William M. White - Geochemistry

1 Cover

2 Preface

3 About the companion website

4 Chapter 1: Introduction1.1 INTRODUCTION 1.2 BEGINNINGS 1.3 GEOCHEMISTRY IN THE TWENTY-FIRST CENTURY 1.4 THE PHILOSOPHY OF SCIENCE 1.5 ELEMENTS, ATOMS, CRYSTALS, AND CHEMICAL BONDS: SOME CHEMICAL FUNDAMENTALS 1.6 A BRIEF LOOK AT THE EARTH 1.7 A LOOK AHEAD REFERENCES AND SUGGESTIONS FOR FURTHER READING NOTES

5 Chapter 2: Energy, entropy, and fundamental thermodynamic concepts2.1 THE THERMODYNAMIC PERSPECTIVE 2.2 THERMODYNAMIC SYSTEMS AND EQUILIBRIUM 2.3 EQUATIONS OF STATE 2.4 TEMPERATURE, ABSOLUTE ZERO, AND THE ZEROTH LAW OF THERMODYNAMICS 2.5 ENERGY AND THE FIRST LAW OF THERMODYNAMICS 2.6 THE SECOND LAW AND ENTROPY 2.7 ENTHALPY 2.8 HEAT CAPACITY 2.9 THE THIRD LAW AND ABSOLUTE ENTROPY 2.10 CALCULATING ENTHALPY AND ENTROPY CHANGES 2.11 FREE ENERGY 2.12 THE MAXWELL RELATIONS* 2.13 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

6 Chapter 3: Solutions and thermodynamics of multicomponent systems3.1 INTRODUCTION 3.2 PHASE EQUILIBRIA 3.3 SOLUTIONS 3.4 CHEMICAL POTENTIAL 3.5 IDEAL SOLUTIONS 3.6 REAL SOLUTIONS 3.7 ELECTROLYTE SOLUTIONS 3.8 IDEAL SOLUTIONS IN CRYSTALLINE SOLIDS AND THEIR ACTIVITIES 3.9 EQUILIBRIUM CONSTANTS 3.10 PRACTICAL APPROACH TO ELECTROLYTE EQUILIBRIUM 3.11 OXIDATION AND REDUCTION 3.12 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

7 Chapter 4: Applications of thermodynamics to the Earth4.1 INTRODUCTION 4.2 ACTIVITIES IN NONIDEAL SOLID SOLUTIONS 4.3 EXSOLUTION PHENOMENA 4.4 THERMODYNAMICS AND PHASE DIAGRAMS 4.5 GEOTHERMOMETRY AND GEOBAROMETRY 4.6 THERMODYNAMIC MODELS OF MAGMAS 4.7 REPRISE: THERMODYNAMICS OF ELECTROLYTE SOLUTIONS 4.8 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

8 Chapter 5: Kinetics: the pace of things5.1 INTRODUCTION 5.2 REACTION KINETICS 5.3 RELATIONSHIPS BETWEEN KINETICS AND THERMODYNAMICS 5.4 DIFFUSION 5.5 SURFACES, INTERFACES, AND INTERFACE PROCESSES 5.6 KINETICS OF DISSOLUTION 5.7 DIAGENESIS 5.8 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

9 Chapter 6: Aquatic chemistry6.1 INTRODUCTION 6.2 ACID–BASE REACTIONS 6.3 COMPLEXATION 6.4 DISSOLUTION AND PRECIPITATION REACTIONS 6.5 CLAYS AND THEIR PROPERTIES 6.6 MINERAL SURFACES AND THEIR INTERACTION WITH SOLUTIONS 6.7 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

10 Chapter 7: Trace elements in igneous processes7.1 INTRODUCTION 7.2 BEHAVIOR OF THE ELEMENTS 7.3 DISTRIBUTION OF TRACE ELEMENTS BETWEEN COEXISTING PHASES 7.4 FACTORS GOVERNING THE VALUE OF PARTITION COEFFICIENTS 7.5 CRYSTAL-FIELD EFFECTS 7.6 TRACE ELEMENT DISTRIBUTION DURING PARTIAL MELTING 7.7 TRACE ELEMENT DISTRIBUTION DURING CRYSTALLIZATION 7.8 SUMMARY OF TRACE ELEMENT VARIATIONS DURING MELTING AND CRYSTALLIZATION REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

11 Chapter 8: Radiogenic isotope geochemistry8.1 INTRODUCTION 8.2 PHYSICS OF THE NUCLEUS AND THE STRUCTURE OF NUCLEI 8.3 BASICS OF RADIOGENIC ISOTOPE GEOCHEMISTRY AND GEOCHRONOLOGY 8.4 DECAY SYSTEMS AND THEIR APPLICATIONS 8.5 “EXTINCT” AND COSMOGENIC NUCLIDES 8.6 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

12 Chapter 9: Stable isotope geochemistry9.1 INTRODUCTION 9.2 THEORETICAL CONSIDERATIONS 9.3 ISOTOPE GEOTHERMOMETRY 9.4 ISOTOPIC FRACTIONATION IN THE HYDROLOGIC SYSTEM 9.5 ISOTOPIC FRACTIONATION IN BIOLOGICAL SYSTEMS 9.6 PALEOCLIMATOLOGY 9.7 HYDROTHERMAL SYSTEMS AND ORE DEPOSITS 9.8 MASS-INDEPENDENT SULFUR ISOTOPE FRACTIONATION AND THE RISE OF ATMOSPHERIC OXYGEN 9.9 STABLE ISOTOPES IN THE MANTLE AND MAGMATIC SYSTEMS 9.10 NONTRADITIONAL STABLE ISOTOPES 9.11 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

