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Geochemistry

Author: William M White
Publisher: Chichester : Wiley Blackwell, 2020.
Edition/Format:   eBook : Document : English : Second editionView all editions and formats
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Material Type: Document, Internet resource
Document Type: Internet Resource, Computer File
All Authors / Contributors: William M White
ISBN: 9781119438106 1119438101
OCLC Number: 1191036611
Description: 1 online resource
Contents: Preface xvAbout the companion website xviiChapter 1: Introduction 11.1 Introduction 11.2 Beginnings 11.3 Geochemistry in the twenty-first century 31.4 The philosophy of science 41.4.1 Building scientific understanding 41.4.2 The scientist as skeptic 51.5 Elements, atoms, crystals, and chemical bonds: some chemical fundamentals 61.5.1 The periodic table 61.5.2 Electrons and orbits 71.5.3 Some chemical properties of the elements 91.5.4 Chemical bonding 121.5.5 Molecules, crystals, and minerals 141.6 A brief look at the Earth 191.6.1 Structure of the Earth 191.6.2 Plate tectonics and the hydrologic cycle 201.7 A look ahead 22References and suggestions for further reading 30Chapter 2: Energy, entropy, and fundamental thermodynamic concepts 312.1 The thermodynamic perspective 312.2 Thermodynamic systems and equilibrium 322.2.1 Fundamental thermodynamic variables 342.2.2 Properties of state 342.3 Equations of state 352.3.1 Ideal gas law 352.3.2 Equations of state for real gases 362.3.3 Equation of state for other substances 372.4 Temperature, absolute zero, and the zeroth law of thermodynamics 372.5 Energy and the first law of thermodynamics 382.5.1 Energy 382.5.2 Work 392.5.3 Path independence, exact differentials, state functions, and the first law 402.6 The second law and entropy 412.6.1 Statement 412.6.2 Statistical mechanics: a microscopic perspective of entropy 422.6.3 Integrating factors and exact differentials 482.7 Enthalpy 502.8 Heat capacity 512.8.1 Constant volume heat capacity 522.8.2 Constant pressure heat capacity 522.8.3 Energy associated with volume and the relationship between Cv and Cp 522.8.4 Heat capacity of solids: a problem in quantum physics 532.8.5 Relationship of entropy to other state variables 582.8.6 Additive nature of silicate heat capacities 582.9 The third law and absolute entropy 592.9.1 Statement of the third law 592.9.2 Absolute entropy 592.10 Calculating enthalpy and entropy changes 602.10.1 Enthalpy changes due to changes in temperature and pressure 602.10.2 Changes in enthalpy due to reactions and change of state 612.10.3 Entropies of reaction 622.11 Free energy 652.11.1 Helmholtz free energy 652.11.2 Gibbs free energy 652.11.3 Criteria for equilibrium and spontaneity 652.11.4 Temperature and pressure dependence of the Gibbs free energy 662.12 The Maxwell relations 692.13 Summary 70References and suggestions for further reading 71Problems 71Chapter 3: Solutions and thermodynamics of multicomponent systems 743.1 Introduction 743.2 Phase equilibria 753.2.1 Some definitions 753.2.2 The Gibbs phase rule 773.2.3 The Clapeyron equation 783.3 Solutions 803.3.1 Raoult's law 803.3.2 Henry's law 813.4 Chemical potential 813.4.1 Partial molar quantities 813.4.2 Definition of chemical potential and relationship to Gibbs free energy 823.4.3 Properties of the chemical potential 823.4.4 The Gibbs-Duhem relation 833.4.5 Derivation of the phase rule 843.5 Ideal solutions 843.5.1 Chemical potential in ideal solutions 843.5.2 Volume, enthalpy, entropy, and free energy changes in ideal solutions 843.6 Real solutions 863.6.1 Chemical potential in real solutions 863.6.2 Fugacities 873.6.3 Activities and activity