W. M.

Wh i t e

G eoc h emi s t ry
Table of Contents

Part I: The Geochemical Toolbox

Chapter 1: Introduction ............................................................................................................1
Geochemistry.....................................................................................................................1
This Book ..........................................................................................................................2
The Philosophy of Science..................................................................................................4
Building Scientific Understanding ................................................................................4
The Scientist as Skeptic ...............................................................................................5
Elements, Atoms, and Chemical Bonds................................................................................6
The Periodic Table.......................................................................................................6
Electrons and Orbits .....................................................................................................7
Some Chemical Properties of the Elements....................................................................13
Chemical Bonding........................................................................................................16
A Brief Look at the Earth...................................................................................................18
Structure of the Earth...................................................................................................18
Plate Tectonics and the Hydrologic Cycle .....................................................................19
Earth Materials...........................................................................................................21
References and Suggestions for Further Reading...................................................................23
Chapter 2: Energy, Entropy and Fundamental Thermodynamic Concepts ....................................24
The Thermodynamic Perspective........................................................................................24
Thermodynamic Systems and Equilibrium ...........................................................................24
Fundamental Thermodynamic Variables ......................................................................26
Equations of State ..............................................................................................................28
Ideal Gas Law..............................................................................................................28
Equations of State for Real Gases ..................................................................................29
Critical phenomena .....................................................................................................31
Equation of State for Other Substances ..........................................................................32
Temperature, Absolute Zero, and The Zeroth Law Of Thermodynamics................................33
Energy and The First Law of Thermodynamics.....................................................................34
Energy .........................................................................................................................34
Work ...........................................................................................................................34
Path independence, Exact differentials, State functions, and the First Law....................35
The Second Law and Entropy ..............................................................................................37
Statement ....................................................................................................................37
Statistical Mechanics: A Microscopic Perspective of Entropy.........................................38
Integrating Factors and Exact Differentials...................................................................44
Enthalpy ...........................................................................................................................45
Heat Capacity...................................................................................................................46
Constant Volume Heat Capacity ..................................................................................47
Constant Pressure Heat Capacity..................................................................................47
Energy Associated with Volume Occupied and the Relationshp between Cv and Cp .........47
Heat Capacity of Solids: A Problem in Quantum Physics...............................................50
Relationship of Entropy to Other State Variables ........................................................57
Additive Nature of Silicate Heat Capacities...............................................................57
The Third Law and Absolute Entropy..................................................................................58
Statement of the Third Law .........................................................................................58
Absolute Entropy..........................................................................................................58
Calculating Enthalpy and Entropy Changes........................................................................59
Adiabatic Changes ......................................................................................................59
Isobaric and Isothermal Changes in Enthalpy ...............................................................59
Enthalpies of Formation, Vaporization and Fusion........................................................60
Entropies of Reaction....................................................................................................61

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Free Energy ........................................................................................................................62

Helmholtz Free Energy ................................................................................................63
Gibbs Free Energy.........................................................................................................64
Criteria for Equilibrium and Spontaneity......................................................................64
Temperature and Pressure Dependence of the Gibbs Free Energy .....................................65
The Maxwell Relations......................................................................................................67
References and Suggestions for Further Reading...................................................................67
Problems ............................................................................................................................68
Chapter 3: Solutions and Thermodynamics of Multicomponent Systems ......................................70
Introduction .......................................................................................................................70
Phase Equilibria ................................................................................................................70
Some Definitions..........................................................................................................70
The Gibbs Phase Rule...................................................................................................73
The Clapeyron Equation...............................................................................................75
Solutions............................................................................................................................77
Raoult's Law................................................................................................................77
Henry's Law ................................................................................................................77
The Chemical Potential .....................................................................................................78
Partial Molar Quantities .............................................................................................78
Definition of Chemical Potential and Relationship to Gibbs Free Energy.......................79
Properties of the Chemical Potential............................................................................80
The Gibbs-Duhem Relation ..........................................................................................80
Derivation of the Phase Rule .......................................................................................81
Ideal Solutions...................................................................................................................82
Real solutions ....................................................................................................................84
Chemical Potential in Real Solutions ...........................................................................84
Fugacities....................................................................................................................85
Activities and Activity Coefficients.............................................................................86
Excess Functions............................................................................................................88
Electrolyte Solutions..........................................................................................................90
The Nature of Water and Water-Electrolyte Interaction ...............................................90
Some Definitions and Conventions ................................................................................92
Activities in Electrolytes .............................................................................................94
Solid Solutions and Their Activities...................................................................................100
Ideal Solutions in Crystalline Solids ............................................................................100
Equilibrium Constants ........................................................................................................101
Derivation and Definition............................................................................................101
KD Values, Apparent Equilibrium Constants and the Solubility Product .........................104
Henrys Law and Gas Solubilities.................................................................................105
Temperature Dependence of Equilibrium Constant .........................................................106
Pressure Dependence of Equilibrium Constant ................................................................107
Practical Approach to Electrolyte Equilibrium....................................................................107
Chosing Components and Species ..................................................................................107
Mass Balance...............................................................................................................108
Electrical Neutrality...................................................................................................108
Equilibrium Constant Expressions..................................................................................109
Oxidation and Reduction....................................................................................................110
Redox in Aqueous Solutions ...........................................................................................111
Redox in Magmatic Systems..........................................................................................119
References and Suggestions for Further Reading...................................................................120
Problems ............................................................................................................................120
Chapter 4: Applications of Thermodynamics to the Earth.........................................................124
Introduction .......................................................................................................................124

