WILLIAM M. WHITE received his B.Sc. in Geology from the University of California, Berkeley, and a Ph.D. in Oceanography from the University of Rhode Island. He is a professor of earth and atmospheric sciences at Cornell University where he teaches geochemistry. He has been elected a fellow at the Geochemical Society/European Association of Geochemistry and the AGU and named as an ISI highly cited researcher.

Preface

Chapter 1 Introduction

1.1 Introduction

1.2 Beginnings

1.3 Geochemistry in the 21st Century

1.4 The Philosophy of Science

1.4.1 Building scientific understanding

1.4.2 The scientist as skeptic

1.5 Elements, Atoms, crystals and Chemical Bonds: Some Chemical Fundamentals

1.5.1 The periodic table

1.5.2 Electrons and orbits

1.5.3 Some chemical properties of the elements

1.5.4 Chemical bonding

1.5.5 Molecules, crystals, and minerals

1.6 A Brief Look at the Earth

1.6.1 Structure of the Earth

1.6.2 Plate tectonics and the hydrologic cycle

1.7 A Look Ahead

Chapter 2 Energy, entropy and fundamental thermodynamic concepts

2.1 The Thermodynamic Perspective

2.2 Thermodynamic Systems And Equilibrium

2.2.1 Fundamental thermodynamic variables

2.2.2 Properties of state

2.3 Equations Of State

2.3.1 Ideal gas law

2.3.2 Equations of state for real gases

2.4 Temperature, Absolute Zero, And The Zeroth Law Of Thermodynamics

2.5 Energy And The First Law Of Thermodynamics

2.5.1 Energy

2.5.2 Work

2.6 The Second Law And Entropy

2.6.1 Statement

2.6.2 Statistical mechanics: a microscopic perspective of entropy

2.6.3 Integrating factors and exact differentials

2.7 Enthalpy

2.8 Heat Capacity

2.8.1 Constant volume heat capacity

2.8.2 Constant pressure heat capacity

2.8.3 Energy associated with volume and the relationship between Cv and Cp

2.8.4 Heat capacity of solids: a problem in quantum physics

2.8.5 Relationship of entropy to other state variables

2.8.6 Additive nature of silicate heat capacities

2.9 The Third Law And Absolute Entropy

2.9.1 Statement of the third law

2.9.2 Absolute entropy

2.9 Calculating Enthalpy And Entropy Changes

2.9.1 Enthalpy changes due to changes in temperature and pressure

2.9.2 Changes in enthalpy due to reactions and change of state

2.9.3 Entropies of reaction

2.10 Free Energy

2.10.1 Helmholtz free energy

2.10.2 Gibbs free energy

2.10.3 Criteria for equilibrium and spontaneity

2.10.4 Temperature and pressure dependence of the Gibbs free energy

 2.11 The Maxwell Relations

2.12 Summary

Chapter 3 Solutions and Thermodynamics of Multicomponent Systems

3.1 Introduction

3.2 Phase Equilibria

3.2.1 Some definitions

3.2.2 The Gibbs phase rule

3.2.3 The Clapeyron equation

3.3 Solutions

3.3.1 Raoult’s Law

3.3.2 Henry’s Law

3.4 Chemical Potential

3.4.1 Partial molar quantities

3.4.2 Definition of chemical potential and relationship to Gibbs free energy

3.4.3 Properties of the chemical potential

3.4.4 The Gibbs-Duhem relation

3.4.5 Derivation of the phase rule

3.5 Ideal Solutions

3.5.1 Chemical potential in ideal solutions

3.5.2 Volume, enthalpy, entropy, and free energy changes in ideal solutions

3.6 Real solutions

3.6.1 Chemical potential in real solutions

3.6.2 Fugacities

3.6.3 Activities and activity coefficients

3.6.4 Excess functions

3.7 Electrolyte Solutions

3.7.1 The nature of water and water–electrolyte interaction

3.7.2 Some definitions and conventions

3.7.3 Activities in electrolytes

3.8 Ideal Solutions in Crystalline Solids and Their Activities

3.8.1 Mixing-on-site model

3.8.2 Local charge balance model

3.9 Equilibrium Constants

3.9.1 Derivation and definition

3.9.2 The Law of mass action

3.9.3 KD values, apparent equilibrium constants, and the solubility product

3.9.4 Henry’s Law and gas solubilities

3.9.5 Temperature dependence of equilibrium constant

3.9.6 Pressure dependence of equilibrium constant

3.10 Practical Approach to Electrolyte Equilibrium

3.10.1 Choosing components and species

3.10.2 Mass balance

3.10.3 Electrical neutrality

3.10.4 Equilibrium constant expressions