coefficients 883.6.4 Excess functions 903.7 Electrolyte solutions 933.7.1 The nature of water and water-electrolyte interaction 933.7.2 Some definitions and conventions 943.7.3 Activities in electrolytes 963.8 Ideal solutions in crystalline solids and their activities 1013.8.1 Mixing-on-site model 1013.8.2 Local charge balance model 1033.9 Equilibrium constants 1043.9.1 Derivation and definition 1043.9.2 Law of mass action 1053.9.3 KD values, apparent equilibrium constants, and the solubility product 1073.9.4 Henry's law and gas solubilities 1083.9.5 Temperature dependence of equilibrium constant 1083.9.6 Pressure dependence of equilibrium constant 1093.10 Practical approach to electrolyte equilibrium 1103.10.1 Choosing components and species 1103.10.2 Mass balance 1103.10.3 Electrical neutrality 1113.10.4 Equilibrium constant expressions 1123.11 Oxidation and reduction 1133.11.1 Redox in aqueous solutions 1143.11.2 Redox in magmatic systems 1223.12 Summary 123References and suggestions for further reading 124Problems 125Chapter 4: Applications of thermodynamics to the Earth 1304.1 Introduction 1304.2 Activities in nonideal solid solutions 1304.2.1 Mathematical models of real solutions: Margules equations 1304.3 Exsolution phenomena 1354.4 Thermodynamics and phase diagrams 1374.4.1 The thermodynamics of melting 1384.4.2 Thermodynamics of phase diagrams for binary systems 1404.4.3 Phase diagrams for multicomponent systems 1434.5 Geothermometry and geobarometry 1454.5.1 Theoretical considerations 1454.5.2 Practical thermobarometers 1464.6 Thermodynamic models of magmas 1564.6.1 Structure of silicate melts 1574.6.2 Magma solution models 1584.7 Reprise: thermodynamics of electrolyte solutions 1624.7.1 Equation of state for water 1634.7.2 Activities and mean ionic and single ion quantities 1634.7.3 Activities in high ionic strength solutions 1684.7.4 Electrolyte solutions at elevated temperature and pressure 1764.8 Summary 180References and suggestions for further reading 181Problems 184Chapter 5: Kinetics: the pace of things 1885.1 Introduction 1885.2 Reaction kinetics 1895.2.1 Elementary and overall reactions 1895.2.2 Reaction mechanisms 1895.2.3 Reaction rates 1905.2.4 Rates of complex reactions 1965.2.5 Steady state and equilibrium 1995.3 Relationships between kinetics and thermodynamics 2015.3.1 Principle of detailed balancing 2015.3.2 Enthalpy and activation energy 2015.3.3 Aspects of transition state theory 2025.4 Diffusion 2085.4.1 Diffusion flux and Fick's laws 2085.4.2 Diffusion in multicomponent systems 2125.4.3 Driving force and mechanism of diffusion 2185.4.4 Diffusion in solids and the temperature dependence of the diffusion coefficient 2195.4.5 Diffusion in liquids 2215.4.6 Diffusion in porous media 2235.5 Surfaces, interfaces, and interface processes 2235.5.1 The surface free energy 2255.5.2 The Kelvin effect 2255.5.3 Nucleation and crystal growth 2265.5.4 Adsorption 2335.5.5 Catalysis 2345.6 Kinetics of dissolution 2375.6.1 Simple oxides 2385.6.2 Silicates 2405.6.3 Nonsilicates 2445.7 Diagenesis 2445.7.1 Compositional gradients in accumulating sediment 2455.7.2 Reduction of sulfate in accumulating sediment 2475.8 Summary 248References and suggestions for further reading 250Problems 252Chapter 6: Aquatic chemistry 2566.1 Introduction 2566.2 Acid-base reactions 2566.2.1 Proton accounting, charge balance, and conservation equations 2576.2.2 The carbonate system 2606.2.3 Conservative and nonconservative ions 2646.2.4 Total alkalinity and carbonate alkalinity 2646.2.5 Buffer intensity 2686.3 Complexation 2696.3.1 Stability constants 2706.3.2 Water-related complexes 2716.3.3 Other complexes 2746.3.4 Complexation