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Geochemistry
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Table of Contents

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

About the Author

William White teaches geochemistry as a Professor of earth and atmospheric sciences at Cornell University. He received a B.A. in geology from the University of California, Berkeley and a PhD in oceanography from the University of Rhode Island. He is a fellow of the Geochemical Society/European Association of Geochemistry and the AGU, and has been named a highly cited author by ISI.

Reviews

The book would also serve well as a complete geochemistryreference book for an introductory class for those students wantingextensive equations and more detailed technicalexplanations. (The Reading Geologist, 1 January2014)

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