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Activities in Non-Ideal Solid Solutions..............................................................................124

Mathematical Models of Real Solutions .......................................................................124
Exsolution Phenomena ........................................................................................................127
Thermodynamics and Phase Diagrams................................................................................129
The Thermodynamics of Melting...................................................................................131
Thermodynamics of Phase Diagrams for Binary Systems ...............................................132
Geothermometry and Geobarometry....................................................................................138
Theoretical considerations ...........................................................................................138
Practical Thermobarometers.........................................................................................139
Thermodynamic Models of Magmas ....................................................................................148
Structure of Silicate Melts ............................................................................................149
Magma Solution Models ...............................................................................................150
Reprise: Thermodynamics of Electrolyte Solutions ..............................................................155
Mean Ionic Quantities ..................................................................................................155
Activities in High Ionic Strength Solutions...................................................................158
References and Suggestions For Further Reading ..................................................................164
Problems ............................................................................................................................166
Chapter 5: Kinetics: The Pace of Things....................................................................................169
Introduction .......................................................................................................................169
Reaction Kinetics...............................................................................................................170
Elementary and Overall Reactions ...............................................................................170
Reaction Mechanisms...................................................................................................170
Reaction Rates.............................................................................................................171
Rates of Complex Reactions ..........................................................................................176
Steady-State and Equilibrium......................................................................................179
Relationships between Kinetics and Thermodynamics.........................................................181
Principle of Detailed Balancing ...................................................................................181
Enthalpy and Activation Energy ..................................................................................183
Aspects of Transition State Theory ...............................................................................184
Diffusion ...........................................................................................................................188
Diffusion Flux and Fick's Law.......................................................................................190
Diffusion in Multicomponent Systems and The Diffusion Coefficient ..............................192
Diffusion in Solds and the Temperature Dependence of the Diffusion Coefficient ...........196
Diffusion in Liquids......................................................................................................198
Surfaces, Interfaces, and Inferface Processes ........................................................................199
The Surface Free Energy ...............................................................................................200
The Kelvin Effect.........................................................................................................201
Nucleation and Crystal Growth....................................................................................201
Adsorption...................................................................................................................206
Catalysis.....................................................................................................................2 09
Kinetics of Dissolution and Leaching ..................................................................................211
Diagenesis .........................................................................................................................217
Compostional Gradients in Accumulating Sediment .......................................................217
References and Suggestions for Further Reading...................................................................221
Problems ............................................................................................................................223
Chapter 6: Aquatic Chemistry..................................................................................................227
Introduction .......................................................................................................................227
Acid-Base Reactions ..........................................................................................................227
Proton Accounting, Charge Balance, and Conservation Equations....................................228
The Carbonate System..................................................................................................230
Conservative and Non-Conservative Ions......................................................................233
Total Alkalinity and Carbonate Alkalinity .................................................................234
Buffer Intensity............................................................................................................237