in fresh waters 2756.4 Dissolution and precipitation reactions 2786.4.1 Calcium carbonate in groundwaters and surface waters 2786.4.2 Solubility of Mg 2796.4.3 Solubility of SiO2 2846.4.4 Solubility of Al(OH)3 and other hydroxides 2856.4.5 Dissolution of silicates and related minerals 2866.5 Clays and their properties 2886.5.1 Clay mineralogy 2896.5.2 Ion-exchange properties of clays 2916.6 Mineral surfaces and their interaction with solutions 2926.6.1 Adsorption 2936.6.2 Development of surface charge and the electric double layer 2976.7 Summary 305References and suggestions for further reading 306Problems 306Chapter 7: Trace elements in igneous processes 3097.1 Introduction 3097.1.1 Why care about trace elements? 3097.1.2 What is a trace element? 3107.2 Behavior of the elements 3117.2.1 Goldschmidt's classification 3117.2.2 The geochemical periodic table 3137.3 Distribution of trace elements between coexisting phases 3247.3.1 The partition coefficient 3247.3.2 Thermodynamic basis 3247.4 Factors governing the value of partition coefficients 3257.4.1 Temperature and pressure dependence of the partition coefficient 3257.4.2 Ionic size and charge 3257.4.3 Compositional dependency 3317.4.4 Mineral-liquid partition coefficients for mafic and ultramafic systems 3357.5 Crystal-field effects 3387.5.1 Crystal-field theory 3387.5.2 Crystal-field influences on transition metal partitioning 3427.6 Trace element distribution during partial melting 3437.6.1 Equilibrium or batch melting 3437.6.2 Fractional melting 3447.6.3 Zone refining 3447.6.4 Multiphase solids 3447.6.5 Continuous melting 3457.6.6 Constraints on melting models 3497.7 Trace element distribution during crystallization 3567.7.1 Equilibrium crystallization 3567.7.2 Fractional crystallization 3567.7.3 In situ crystallization 3577.7.4 Crystallization in open system magma chambers 3587.7.5 Comparing partial melting and crystallization 3607.8 Summary of trace element variations during melting and crystallization 361References and suggestions for further reading 362Problems 364Chapter 8: Radiogenic isotope geochemistry 3678.1 Introduction 3678.2 Physics of the nucleus and the structure of nuclei 3698.2.1 Nuclear structure and energetics 3698.2.2 The decay of excited and unstable nuclei 3738.3 Basics of radiogenic isotope geochemistry and geochronology 3788.4 Decay systems and their applications 3838.4.1 Rb-Sr 3838.4.2 Sm-Nd 3848.4.3 Lu-Hf 3888.4.4 Re-Os 3918.4.5 La-Ce 3968.4.6 U-Th-Pb 3978.4.7 U and Th decay series isotopes 4038.4.8 Isotopes of He and other rare gases 4108.5 "Extinct" and cosmogenic nuclides 4178.5.1 "Extinct" radionuclides and their daughters 4178.5.2 Cosmogenic nuclides 4208.5.3 Cosmic-ray exposure ages of meteorites 4248.6 Summary 424References and suggestions for further reading 425Problems 429Chapter 9: Stable isotope geochemistry 4329.1 Introduction 4329.1.1 Scope of stable isotope geochemistry 4339.1.2 Some definitions 4349.2 Theoretical considerations 4359.2.1 Equilibrium isotope fractionations 4359.2.2 Kinetic isotope fractionations 4439.2.3 Mass-dependent and mass-independent fractionations 4459.2.4 Isotopic clumping 4479.3 Isotope geothermometry 4499.4 Isotopic fractionation in the hydrologic system 4539.5 Isotopic fractionation in biological systems 4559.5.1 Carbon isotope fractionation during photosynthesis 4559.5.2 Nitrogen isotope fractionation in biological processes 4589.5.3 Oxygen and hydrogen isotope fractionation by plants 4599.5.4 Biological fractionation of sulfur isotopes 4599.5.5 Isotopes and diet: you are what you eat 4609.5.6 Isotopic "fossils" and the earliest life 4639.6 Paleoclimatology 4649.6.1 The marine Quaternary ?18O record and