13 Chapter 10: The big picture: cosmochemistry10.1 INTRODUCTION 10.2 IN THE BEGINNING … NUCLEOSYNTHESIS 10.3 METEORITES: ESSENTIAL CLUES TO THE BEGINNING 10.4 TIME AND THE ISOTOPIC COMPOSITION OF THE SOLAR SYSTEM 10.5 ASTRONOMICAL AND THEORETICAL CONSTRAINTS ON SOLAR SYSTEM FORMATION 10.6 BUILDING A HABITABLE SOLAR SYSTEM 10.7 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

14 Chapter 11: Geochemistry of the solid Earth11.1 INTRODUCTION 11.2 THE EARTH'S MANTLE 11.3 ESTIMATING MANTLE AND BULK EARTH COMPOSITION 11.4 THE EARTH'S CORE AND ITS COMPOSITION 11.5 MANTLE GEOCHEMICAL RESERVOIRS 11.6 THE CRUST 11.7 SUBDUCTION ZONE PROCESSES 11.8 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

15 Chapter 12: Organic geochemistry, the carbon cycle, and climate12.1 INTRODUCTION 12.2 A BRIEF BIOLOGICAL BACKGROUND 12.3 ORGANIC COMPOUNDS AND THEIR NOMENCLATURE 12.4 THE CHEMISTRY OF LIFE: IMPORTANT BIOCHEMICAL PROCESSES 12.5 ORGANIC MATTER IN NATURAL WATERS AND SOILS 12.6 CHEMICAL PROPERTIES OF ORGANIC MOLECULES 12.7 SEDIMENTARY ORGANIC MATTER 12.8 PETROLEUM AND COAL FORMATION 12.9 THE CARBON CYCLE AND CLIMATE 12.10 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

16 Chapter 13: The land surface: weathering, soils, and streams13.1 INTRODUCTION 13.2 REDOX IN NATURAL WATERS 13.3 WEATHERING, SOILS, AND BIOGEOCHEMICAL CYCLING 13.4 WEATHERING RATES 13.5 THE COMPOSITION OF RIVERS 13.6 CONTINENTAL SALINE WATERS 13.7 SUMMARY REFERENCES AND SUGGESTIONS FOR FURTHER READING PROBLEMS NOTES

17 Chapter 14: The ocean as a chemical system14.1 INTRODUCTION 14.2 SOME BACKGROUND OCEANOGRAPHIC CONCEPTS 14.3 COMPOSITION OF SEAWATER 14.4 SOURCES AND SINKS OF DISSOLVED MATTER IN SEAWATER 14.5 SUMMARY REFERENCES PROBLEMS NOTES

18 Chapter 15: Applied geochemistry15.1 INTRODUCTION 15.2 MINERAL RESOURCES 15.3 ENVIRONMENTAL GEOCHEMISTRY 15.4 SUMMARY REFERENCES PROBLEMS NOTES

19 Appendix: Constants, units and conversionsPHYSICAL AND CHEMICAL CONSTANTS THE EARTH SI UNITS AND CONVERSIONS SI PREFIXES

20 Index LIST OF EXAMPLES

21 End User License Agreement

1 Chapter 2 Table 2.1 Van der Waals constants for selected gases. Table 2.2 Standard state thermodynamic data for some important minerals.

2 Chapter 3 Table 3.1 H 2O and CO 2fugacity coefficients. Table 3.2a Debye–Hückel solvent parameters. Table 3.2b Debye–Hückel effective radii. Table 3.3 EH° and pε° for some half-cell reactions.

3 Chapter 4 Table 4.1 Margules parameters for ilmenite and titanomagnetite solid solution... Table 4.2 Commonly used thermobarometers. Table 4.3 Ion solvation numbers. Table 4.4 Truesdell–Jones parameters.

4 Chapter 5Table 5.1 Activation energies of some geochemical reactions.Table 5.2 Frequency factors and activation energies of diffusion coefficients...Table 5.3 Trace diffusion coefficients for ions in infinitely dilute aqueous ...Table 5.4 Tracer diffusion coefficients in silicate melts.Table 5.5 Dissolution rates and mean lifetimes of crystals at 25°C and pH 5.Table 5.6 Apparent activation energies for dissolution reactions in near-neut...

5 Chapter 6Table 6.1 Equilibrium constants for the carbonate system.Table 6.2 Classification of metal ions.Table 6.3 Ion exchange capacity of clays.Table 6.4 Point of zero net proton charge of common sedimentary particles.

6 Chapter 7Table 7.1 Goldschmidt's classification of the elements.Table 7.2 Free energy of formation of some oxides.Table 7.3 Normalizing values used for rare earth plots.Table 7.4 Mineral-melt partition coefficients.Table 7.5 Electronic configurations and crystal-field stabilization energies ...Table 7.6 Crystal-field splittings and stabilization energies in transition-m...

7 Chapter 8Table 8.1 Numbers of stable odd and even nuclei.Table 8.2 Long-lived radioactive decay systems of geochemical interest.Table 8.3 Initial isotopic compositions and parent/daughter ratios.Table 8.4 Half-lives and decay constants of long-lived U and Th daughters.Table 8.5 Some radioactive cosmogenic nuclides of geologic interest.