ENCYCLOPEDIA OF E A R T H SCIENCES SERIES

ENCYCLOPEDIA of GEOCHEMISTRY

\ \̂

r edited by

C L A R E P. MARSHALL

RHODES W. FAIRBRIDGE

KLUWER ACADEMIC PUBLISHERS D O R D R E C H T | B O S T O N | L O N D O N

C BIBLIOTFCAH

Contents

Li>: of Contributors

Preface

Acknowledgements

.Acid Deposition Martin Mihaljevic

Acids and Bases Carl O. Moses

Actinium Cynthia E.A. Palmer

.Activation Energy, Activation Enthalpy, -Activation Volume

Thomas J. Wolery

Activity and Activity Coefficients Thomas J. Wolery

A/_minum •̂c Ildefonse

. cium: Element and Geochemistry - - R. Janecky, Wolfgang H. Runde and

Mary P. Neu

Analysis: Field Methods RR Barefoot

'.Tihrical Geochemistry / _.;:</>! Ruiz

- " • • T ical Techniques ./. Potts

-.r.-.imony: Element and Geochemistry W. Lueth

. us Solutions : L?/i A. Burton

XIX

xxxiii

X X X V

1

2

5

5

7

10

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11

12

13

15

16

Argon Thomas Staudacher

^"Ar/^Mr Dating Method T. Mark Harrison >

Arsenic Jenny G. Webster

Astatine Ronald S. Kaufmann Atomic Absorption Spectrometry Philip J. Potts

Atomic Mass Unit, Avogadro Constant and Mole

Cesare Emiliani (deceased)