Milankovitch cycles 4659.6.2 The record in glacial ice 4689.6.3 Soils and paleosols 4699.7 Hydrothermal systems and ore deposits 4719.7.1 Water in hydrothermal systems 4719.7.2 Water-rock ratios 4729.7.3 Sulfur isotopes and ore deposits 4739.8 Mass-independent sulfur isotope fractionation and the rise of atmospheric oxygen 4769.9 Stable isotopes in the mantle and magmatic systems 4789.9.1 Stable isotopic composition of the mantle 4789.9.2 Stable isotopes in crystallizing magmas 4849.9.3 Combined fractional crystallization and assimilation 4859.10 Non-traditional stable isotopes 4869.10.1 Boron isotopes 4869.10.2 Li isotopes 4909.10.3 Calcium isotopes 4929.10.4 Silicon isotopes 4949.10.5 Iron isotopes 4989.10.6 Mercury isotopes 5019.11 Summary 503References and suggestions for further reading 504Problems 510Chapter 10: The big picture: cosmochemistry 51210.1 Introduction 51210.2 In the beginning . . . nucleosynthesis 51310.2.1 Astronomical background 51310.2.2 The polygenetic hypothesis of Burbidge, Burbidge, Fowler, and Hoyle 51410.2.3 Cosmological nucleosynthesis 51610.2.4 Nucleosynthesis in stellar interiors 51710.2.5 Explosive nucleosynthesis 52010.2.6 Nucleosynthesis in interstellar space 52410.2.7 Summary 52510.3 Meteorites: essential clues to the beginning 52610.3.1 Chondrites: the most primitive objects 52610.3.2 Differentiated meteorites 53610.4 Time and the isotopic composition of the solar system 53910.4.1 Meteorite ages 53910.4.2 Cosmic ray exposure ages and meteorite parent-bodies 54510.4.3 Asteroids as meteorite parent-bodies 54610.4.4 Isotopic anomalies in meteorites 55010.5 Astronomical and theoretical constraints on solar system formation 55610.5.1 Evolution of young stellar objects 55710.5.2 The condensation sequence 56010.5.3 The solar system 56510.5.4 Other solar systems 56910.6 Building a habitable solar system 56910.6.1 Summary of observations 56910.6.2 Formation of the planets 57010.6.3 Chemistry and history of the moon 57410.6.4 The giant impact hypothesis and formation of the earth and the moon 57710.6.5 Tungsten isotopes and the age of the Earth 57710.7 Summary 579References and suggestions for further reading 580Problems 584Chapter 11: Geochemistry of the solid Earth 58611.1 Introduction 58611.2 The Earth's mantle 58611.2.1 Structure of the mantle and geophysical constraints on mantle composition 58811.2.2 Cosmochemical constraints on mantle composition 58911.2.3 Observational constraints on mantle composition 59011.2.4 Mantle mineralogy and phase transitions 59111.3 Estimating mantle and bulk Earth composition 59611.3.1 Major element composition 59611.3.2 Trace element composition 59711.3.3 Composition of the bulk silicate earth 60011.4 The Earth's core and its composition 60211.4.1 Geophysical constraints 60211.4.2 Cosmochemical constraints 60311.4.3 Experimental constraints 60511.5 Mantle geochemical reservoirs 60811.5.1 Evidence from oceanic basalts 60911.5.2 Evolution of the depleted MORB mantle 61211.5.3 Evolution of mantle plume reservoirs 61611.5.4 The subcontinental lithospheric mantle 62311.6 The crust 62611.6.1 The oceanic crust 62611.6.2 The continental crust 63111.6.3 Growth of the continental crust 64111.6.4 Refining the continental crust 64711.7 Subduction zone processes 64811.7.1 Major element composition 64811.7.2 Trace element composition 64911.7.3 Isotopic composition and sediment subduction 65011.7.4 Magma genesis in subduction zones 65211.8 Summary 655References and suggestions for further reading 656Problems 662Chapter 12: Organic geochemistry, the carbon cycle, and climate 66412.1 Introduction 66412.2 A brief biological background 66512.3 Organic compounds and their