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Complexation ....................................................................................................................238
Stability Constants......................................................................................................239
Water-Related Complexes...........................................................................................240
Other Complexes .........................................................................................................242
Complexation in Fresh Waters .....................................................................................244
Dissolution and Precipitation Reactions..............................................................................244
Dissolution of Carbonates by Ground and Surface Waters ...............................................244
Solubility of Mg...........................................................................................................248
Solubility of SiO2.........................................................................................................249
Solubility of Al(OH)3 and Other Hydroxides ...............................................................250
Solubility of Silicates and Related Minerals ................................................................253
Clays and Their Properties.................................................................................................255
Clay Mineralogy..........................................................................................................256
Ion-Exchange Properties of Clays..................................................................................258
Mineral Surfaces and Their Interaction With Solutions .......................................................259
Adsorption...................................................................................................................260
Development of Surface Charge and the Electric Double Layer ......................................264
References and Suggestions for Further Reading...................................................................270
Problems ............................................................................................................................271
Chapter 7: Trace Elements in Igneous Processes ..........................................................................273
Introduction .......................................................................................................................273
What is a Trace Element?...................................................................................................274
Goldschmidt's Classification of the Elements .....................................................................275
The Geochemical Periodic Table.........................................................................................277
The Volatile Elements .................................................................................................277
The Semi-Volatiles .....................................................................................................278
The Alkali and Alkaline Earth Elements .....................................................................279
The Rare Earth Elements and Y ....................................................................................280
The HFS Elements........................................................................................................283
The First Series Transition Metals................................................................................283
The Noble Metals ........................................................................................................284
Other Elements............................................................................................................285
Distribution of Trace Elements Between Co-existing Phases.................................................286
The Partition Coefficient .............................................................................................286
Factors Governing the Value of Parition Coefficients...........................................................288
Temperature and Pressure Dependence of the Partition Coefficient ................................288
Ionic Size and Charge...................................................................................................289
Compositional Dependency ..........................................................................................292
Mineral-Liquid Partition Coefficients for Mafic and Ultramafic Systems ......................297
Crystal-Field Effects .........................................................................................................298
Crystal Field Influences on Transition Metal Partitioning..............................................303
Trace Element Distribution During Partial Melting .............................................................304
Equilibrium or Batch Melting .......................................................................................305
Fractional Melting.......................................................................................................305
Zone Refining...............................................................................................................306
Multiphase Solids .......................................................................................................306
Continuous Melting.......................................................................................................307
Constraints on Melting Models ......................................................................................308
Trace Element Distribution during Crystallization ..............................................................314
Equilibrium Crystallization .........................................................................................314
Fractional Crystallization ...........................................................................................314
In Situ Crystallization .................................................................................................315
Crystallization in Open System Magma Chambers........................................................316

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Summary of Trace Element Variations during Melting and Crystallization ..........................318

References and Suggestions for Further Reading...................................................................320
Problems ............................................................................................................................323
Chapter 8: Radiogenic Isotope Geochemistry ............................................................................325
Introduction .......................................................................................................................325
Physics of the Nucleus and the Structure of Nuclei ..............................................................326
Nuclear Structure and Energetics...................................................................................326
The Decay of Excited and Unstable Nuclei....................................................................330
Basics of Radiogenic Isotope Geochemistry .........................................................................333
Geochronology ...................................................................................................................335
Decay Systems and Their Applications...............................................................................336
Rb-Sr ...........................................................................................................................336
Sm-Nd.........................................................................................................................338
Lu-Hf ..........................................................................................................................343
Re-Os ..........................................................................................................................344
La-Ce ..........................................................................................................................348
U-Th-Pb ......................................................................................................................348
U and Th Decay Series Isotopes ....................................................................................352
Isotopes of He and Other Rare Gases.............................................................................358
Cosmogenic and Fossil Isotopes ...........................................................................................362
14
C ...............................................................................................................................362
36
Cl in hydrology..........................................................................................................363
10
Be in Subduction Zone Studies.....................................................................................364
Cosmic-Ray Exposure Ages of Meteorites.......................................................................364
Fossil Nuclides ............................................................................................................364
References and Suggestions for Further Reading...................................................................364
Problems ............................................................................................................................366
Chapter 9: Stable Isotope Geochemistry...................................................................................370
Introduction .......................................................................................................................370
Scope of Stable Isotope Geochemistry ...........................................................................370
Notation......................................................................................................................371
Theoretical Considerations ................................................................................................372
Equilibrium Isotope Fractionations ...............................................................................372
Kinetic Isotope Fractionations ......................................................................................378
Isotope Geothermometry ....................................................................................................380
Isotope Fractionation in the Hydrologic System ..................................................................383
Isotope Fractionation in Biological Systems ........................................................................385
Carbon Isotope Fractionation During Photosynthesis .....................................................385
Nitrogen Isotope Fractionation in Biological Processes ..................................................387
Oxygen and Hydrogen Isotope Fractionation by Plants...................................................388
Biological Fractionation of Sulfur Isotopes....................................................................389
Isotopes and Diet: You Are What You Eat .....................................................................389
Paleoclimatology...............................................................................................................393
The Marine Quaternary 18O Record and Milankovitch Cycles.......................................393
The Record in Glacial Ice..............................................................................................397
Soils and Paleosols.......................................................................................................397
Hydrothermal Systems and Ore Deposits ...........................................................................399
Water-Rock Ratios ......................................................................................................400
Sulfur Isotopes and Ore Deposits...................................................................................402
Stable Isotopes in the Mantle and Magmatic Systems ..........................................................404
Stable Isotopic Composition of the Mantle....................................................................404

