Hoefs J. Stable isotope geochemistry
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Stable Isotope Geochemistry
Jochen Hoefs
Stable Isotope Geochemistry
Sixth Edition
ABC
Jochen Hoefs
University of Göttingen
Goldschmidtstr. 1
37077 Göttingen
Germany
ISBN: 978-3-540-70703-5 e-ISBN: 978-3-540-70708-0
Library of Congress Control Number: 2008933507
c
° 2009 Springer-Verlag Berlin Heidelberg
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Preface
Stable isotope investigations in the earth sciences continue to grow, maybe faster
than ever before. After publication of the 5th edition, tremendous progress has been
achieved in many subfields of stable isotope geochemistry. To name a few:
– Applications of Multicollector - ICP-MS has grown rapidly and now enable in-
vestigations on natural isotope variations of a wide range of transition and heavy
elements that could not previously be measured with adequate precision.
– Precise ion probe measurements on the micrometer scale allow the detection of
the growth and dissolution history of minerals.
– Evidence for mass-independent fractionation in a variety of compounds and ele-
ments has increased considerably.
– High precision analysis of the multiple rare isotopes of a specific element permit
the distinction of different mass-dependent fractionation mechanisms.
– Precise measurements of molecules containing more than one rare isotope in-
dicate non-random distributions of the rare isotopes, which potentially may be
utilized as one-mineral thermometers.
These recent advances made a further revision necessary. Again I have tried to
provide a contemporary overview of the entire field of stable isotope geochemistry
enabling a quick access to the most recent literature, although many references date
back to the 1960 and 1970s when seminal papers were published. I am fully aware
of omissions and shortcomings, but I hope the new edition gives a well balanced
discussion of the whole field including the new isotope systems introduced mainly
by MC-ICP-MS techniques.
My colleagues Michael B
¨
ottcher, Max Coleman, Alan Matthews and Harald
Strauß have reviewed an early draft, which is gratefully acknowledged. Yongsheng
He was of great help during the preparation of some figures. I take, however, full
responsibility for any shortcomings that remain.
v
Contents
1 Theoretical and Experimental Principles.......................... 1
1.1 General Characteristics of Isotopes. ............................ 1
1.2 IsotopeEffects.............................................. 4
1.3 IsotopeFractionationProcesses ............................... 5
1.3.1 Isotope Exchange. . . . ................................ 6
1.3.2 KineticEffects...................................... 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 IsotopeGeothermometers............................. 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 LaserMicroprobe ................................... 31
1.7.2 Secondary Ion Mass Spectrometry ..................... 31
1.8 StableIsotopeVariationsofHeavyElements .................... 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 FractionationProcesses............................... 38
vii
viii Contents
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 FractionationProcesses............................... 49
2.4.4 Interactions between the Carbonate-Carbon Reservoir
andOrganicCarbonReservoir......................... 53
2.5 Nitrogen . .................................................. 54
2.6 Oxygen. . .................................................. 58
2.6.1 Preparation Techniques . . . ............................ 58
2.6.2 Standards . . . ....................................... 60
2.6.3 FractionationProcesses............................... 61
2.6.4 Fluid-RockInteractions .............................. 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
2.10Chlorine................................................... 78
2.10.1 Methods ........................................... 79
2.10.2 Characteristic Features of Cl Isotope Geochemistry . . . . . . . 79
2.10.3 Chlorine Isotopes in the Environment . . . . . .............. 80
2.11Calcium ................................................... 81
2.12Chromium ................................................. 83
2.13Iron....................................................... 83
2.14 Copper . . .................................................. 86
2.15Zinc ...................................................... 87
2.16Germanium ................................................ 88
2.17Selenium .................................................. 88
2.18 Molybdenum . . . . ........................................... 89
2.19Mercury................................................... 90
2.20 Thallium .................................................. 92
Contents ix
3 Variations of Stable Isotope Ratios in Nature ...................... 93
3.1 ExtraterrestrialMaterials..................................... 93
3.1.1 Chondrites . . ....................................... 94
3.1.2 EvolvedExtraterrestrialMaterials...................... 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 LithiumandBoron ..................................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-TemperatureAlterationProcesses..................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 IsotopeThermometersinGeothermalSystems ...........123
3.5 Ore Deposits and Hydrothermal Systems. . . .....................123
3.5.1 OriginofOreFluids .................................125
3.5.2 Wall-RockAlteration ................................128
3.5.3 FossilHydrothermalSystems..........................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 IceCores...........................................141
3.6.3 Groundwater .......................................142
3.6.4 Isotope Fractionations during Evaporation . ..............143
3.6.5 Ocean Water ........................................144
3.6.6 PoreWaters ........................................146
3.6.7 FormationWater ....................................147
3.6.8 WaterinHydratedSaltMinerals .......................149
x Contents
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 CarbonDioxide.....................................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 LivingOrganicMatter................................177
3.10.2 IndicatorsofDietandMetabolism .....................182
3.10.3 Tracing Anthropogenic Organic Contaminant Sources . . . . . 183
3.10.4 FossilOrganicMatter ................................183
3.10.5 Marinevs.TerrestrialOrganicMatter...................184
3.10.6 Oil................................................185
3.10.7 Coal...............................................187
3.10.8 NaturalGas ........................................187
3.11 Sedimentary Rocks . . . .......................................191
3.11.1 ClayMinerals.......................................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 IronOxides.........................................206
3.11.11 Sedimentary Sulfur . . ................................207
Contents xi
3.12 Palaeoclimatology. . . . .......................................208
3.12.1 Continental Records . ................................209
3.12.2 Marine Records . . . . . ................................214
3.13 Metamorphic Rocks . . .......................................217
3.13.1 ContactMetamorphism...............................221
3.13.2 Regional Metamorphism. . ............................222
3.13.3 Lower Crustal Rocks . ................................224
3.13.4 Thermometry.......................................224
References .........................................................229
Index .............................................................281