nomenclature 66612.3.1 Hydrocarbons 66612.3.2 Functional groups 66812.3.3 Short-hand notations of organic molecules 67112.3.4 Biologically important organic compounds 67112.4 The chemistry of life: important biochemical processes 67812.4.1 Photosynthesis 67812.4.2 Respiration 68012.4.3 The stoichiometry of life 68212.5 Organic matter in natural waters and soils 68212.5.1 Organic matter in soils 68212.5.2 Dissolved organic matter in aquatic and marine environments 68412.5.3 Hydrocarbons in natural waters 69012.6 Chemical properties of organic molecules 69112.6.1 Acid-base properties 69112.6.2 Complexation 69112.6.3 Adsorption phenomena 69712.7 Sedimentary organic matter 70112.7.1 Preservation of organic matter 70112.7.2 Diagenesis of marine sediments 70412.7.3 Diagenesis of aquatic sediments 70612.7.4 Summary of diagenetic changes 70712.7.5 Biomarkers 70712.7.6 Kerogen and bitumen 71212.7.7 Isotope composition of sedimentary organic matter 71512.8 Petroleum and coal formation 71812.8.1 Petroleum 71812.8.2 Compositional evolution of coal 72212.9 The carbon cycle and climate 72412.9.1 Greenhouse energy balance 72412.9.2 The exogenous carbon cycle 72512.9.3 The deep carbon cycle 72812.9.4 Evolutionary changes affecting the carbon cycle 73012.9.5 The carbon cycle and climate through time 73112.9.6 Fossil fuels and anthropogenic climate change 73412.10 Summary 737References and suggestions for further reading 738Problems 742Chapter 13: The land surface: weathering, soils, and streams 74513.1 Introduction 74513.2 Redox in natural waters 74613.2.1 Biogeochemical redox reactions 74713.2.2 Eutrophication 74813.2.3 Redox buffers and transition metal chemistry 74913.3 Weathering, soils, and biogeochemical cycling 75413.3.1 Soil profiles 75513.3.2 Chemical cycling in soils 75713.3.3 Biogeochemical cycling 75813.4 Weathering rates 76113.4.1 The in situ approach 76213.4.2 The watershed approach 76713.4.3 Factors controlling weathering rates 77313.5 The composition of rivers 77713.6 Continental saline waters 78013.7 Summary 783References and suggestions for further reading 784Problems 785Chapter 14: The ocean as a chemical system 78814.1 Introduction 78814.2 Some background oceanographic concepts 78814.2.1 Salinity, chlorinity, temperature, and density 78914.2.2 Circulation of the ocean and the structure of ocean water 78914.3 Composition of seawater 79414.3.1 Speciation in seawater 79714.3.2 Conservative elements 79814.3.3 Dissolved gases 79814.3.4 Seawater pH and alkalinity 80214.3.5 Carbonate dissolution and precipitation 80314.3.6 Nutrient elements 80714.3.7 Particle-reactive elements 81114.3.8 One-dimensional advection-diffusion model 81214.4 Sources and sinks of dissolved matter in seawater 81614.4.1 Residence time 81714.4.2 River and groundwater flux to the oceans 81814.4.3 The hydrothermal flux 82314.4.4 The atmospheric source 83114.4.5 Sedimentary sinks and sources 83414.5 Summary 842References 843Problems 846Chapter 15: Applied geochemistry 84915.1 Introduction 84915.2 Mineral resources 84915.2.1 Ore deposits: definitions and classification 85015.2.2 Orthomagmatic ore deposits 85115.2.3 Hydromagmatic ore deposits 85415.2.4 Hydrothermal ore deposits 86415.2.5 Sedimentary ore deposits 87015.2.6 Weathering-related ore deposits 87615.2.7 Rare earth ore deposits 87815.2.8 Geochemical exploration: finding future resources 88215.3 Environmental geochemistry 88615.3.1 Eutrophication redux 88715.3.2 Toxic metals in the environment 88915.3.3 Acid deposition 89915.4 Summary 904References 905Problems 910Appendix: constants, units and conversions 912Index 915
Responsibility: William M. White.

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