Treatise on Geochemistry

Karl K. Turekian; Heinrich D. Holland

BOOK

Treatise on Geochemistry

Karl K. Turekian | Heinrich D. Holland

(2013)

Additional Information

Book Details

ISBN: 978-0-08-098300-4
Edition: 2
Language: English
Pages: 9144
Subjects: Surgical orthopaedics & fractures
Medicinal chemistry
Mineralogy & gems
Geology & the lithosphere
Geochemistry
Computer programming / software engineering

Abstract

This extensively updated new edition of the widely acclaimed Treatise on Geochemistry has increased its coverage beyond the wide range of geochemical subject areas in the first edition, with five new volumes which include: the history of the atmosphere, geochemistry of mineral deposits, archaeology and anthropology, organic geochemistry and analytical geochemistry. In addition, the original Volume 1 on "Meteorites, Comets, and Planets" was expanded into two separate volumes dealing with meteorites and planets, respectively. These additions increased the number of volumes in the Treatise from 9 to 15 with the index/appendices volume remaining as the last volume (Volume 16). Each of the original volumes was scrutinized by the appropriate volume editors, with respect to necessary revisions as well as additions and deletions. As a result, 27% were republished without major changes, 66% were revised and 126 new chapters were added.

In a many-faceted field such as Geochemistry, explaining and understanding how one sub-field relates to another is key. Instructors will find the complete overviews with extensive cross-referencing useful additions to their course packs and students will benefit from the contextual organization of the subject matter
Six new volumes added and 66% updated from 1^st edition. The Editors of this work have taken every measure to include the many suggestions received from readers and ensure comprehensiveness of coverage and added value in this 2^nd edition
The esteemed Board of Volume Editors and Editors-in-Chief worked cohesively to ensure a uniform and consistent approach to the content, which is an amazing accomplishment for a 15-volume work (16 volumes including index volume)!

"This landmark 10-volume publication is a comprehensive review of the many-faceted field of geochemistry. (...)
The Treatise will be an indispensable reference not only to academics but to contamination cleanup professionals, resource managers, and environmental regulators as well." --David W. Morganwalp, U.S. Geological Survey, Reston, VA, USA

Section Title	Page	Action	Price
e9780080983004v1.pdf	1
Front Cover	1
Meteorites and Cosmochemical Processes	4
Copyright	5
In Memoriam	7
Heinrich Dieter Holland (1927–2012)	9
Karl Karekin Turekian (1927–2013)	11
References	13
Dedication	15
Contents	17
Executive Editors’ Foreword to the Second Edition	19
Contributors	23
Volume Editor’s Introduction	25
References	26
Chapter 1.1: Classification of Meteorites and Their Genetic Relationships	27
1.1.1. Introduction	28
1.1.2. Classification of Chondritic Meteorites	29
1.1.2.1. Taxonomy	29
1.1.2.2. Primary Classification Parameters	31
1.1.2.2.1. Bulk chemical compositions	31
1.1.2.2.2. Bulk oxygen isotopic compositions	32
1.1.2.2.3. Bulk carbon and nitrogen abundances and isotopic compositions	32
1.1.2.2.4. Bulk stable-isotope anomalies	32
1.1.2.2.5. Oxidation state	32
1.1.2.3. Secondary Classification Parameters	33
1.1.2.3.1. Petrologic type	33
1.1.2.3.2. Shock metamorphism stages	35
1.1.2.3.3. Classification of breccias	35
1.1.2.3.4. Degree of terrestrial weathering	35
1.1.2.4. Mineralogical and Geochemical Characteristics of Chondrite Groups	36
1.1.2.4.1. Carbonaceous chondrites	36
1.1.2.4.1.1. CI (Ivuna-like) chondrites	36
1.1.2.4.1.2. CM (Mighei-like) chondrites	36
1.1.2.4.1.3. Ungrouped CM/CI-like chondrites	38
1.1.2.4.1.4. CO (Ornans-like) chondrites	38
1.1.2.4.1.5. Ungrouped CO/CM-like chondrites	38
1.1.2.4.1.6. CR (Renazzo-like) chondrites	40
1.1.2.4.1.7. Ungrouped CR-related chondrites	40
1.1.2.4.1.8. CH (ALH 85085-like) chondrites	40
1.1.2.4.1.9. CB (Bencubbin-like) chondrites	40
1.1.2.4.1.10. CV (Vigarano-like) chondrites	42
1.1.2.4.1.11. Ungrouped CV-like chondrites	45
1.1.2.4.1.12. CK (Karoonda-like) chondrites	46
1.1.2.4.2. Ordinary chondrites and related meteorites	47
1.1.2.4.2.1. H, L, and LL chondrites	47
1.1.2.4.2.2. Low-FeO ordinary chondrites	48
1.1.2.4.2.3. Metal-rich chondrites	48
1.1.2.4.3. Enstatite chondrites	48
1.1.2.4.4. K (Kakangari-like) chondrites	50
1.1.2.4.5. R (Rumuruti-like) chondrites	51
1.1.3. Classification of Interplanetary Dust Particles (IDPs)	51
1.1.4. Classification of Nonchondritic Meteorites	51
1.1.4.1. Winonaites and the Silicate-Bearing IAB Irons	52
1.1.4.2. Acapulcoites and Lodranites	52
1.1.4.3. Ungrouped primitive achondrites	55
1.1.4.3.1. Primitive enstatite achondrites	55
1.1.4.3.2. Tafassasset	56
1.1.4.4. Brachinites and Brachinite-Like Ultramafic Achondrites	56
1.1.4.5. Ungrouped Achondrites	58
1.1.4.5.1. Divnoe	58
1.1.4.5.2. Ungrouped felsic achondrite	58
1.1.4.6. Ureilites	59
1.1.4.6.1. Almahata Sitta	61
1.1.4.7. Angrites	61
1.1.4.8. Aubrites	62
1.1.4.9. HED Meteorites: Howardites, Eucrites, and Diogenites	62
1.1.4.9.1. Eucrites	62
1.1.4.9.2. Diogenites	64
1.1.4.9.3. Howardites and other eucrite-diogenite breccias	64
1.1.4.9.4. Anomalous eucrites	64
1.1.4.9.4.1. Ungrouped eucrites	66
1.1.4.9.4.2. Anomalous metal-rich eucrites	66
1.1.4.9.4.3. Other anomalous eucrites	66
1.1.4.10. Mesosiderites	67
1.1.4.11. Pallasites	68
1.1.4.11.1. Main-group pallasites	68
1.1.4.11.2. Eagle Station pallasite grouplet	69
1.1.4.11.3. Other pallasites	69
1.1.4.12. Iron Meteorites	69
1.1.4.12.1. Chemical groups	70
1.1.4.12.2. Groups IAB and IIICD	72
1.1.4.12.3. Group IIAB	73
1.1.4.12.4. Group IIE	74
1.1.4.12.5. Group IIIAB	75
1.1.4.12.6. Group IVA	75
1.1.4.12.7. Group IVB	75
1.1.4.12.8. Ungrouped irons	75
1.1.4.13. Martian Meteorites	75
1.1.4.13.1. Shergottites	75
1.1.4.14. Nakhlites (Clinopyroxenites/Wehrlites)	78
1.1.4.14.1. Chassignites (Dunites)	78
1.1.4.14.2. Allan Hills 84001 (Orthopyroxenite)	78
1.1.4.15. Lunar Meteorites	78
1.1.5. Genetic Relations Among Meteorite Groups	78
Acknowledgments	79
References	79
Chapter 1.2: Chondrites and Their Components	91
1.2.1. Introduction	92
1.2.1.1. What Are Chondrites?	92
1.2.1.2. Why Study Chondrites?	92
1.2.1.3. Historical Views on Chondrite Origins	93
1.2.1.4. Chondrites and the Solar Nebula	94