Atomic Number Russell S. Harmon

Authigenesis Rhodes W. Eairbridge

Barium Kathleen S. Smith

Berkelium Cynthia E.A. Palmer Beryllium Jeffrey G. Ryan

Biogenic Methane and Gas Hydrate Keith A. Kvenvolden

Biogeochemistry John K. Volkman

Biomarker: Aliphatic Kenneth E. Peters and Clifford C. Walters

18

19

21

23

23

23

25

26

28

29

29

30

31

31

X CONTENTS

Biomarker: Aromatic 33 Bernd R. T. Simoneit

Biomarker: Assessment of Thermal Maturity 36 Kenneth E. Peters

Biomarker: Coals 39 Matthias Radke

Biomarker: Higher Plant 39 Bernd R. T. Simoneit

Biomarkers: Lipid. Bacterial Chemical Fossils 40 Michel Rohmer

Biopolymers and Macromolecules 42 Claude Largeau

Bismuth: Element and Geochemistry 43 Virgil W. Lueth

Black Shales and Sapropels 44 Jan Jehlicka

Boron 44 Jugdeep Aggarwal

Bromine 49 Ronald S. Kaufmann

Cadmium 50 Kathleen S. Smith

Calcium 51 David W. Mittlefehldt

Calcium Carbonate and the Carbonic Acid System 51

Sylvia Frisia

Californium 57 Cynthia E.A. Palmer

Calorimetry 58 Charles A. Geiger

Carbon 58 Austin Long

Carbon-14 Dating and other Applications in Earth Sciences 59

D. Lai and S. Krishnaswami

Carbon Cycle 65 Peter S. Bakwin

Carbon Isotopes 67 Juha Karhu

Carbonate Compensation Depth 73 Elizabeth A. Burton

Carbonate Sediments Abigail M. Smith

Cerium

Scott M. McLennan

Cesium David W. Mittlefehldt Chelation Richard M. Kettler

Chemical Kinetics Youxue Zhang

Chlorine Ronald S. Kaufmann

Chromium Eugene S. Ilton

Clapeyron's Equation Jae-Young Yu

Clay Membranes P.M. Whitworth

Clay Minerals: Ion Exchange P.M. Whitworth

Coal: Organic Petrography J.C Shearer and P. A. Moore

Coal: Origin and Diagenesis R.M. Bustin

Coal: Types and Characteristics P.A. Moore and J.C. Shearer

Coal: Vitrinite Reflectance and Maturity RalfLittke

Cobalt

Achim Albrecht

Colloids Montserrat Eilella and Jacques Buffle Complexes Helen Mango

Compound-Specific Isotope Analysis Roger E. Summons

Copper Mark A. Williamson

Cosmic Elemental Abundances D. Lai

Cosmogenic Nuclides Eric Phorson Brown

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75

76

76

77

80

81

82

83

85

87

90

92

96

97

98

99

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101

102

104

CONTENTS xi

Counters Emest B. Ledger

Critical Points Peter A. Rock and William H. Casey

Crystal Chemistry Dana T. Griffen

Cry stal Field Theory Hans Keppler

Crystal Growth Youxue Zhang

Curium: Element and Geochemistry Wolfgang H. Runde, Mary P. Neu and

David R. Janecky

Dating Methods Brian D. Marshall

Debye-Hiickel Equation Thomas J. Wolery

Diagenesis L'we Brand, Joan O. Morrison and

Ian T. Campbell

Differential Thermal Analysis and Scanning Calorimetry

Janies L . Gooding

Diffusion K. Stuwe

Dolomite and Dolomitization Sylvia Frisia

Dysprosium Scott M. McLennan

Earth's Atmosphere M.A.K. Khalil

Earth's Continental Crust Scott M. McLennan and Stuart Ross Taylor

Earth's Core William F. McDonough

Earth's Formation and Geochemical Evolution H. Palme

Earth's Mantle Geochemistry Ian Ridley

Earth's Ocean Geochemistry Joris M. Gieskes

Earth's Oceanic Crust Michael Perfit

108 Eh-pH Relations Richard B. Wanty

110 Einsteinium Cynthia E.A. Palmer

110 Electrolyte Theory Thomas J. Wolery

118 Electron Capture Car la W. Montgomery

120 Electron Microprobe C. Wagner

123 Electronegativity Jae-Young Yu

Elementary Particles 124 R,K. Varma