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Stable Isotopes in Crystallizing Magmas ......................................................................409

Combined Fractional Crystallization and Assimilation ................................................411
Isotopes of Boron and Lithium.............................................................................................412
References and Suggestions for Further Reading...................................................................416
Problems ............................................................................................................................419

Part II: Understanding the Earth

Chapter 10: The Big Picture: Cosmochemistry ...........................................................................421
Introduction .......................................................................................................................421
In the Beginning...Nucleosynthesis .....................................................................................421
Astronomical Background.............................................................................................421
The Polygenetic Hypothesis of Burbidge, Burbidge, Fowler and Hoyle ..........................423
Cosmological Nucleosynthesis......................................................................................425
Nucleosynthesis in Stellar Interiors..............................................................................425
Explosive Nucleosynthesis ...........................................................................................428
Nucleosynthesis in Interstellar Space...........................................................................431
Summary .....................................................................................................................431
Meteorites: Essential Clues to the Beginning .......................................................................432
Chondrites: The Most Primitive Objects ........................................................................434
Differentiated Meteorites ............................................................................................441
Meteorite Mineralogy ..................................................................................................443
Relationships among Meteorites and Meteorite Parent-Bodies ......................................440
Time and the Isotopic composition of the Solar System ........................................................444
Meteorite Ages.............................................................................................................444
Cosmic Ray Exposure Ages and the Origin of Meteorites ................................................447
Isotopic Anomalies in Meteorites..................................................................................449
Formation of the Solar System............................................................................................453
Astronomical Observations and Theoretical Models of Star Formation...........................454
Formation of Chondritic Meteorites and Processes in the Solar Nebula...........................458
Formation of the Planets ....................................................................................................464
The Moon: Its Chemistry and History .................................................................................468
The Giant Impact Hypothesis ......................................................................................468
Geology and History of the Moon..................................................................................469
References and Suggestions for Further Reading...................................................................471
Problems ............................................................................................................................472
Chapter 11: Geochemistry of the Solid Earth I: The Mantle and Core ........................................474
Introduction .......................................................................................................................474
Composition of the Earths Mantle .....................................................................................474
Cosmochemical Constraints on the Earths Composition ................................................474
Upper Mantle Composition...........................................................................................475
Phase Transitions in the Mantle .........................................................................................480
The Transition Zone .....................................................................................................481
Composition of the Lower Mantle .......................................................................................482
The Primitive Mantle ........................................................................................................484
Magma Ocean and Mantle Differentiation ..........................................................................486
The Core and Core Formation..............................................................................................487
Mantle Geochemical Reservoirs..........................................................................................490
Evidence from Oceanic Basalts .....................................................................................490
Evolution of the Depleted Upper Mantle ......................................................................493
Geochemical Evolution of Mantle Plume Reservoirs.......................................................500
The Subcontinental Lithosphere...................................................................................505
References and Suggestions for Further Reading...................................................................508