1.2.2. Classification and Parent Bodies of Chondrites	94
1.2.2.1. Chondrite Groups, Clans, and Parent Bodies	94
1.2.2.2. Ordinary Chondrites	96
1.2.2.3. Carbonaceous Chondrites	96
1.2.2.4. Enstatite Chondrites	96
1.2.3. Bulk Composition of Chondrites	97
1.2.3.1. Cosmochemical Classification of Elements	97
1.2.3.2. Chemical Compositions of Chondrites	97
1.2.3.3. Isotopic Compositions of Chondrites	98
1.2.3.4. Oxygen Isotopic Compositions	99
1.2.4. Metamorphism, Alteration, and Impact Processing	99
1.2.4.1. Petrologic Types	100
1.2.4.1.1. Type 1-2 chondrites	100
1.2.4.1.2. Type 3 chondrites	101
1.2.4.1.3. Type 4-6 chondrites	101
1.2.4.2. Thermal History and Modeling	102
1.2.4.3. Impact Processing of Chondritic Asteroids	102
1.2.5. Chondritic Components	103
1.2.5.1. Calcium- and Aluminum-Rich Inclusions	103
1.2.5.1.1. Comparison of CAIs from different chondrite groups	103
1.2.5.1.2. Oxygen-isotope compositions of CAIs	104
1.2.5.2. Forsterite-Rich Accretionary Rims around CAIs	106
1.2.5.3. Amoeboid Olivine Aggregates	108
1.2.5.3.1. Mineralogy and petrology of AOAs	108
1.2.5.3.2. Trace elements and isotopic composition of AOAs•	109
1.2.5.3.3. Origin of AOAs	110
1.2.5.4. Aluminum-Rich Chondrules	112
1.2.5.4.1. Isotopic and trace element studies of aluminum-rich chondrules	113
1.2.5.4.2. Origin of aluminum-rich chondrules	115
1.2.5.4.3. Relict CAIs and AOAs in ferromagnesian chondrules	116
1.2.5.4.4. Relict chondrules in igneous CAIs and igneous CAIs overgrown by chondrule material	116
1.2.5.5. Refractory Forsterite-Rich Objects	119
1.2.5.6. Chondrules	121
1.2.5.6.1. Chondrule textures, types, and thermal histories	121
1.2.5.6.2. Chemical compositions of chondrules	122
1.2.5.6.3. Oxygen-isotope compositions of chondrules	122
1.2.5.6.4. Stable isotope anomalies and aluminum-magnesium isotope systematics of chondrules	123
1.2.5.6.5. Noble gas abundances in chondrules	123
1.2.5.6.6. Compound chondrules, relict grains, and chondrule rims	124
1.2.5.6.7. Chondrule forming environment	126
1.2.5.6.8. Chondrules that formed by condensation	129
1.2.5.6.9. Chondrules that formed on asteroids	130
1.2.5.7. Metal and Troilite	132
1.2.5.7.1. CR chondrite metallic Fe,Ni	133
1.2.5.7.2. CH and CB chondrite metallic Fe,Ni	133
1.2.5.7.3. Troilite	134
1.2.5.8. Matrix Material	134
1.2.5.8.1. CI1 chondrites	136
1.2.5.8.2. CM2 chondrite matrices	136
1.2.5.8.3. CR2-3 chondrite matrices	137
1.2.5.8.4. CO3 chondrite matrices	137
1.2.5.8.5. CK3-6 chondrite matrices	140
1.2.5.8.6. CV3 chondrite matrices	140
1.2.5.8.7. Matrix of ungrouped C chondrites, Acfer 094, and Adelaide	141
1.2.5.8.8. H-L-LL3 chondrite matrices	142
1.2.5.8.9. EH3 and EL3 chondrite matrices	142
1.2.5.8.10. K3 chondrite matrices (Kakangari and LEW 87232)	142
1.2.5.8.11. Matrix-rich lithic clasts	144
1.2.5.8.12. Origins of matrix phases	145
1.2.6. Formation and Accretion of Chondritic Components	148
1.2.7. Heating Mechanisms in the Early Solar System	148
1.2.7.1. Nebular Shocks	150
1.2.7.2. Jets and Outflows	150
1.2.7.3. Impacts on Planetesimals	150
Acknowledgments	151
References	151
Chapter 1.3: Calcium-Aluminum-Rich Inclusions in Chondritic Meteorites	165
1.3.1. Introduction	165
1.3.2. Changes in this Revision	166
1.3.3. Some Essential Terminology: Structural Elements of a CAI	166
1.3.3.1. The Generic CAI	166
1.3.3.2. Comments on Primary and Secondary Mineralogy	167
1.3.3.3. Rim Sequences	167
1.3.3.4. Metal Grains and Fremdlinge	168
1.3.4. Mineralogy and Mineral Chemistry	168
1.3.4.1. Melilite	170
1.3.4.2. Spinel	171
1.3.4.3. Pyroxene	171
1.3.4.4. Hibonite	172
1.3.4.5. Perovskite	173
1.3.4.6. Grossite (CaAl4O7) and Krotite/Dmitryivanovite (CaAl2O4)	173
1.3.4.7. Anorthite	173
1.3.5. Diversity and Major Element Bulk Chemistry	173
1.3.6. Type C CAIs, Compound Objects, and the Chondrule-CAI Connection	180
1.3.7. Fun CAIs and Hibonite Grains	180
1.3.8. Distribution Among Chondrite Types	182
1.3.8.1. CV3 Chondrites	183
1.3.8.2. CO3 Chondrites	183
1.3.8.3. CM Chondrites	183
1.3.8.4. CR Clan Chondrites	184
1.3.8.5. CAIs in Acfer 094	185
1.3.8.6. Ordinary Chondrites	186
1.3.8.7. Enstatite Chondrites	186
1.3.8.8. Stardust CAIs	188
1.3.9. Ages	188
1.3.10. Trace Elements	188
1.3.11. Oxygen Isotopes	190
1.3.11.1. General	190
1.3.11.2. The Data	190
1.3.11.3. Nebular and Intra-CAI heterogeneity: Progress on Two Great Debates	193
1.3.12. Short-Lived Radionuclides in CAIs	194
1.3.12.1. 26Al	194
1.3.12.2. 41Ca	198
1.3.12.3. 10Be	198
1.3.13. CAIS, Chondrules, Condensation, and Melt Distillation	198
1.3.14. Wark-Lovering Rim Sequences: One Terminal Event or Many?	199
1.3.15. Conclusions and Reflections: Technology, the Big Picture, and the Convergence of Cosmochemistry and Astronomy	199
Acknowledgments	199
References	200
Chapter 1.4: Presolar Grains	207
1.4.1. Introduction	207
1.4.2. Historical Background	208
1.4.3. Types of Presolar Grains	208
1.4.4. Analysis Techniques	209
1.4.5. Astrophysical Implications of the Study of Presolar Grains	210
1.4.6. Silicon Carbide	210
1.4.6.1. Mainstream Grains	213
1.4.6.2. Type Y and Z Grains	216
1.4.6.3. Type AB Grains	217
1.4.6.4. Type X Grains	217
1.4.6.5. Nova Grains	220
1.4.6.6. Type C Grains	220
1.4.6.7. Abundances and Grain-Size Effect	220
1.4.7. Silicon Nitride	221
1.4.8. Graphite	221
1.4.8.1. Physical Properties	221
1.4.8.2. Isotopic Compositions	222
1.4.9. Oxygen-Rich Grains	225
1.4.9.1. Oxide Grains	225
1.4.9.2. Silicate Grains	228
1.4.10. Diamond	230
1.4.11. Conclusion and Future Prospects	231
Acknowledgments	231
References	231
Chapter 1.5: Structural and Isotopic Analysis of Organic Matter in Carbonaceous Chondrites	241
1.5.1. Introduction	241
1.5.2. Organic Material in Carbonaceous Chondrites	242
1.5.3. Extractable Organic Matter	242
1.5.3.1. Abundance and Distribution of Extractable Compounds	242
1.5.3.1.1. Carboxylic acids	242
1.5.3.1.2. Sulfonic and phosphonic acids	243
1.5.3.1.3. Amino acids	244
1.5.3.1.4. Aromatic hydrocarbons	245
1.5.3.1.5. Heterocyclic compounds	245
1.5.3.1.6. Aliphatic hydrocarbons	246
1.5.3.1.7. Amines and amides	246
1.5.3.1.8. Alcohols, aldehydes, ketones, and sugar-related compounds	246
1.5.3.2. Stable-Isotopic Investigations of Classes of Organic Compounds	247
1.5.3.3. Compound-Specific Isotopic Studies	247
1.5.3.3.1. Carbon	248
1.5.3.3.2. Nitrogen	249
1.5.3.3.3. Hydrogen	249
1.5.3.3.4. Sulfur	249
1.5.4. Macromolecular Material	251
1.5.4.1. Structural Studies Using Pyrolysis and Chemical Degradation	251