Elements: Actinide Series 124 Benoit Villemant

Elements: Alkali and Alkaline Earth 126 David W. Mittlefehldt

Elements: Chalcophile H. Palme

J3J Elements: Distribution Frederick A. Frey

133 Elements: Halogen Ronald S. Kaufmann

14Q Elements: Heat-producing Fernando Bea

142 Elements: High Field Strength V.J.M. Salters

143 Elements: Incompatible W. Ian Ridley

145 Elements: Lanthanide Series, Rare Earths Scott M. McLennan

151 Elements: Large-ion Lithophile Roberta L . Rudnick

156 Elements: Lithophile • . H.G. Stosch

162 Elements: Metalloids Graeme E. Bat ley

168 Elements: Noble Gases Thomas Staudacher

179 Elements: Platinum Group Sarah-Jane Barnes

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187

187

189

190

191

193

195

198

204

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207

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209

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211

214

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215

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218

xii CONTENTS

Elements: Radioactive 219 Paul R. Dixon

Elements: Siderophile 221 H. Palme

Elements: Trace 222 M. Elaine Kennedy

Elements: Transition 223 L . Galoisy and C. Marshall

Enthalpy 226 Carl O. Moses

Entropy 227 Carl O. Moses

Epigenesis 232 Vidojko Jovic

Equilibrium 232 Heinz Gamsjdger

Equilibrium Constant 233 Erich Konigsberger

Erbium 236 Scott M. McLennan

Europium 236 Scott M. McLennan

Experimental Mineralogy and Petrology 237 Charles A. Geiger

Exsolution 239 Jae-Young Yu

Fermium 245 Cynthia E.A. Palmer

Fick's Law 245 Ronald S. Kaufmann

Fission-track Analysis 246 Charles H. Naeser and Nancy D. Naeser

Fluid-Rock Interaction 248 William E. Glassley

Fluids in Volcanic and Plutonic Environments: Evidence From Fluid Inclusions 250

B. De Vivo

Fluorine 252 Ronald S. Kaufmann

Francium 253 David W. Mittlefehldt

Free Energy 253 Carl O. Moses

Fugacity 256 Uwe Brand and Ian T. Campbell

Gadolinium 257 Scott M. McLennan

Gallium: Element and Geochemistry 257 Erich Schroll

Gas Chromatography-Mass Spectrometry (GS-MS) 259

Andrew T. Revill

Gas Source Mass Spectrometry 261 LP. Wright

Geoavailability 262 Kathleen S. Smith

Geochemical Classification of the Elements 263 Scott M. McLennan

Geochemical Exploration 266 Arthur W. Rose

Geochemical Reference Materials 269 K. Govindaraju

Geochemical Tectonics 270 Joaquin Ruiz

Geochemical Thermodynamics 271 Peter A. Rock and William H. Casey

Geochemistry 277 William S. Fyfe

Geochemistry: Low-temperature 280 Elizabeth A. Burton

Geochemistry of Sediments 282 Scott M. McLennan and Richard W. Murray

Geochronology and Radioisotopes 292 Carla W. Montgomery

Geologic Time Scale 295 R. Michael Easton

Geothermal Systems 298 Steven W. Lonker

Geothermometers 3<^ Maurice Pagel and Pierre Barbey

Geothermometry and Geobarometry 305 Richard E. Wendlandt

Germanium: Element and Geochemistry 307 Erich Schroll

Gibbs-Duhem Equation 3C® Peter A. Rock and William H. Casey

CONTENTS XIII

J. Webster

'•:an Patchett

Staudacher

~ Isotopes i Graham

- Law T. Campbell and Uwe Brand

?f Geochemistry • I" Fairbridge

'•!. McLennan

.- .-rbons •J Volkman

\ Kaufman

: r " Isotopes imurthy

: gic Cycle k£my

-ermal Alteration ~ Berger

;;riial Solutions / Bodnar

Jovic

Element and Geochemistry '-'•oil

.. Coupled Plasma Mass Spectrometry ^-MS)