3.11 Oxidation and Reduction

3.11.1 Redox in aqueous solutions

3.11.2 Redox in magmatic systems

3.12 Summary

Chapter 4 Applications of thermodynamics to the Earth

4.1 Introduction

4.2 Activities in Non-Ideal Solid Solutions

4.2.1 Mathematical models of real solutions: Margules equations

4.3 Exsolution Phenomena

4.4 Thermodynamics and Phase Diagrams

4.4.1 The thermodynamics of melting

4.4.2 Thermodynamics of phase diagrams for binary systems

4.4.3 Phase diagrams for multi-component systems

4.5 Geothermometry and Geobarometry

4.5.1 Theoretical considerations

4.5.2 Practical thermobarometers

4.6 Thermodynamic models of magmas

4.6.1 Structure of silicate melts

4.6.2 Magma solution models

4.7 Reprise: Thermodynamics of Electrolyte Solutions

4.7.1 The Equation of state for water

4.7.2 Activities and mean ionic and single ion quantities

4.7.3 Activities in high ionic strength solutions

4.7.4 Electrolyte Solutions at elevated temperature and pressure

4.8 Summary

Chapter 5 Kinetics: The Pace of Things

5.1 Introduction

5.2 Reaction Kinetics

5.2.1 Elementary and overall reactions

5.2.2 Reaction mechanisms

5.2.3 Reaction rates

5.2.4 Rates of complex reactions

5.2.5 Steady state and equilibrium

5.3 Relationships between Kinetics and Thermodynamics

5.3.1 Principle of detailed balancing

5.3.2 Enthalpy and activation energy

5.3.3 Aspects of transition state theory

5.4 Diffusion

5.4.1 Diffusion flux and Fick’s Laws

5.4.2 Diffusion in multicomponent systems

5.4.3 Driving force and mechanism of diffusion

5.4.4 Diffusion in solids and the temperature dependence of the diffusion coefficient

5.4.5 Diffusion in liquids

5.4.6 Diffusion in porous media

5.5 Surfaces, Interfaces, and Interface Processes

5.5.1 The surface free energy

5.5.2 The Kelvin effect

5.5.3 Nucleation and crystal growth

5.5.4 Adsorption

5.5.5 Catalysis

5.6 Kinetics of Dissolution

5.6.1 Simple oxides

5.6.2 Silicates

5.6.3 Non-silicates

5.7 Diagenesis

5.7.1 Compositional gradients in accumulating sediment

5.7.2 Reduction of sulfate in accumulating sediment

5.8 summary

Chapter 6 Aquatic Chemistry

6.1 Introduction

6.2 Acid–Base Reactions

6.2.1 Proton accounting, charge balance, and conservation equations

6.2.2 The carbonate system

6.2.3 Conservative and non-conservative ions

6.2.4 Total alkalinity and carbonate alkalinity

6.2.5 Buffer intensity

6.3 Complexation

6.3.1 Stability constants

6.3.2 Water-related complexes

6.3.3 Other complexes

6.3.4 Complexation in fresh waters

6.4 Dissolution And Precipitation Reactions

6.4.1 Calcium carbonate in ground and surface waters

6.4.2 Solubility of Mg

6.4.3 Solubility of SiO2

6.4.4 Solubility of Al(OH)3 and other hydroxides

6.4.5 Dissolution of silicates and related minerals

6.5 Clays And Their Properties

6.5.1 Clay mineralogy

6.5.2 Ion-exchange properties of clays

6.6 Mineral Surfaces And Their Interaction With Solutions

6.6.1 Adsorption

6.6.2 Development of surface charge and the electric double layer

6.7 Summary

Chapter 7 Trace Elements in Igneous Processes

7.1 Introduction

7.1.1 Why care about trace elements?

7.1.2 What is a trace element?

7.2 Behavior of the Elements

7.2.1 Goldschmidt’s classification

7.2.2 The geochemical periodic table

7.3 Distribution of Trace Elements Between Coexisting Phases

7.3.1 The partition coefficient

7.4 Factors Governing the Value of Partition Coefficients

7.4.1 Temperature and pressure dependence of the partition coefficient

7.4.2 Ionic size and charge

7.4.3 Compositional dependency

7.4.4 Mineral–liquid partition coefficients for mafic and ultramafic systems

7.5 Crystal-Field Effects

7.5.1 Crystal field theory

7.5.2 Crystal field influences on transition metal partitioning

7.6 Trace Element Distribution During Partial Melting

7.6.1 Equilibrium or batch melting

7.6.2 Fractional melting

7.6.3 Zone refining

7.6.4 Multiphase solids

7.6.5 Continuous melting

7.6.6 Constraints on melting models

7.7 Trace Element Distribution during Crystallization

7.7.1 Equilibrium crystallization