1.5.4.2. NMR and Electron Spin Resonance Studies	251
1.5.4.3. Stable-Isotopic Studies	253
1.5.5. In Situ Examination of Meteoritic Organic Matter	254
1.5.6. Environments of Formation	255
References	257
Chapter 1.6: Achondrites	261
1.6.1. Introduction	261
1.6.2. Primitive Achondrites	262
1.6.2.1. Acapulcoite-Lodranite Clan	262
1.6.2.2. Winonaite-IAB-Iron Silicate Inclusion Clan	272
1.6.2.3. Zag (b)	273
1.6.3. Differentiated Achondrites	273
1.6.3.1. Angrites	273
1.6.3.2. Aubrites	276
1.6.3.3. Brachinites	277
1.6.3.4. Howardite-Eucrite-Diogenite Clan	279
1.6.3.5. Mesosiderite Silicates	280
1.6.3.6. Ureilites	282
1.6.3.7. Ibitira	284
1.6.3.8. Itqiy	284
1.6.3.9. Northwest Africa 011	285
1.6.4. Uncategorized Achondrites	285
1.6.4.1. IIE Iron Meteorite Silicates	285
1.6.5. Summary	286
Acknowledgments	286
References	287
Chapter 1.7: Iron and Stony-Iron Meteorites	293
1.7.1. Introduction	293
1.7.2. Classification and Chemical Composition of Iron Meteorites	294
1.7.2.1. Group IIAB Iron Meteorites	295
1.7.2.2. Group IIIAB Iron Meteorites	295
1.7.2.3. Group IVA Iron Meteorites	295
1.7.2.4. Group IVB Iron Meteorites	296
1.7.2.5. Silicate-Bearing IAB Complex and IIE Iron Meteorites	296
1.7.2.6. Mesosiderites	296
1.7.2.7. Ungrouped Iron Meteorites	297
1.7.3. Accretion and Differences in Bulk Chemistry Between Groups of Iron Meteorites	297
1.7.4. Heating and Differentiation	298
1.7.5. Fractional Crystallization of Metal Cores	300
1.7.5.1. Imperfect Mixing During Crystallization	301
1.7.5.2. Late-Stage Crystallization and Immiscible Liquid	301
1.7.5.3. The Missing Sulfur-Rich Meteorites	302
1.7.6. Cooling Rates and Sizes of Parent Bodies	303
1.7.7. Pallasites	304
1.7.8. Parent Bodies of Iron and Stony-Iron Meteorites	305
1.7.9. Future Research Directions	306
References	307
Chapter 1.8: Early Solar Nebula Grains - Interplanetary Dust Particles	313
1.8.1. Introduction	313
1.8.2. Particle Size, Morphology, Porosity, and Density	315
1.8.3. Mineralogy	315
1.8.3.1. CPIDPs	316
1.8.3.2. Glass with Embedded Metal and Sulfides	320
1.8.3.3. CSIDPs	323
1.8.4. Optical Properties	324
1.8.5. Compositions	325
1.8.5.1. Major Elements	325
1.8.5.2. Trace Elements	327
1.8.5.3. Isotopes	329
1.8.5.4. Noble Gases	330
1.8.6. Conclusions	330
Acknowledgments	332
References	332
Chapter 1.9: Nebular Versus Parent Body Processing	335
1.9.1. Introduction	335
1.9.2. Nebular or Asteroidal Processing: Some Criteria	336
1.9.3. Aqueous Alteration	336
1.9.3.1. CI Carbonaceous Chondrites	336
1.9.3.1.1. Evidence for asteroidal alteration	336
1.9.3.1.2. Timing of alteration	337
1.9.3.1.3. Summary	338
1.9.3.2. CM Carbonaceous Chondrites	338
1.9.3.2.1. Timing of alteration	339
1.9.3.2.2. Appraisal of the evidence for preaccretionary alteration	340
1.9.3.2.3. Evidence for asteroidal alteration	341
1.9.3.2.3.1. Veining in CM chondrites	341
1.9.3.2.3.2. Fe-rich aureoles	341
1.9.3.2.3.3. Bulk compositional homogeneity of CM chondrites	341
1.9.3.2.3.4. Elemental exchange between chondrules and matrix during progressive alteration	342
1.9.3.2.3.5. Homogeneity of chondrule alteration	342
1.9.3.2.3.6. Presence of oriented aragonite clusters in CM chondrites	342
1.9.3.2.3.7. Microchemical environments	342
1.9.3.2.3.8. Oxygen isotopic compositions	343
1.9.3.2.4. Summary	343
1.9.3.3. CR Carbonaceous Chondrites	343
1.9.3.4. CO Carbonaceous Chondrites	344
1.9.3.5. CV Carbonaceous Chondrites	345
1.9.3.5.1. Evidence for preaccretionary alteration	346
1.9.3.5.2. Evidence for parent body alteration	346
1.9.3.6. Unequilibrated Ordinary Chondrites	346
1.9.4. Oxidation and Metasomatism	347
1.9.4.1. CV Carbonaceous Chondrites	347
1.9.4.1.1. Iron-alkali-halogen metasomatism	347
1.9.4.1.2. Fayalitic rims on chondrules, CAIs, etc.	348
1.9.4.1.3. Oxidation and sulfidization of opaque assemblages	348
1.9.4.2. Dark Inclusions in CV Chondrites	348
1.9.4.3. Nebular and Parent Body Alteration Models for CV Chondrites	348
1.9.4.3.1. Nebular alteration	348
1.9.4.3.2. Parent body alteration	349
1.9.4.3.3. Problems with the nebular alteration model	349
1.9.4.3.3.1. Origin of platy matrix olivine grains	349
1.9.4.3.3.2. Presence of veins in dark inclusions	349
1.9.4.3.3.3. Formation of calcium-iron pyroxenes	349
1.9.4.3.3.4. Rims of calcium-iron pyroxene around dark inclusions	350
1.9.4.3.3.5. Calcium-rich halos around altered CAIs	350
1.9.4.3.3.6. Timing of alteration	350
1.9.4.3.4. Problems with the asteroidal alteration model	351
1.9.4.3.4.1. Oxygen isotopes	351
1.9.4.3.4.2. Formation of platy olivines	351
1.9.4.3.4.3. Timing of metasomatism and aqueous alteration	351
1.9.4.4. CO Carbonaceous Chondrites	352
1.9.4.4.1. Evidence for parent body alteration of CO chondrites	353
1.9.4.4.2. Evidence for nebular alteration of CO chondrites	354
1.9.4.5. Unequilibrated Ordinary Chondrites	354
1.9.4.5.1. Carbide-magnetite assemblages	354
1.9.5. Future Work	355
Acknowledgments	355
References	355
Chapter 1.10: Condensation and Evaporation of Solar System Materials	361
1.10.1. Introduction	361
1.10.2. Theoretical Framework	362
1.10.2.1. Thermodynamic Equilibrium	363
1.10.2.1.1. Condensation of the major elements	363
1.10.2.1.2. Condensation of trace elements	364
1.10.2.1.3. High-temperature equilibrium isotopic fractionation	365
1.10.2.2. Kinetic Effects	365
1.10.3. Laboratory Experiments	368
1.10.3.1. Evaporation of Metals and Simple Oxides	368
1.10.3.2. Evaporation of Olivine	369
1.10.3.3. Evaporation of CMAS Melts	369
1.10.3.4. Evaporation of Chondritic Meteorites and Chondritic Melts	373
1.10.3.5. Kinetic Isotope Fractionation Factors for Molten Oxides and Silicates	373
1.10.4. Applications	375
1.10.4.1. Bulk Compositions of Planets and Meteorite Parent Bodies	375
1.10.4.2. Calcium- and Aluminum-Rich Inclusions	376
1.10.4.2.1. Ultrarefractory inclusions	376
1.10.4.2.2. Textural evidence	377
1.10.4.2.3. Bulk elemental and isotopic compositions of type B CAIs	377
1.10.4.2.4. Reheating mechanisms for the type B CAIs	379
1.10.4.2.5. Isotopic fractionation of refractory elements in CAIs	380
1.10.4.2.6. Refractory metal inclusions	380
1.10.4.2.7. FUN CAIs	381
1.10.4.2.8. Hibonites with cerium anomalies	381
1.10.4.3. Chondrites	381
1.10.4.3.1. Chondrules	381
1.10.4.3.2. Metal Grains	382
1.10.4.4. Deep-Sea Spherules	382
1.10.5. Outlook	382
Acknowledgments	382
References	382
Chapter 1.11: Short-Lived Radionuclides and Early Solar System Chronology	387
1.11.1. Introduction	387
