 214 2.1 Stoichiometric Aspects of Nutrient Recycling in Terrestrial Ecosystems 214 2.2 Stoichiometric Aspects of Nutrient Recycling in Aquatic Ecosystems 219

3. Thermodynamics of Bacterial Energetics 221 4. Biogeochemical modelling 225 iv

4.1 General Principles 225 4.2 Models 229 Further Reading 235 Questions and Problems 236

CHAPTER 6: REGIONAL BIOGEOCHEMISTRY 239

1. Biogeochemistry of Arctic Ecosystems 239 1.1 Geographical Peculiarities 239 1.2 Landscape and Vegetation Impacts 240 1.3 Chemical Composition of Plants 242 1.4 Biogeochemistry of Soils 243 1.5 Biogeochemical Cycles 244

2. Biogeochemistry of Tundra Ecosystems 246 2.1 Plant Uptake of Trace Metals 246 2.2 Biogeochemistry of Tundra Soils 246 2.3 Productivity of Tundra Ecosystems and Cycling of Elements 247

3. Biogeochemistry of Boreal and Sub-Boreal Forest Ecosystems 247 3.1 Biogeochemical Cycling of Elements in Forest Ecosystems 247 3.2 Biogeochemical Fluxes in Soils of Boreal Forest Ecosystems 265 3.3 Biogeochemical Processes in the Soil-Water System of Boreal and Sub-Boreal Forest Ecosystems 269

4. Biogeochemistry of Steppes and Deserts 274 4.1 Biogeochemical Cycle of Nutrients in Arid Ecosystems 274 4.2 Soil Biogeochemistry in Arid Ecosystems 282 4.3 Role of Biogeochemical Processes in Aqueous Migration of Elements in Steppe Ecosystems 285

5. Biogeochemistry of Tropical Ecosystems 287 5.1 Biogeochemical Cycles of Chemical Species in Tropical Ecosystems 288 5.2 Biogeochemical Peculiarities of Tropical Soils 294 5.3 Biogeochemistry of Mangrove Ecosystems 299 Further Reading 304 Questions and Problems 304

CHAPTER 7: BIOGEOCHEMICAL MAPPING 307

1. Characterization of Soil-Biogeochemical Conditions in the World’s Terrestrial Ecosystems 307 1.1 Eurasia 312 1.2 North America 320 1.3 Latin and South America 325 v

1.4 Africa 328 1.5 Australia 330

2. Biogeochemical Classification and Simulation of Biosphere Organization 332 2.1 Biogeochemical Classification of the Biosphere 332 2.2 Methodology of biogeochemical cycling simulation for biosphere mapping 335

3. Biogeochemical Mapping on Continental, Regional and Local Scales 341 3.1 Methods of Biogeochemical Mapping 341 3.2 Regional Biogeochemical Mapping of North Eurasia 343 3.3 Biogeochemical Mapping of the South Ural Region, Russia 343 Further Reading 352 Questions and Problems 353

CHAPTER 8: ENVIRONMENTAL BIOGEOCHEMISTRY 355

1. Environmental Biogeochemistry of Nitrogen 356 1.1 Environmental Biogeochemistry of Nitrogen in the North Atlantic Region 356 1.2 Environmental Biogeochemistry of Nitrogen in the East Asian Region 382

2. Environmental Biogeochemistry of Mercury 403 2.1 Speciation of Mercury 404 2.2 Anthropogenic Mercury Loading 407 2.3 Biological Effects of Mercury 407 2.4 Environmental Biogeochemical Cycling of Mercury 409 2.5 Global Mass Balance of Mercury 413

3. Environmental Biogeochemistry of Lead 416 3.1 Speciation of Lead 417 3.2 Anthropogenic Lead Loading 417 3.3 Biological Effects of Lead 417 3.4 Environmental Biogeochemistry of Lead 418 3.5 Global Mass Balance of Lead 424 Further Reading 427 Questions and Problems 428

CHAPTER 9: HUMAN BIOGEOCHEMISTRY 431

1. Biogeochemical and Physiological Peculiarities of Human Population Health 431 1.1 Cancer Diseases in the Carpathian Mountain Sub-Region of the Biosphere 435 vi

1.2 Cancer Diseases in Middle Volga Silicon Sub-Region of the Biosphere 436 1.3 Cancer Diseases in the Boron Biogeochemical Sub-Region of the Biosphere 440

2. Human Health Indices in Technogenic and Agrogenic Biogeochemical Provinces 447 2.1 Physiological Indices for Human Biogeochemical Studies 447 2.2 Case study of Interactions between Human Health Indexes and Pollution in Crimea Dry Steppe Region of the Biosphere 452 Further Reading 455 Questions And Problems 455

CHAPTER 10: BIOGEOCHEMICAL STANDARDS 457

1. Critical Load Concept for Impact Oriented Emission Abatement Strategy of Sulfur and Nitrogen Acid-Forming and Eutrophication Compounds 457 1.1 Critical Load Approach: Challenges and Biogeochemical Fundamentals 457 1.2 General Approaches for Calculating Critical Loads 464 1.3 Environmental Risk Assessment under Critical Load Calculations 466 1.4 Sensitivity of European Ecosystems to Acid Deposition 471 1.5 Sensitivity of North American Ecosystems to Acid Deposition 476 1.6 Sensitivity of East Asian Ecosystem to Acid Deposition 489 1.7 Acid Deposition Influence on the Biogeochemical Migration of Heavy Metals in the Food Web 508 2. Calculation of critical loads for heavy metals at terrestrial and aquatic ecosystems 510 2.1 Selection of Receptor 512 2.2 Critical Limits 514 2.3 Calculation Methods 520 2.4 Input Data 524