Bea

C V. Butler

:ge Chromatography S.dsteren

rrobe Shimizu

Griffen

Bmtfoot

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312

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322

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325

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330

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333

337

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341

342

343

344

347

Iron Mark A. Williamson ,

Isotope Dilution Carla W. Montgomery

Isotope Fractionation Ian D. Clark

Krypton Thomas Staudacher

Laboratory Simulations of Oil and Natural Formation

J.S. Seewald and T.I. Eglinton

Lanthanum Scott M. McLennan

Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Douglas L . Miles

Lawrencium Cynthia E.A. Palmer

Lead Martin Mihaljevic

Lead: Stable Isotopes Leon E. Long

Lipids (Eubacteria and Archebacteria) Michel Rohmer

Lithium: Element and Geochemistry Ju-chin Chen

Luminescence G. Galas

Lutetium Scott M. McLennan

Lutetium-Hafnium Decay System P. Jonathan Patchett

Magmatic Processes Robert L . Cullers

Magnesium David W. Mittlefehldt

Magnetism Guillaume Morin

Manganese Lloyd M. Petrie

Mass Transfer Ross C. Kerr

Gas

348

353

354

35^

359

360

360

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362

363

368

369

: 370

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379

, 379

382

384

xiv CONTENTS

Mendelevium Cynthia E.A. Palmer

Mercury Martin Mihaljevic

Metamorphic Environments: Chemical Mobility D. R. Bowes and J. Rosier

Meteorites Gregory A. Snyder

Micro-Raman Spectroscopy Stephen Roberts

Mid-Ocean Ridge Basalt (MORB) Anton P. le Roex

Mineral Defects Annemarie Meike

Mineral Genesis Alain J. Baronnet

Mineralogy William S. Eyfe

Molybdenum A.A. Bookstrom

Mossbauer Spectroscopy D.G. Rancourt

Natural Gas Alain Prinzhofer

Natural Resources Martin Hale

Neodymium Scott M. McLennan

Neodymium in Igneous Rocks / Rosier

Neodymium in Sedimentary Rocks Carol D. Frost

Neon Thomas Staudacher

Neptunium: Element and Geochemistry Wolfgang H. Runde, David R. Janecky and

Mary P. Neu

Neutron Activation Analysis James R. Budahn

Nickel Laurence Galoisy

Niobium A.M.R. Neiva

387 Nitrogen A. Hall

387 Nitrogen Cycle Elisabeth A. Holland

389 Nitrogen Isotopes Nathaniel E. Ostrom and Peggy H. Ostrom

395 Nobelium Cynthia E.A. Palmer

400 Nucleosynthesis J.N. Goswami

401 Nutrients J. Faganeli

401 Occurrence of Organic Facies R. Basil Johns

404 Oil Seeps and Coastal Bitumens Andrew T. Revill

409 Oil Shales A.T Revill

411 Oil-Oil and Oil-Source Rock Correlation Clijford C. Walters

413 Oklo Natural Nuclear Reactor Mark J. Rigali and Bartholomew S. Nagy

415 (deceased)

Onuma Diagrams 416 Jean M. Richardson

Ore Deposits 418 Martin Hale

Organic Geochemistry 418 John K. Volkman

Organic Matter in Fossils 421 Stephen A. Macko and Michael H. Engel

Organic Matter in Meteorites 422 Scott Messenger

Organics: Contemporary Degradation and 423 Preservation

Stuart G. Wakeham

Organics: Sources and Depositional 424 Environments

Stuart G. Wakeham

425 Osmium John W. Morgan

426 Oxidation-Reduction Charles G. Patterson

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428

431

434

434

437

439

441

441

442

444

446

447

453

456

458

458

460

461

462

CONTENTS XV

Oxygen 467 Steven C. Semken

Oxygen Isotopes 469 Ethan L . Grossman

Paleo-Sea Surface Temperature Estimations: Organic Geochemistry and Paleoclimates 475