1.11.1.1. Chondritic Meteorites as Probes of Early Solar System Evolution	387
1.11.1.2. Short-Lived Radioactivity at the Origin of the Solar System	388
1.11.1.3. A Brief History and the Scope of the Present Review	388
1.11.2. Dating with Ancient Radioactivity	390
1.11.3 ‘Absolute’ and ‘Relative’ Timescales	391
1.11.3.1. An Absolute Timescale for Solar System Formation	391
1.11.3.2. An Absolute Timescale for Chondrule Formation	393
1.11.3.3. An Absolute Timescale for Early Differentiation of Planetesimals	394
1.11.4. The Record of Short-Lived Radionuclides in Early Solar System Materials	394
1.11.4.1. Beryllium-7	395
1.11.4.2. Calcium-41	395
1.11.4.3. Chlorine-36	396
1.11.4.4. Aluminum-26	396
1.11.4.4.1. Bulk and internal isochrons and the solar system initial 26Al/27Al	396
1.11.4.4.2. Mass fractionation correction	397
1.11.4.4.3. Magnesium isotopic evolution in the early solar system	398
1.11.4.4.4. 26Al-26Mg systematics in CAIs	399
1.11.4.4.5. 26Al-26Mg systematics in chondrules	400
1.11.4.4.6. 26Al-26Mg systematics in achondrites	401
1.11.4.5. Beryllium-10	401
1.11.4.6. Cesium-135	402
1.11.4.7. Iron-60	402
1.11.4.8. Manganese-53	404
1.11.4.9. Palladium-107	406
1.11.4.10. Hafnium-182	406
1.11.4.11. Curium-247	409
1.11.4.12. Iodine-129	409
1.11.4.13. Lead-205	409
1.11.4.14. Niobium-92	410
1.11.4.15. Samarium-146	410
1.11.4.16. Plutonium-244	410
1.11.5. Origins of the Short-Lived Nuclides	410
1.11.5.1. Sources of Short-Lived Nuclides	410
1.11.6. Short-Lived Nuclides as Chronometers	411
1.11.6.1. Formation Timescales of Nebular Materials	412
1.11.6.2. Timescales of Planetesimal Accretion and Early Chemical Differentiation	413
1.11.7. Conclusions	413
1.11.7.1. Implications for Solar Nebula Origin and Evolution	414
1.11.7.2. Future Directions	415
Acknowledgments	415
References	415
Chapter 1.12: Solar System Time Scales from Long-Lived Radioisotopes in Meteorites and Planetary Materials	423
1.12.1. Introduction	423
1.12.1.1. Basic Principles	423
1.12.1.2. Application to Meteorites and Planetary Materials: A Historical Perspective and Some New Developments	424
1.12.2. Chondrites and Their Components	425
1.12.2.1. Formation Ages of Chondritic Components	425
1.12.2.1.1. Calcium-aluminum-rich inclusions	425
1.12.2.1.2. Chondrules	427
1.12.2.2. Ages of Secondary Events Recorded in Chondrites	427
1.12.2.2.1. Aqueous alteration	427
1.12.2.2.2. Thermal metamorphism	428
1.12.2.2.3. Shock metamorphism	429
1.12.3. Differentiated Meteorites	429
1.12.3.1. Primitive Achondrites: Timing of Incipient Differentiation on Planetesimals	429
1.12.3.2. Basaltic and Other Achondrites: Timing of Asteroidal Differentiation and Cataclysm	430
1.12.3.2.1. Crust formation time scales from chronology of achondrites and their components	430
1.12.3.2.2. Global differentiation time scales based on whole-rock isochrons and initial 87S/86Sr	432
1.12.3.2.3. Inner solar system bombardment history based on reset ages	434
1.12.3.3. Iron Meteorites and Pallasites: Time Scales of Core Crystallization on Planetesimals	434
1.12.4. Planetary Materials	436
1.12.4.1. Timing of Lunar Differentiation and Cataclysm from Chronology of Lunar Samples	437
1.12.4.1.1. Lunar differentiation history	437
1.12.4.1.2. Lunar bombardment history	438
1.12.4.2. Time Scales for the Evolution of Mars from Chronology of Martian Meteorites	438
1.12.5. Conclusions	439
1.12.5.1. A Timeline for Solar System Events	439
1.12.5.2. Outlook and Future Prospects	440
Acknowledgments	440
References	441
Chapter 1.13: Cosmic-Ray Exposure Ages of Meteorites	445
1.13.1. Introduction	446
1.13.2. Calculation of Exposure Ages	447
1.13.2.1. Basic Equations	447
1.13.2.2. Factors Influencing Production Rates	447
1.13.2.3. Measurement Units and Quantities	448
1.13.2.4. Determination of Production Rates	448
1.13.2.4.1. Radionuclide production rates	448
1.13.2.4.2. 26Al and 21Ne	449
1.13.2.4.3. 83Kr/81Kr calibration	449
1.13.2.5. Equations for Calculating One-Stage CRE Ages	450
1.13.2.5.1. 21Ne-22Ne/21Ne ages	450
1.13.2.5.2. 38Ar-22Ne/21Ne ages	450
1.13.2.5.3. 3He ages	451
1.13.2.5.4. 36Cl/ 36Ar ages	451
1.13.2.5.5. 81Kr/Kr ages	452
1.13.2.5.6. 40K/K ages of meteoritic metal	452
1.13.2.6. The Importance of Half-Lives	453
1.13.2.7. CRE Ages and Long-Lived Chronometers	454
1.13.3. Carbonaceous Chondrites	454
1.13.3.1. CI, CM, CO, CV, and CK Chondrites	454
1.13.3.2. The CR Clan	455
1.13.4. H Chondrites	456
1.13.5. L Chondrites	456
1.13.6. LL Chondrites	457
1.13.7. E Chondrites	457
1.13.8. R Chondrites	458
1.13.9. Lodranites and Acapulcoites	458
1.13.10. Lunar Meteorites	459
1.13.10.1. Overview	459
1.13.10.2. Construction of CRE Histories	459
1.13.10.3. Production Rate of Lunar Meteorites	461
1.13.11. Howardite-Eucrite-Diogenite (HED) Meteorites	461
1.13.11.1. Eucrites	461
1.13.11.2. Diogenites	462
1.13.11.3. Howardites	462
1.13.11.4. Kapoeta	463
1.13.12. Angrites	463
1.13.13. Ureilites	463
1.13.14. Aubrites (Enstatite Achondrites)	464
1.13.15. Brachinites	465
1.13.16. Martian Meteorites	465
1.13.17. Mesosiderites	467
1.13.18. Pallasites	468
1.13.19. Irons	468
1.13.20. The Smallest Particles: Micrometeorites, Interplanetary Dust Particles, and Interstellar Grains	470
1.13.20.1. Background	470
1.13.20.2. Exposure Histories from Noble Gases	470
1.13.20.3. Exposure Histories from 10Be and 26Al	470
1.13.20.4. Interstellar (Presolar) Grains	471
1.13.21. Conclusions	472
Acknowledgments	473
References	473
e9780080983004v2	481
Front Cover	481
Planets, Asteroids, Comets and the Solar System	484
Copyright	485
In Memoriam	486
Heinrich Dieter Holland (1927–2012)	488
Karl Karekin Turekian (1927–2013)	490
References	492
Dedication	494
Contents	496
Executive Editors’ Foreword to the Second Edition	498
Contributors	502
Volume editor’s Introduction	504
References	505
Chapter 2.1: Origin of the Elements	506
2.1.1. Introduction	506
2.1.2. Abundances and Nucleosynthesis	507
2.1.3. IMS: Evolution and Nucleosynthesis	508
2.1.3.1. Shell Helium Burning and 12C Production	509
2.1.3.2. s-Process Synthesis in Red Giants	509
2.1.4. Massive Star Evolution and Nucleosynthesis	509
2.1.4.1. Nucleosynthesis in Massive Stars	511
2.1.4.1.1. Hydrogen burning	511
2.1.4.1.2. Helium burning and the s-process	511
2.1.4.1.3. Hydrogen and helium shell burning	512
2.1.4.1.4. Carbon burning	512
2.1.4.1.5. Neon and oxygen burning	512
2.1.4.1.6. Silicon burning	512
2.1.4.1.7. Explosive nucleosynthesis	512
2.1.4.1.8. The p-process	513
