Geochemistry

About the companion website viii
Chapter 1: Introduction 1
1.1 Geochemistry 1
1.2 This book 2
1.3 The philosophy of science 4
1.4 Elements, atoms, and chemical bonds: some chemical fundamentals 6
1.5 A brief look at the Earth 15
References and suggestions for further reading 19
Chapter 2: Energy, entropy and fundamental thermodynamic concepts 20
2.1 The thermodynamic perspective 20
2.2 Thermodynamic systems and equilibrium 21
2.3 Equations of state 24
2.4 Temperature, absolute zero, and the zeroth law of thermodynamics 26
2.5 Energy and the fi rst law of thermodynamics 27
2.6 The second law and entropy 30
2.7 Enthalpy 38
2.8 Heat capacity 39
2.9 The third law and absolute entropy 47
2.10 Calculating enthalpy and entropy changes 48
2.11 Free energy 51
2.12 The maxwell relations 58
References and suggestions for further reading 58
Problems 59
Chapter 3: Solutions and thermodynamics of multicomponent systems 61
3.1 Introduction 61
3.2 Phase equilibria 62
3.3 Solutions 67
3.4 Chemical potential 68
3.5 Ideal solutions 71
3.6 Real solutions 73
3.7 Electrolyte solutions 80
3.8 Ideal solutions in crystalline solids and their activities 88
3.9 Equilibrium constants 89
3.10 Practical approach to electrolyte equilibrium 96
3.11 Oxidation and reduction 100
References and suggestions for further reading 110
Problems 111
Chapter 4: Applications of thermodynamics to the Earth 116
4.1 Introduction 116
4.2 Activities in non-ideal solid solutions 116
4.3 Exsolution phenomena 120
4.4 Thermodynamics and phase diagrams 122
4.5 Geothermometry and geobarometry 128
4.6 Thermodynamic models of magmas 137
4.7 Reprise: thermodynamics of electrolyte solutions 145
References and suggestions for further reading 154
Problems 156
Chapter 5: Kinetics: the pace of things 160
5.1 Introduction 160
5.2 Reaction kinetics 161
5.3 Relationships between kinetics and thermodynamics 172
5.4 Diffusion 179
5.5 Surfaces, interfaces, and interface processes 191
5.6 Kinetics of dissolution and leaching 201
5.7 Diagenesis 207
References and suggestions for further reading 211
Problems 213
Chapter 6: Aquatic chemistry 217
6.1 Introduction 217
6.2 Acid-base reactions 217
6.3 Complexation 231
6.4 Dissolution and precipitation reactions 239
6.5 Clays and their properties 249
6.6 Mineral surfaces and their interaction with solutions 253
References and suggestions for further reading 265
Problems 265
Chapter 7: Trace elements in igneous processes 268
7.1 Introduction 268
7.2 Behavior of the elements 270
7.3 Distribution of trace elements between coexisting phases 281
7.4 Factors governing the value of partition coefficients 283
7.5 Crystal-fi eld effects 294
7.6 Trace element distribution during partial melting 299
7.7 Trace element distribution during crystallization 310
7.8 Summary of trace element variations during melting and crystallization 315
References and suggestions for further reading 316
Problems 318
Chapter 8: Radiogenic isotope geochemistry 321
8.1 Introduction 321
8.2 Physics of the nucleus and the structure of nuclei 322
8.3 Basics of radiogenic isotope geochemistry 330
8.4 Decay systems and their applications 334
8.5 Cosmogenic and fossil isotopes 360
References and suggestions for further reading 365
Problems 367
Chapter 9: Stable isotope geochemistry 371
9.1 Introduction 371
9.2 Theoretical considerations 373
9.3 Isotope geothermometry 384
9.4 Isotopic fractionation in the hydrologic system 387
9.5 Isotopic fractionation in biological systems 388
9.6 Paleoclimatology 396
9.7 Hydrothermal systems and ore deposits 404
9.8 Stable isotopes in the mantle and magmatic systems 409
9.9 Isotopes of boron and lithium 417
References and suggestions for further reading 424
Problems 428
Chapter 10: The big picture: cosmochemistry 430
10.1 Introduction 430
10.2 In the beginning . . . nucleosynthesis 431
10.3 Meteorites: essential clues to the beginning 442
10.4 Time and the isotopic composition of the solar system 456
10.5 Astronomical and theoretical constraints on
solar system formation 467
10.6 Building a habitable solar system 478
References and suggestions for further reading 489
Problems 492
Chapter 11: Geochemistry of the solid earth 493
11.1 Introduction 493
11.2 The Earth's mantle 493
11.3 Estimating mantle and bulk earth composition 502
11.4 The Earth's core and its composition 510
11.5 Mantle geochemical reservoirs 516
11.6 The crust 529
References and suggestions for further reading 557
Problems 561
Chapter 12: Organic geochemistry, the carbon cycle, and climate 563
12.1 Introduction 563
12.2 A brief biological background 564
12.3 Organic compounds and their nomenclature 565
12.4 The chemistry of life: important biochemical processes 575
12.5 Organic matter in natural waters and soils 580
12.6 Chemical properties of organic molecules 589
12.7 Sedimentary organic matter and coal and oil formation 599
12.8 Isotope composition of hydrocarbons 614
12.9 The carbon cycle and climate 617
References and suggestions for further reading 629
Problems 633
Appendix 635
Index 637