Table of Contents
1 Theoretical and Experimental Principles 1
1.1 General Characteristics of Isotopes 1
1.2 Isotope Effects 4
1.3 Isotope Fractionation Processes 5
1.3.1 Isotope Exchange 6
1.3.2 Kinetic Effects 11
1.3.3 Mass Dependent and Mass Independent Isotope Effects 12
1.3.4 Multiply Substituted Isotopologues 13
1.3.5 Diffusion 15
1.3.6 Other Factors Influencing Isotopic Fractionations 17
1.3.7 Isotope Geothermometers 19
1.4 Basic Principles of Mass Spectrometry 23
1.4.1 Continuous Flow: Isotope Ratio Monitoring Mass Spectrometers 26
1.5 Standards 27
1.6 General Remarks on Sample Preparation Methods for Gases 29
1.7 Microanalytical Techniques 31
1.7.1 Laser Microprobe 31
1.7.2 Secondary Ion Mass Spectrometry 31
1.8 Stable Isotope Variations of Heavy Elements 32
2 Isotope Fractionation Processes of Selected Elements 35
2.1 Hydrogen 36
2.1.1 Preparation Techniques and Mass Spectrometric Measurements 36
2.1.2 Standards 37
2.1.3 Fractionation Processes 38
2.2 Lithium 42
2.3 Boron 45
2.4 Carbon 48
2.4.1 Preparation Techniques 48
2.4.2 Standards 49
2.4.3 Fractionation Processes 49
2.4.4 Interactions between the Carbonate-Carbon Reservoir and Organic Carbon Reservoir 53
2.5 Nitrogen 54
2.6 Oxygen 58
2.6.1 Preparation Techniques 58
2.6.2 Standards 60
2.6.3 Fractionation Processes 61
2.6.4 Fluid-Rock Interactions 66
2.7 Magnesium 68
2.8 Silicon 70
2.9 Sulfur 71
2.9.1 Preparation Techniques 72
2.9.2 Fractionation Mechanisms 73
2.10 Chlorine 78
2.10.1 Methods 79
2.10.2 Characteristic Features of CI Isotope Geochemistry 79
2.10.3 Chlorine Isotopes in the Environment 80
2.11 Calcium 81
2.12 Chromium 83
2.13 Iron83
2.14 Copper 86
2.15 Zinc 87
2.16 Germanium 88
2.17 Selenium 88
2.18 Molybdenum 89
2.19 Mercury 90
2.20 Thallium 92
3 Variations of Stable Isotope Ratios in Nature 93
3.1 Extraterrestrial Materials 93
3.1.1 Chondrites 94
3.1.2 Evolved Extraterrestrial Materials 99
3.2 The Isotopic Composition of the Earth's Upper Mantle 103
3.2.1 Oxygen 104
3.2.2 Hydrogen 105
3.2.3 Carbon 107
3.2.4 Nitrogen 108
3.2.5 Sulfur 109
3.2.6 Lithium and Boron 110
3.3 Magmatic Rocks 111
3.3.1 Fractional Crystallization 111
3.3.2 Differences between Volcanic and Plutonic Rocks 112
3.3.3 Low-Temperature Alteration Processes 112
3.3.4 Assimilation of Crustal Rocks 112
3.3.5 Basaltic Rocks from Different Tectonic Settings 113
3.3.6 Ocean Water/Basaltic Crust Interactions 115
3.3.7 Granitic Rocks 115
3.4 Volatiles in Magmatic Systems 117
3.4.1 Glasses 118
3.4.2 Volcanic Gases and Hot Springs 120
3.4.3 Isotope Thermometers in Geothermal Systems 123
3.5 Ore Deposits and Hydrothermal Systems 123
3.5.1 Origin of Ore Fluids 125
3.5.2 Wall-Rock Alteration 128
3.5.3 Fossil Hydrothermal Systems 128
3.5.4 Hydrothermal Carbonates 129
3.5.5 Sulfur Isotope Composition of Ore Deposits 130
3.5.6 Metal Isotopes 136
3.6 Hydrosphere 136
3.6.1 Meteoric Water: General Considerations 137
3.6.2 Ice Cores 141
3.6.3 Groundwater 142
3.6.4 Isotope Fractionations during Evaporation 143
3.6.5 Ocean Water 144
3.6.6 Pore Waters 146
3.6.7 Formation Water 147
3.6.8 Water in Hydrated Salt Minerals 149
3.7 The Isotopic Composition of Dissolved and Particulate Compounds in Ocean and Fresh Waters 149
3.7.1 Carbon Species in Water 150
3.7.2 Nitrogen 154
3.7.3 Oxygen 155
3.7.4 Sulfate 155
3.8 Isotopic Composition of the Ocean during Geologic History 157
3.8.1 Oxygen 157
3.8.2 Carbon 159
3.8.3 Sulfur 161
3.8.4 Iron 162
3.9 Atmosphere 163
3.9.1 Atmospheric Water Vapor 164
3.9.2 Nitrogen 164
3.9.3 Oxygen 166
3.9.4 Carbon Dioxide 167
3.9.5 Carbon Monoxide 172
3.9.6 Methane 173
3.9.7 Hydrogen 174
3.9.8 Sulfur 174
3.9.9 Mass-Independent Isotope Effects in Atmospheric Compounds 175
3.10 Biosphere 177
3.10.1 Living Organic Matter 177
3.10.2 Indicators of Diet and Metabolism 182
3.10.3 Tracing Anthropogenic Organic Contaminant Sources 183
3.10.4 Fossil Organic Matter 183
3.10.5 Marine vs. Terrestrial Organic Matter 184
3.10.6 Oil 185
3.10.7 Coal 187
3.10.8 Natural Gas 187
3.11 Sedimentary Rocks 191
3.11.1 Clay Minerals 191
3.11.2 Clastic Sedimentary Rocks 193
3.11.3 Biogenic Silica and Cherts 195
3.11.4 Marine Carbonates 196
3.11.5 Diagenesis 201
3.11.6 Limestones 202
3.11.7 Dolomites 202
3.11.8 Freshwater Carbonates 203
3.11.9 Phosphates 205
3.11.10 Iron Oxides 206
3.11.11 Sedimentary Sulfur 207
3.12 Palaeoclimatology 208
3.12.1 Continental Records 209
3.12.2 Marine Records 214
3.13 Metamorphic Rocks 217
3.13.1 Contact Metamorphism 221
3.13.2 Regional Metamorphism 222
3.13.3 Lower Crustal Rocks 224
3.13.4 Thermometry 224
References 229
Index 281