2.1.4.1.9. The r-process	514
2.1.5. Type Ia Supernovae: Progenitors and Nucleosynthesis	514
2.1.6. Nucleosynthesis and Galactic Chemical Evolution	515
References	517
Chapter 2.2: Solar System Abu	520
2.2.1. Abundances of the Elements in the Solar Nebula	520
2.2.1.1. Historical Remarks	520
2.2.1.2. Solar System Abundances of the Elements	521
2.2.1.2.1. Is the solar nebula compositionally uniform?	521
2.2.1.2.2. The composition of the solar photosphere	522
2.2.1.3. Abundances of Elements in Meteorites	524
2.2.1.3.1. Differentiated and undifferentiated meteorites	524
2.2.1.3.2. Cosmochemical classification of elements	524
2.2.1.4. CI Chondrites as the Standard for Solar Abundances	526
2.2.1.4.1. Chemical variations among chondritic meteorites	526
2.2.1.4.2. CI chondrites	529
2.2.1.4.3. The CI chondrite abundance table	530
2.2.1.5. Solar System Abundances of the Elements	533
2.2.1.5.1. Comparison of meteorite and solar a&	533
2.2.1.5.2. Solar system abundances versus mass number	535
2.2.1.5.3. Other sources for solar system abundances	535
2.2.2. The Abundances of the Elements in the ISM	536
2.2.2.1. Introduction	536
2.2.2.2. The Nature of the ISM	536
2.2.2.3. The Chemical Composition of the ISM	537
2.2.2.3.1. The composition of the interstellar gas and elemental depletions	537
2.2.2.3.2. The composition of interstellar dust	537
2.2.2.3.3. Interstellar oxygen problems	538
2.2.3. Summary	539
References	539
Chapter 2.3: The Solar Nebula	542
2.3.1. Introduction	542
2.3.2. Formation of the Solar Nebula	543
2.3.2.1. Observations of Precollapse Clouds	543
2.3.2.1.1. Cloud properties	543
2.3.2.1.1.1. Density profiles	544
2.3.2.1.1.2. Cloud shapes	544
2.3.2.1.1.3. Angular momentum distributions	544
2.3.2.1.2. Onset of collapse phase	544
2.3.2.1.2.1. Ambipolar diffusion and loss of magnetic support	544
2.3.2.1.2.2. Shock-triggered collapse	545
2.3.2.1.3. Outcome of collapse phase	545
2.3.2.1.3.1. Fragmentation leading to ejection of single stars	545
2.3.2.1.3.2. Collapse leading to single star formation	546
2.3.2.1.4. Ubiquity of bipolar outflows from earliest phases	546
2.3.2.1.5. The chemistry of infall and outflows	546
2.3.3. Solar Nebula Structure and Evolution	547
2.3.3.1. Search for Astrophysical Analogues for the Solar Nebula	547
2.3.3.1.1. Optical and IR-wave observations	547
2.3.3.1.1.1. Mass accretion rates – episodicity and outbursts	547
2.3.3.1.1.2. Temperature profiles from spectral energy distributions	548
2.3.3.1.2. Millimeter-wave observations	548
2.3.3.1.2.1. Disk masses	549
2.3.3.1.2.2. Keplerian rotation	549
2.3.3.2. Angular Momentum Transport Mechanisms in Protoplanetary Disks	549
2.3.3.2.1. Magnetorotational-driven turbulence	549
2.3.3.2.1.1. Balbus–Hawley instability	550
2.3.3.2.1.2. Ionization structure and layered accretion	550
2.3.3.2.2. Gravitational torques in a marginally unstable disk	550
2.3.3.2.2.1. Rapid mass and angular momentum transport	551
2.3.3.2.2.2. Global process versus local viscosity	551
2.3.3.3. Evolution of the Solar Nebula	551
2.3.3.3.1. Viscous accretion disk models	551
2.3.3.3.2. Turbulent and gas drag transport	553
2.3.3.3.3. Volatility patterns and transport in inner solar system	553
2.3.3.4. Clump Formation in a Marginally Gravitationally Unstable Disk	554
2.3.3.4.1. Chondrule formation in nebular shock fronts	554
2.3.3.4.2. Mixing processes in marginally gravitationally unstable disks	554
2.3.4. Solar Nebula Removal	555
2.3.4.1. Observational Constraints on Disk Lifetimes	555
2.3.4.2. Removal Mechanisms	555
2.3.4.2.1. Inward flow onto protosun	555
2.3.4.2.2. UV photoevaporation by protosun	555
2.3.4.2.3. UV photoevaporation in Orion-like regions	556
2.3.4.2.4. Final scouring by widened stellar outflow	556
2.3.5. Summary	556
References	556
Chapter 2.4: Planet Formation	560
2.4.1. Introduction	560
2.4.2. The Protoplanetary Nebula and the First Solids	561
2.4.2.1. Protoplanetary Disks	561
2.4.2.2. Disk Evolution	561
2.4.2.3. The Solar Nebula	562
2.4.3. Planetesimals and the First Solids	562
2.4.3.1. Particle Motions	562
2.4.3.2. Chondritic Meteorites and their Components	563
2.4.3.3. Short-Lived Isotopes	564
2.4.3.4. Planetesimal Formation	564
2.4.4. Terrestrial Planet Formation	565
2.4.4.1. Runaway and Oligarchic Growth	565
2.4.4.2. Late-Stage Accretion and Giant Impacts	566
2.4.4.3. Planetary Compositions and Core Formation	566
2.4.4.4. Formation of the Moon	567
2.4.4.5. Water and the Terrestrial Planets	567
2.4.5. The Asteroid Belt	568
2.4.5.1. Formation of the Asteroid Belt	568
2.4.5.2. Asteroid Physical Evolution	569
2.4.6. Giant-Planet Formation	569
2.4.6.1. Giant-Planet Compositions	569
2.4.6.2. Formation of Gas Giant Planets	569
2.4.6.3. Formation of Uranus and Neptune	570
2.4.6.4. Planetary Migration and Scattering	570
2.4.6.5. Planetesimal-Driven Migration and the Nice Model	571
References	572
Chapter 2.5: The Geochemistry and Cosmochemistry of Impacts	578
2.5.1. Introduction: The Use of Geochemistry in Impact Studies	578
2.5.2. Background on Impact Craters and Processes	579
2.5.3. Methods	584
2.5.3.1. General Geochemistry: Major and Trace Elements	584
2.5.3.1.1. Sample preparation	585
2.5.3.2. Rb–Sr, Sm–Nd, and Pb Isotopes	585
2.5.3.3. Siderophile Element Studies	586
2.5.3.4. Osmium Isotopes	588
2.5.3.5. Chromium Isotopes	590
2.5.3.6. Tungsten Isotopes	591
2.5.3.7. Stable Isotopes	591
2.5.3.8. Other Methods	592
2.5.3.8.1. Helium-3	592
2.5.3.8.2. Beryllium-10	593
2.5.3.8.3. Remote sensing	593
2.5.3.8.4. Chromian spinels	593
2.5.3.8.5. x-Ray absorption near-edge spectroscopy	593
2.5.4. Examples	595
2.5.4.1. Meteorite Craters: Source Rocks and Impactites	595
2.5.4.2. Extraterrestrial Components in Impactites	596
2.5.4.2.1. Vredefort impact structure (South Africa)	599
2.5.4.2.2. Morokweng impact structure (South Africa)	600
2.5.4.2.3. Bosumtwi crater, Ghana	601
2.5.4.2.4. Other examples	602
2.5.4.3. Tektites	603
2.5.4.4. Libyan Desert Glass	606
2.5.4.5. K–T Boundary	607
2.5.4.6. Permian–Triassic Boundary	609
2.5.4.7. Early Archean Spherule Layers	610
2.5.4.8. The Earth's Earliest Impact History	612
2.5.5. Summary	614
Acknowledgments	615
References	615
Chapter 2.6: Mercury	624
2.6.1. Introduction: The Importance of Mercury	624
2.6.2. Pre-MESSENGER View of the Chemical Composition of Mercury	624
2.6.3. Pre-MESSENGER Models for the Origin of Mercury	625
2.6.3.1. Physical Models for Metal Enrichment in Mercury	625