7.7.2 Fractional crystallization

7.7.3 In situ crystallization

7.7.4 Crystallization in open system magma chambers

7.7.5 Comparing Partial Melting and Crystallization

7.8 Summary Of Trace Element Variations During Melting And Crystallization

Chapter 8 Radiogenic Isotope Geochemistry

8.1 Introduction

8.2 Physics of the Nucleus and the Structure of Nuclei

8.2.1 Nuclear structure and energetics

8.2.2 The decay of excited and unstable nuclei

8.3 Basics of Radiogenic Isotope Geochemistry and Geochronology

8.4 Decay Systems and Their Applications

8.4.1 Rb-Sr

8.4.2 Sm-Nd

8.4.3 Lu-Hf

8.4.4 Re-Os

8.4.5 La-Ce

8.4.6 U-Th-Pb

8.4.7 U and Th decay series isotopes

8.4.8 Isotopes of He and other rare gases

8.5  “Extinct” And Cosmogenic Nuclides

8.5.1 ”Extinct” radionuclides and their daughters

8.5.2 Cosmogenic Nuclides

8.5.3 Cosmic-ray exposure ages of meteorites

8.7 Summary

Chapter 9 Stable Isotope Geochemistry

9.1 Introduction

9.1.1 Scope of stable isotope geochemistry

9.1.2 Some definitions

9.2 Theoretical Considerations

9.2.1 Equilibrium isotope fractionations

9.2.2 Kinetic isotope fractionations

9.2.3 Mass-dependent and mass-independent fractionations

9.2.4 Isotopic “Clumping”

9.3 Isotope Geothermometry

9.4 Isotopic Fractionation in the Hydrologic System

9.5 Isotopic Fractionation in Biological Systems

9.5.1 Carbon isotope fractionation during photosynthesis

9.5.2 Nitrogen isotope fractionation in biological processes

9.5.3 Oxygen and hydrogen isotope fractionation by plants

9.5.4 Biological fractionation of sulfur isotopes

9.5.5 Isotopes and diet: you are what you eat

9.5.6 Isotopic “fossils” and the earliest life

9.6 Paleoclimatology

9.6.1 The marine Quaternary 18O record and Milankovitch cycles

9.6.2 The record in glacial ice

9.6.3 Soils and paleosols

9.7 Hydrothermal Systems and Ore Deposits

9.7.1 Water in Hydrothermal Systems

9.7.2 Water–rock ratios

9.7.3 Sulfur isotopes 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

9.9.1 Stable isotopic composition of the mantle

9.9.2 Stable isotopes in crystallizing magmas

9.9.3 Combined fractional crystallization and assimilation

9.10 Non-Traditional Stable Isotopes

9.10.1 Boron isotopes

9.10.2 Li isotopes

9.10.3 Calcium isotopes

9.10.4 Silicon isotopes

9.10.5 Iron isotopes

9.10.6 Mercury isotopes

9.11 Summary

Chapter 10 The Big Picture: Cosmochemistry

10.1 Introduction

10.2 In the Beginning ... Nucleosynthesis

10.2.1 Astronomical background

10.2.2 The polygenetic hypothesis of Burbidge, Burbidge, Fowler and Hoyle

10.2.3 Cosmological nucleosynthesis

10.2.4 Nucleosynthesis in stellar interiors

10.2.5 Explosive nucleosynthesis

10.2.6 Nucleosynthesis in interstellar space

10.2.7 Summary

10.3 Meteorites: Essential Clues to the Beginning

10.3.1 Chondrites: the most primitive objects

10.3.2 Differentiated meteorites

10.4 Time and the Isotopic Composition of the Solar System

10.4.1 Meteorite ages

10.4.2 Cosmic ray exposure ages and meteorite parent-bodies

10.4.3 Asteroids as meteorite parent-bodies

10.4.3 Isotopic anomalies in meteorites

10.5 Astronomical and Theoretical Constraints on Solar System Formation

10.5.1 Evolution of young stellar objects

10.5.2 The condensation sequence

10.5.3 The solar system

10.5.4 Other solar systems

10.6 Building a Habitable Solar System

10.6.1 Summary of observations

10.6.2 Formation of the planets

10.6.3 Chemistry and history of the Moon

10.6.4 The giant impact hypothesis and formation of the Earth and the Moon

10.6.5 Tungsten isotopes and the age of the Earth

10.7 Summary

Chapter 11 Geochemistry Of The Solid Earth

11.1 Introduction

11.2 The Earth’s Mantle

11.2.1 Structure of the mantle and geophysical constraints on mantle composition

11.2.2 Cosmochemical constraints on mantle composition

11.2.3 Observational constraints on mantle composition

11.2.4 Mantle mineralogy and phase transitions

11.3 Estimating Mantle and Bulk Earth Composition

11.3.1 Major element composition

11.3.2 Trace Element composition

11.3.3 Composition of the bulk silicate Earth