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Problems ............................................................................................................................510
Chapter 12: Geochemistry of the Solid Earth II: The Crust ........................................................512
Introduction .......................................................................................................................512
The Oceanic Crust ..............................................................................................................512
Processes in Subduction Zones and Island Arc Geochemistry..................................................517
Major Element Composition ..........................................................................................517
Trace Element Composition...........................................................................................519
Isotopic Composition and Sediment Subduction..............................................................521
Magma Genesis in Subduction Zones ..............................................................................523
CrustMantle Interaction: Assimilation ............................................................................526
Geochemistry of Two-Component Mixtures ....................................................................526
AssimilationFractional Crystallization .....................................................................529
Composition of the Continental Crust..................................................................................530
The Upper Crust...........................................................................................................531
The Middle and Lower Crust.........................................................................................534
The Total Continental Crust .........................................................................................538
Growth of the Continental Crust .........................................................................................540
The Pace of Crustal Growth ..........................................................................................541
Mechanisms of Crustal Growth .....................................................................................544
Crustal Growth in the Archean...............................................................................546
References and Suggestions for Further Reading...................................................................550
Problems ............................................................................................................................553
Chapter 13: Reactions at the Earths Surface: Weathering, Soils, and Stream Chemistry...........555
Introduction .......................................................................................................................555
Redox in Natural Waters ...................................................................................................555
Biogeochemical Reodox Reactions ................................................................................557
Redox Buffers and Transition Metal Chemistry.............................................................559
Weathering, Soils, and Biogeochemical Cycling .................................................................563
Soil Profiles.................................................................................................................564
Chemical Cycling in Soils ............................................................................................567
Biogeochemical Cycling...............................................................................................568
Weathering Rates and Reactions ........................................................................................570
The Watershed Approach............................................................................................568
Thermodynamic and Kinetic Assessment of Stream Compositions...................................575
Factors Controlling Weathering Rates ..........................................................................577
The Composition of Rivers..................................................................................................580
Continental Saline Waters.................................................................................................584
References and Suggestions for Further Reading...................................................................587
Problems ............................................................................................................................588
Chapter 14: Organic Geochemistry ...........................................................................................589
Introduction .......................................................................................................................589
A Brief Biological Background ...........................................................................................589
Organic Compounds and Their Nomenclature ......................................................................590
Hydrocarbons...............................................................................................................591
Functional Groups.........................................................................................................593
Biologically Important Organic Compounds..................................................................596
The Chemistry of Life: Important Biochemical Processes....................................................602
Photosynthesis ............................................................................................................602
Respiration..................................................................................................................604
Organic Matter in Soils and Natural Waters.......................................................................606
Dissolved Organic Substances.......................................................................................606

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Organic Matter in Soils ................................................................................................613

Chemical Properties of Organic Molecules ..........................................................................615
Acid-Base Properties ...................................................................................................615
Complexation ..............................................................................................................616
Adsorption Phenomena.................................................................................................622
Sedimentary Organic Matter and Coal and Oil Formation ...................................................626
Formation and Diagenesis of Organic-Rich Sediments...................................................627
Kerogen and Bitumen....................................................................................................631
Thermal Evolution of Organic Matter and Petroleum Generation....................................633
Compositional Evolution of Coal ..................................................................................637
Isotopic Composition of Hydrocarbons...........................................................................638
References and Suggestions for Further Reading...................................................................640
Problems ............................................................................................................................642
Chapter 15: The Oceans as a Chemical System..........................................................................645
Introduction .......................................................................................................................645
Some Background Oceanographic Concepts..........................................................................645
Salinity, Chlorinity, Density, and Temperature ...........................................................645
Circulation of the Ocean and the Structure of Ocean Water............................................646
Composition of Seawater....................................................................................................650
Conservative Elements .................................................................................................654
Dissolved Gases...........................................................................................................654
Nutrient Elements........................................................................................................663
Particle-Reactive Elements..........................................................................................666
Sources and Sinks of Dissolved Matter in Seawater .............................................................670
Residence Time ............................................................................................................671
The Riverine Source .....................................................................................................672
Ridge Hydrothermal Systems ......................................................................................677
The Atmospheric Source...............................................................................................688
Sedimentary Sinks and Sources .....................................................................................689
References and Suggestions for Further Reading...................................................................696
Problems ............................................................................................................................700

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