2.6.3.2. High-Temperature Evaporation and Condensation Models for Mercury	625
2.6.3.3. Refractory-Volatile Mixtures	626
2.6.3.4. Formation of Mercury from Known Chondritic Meteorites	626
2.6.4. Results from the MESSENGER Mission	626
2.6.5. Evaluating Models for the Origin of Mercury	629
2.6.6. The Future for the Exploration of Mercury	629
Acknowledgments	630
References	630
Chapter 2.7: Venus	632
2.7.1. Brief History of Observations	632
2.7.1.1. Pre-Twentieth Century	632
2.7.1.2. The Twentieth Century to the Present Day	632
2.7.2. Overview of Important Orbital Properties	634
2.7.3. Atmosphere	635
2.7.3.1. Composition	635
2.7.3.1.1. Basic definitions and general remarks	635
2.7.3.1.2. Carbon, sulfur, and halogen gases	635
2.7.3.1.3. Water vapor	639
2.7.3.1.4. Nitrogen and noble gases	639
2.7.3.1.5. Isotopic composition	640
2.7.3.2. Thermal Structure and Greenhouse Effect	641
2.7.3.3. Clouds and Photochemical Cycles	641
2.7.3.4. Atmospheric Dynamics	643
2.7.3.5. Upper Atmosphere and Solar Wind Interactions	643
2.7.4. Surface and Interior	643
2.7.4.1. Geochemistry and Mineralogy	643
2.7.4.2. Atmosphere–Surface Interactions	645
2.7.4.2.1. Carbonate–silicate equilibria	646
2.7.4.2.2. Equilibria involving HCl and HF	646
2.7.4.2.3. Redox reactions involving Fe-bearing minerals	647
2.7.4.2.4. Minerals present in low radar emissivity regions	647
2.7.4.3. The Venus Sulfur Cycle and Climate Change	647
2.7.4.4. Topography and Geology	648
2.7.4.5. Interior	649
2.7.5. Summary of Key Questions	650
Acknowledgments	651
References	651
Chapter 2.8: The Origin and Earliest History of the Earth	654
2.8.1. Introduction	655
2.8.2. Observational Evidence and Theoretical Constraints Pertaining to the Nebular Environment from Which Earth Originated	655
2.8.2.1. Circumstellar Disks and the Solar Nebula	655
2.8.2.2. Earth-Like and Jupiter-Like Planets	656
2.8.2.3. Longevity of the Solar Nebula	657
2.8.2.4. Solar Mass Stars and Heating of the Inner Disk	658
2.8.3. The Dynamics of Accretion of the Earth	660
2.8.3.1. Introduction	660
2.8.3.2. Starting Accretion: Settling and Sticking of Dust at 1AU	660
2.8.3.3. Starting Accretion: Gravitational Instabilities	661
2.8.3.4. Runaway Growth	661
2.8.3.5. Migration	661
2.8.3.5.1. The Nice model	661
2.8.3.5.2. The Grand Tack hypothesis	662
2.8.3.6. Larger Collisions	662
2.8.4. Chemical and Isotopic Constraints on the Nature of the Components That Accreted to Form the Earth	663
2.8.4.1. Chondrites and the Composition of the Disk from Which Earth Accreted	663
2.8.4.2. Chondritic Component Models	665
2.8.4.3. Nonchondritic Refractory Lithophile Elements	666
2.8.4.4. Nonchondritic Moderately Volatile Lithophile Elements	666
2.8.4.5. Oxygen Isotopic Models and Volatile Losses	668
2.8.4.6. Compositional Models Based on Simple Theoretical Components	669
2.8.4.7. The `Hot Nebula´ Model	669
2.8.4.8. The `Hot Nebula´ Model and Heterogeneous Accretion	671
2.8.4.9. Nonradiogenic Isotopic Differences Between Silicate Reservoirs and Chondrites	672
2.8.4.9.1. Nucleosynthetic variations in nonvolatile elements	672
2.8.4.9.2. Mass-dependent fractionations in strongly lithophile elements	672
2.8.4.9.3. Mass-dependent fractionations in siderophile elements	673
2.8.5. Core Formation	674
2.8.5.1. Introduction	674
2.8.5.2. Magma Oceans	674
2.8.5.3. Early Core Growth	675
2.8.5.4. Core Formation Mechanisms	676
2.8.6. Lead and Tungsten Isotopes and the Timing, Rates, and Mechanisms of Accretion and Core Formation	677
2.8.6.1. Introduction: Uses and Abuses of Isotopic Models	677
2.8.6.2. Lead Isotopes	679
2.8.6.3. Tungsten Isotopes	680
2.8.7. Earth's Earliest Atmospheres and Hydrospheres	685
2.8.7.1. Introduction	685
2.8.7.2. Did Earth Once Have a Nebular Protoatmosphere?	685
2.8.7.3. Earth's Degassed Protoatmosphere	687
2.8.7.4. Loss of Earth's Earliest Atmosphere(s)	689
2.8.8. The Formation of the Moon	691
2.8.8.1. Background to Theories	691
2.8.8.2. Isotopic Evidence That the Moon Formed Late	692
2.8.8.3. Poorly Understood Facets of the Giant Impact Theory	692
2.8.8.4. A More Exact Age of the Moon	694
2.8.9. Mass Loss and Compositional Changes During Accretion	695
2.8.10. The Late Veneer	696
2.8.10.1. The Evidence for the Late Veneer	696
2.8.10.2. A Volatile-Depleted Late Veneer	698
2.8.10.3. Water and the Late Veneer	698
2.8.10.4. Earth–Moon Isotopic Similarities and the Late Veneer	699
2.8.11. Early Mantle and Crust	700
2.8.11.1. Introduction	700
2.8.11.2. Earth's Hadean Environment	700
2.8.11.3. Earth’s Hadean Crust – The Zircon Archive	701
2.8.11.4. Hafnium Isotopes	702
2.8.11.5. Early Mantle Heterogeneity Recorded in the 146Sm–142Nd and 182Hf–182W Systems	703
Acknowledgments	704
References	704
Chapter 2.9: The Moon	718
2.9.1. Introduction: The Lunar Context	718
2.9.2. The Lunar Geochemical Database	719
2.9.2.1. Artificially Acquired Samples	719
2.9.2.2. Lunar Meteorites	719
2.9.2.3. Remote-Sensing Data	720
2.9.3. Mare Volcanism	721
2.9.3.1. Classification of Mare Rocks	721
2.9.3.2. Chronology and Styles of Mare Volcanism	723
2.9.3.3. Mare Basalt Trace Element and Isotopic Trends	729
2.9.4. The Highland Crust: Impact Bombardment and Early Differentiation	732
2.9.4.1. Polymict Breccias and the KREEP Component	732
2.9.4.2. Bombardment History of the Moon	734
2.9.4.3. Impactor Residues: Siderophile and Fragmental	735
2.9.4.4. Pristine Highland Rocks: Distinctiveness of the Ferroan Anorthositic Suite	736
2.9.4.5. The Magma Ocean Hypothesis	740
2.9.4.6. Alternative Models	742
2.9.5. Water in the Moon	743
2.9.5.1. Traditional View of a Dry Moon	743
2.9.5.2. Water in Pyroclastic Glasses	744
2.9.5.3. Water in Apatite in Mare Basalts and KREEP-Related Samples	744
2.9.5.4. Water in the Lunar Mantle	745
2.9.5.5. Implications of Water in the Lunar Interior	745
2.9.6. The Bulk Composition and Origin of the Moon	746
Acknowledgments	747
References	747
Chapter 2.10: Mars	756
2.10.1. Geochemical Exploration of Mars	756
2.10.1.1. The Pace of Discovery	756
2.10.1.2. Planetary Geology Overview	757
2.10.2. Sources of Geochemical Data	757
2.10.2.1. Geologic Context for Geochemical Data Sets	757
2.10.2.2. Global Surface Chemistry from Orbiter Measurements	759
2.10.2.3. In Situ Chemical Analyses of Rocks and Soils by Landers and Rovers	760
2.10.2.4. Chemical Analyses of the Atmosphere	761
2.10.2.5. Chemical Analyses of Martian Meteorites	761
2.10.2.6. Geophysical Constraints on Chemistry of the Planet's Interior	762