11.4 The Earth’s Core and Its Composition

11.4.1 Geophysical constraints

11.4.2 Cosmochemical constraints

11.4.3 Experimental constraints

11.5 Mantle Geochemical Reservoirs

11.5.1 Evidence from oceanic basalts

11.5.2 Evolution of the depleted MORB mantle

11.5.3 Evolution of mantle plume reservoirs

11.5.4 The subcontinental lithospheric mantle

11.6 The Crust

11.6.1 The oceanic crust

11.6.2 The continental crust

11.6.3 Growth of the continental crust

11.7 Subduction zone Processes

11.7.1 Major element composition

11.7.2 Trace element composition

11.7.3 Isotopic composition and sediment subduction

11.7.4 Magma genesis in subduction zones

11.8 Summary

Chapter 12 Organic Geochemistry, The Carbon Cycle, And Climate

12.1 Introduction

12.2 A Brief Biological Background         

12.3 Organic Compounds and Their Nomenclature

12.3.1 Hydrocarbons

12.3.2 Functional groups

12.3.3 Short-hand notations of organic molecules

12.3.4 Biologically important organic compounds

12.4 The Chemistry of Life: Important Biochemical Processes

12.4.1 Photosynthesis

12.4.2 Respiration

12.4.3 The stoichiometry of life

12.5 Organic Matter in Natural Waters and Soils

12.5.1 Organic matter in soils

12.5.2 Dissolved organic matter in aquatic and marine environments

12.6 Chemical Properties of Organic Molecules

12.6.1 Acid–base properties

12.6.2 Complexation

12.6.3 Adsorption phenomena

12.7 Sedimentary Organic Matter

12.7.1 Preservation of organic matter

12.7.2 Diagenesis of marine sediments

12.7.3 Diagenesis of aquatic sediments

12.7.4 Summary of diagenetic changes

12.7.5 Biomarkers

12.7.6 Kerogen and bitumen

12.7.7 Isotope composition of sedimentary organic matter

12.8 Petroleum and Coal Formation

12.8.1 Petroleum

12.8.2 Compositional evolution of coal

12.9 The Carbon Cycle and Climate

12.9.1 Greenhouse energy balance

12.9.2 The exogenous carbon cycle

12.9.3 The deep carbon cycle

12.9.4 Evolutionary changes affecting the carbon cycle

12.9.5 The carbon cycle and climate through time

12.9.6 Fossil fuels and anthropogenic climate change

12.10 Summary

Chapter 13 The Land Surface: Weathering, Soils, and Streams

13.1 Introduction

13.2 Redox in Natural Waters

13.2.1 Biogeochemical redox reactions

13.2.2 Eutrophication

13.2.3 Redox buffers and transition metal chemistry

13.3 Weathering, Soils, and Biogeochemical Cycling

13.3.1. Soil profiles

13.3.2 Chemical cycling in soils

13.3.3 Biogeochemical cycling

13.4 Weathering Rates

13.4.1 The in situ approach

13.4.2 The watershed approach

13.4.3 Factors controlling weathering rates

13.5 The Composition of Rivers

13.6 Continental Saline Waters

13.7 Summary

Chapter 14 The Ocean as a Chemical System

14.1 Introduction

14.2 Some Background Oceanographic Concepts

14.2.1 Salinity, chlorinity, temperature and density

14.2.2 Circulation of the ocean and the structure of ocean water

14.3 The Composition of Seawater

14.3.1 Speciation in seawater

14.3.2 Conservative elements

14.3.3 Dissolved gases

14.3.4 Seawater pH and alkalinity

14.3.5 Carbonate dissolution and precipitation

14.3.5 Nutrient elements

14.3.6 Particle-reactive elements

14.3.7 The one-dimensional advection-diffusion model

14.4 Sources and Sinks of Dissolved Matter in Seawater

14.4.1 Residence time

14.4.2 The river and groundwater flux to the oceans

14.4.3 The hydrothermal flux

14.4.4 The atmospheric source

14.4.5 Sedimentary sinks and sources

14.5 Summary

Chapter 15 Applied Geochemistry

15.1 Introduction

15.2 Mineral Resources

15.2.1 Ore deposits: definitions and classification

15.2.2 Orthomagmatic ore deposits

15.2.3 Hydromagmatic ore deposits

15.2.4 Hydrothermal ore deposits

15.2.5 Sedimentary ore deposits

15.2.6 Weathering-related ore deposits

15.2.7 Rare Earth Ore Deposits

15.2.8 Geochemical exploration: finding future resources

15.3 Environmental Geochemistry

15.3.1 Eutrophication redux

15.3.2 Toxic metals in the environment

15.3.3 Acid deposition

15.4 Summary

Appendix

Index

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