3. Examples of Critical Loads Calculations for Heavy Metals 525 3.1 Calculation and Mapping of Critical Loads for HM in Germany 525 3.2 Calculation and Mapping of Critical Loads for Cd and Pb in the European Part of Russia 528 Further Reading 531 Questions and Problems 532

CHAPTER 11: FUTURE TRENDS IN MODERN BIOGEOCHEMISTRY 535 References 539 Index 555 vii

PREFACE

Biogeochemistry is becoming an increasingly popular subject in graduate edu- cation. Courses in ecology, geography, biology, chemistry, environmental science, public health, and environmental engineering all have to include biogeochemistry in their syllabuses to a greater or lesser extent. Humanity’s ever growing impact on the Environment, and the consequent local, regional, and global effect demand a profound understanding of the mechanisms underlying the sustainability of the biosphere and its compounds. The ideas of biogeochemistry about the universality of biogeochemical cycles involving the mass exchange of chemical elements between living organisms and the environment in the Earth’s surface appear to be quite productive in this high priority academic and scientific discipline. In biogeochemical cycling the active prin- ciples come from biota which global biological and geological activity alter slowly the biosphere’s compartments. On the other hand, the environment causes the living organisms evolve. Biogeochemistry is the study of biological controls on the chemistry of the envi- ronment and geochemical regulation of ecological structure and function. Although the term was first used some 75 years ago, roots of this discipline can be traced to the earliest development of the natural sciences, before biology, geology, and chemistry became separate disciplines. Today biogeochemistry serves as a force of reintegration across these fields. This textbook is aimed at generalizing the modern ideas of biogeochemical devel- opment during recent decades. Only a few textbooks are available for undergraduate and graduate students, however, as most books deal mainly with advanced research aspects of the subject. This book aims at supplementing the existing textbooks by pro- viding a modern understanding of biogeochemistry, from evolutionary biogeochem- istry to the practical application of biogeochemical ideas as a human biogeochemistry, biogeochemical standards, and biogeochemical technologies. The reader will start from the history of biogeochemistry, which is important in this science inspite of being relatively young. The names of V. Vernadsky, F. Clark, A. Vinogradov, G. Hutchinson, A. Fersman, V. Goldschmidt, V. Kovalsky, E. Degans, V. Kovda, D. Atkinson, G. Likens, S. Miller, V. Dobrovolsky and many other scientists who carried out the biogeochemical research in various countries have to be known to students. During the last 3.5–3.8 billion years the evolution of the Earth and biogeochemical cycles have been developing in parallel and consequently the ideas of evolutionary biogeochemistry (Chapter 2) provide a key to understanding of the modern atmosphere, biosphere, and hydrosphere. The biogenic depositions which are very important for our civilization, were formed during geological history under the active influence of biogeochemical cycles, and this item is also discussed in this text. The biogeochemical cycling of macro and trace elements is a crucial point of the textbook (Chapters 3 & 4). However, the main attention here is given to the description of natural regularities of global biogeochemical cycling. The conceptual ways of considering the interactions of element cycles such as stoichiometric aspects of nutrient uptake (and nutrient limitation of production), stoichoimetric aspects of viii nutrient recycling, thermodynamics as applicable to bacterial energetics (and the use of different electron acceptors), etc., are elucidated in Chapter 5. The descrip- tion of regional biogeochemistry gives readers the possibility of understanding the qualitative and quantitative parameters of different cycles in different places of the Earth (Chapter 6). The text also presents a general understanding of the ideas of biogeochemical mapping. Although this has still not been carried out for the whole planet, some examples are shown, for instance, in North Eurasia. Soil-biogeochemical regionalization is considered as a key for the preliminary mapping on a continental scale (Chapter 7). As a complement to the biogeochemistry of natural ecosystems, environmental biogeochemistry is to show the pollution processes as a disturbance of natural biogeochemical cycles (Chapter 8). Human biogeochemistry is now devel- oping in various countries. This is considered to be very important for understanding human illnesses, human diet, and human adaptation, and the relevant state of the art of human biogeochemistry is shown in Chapter 9. At present ecological standards and norms based on the understanding and simulation of biogeochemical cycles of different elements are forming in many countries. The critical load calculation and mapping are widely used in Europe, North America, and Asia. I think this would be of interest for students as well (Chapter 10). This text is to a certain extent a summary of both scientific results of various authors and of classes in biogeochemistry, which were given to students by the author during the last 5–10 years in different universities. So we thank the many students of the Universities of Cornell, Moscow, Pushchino, Seoul, and Bangkok, who explored this subject initially without a textbook. The critical discussion and comments during these classes have provided us with the possibility of presenting this book.

Vladimir Bashkin, Professor, Moscow State University, Russia