2.10.3. Geochemistry of Planetary Differentiation	762
2.10.3.1. Bulk Planet Composition and Consistency with Geophysical Constraints	762
2.10.3.2. Geochemical Models for the Mantle	764
2.10.3.3. Geochemical Models for the Core	765
2.10.3.4. Geochemistry of the Crust	766
2.10.3.5. Radioisotope Ages of Planet Formation and Differentiation	770
2.10.4. Geochemistry of Magmatic Processes	771
2.10.4.1. Orbital Analyses of Volcanic Rock Compositions	771
2.10.4.2. Gusev, the Best Studied Igneous Province on Mars	772
2.10.4.3. Other Mars Igneous Rocks – Bounce Rock and Mars Pathfinder	772
2.10.4.4. Geochemistry and Geochronology of Martian Meteorites	773
2.10.4.5. Magma Petrogenesis	778
2.10.5. Geochemistry of Sedimentary and Alteration Processes	780
2.10.5.1. Some Sedimentological Context	780
2.10.5.2. Low-Temperature Weathering and Alteration	781
2.10.5.3. Geochemistry of Depositional Processes	783
2.10.5.4. Chemical Diagenesis	783
2.10.5.5. Hydrothermal Processes	784
2.10.5.6. The Burns Formation	785
2.10.5.7. Other Sediments and Sedimentary Rocks	787
2.10.5.8. Aqueous Geochemistry of Martian Soils	789
2.10.6. Organic Matter, Volatile Reservoirs, and Geochemical Cycles	789
2.10.6.1. Organic Compounds	789
2.10.6.2. Volatile Inventories and Reservoirs	791
2.10.6.3. Outgassing and Atmospheric Loss	792
2.10.6.4. Geochemical Cycles on Mars	793
2.10.7. Geochemical Changes with Time and Comparison with Earth	794
2.10.7.1. Magmatic Evolution	794
2.10.7.2. Sedimentary Evolution	794
2.10.7.3. Comparisons of Mars and Earth	796
2.10.8. Major Unresolved Problems	798
References	798
Chapter 2.11: Giant Planets	806
2.11.1. The Giant Planets in Relation to the Solar System	806
2.11.1.1. Basic Physical and Orbital Parameters	806
2.11.1.2. Discovery and Historical Investigation of the Giant Planets	807
2.11.2. Essential Determinants of the Physical Properties of the Giant Planets	808
2.11.2.1. How We Know the Giant Planets Contain Hydrogen and Helium	808
2.11.2.2. The Equation of State of Hydrogen and Helium as a Determinant of the Structure	809
2.11.2.3. The Thermal Infrared Emission of the Giant Planets and Implications for Evolution	810
2.11.2.4. The Interior Structure of the Giant Planets	812
2.11.2.5. Elemental and Isotopic Abundances	812
2.11.2.6. Atmospheric Dynamics and Magnetic Fields	813
2.11.3. Origin and Evolution of the Giant Planets	814
2.11.3.1. Basic Model for the Formation of the Planets from a Disk of Gas and Dust	814
2.11.3.2. Constraints from the Composition of the Giant Planets	814
2.11.4. Extrasolar Giant Planets	815
2.11.5. Major Unsolved Problems and Future Progress	815
References	816
Chapter 2.12: Major Satellites of the Giant Planets	818
2.12.1. Introduction	818
2.12.2. Cosmochemical Context	819
2.12.3. Bulk Composition	819
2.12.3.1. Bulk Density	819
2.12.3.2. Sources of Data	820
2.12.4. Surface Composition	820
2.12.4.1. Spectral Reflectance	820
2.12.4.2. Temperature and Atmospheres	821
2.12.4.3. Radiation Effects	821
2.12.5. The Jupiter System	821
2.12.5.1. General	821
2.12.5.2. Io	822
2.12.5.2.1. Surface composition and volcanism	822
2.12.5.2.2. Atmosphere and magnetospheric interactions	823
2.12.5.3. Ganymede and Callisto	824
2.12.5.3.1. Surface composition	824
2.12.5.3.2. Atmospheres and magnetospheric interactions	826
2.12.5.4. Europa	826
2.12.5.4.1. Surface composition	826
2.12.5.4.2. Atmosphere and magnetospheric interactions	827
2.12.6. The Saturn System	827
2.12.6.1. General	827
2.12.6.2. Iapetus	829
2.12.6.3. Titan	829
2.12.6.4. Enceladus	830
2.12.6.5. Magnetospheric Interactions	831
2.12.7. The Uranus System	831
2.12.7.1. General	831
2.12.8. The Neptune System – Triton	833
2.12.8.1. General	833
2.12.8.2. Composition	834
2.12.8.3. Atmosphere	835
2.12.9. Major Issues and Future Directions	835
References	836
Chapter 2.13: Comets	840
2.13.1. Introduction	840
2.13.2. Comet and Asteroid Comparisons	841
2.13.3. Comet Activity	842
2.13.4. Comet Types – Orbital Distinction	842
2.13.4.1. Major Comet Source Regions	843
2.13.4.2. The Oort Cloud	843
2.13.4.3. The Kuiper Belt	844
2.13.4.3.1. KBO terminology	844
2.13.4.3.2. KBO orbital distribution	844
2.13.5. Physical Evolution of Comets	845
2.13.5.1. Fragmentation	845
2.13.5.2. Crust/Mantle Formation	846
2.13.5.3. Strength and Structure of Cometary Materials	849
2.13.6. Major Component Composition	849
2.13.6.1. Water Ice	849
2.13.6.2. CO and Very Volatile Compounds	850
2.13.6.2.1. Full volatile composition	851
2.13.6.3. Dust and Rocks	852
2.13.6.3.1. Information from astronomical observations	852
2.13.6.3.2. Information from collected samples	853
2.13.6.3.2.1. Samples collected from active comets	854
2.13.6.3.2.2. Meteoritic samples	858
2.13.6.3.3. Information from in situ measurements at comet Halley	860
2.13.7. Diversity Among Comets	861
2.13.8. Conclusions	863
References	864
Chapter 2.14: Asteroids	870
2.14.1. Introduction	871
2.14.2. Background	871
2.14.3. Remote Observations	873
2.14.3.1. Reflectance Spectroscopy	873
2.14.3.2. Mineral Spectroscopy	874
2.14.3.3. Electronic Transitions	874
2.14.3.4. Vibrational Bands	875
2.14.3.5. Visual Albedo	876
2.14.3.6. Metallic Iron	877
2.14.3.7. Organics	877
2.14.3.8. Space Weathering	877
2.14.3.9. Determining Mineralogies	878
2.14.4. Taxonomy	879
2.14.4.1. A-Types	881
2.14.4.2. C-Complex	882
2.14.4.2.1. B-types	882
2.14.4.2.2. C-types	883
2.14.4.3. D-Types	884
2.14.4.4. K-Types	885
2.14.4.5. L-Types	885
2.14.4.6. O-Types	886
2.14.4.7. Q-Types	886
2.14.4.8. R-Types	886
2.14.4.9. S-Complex	887
2.14.4.9.1. S-types	887
2.14.4.9.2. Sa-types	888
2.14.4.9.3. Sq-types	888
2.14.4.9.4. Sr-types	889
2.14.4.9.5. Sv-types	889
2.14.4.10. T-Types	889
2.14.4.11. V-Types	889
2.14.4.12. X-Complex (E-Types, M-Types, and P-Types)	891
2.14.4.12.1. E-types	891
2.14.4.12.2. M-types	892
2.14.4.12.3. P-types	893
2.14.5. Spacecraft Missions	893
2.14.5.1. Galileo	893
2.14.5.2. Deep Space 1	894
2.14.5.3. NEAR Shoemaker	894
2.14.5.4. Stardust	896
2.14.5.5. Hayabusa	896
2.14.5.6. Rosetta	897
2.14.5.7. Dawn	898
2.14.5.8. OSIRIS-REx	898
2.14.5.9. 2008 TC3 and Almahata Sitta	899
2.14.6. Interesting Groups of Asteroids	899
2.14.6.1. Earth and Martian Trojans	899
2.14.6.2. Near-Earth Asteroids	899
2.14.6.3. Asteroid Families	900
2.14.6.3.1. Inner belt (∼2.06-2.50AU)	900
2.14.6.3.2. Middle belt (∼2.50-2.82AU)	902
2.14.6.3.3. Outer belt (~2.82-3.28AU)	903
2.14.6.3.4. Trojan region (~5.2AU)	904
2.14.7. Taxonomic Distribution of Taxonomic Types	904