Elisabeth L . Sikes

Paleoenvironments 477 .V/. Elaine Kennedy

Paleoproductivity 479 Uwe Brand, Ian T. Campbell and

Joan O. Morrison

Paleotemperature 480 Uwe Brand, Joan O. Morrison and

Ian T. Campbell

Palladium 484 Christopher J. Capobianco

Paragenesis 485 Robert J. Kamilli

Particle-Induced X-Ray Emission (PIXE) 488 J . L . Campbell

Partition Coefficients 489 Robert L . Cullers

Peat 490 William Shotyk

Periodic Table 491 Gregory A. Snyder

Petroleum 494 R.G. Sehaefer

Petroleum: Hydrothermal 497 Bernd R. T. Simoneit

Petroleum: In-reservoir Biodegradation 498 Jacques Connan

Petroleum: Kinetic Modeling 499 RG. Sehaefer

Petroleum: Primary Migration (Generation and Expulsion) 500

Jean Burrus

Petroleum: Surface Geochemistry 502 RP. Philp

Petroleum: Types, Occurrence and Reserves 504 RG. Sehaefer and D.H. Welte

Phase Equilibria 505 Robert W. Luth

Phosphorus 516 Gerald Matisoff

Platinum 516 W. Crawford Elliott

Plutonium: Environmental Chemistry and Geochemistry ' 517

Paul R. Dixon and David B. Curtis

Polonium: Element and Geochemistry 518 Wolfgang H. Runde

Porphyrins , 519 Chris Boreham

Potassium 522 David W. Mittlefelhdt

Potassium-Argon Dating Method 522 K.A. Poland

Potassium-Calcium Decay System 525 Brian D. Marshall

Praseodymium 526 Scott M. McLennan

Precambrian Atmosphere 526 Grant M. Young

Precambrian Geochemistry 532 R. Michael Easton

Precambrian Organic Matter ^ 535 Roger E. Summons

Promethium 537 Scott M. McLennan

Protactinium 537 David A. Pickett

Quantum Numbers 539 D. G. Rancourt

Radioactivity 540 Stephen A. Prevec

Radium M l Arthur W. Rose

Radon 542 Arthur W. Rose

Rare Earth Element Tetrad Effect 543 T. Akagi

Remote Sensing 544 David A. Rot hery

Rhenium 547 John W. Morgan

xvi CONTENTS

Rhenium-Osmium Dating Method John W. Morgan

Rhodium R.R. Barefoot

Rock-Eval Pyrolysis Kenneth E. Peters

Rocks Vidojko Jovic

Rubidium: Element and Geochemistry E. Craig Simmons

Rubidium-Strontium Method Leon E. Long

Ruthenium R.R. Barefoot

Samarium Scott M. McLennan

Samarium-Neodymium Carla W. Montgomery

Sampling

Jean M. Richardson

Scandium Scott M. McLennan Scanning Electron Microscope C. Wagner

Sedimentary Fluids Ian E. Hutcheon

Selenium Eugene S. Ilton

Silicon, Silica Nancy W. Hinman

Silver: Element and Geochemistry Helen N. Mango

Sodium

David W. Mittlefehldt

Soil William S. Fyfe Solid Solution Erich Konigsberger

Solubility Heinz Gamsjdger

Spectrophotometry Ian T. Campbell and Uwe Brand

547

550

551

554

555

556

561

563

563

567

569

569

570

571

572

576

578

578

580

583

587

Stable Isotopes 588 Ian D. Clark

Standard States 592 Peter A. Rock and William H. Casey

Steroidal Compounds 593 John K. Volkman •

Stoichiometry 595 R. Hellmann

Strontium: Element and Geochemistry 598 E. Craig Simmons

Strontium in Igneous Rocks 599 Jon Davidson

Strontium in Sedimentary Rocks 600 Uwe Brand, Joan O. Morrison and

Ian T. Campbell

Sulfate Minerals 603 Jeremy P. Richards

Sulfate Reduction 603 Hans G. Machel

Sulfide Minerals 605 Jeremy P. Richards

Sulfides in Mafic and Ultramafic Magmas 606 Robert D. Francis

Sulfosalt Minerals 607 Jeremy P. Richards

Sulfur 608 Martin A. A. Schoonen

Sulfur Cycle 608 Martin A. A. Schoonen

Sulfur Isotopes in Geochemistry 610 Keith Hannan

Supergene 615 Vidojko Jovic

Surface Geochemistry 616 Christian Ludwig and William H. Casey

Synchrotron X-Ray Fluorescence Analysis 617 Philip J. Potts

Syngenesis 618 Rhodes W. Eairbridge

Tantalum 620 A.M.R. Neiva

Technetium: Environmental Chemistry and Geochemistry 621

Paul R. Dixon and David B. Curtis

CONTENTS xvii

Tellurium 621 Vidojko Jovic

Terbium 622 Scott M. McLennan

Thallium 622 Vidojko Jovic

Thermal Ionization Mass Spectrometry 623 Peter van Calsteren

Thermochemistry 624 Mitchell Schulte

Thermogravimetry 626 Patrick K. Gallagher

Thermoluminescence 628 Christophe Falgueres

Thixotropy 630 H.C. Weed

Thorium: Element and Geochemistry 630 5". Krishnaswami

Thulium 635 Scott M. McLennan

Tin 635 A.M.R. Neiva

Titanium: Element and geochemistry 636 Francois Farges

Trace Element Partitioning Models 637 Roger L . Nielsen

Tritium 639 Austin Long

Tungsten 639 John C. Groen

Uranium: Element and Geochemistry 645 Fernando Bea

Uranium-Lead Thorium-Lead Decay System 648 P. Vidal

Uranium Series Disequilibria 650 Michel Condomines

Van der Waals Force 655 Jae-Young Yu

Vanadium 656 Gregory A. Snyder

Volcanic Gases 656 P.M. Gerlach

Volcanism 658 Peter W. Francis

Water 660 Carl O. Moses

Water: Fresh 667 Arthur H. Brownlow

Weathering: Chemical 668 Patrick V. Brady

X-Ray Diffraction 670 R.J. Angel

X-Ray Fluorescence Analysis 670 Philip J. Potts

Xenon 671 Thomas Staudacher

Ytterbium 673 Scott M. McLennan

Yttrium 673 Scott M. McLennan

Zinc 674 Martin Mihaljevic

Zirconium: Element and Geochemistry 675 Frangois Farges

Appendix A: List of entries by subject 676

Appendix B: Alphabetical list of the chemical

elements (up to 103) 680

Appendix C: The international system of units 682

Index of authors cited 685

Subject index 703