2.14.7.1. Earlier Work	904
2.14.7.2. Recent Work	905
2.14.7.3. Formation of Material in the Solar Nebula	905
2.14.7.4. Origin of the Taxonomic Distribution	906
2.14.8. Conclusions and Future Work	907
Acknowledgments	908
References	909
e9780080983004v3	921
e9780080983004v4	1525
e9780080983004v5	2358
Cover	2358
The Atmosphere	2361
Copyright	2362
In Memoriam	2363
Heinrich Dieter Holland (1927–2012)	2365
Karl Karekin Turekian (1927–2013)	2367
References	2369
Dedication	2371
Contents	2373
Executive Editors’ Foreword to the Second Edition	2375
Contributors	2379
Volume Editor’s Introduction	2381
Chapter 5.1: Ozone, Hydroxyl Radical, and Oxidative Capacity	2385
5.1.1. Introduction	2385
5.1.2. Evolution of Oxidizing Capability	2387
5.1.2.1. Prebiotic Atmosphere	2387
5.1.2.2. Preindustrial Atmosphere	2387
5.1.3. Fundamental Reactions	2388
5.1.3.1. Troposphere	2388
5.1.3.2. Stratosphere	2390
5.1.4. Meteorological Influences	2391
5.1.5. Human Influences	2391
5.1.5.1. Industrial Revolution	2391
5.1.5.2. Future Projections	2392
5.1.6. Measuring Oxidation Rates	2393
5.1.6.1. Direct Measurement	2393
5.1.6.2. Indirect Measurement	2395
5.1.7. Atmospheric Models and Observations	2399
5.1.8. Conclusions	2400
References	2400
Chapter 5.2: Tropospheric Halogen Chemistry	2403
5.2.1. Introduction	2403
5.2.2. Main Reaction Mechanisms	2405
5.2.3. Tropospheric Ozone Depletion at Polar Sunrise	2410
5.2.3.1. Main Features of Polar ODEs	2411
5.2.3.2. Satellite Observations	2413
5.2.3.3. Sources of Active Bromine	2414
5.2.3.4. Chlorine Chemistry in ODEs and Br-Cl Interactions	2416
5.2.3.5. The Role of Iodine in ODEs	2417
5.2.3.6. Halogen-Mercury Interactions	2418
5.2.3.7. Model Studies	2418
5.2.4. Marine Boundary Layer	2419
5.2.4.1. Sea Salt Aerosol	2419
5.2.4.2. Reactive Chlorine	2422
5.2.4.3. Reactive Bromine	2423
5.2.4.3.1. Field observations	2423
5.2.4.3.2. Model results	2425
5.2.4.4. Reactive Iodine	2427
5.2.4.5. Surface-Segregation Effects	2432
5.2.4.6. Halogen-Sulfur Interactions	2433
5.2.5. Salt Lakes	2435
5.2.6. Volcanoes	2436
5.2.7. Free Troposphere	2438
5.2.8. Additional Sources of Reactive Halogens	2441
5.2.8.1. Industry and Fossil Fuel Burning	2441
5.2.8.2. Biomass Burning and Dust Plumes	2441
5.2.8.3. Organic Halogen Compounds	2442
5.2.8.4. Inventories	2443
5.2.9. Summary	2443
Acknowledgments	2444
References	2444
Chapter 5.3: Global Methane Biogeochemistry	2455
5.3.1. Introduction	2455
5.3.2. Global Methane Budget	2456
5.3.2.1. Global Methane Increase	2456
5.3.2.2. Methane Budget with Constraints	2458
5.3.2.3. Gross Methane Budget	2459
5.3.2.4. Atmospheric Models	2459
5.3.2.5. Stable Isotopes	2460
5.3.3. Terrestrial Studies	2462
5.3.3.1. Flux Time Series	2462
5.3.3.2. Flux Transects	2462
5.3.3.3. Process-Level Studies	2462
5.3.3.3.1. Vegetation removal experiments	2462
5.3.3.3.2. Methane flux: net ecosystem exchange relationship	2463
5.3.3.4. Scaling Up	2463
5.3.3.5. Wetland Soil Models	2463
5.3.3.6. Animals and Landfills	2464
5.3.3.7. Microbial Soil Oxidation	2464
5.3.3.7.1. Moist soils	2464
5.3.3.7.2. Waterlogged soils	2466
5.3.3.7.3. Nitrogen fertilization and disturbance	2466
5.3.3.7.4. Effects of drying on paddy soils	2466
5.3.3.8. New Techniques	2466
5.3.4. Marine Studies	2467
5.3.4.1. Ocean Methane Source	2467
5.3.4.2. Aerobic Methane Oxidation	2467
5.3.4.3. Anaerobic Methane Oxidation	2468
5.3.4.4. Methane Clathrate Hydrates	2469
5.3.4.4.1. Methane hydrate reservoir	2469
5.3.4.4.2. Methane hydrate decomposition rates	2469
5.3.4.4.3. How can we estimate the rate of CH4 clathrate decomposition?	2469
5.3.4.4.4. Natural 14C-CH4 measurements	2470
5.3.4.5. Other Ocean Methane Sources	2470
5.3.5. Ice Cores	2472
5.3.6. Future Work	2473
Acknowledgments	2473
References	2474
Chapter 5.4: Tropospheric Aerosols	2479
5.4.1. Introduction	2480
5.4.1.1. Overview	2480
5.4.1.2. Sources	2482
5.4.1.3. Atmospheric Residence, Transport, and Removal	2483
5.4.1.4. Primary versus Secondary Particles and Particle Nucleation	2483
5.4.1.5. Spatial Homogeneity	2483
5.4.2. Aerosol Properties	2485
5.4.2.1. Number and Mass Distributions	2485
5.4.2.2. Composition	2489
5.4.2.3. Optical Properties	2489
5.4.3. Measurement of Aerosol Properties	2490
5.4.3.1. Particle Sizes, Size Distributions, and Number and Mass Concentrations	2490
5.4.3.2. Composition	2493
5.4.3.2.1. Bulk composition	2493
5.4.3.2.2. Off-line measurements of single-particle compositions	2495
5.4.3.2.3. On-line measurements	2497
5.4.3.3. Hygroscopicity	2498
5.4.3.4. Optical Properties	2501
5.4.4. Spatial and Temporal Variation of Tropospheric Aerosols	2501
5.4.4.1. Remote Sensing of Aerosol Using Passive Light Sources	2501
5.4.4.2. Remote Sensing of Aerosol Using an Active Light Source	2503
5.4.5. Aerosol Processes	2506
5.4.5.1. Emissions	2506
5.4.5.2. Gas-to-Particle Conversions and other Atmospheric Reactions	2507
5.4.5.3. Long-Range Transport	2509
5.4.5.4. Removal of Particles from the Atmosphere	2509
5.4.6. Representation of Aerosol Processes in Chemical Transport and Transformation Models	2509
5.4.7. Aerosol Influences on Climate and Climate Change	2512
5.4.7.1. Background	2512
5.4.7.2. Direct Aerosol Shortwave Radiative Forcing	2513
5.4.7.3. Clouds and Indirect Effects	2515
5.4.7.4. Aerosol Forcing Relative to other Forcings of Climate Change over the Industrial Period	2516
5.4.8. Final Thoughts	2517
Acknowledgments	2517
References	2518
Chapter 5.5: Biomass Burning: The Cycling of Gases and Particulates from the Biosphere to the Atmosphere	2523
5.5.1. Introduction: Biomass Burning, Geochemical Cycling, and Global Change	2523
5.5.2. Global Impacts of Biomass Burning	2524
5.5.3. Enhanced Biogenic Soil Emissions of Nitrogen and Carbon Gases: A Postfire Effect	2525
5.5.4. The Geographical Distribution of Biomass Burning	2525
5.5.5. Biomass Burning in the Boreal Forests	2526
5.5.6. Estimates of Global Burning and Global Gaseous and Particulate Emissions	2528
5.5.7. Calculation of Gaseous and Particulate Emissions from Fires	2528
5.5.8. Biomass Burning and Atmospheric Nitrogen and Oxygen	2529
5.5.9. Atmospheric Chemistry Resulting from Gaseous Emissions from the Fires	2529
5.5.9.1. Chemistry of the Hydroxyl Radical (OH) in the Troposphere	2529
5.5.9.2. Production of O3 in the Troposphere	2530
5.5.9.2.1. CO oxidation chain	2530
5.5.9.2.2. Methane oxidation chain	2530
5.5.9.3. Chemistry of Nitrogen Oxides in the Troposphere	2530
5.5.9.4. Chemistry of the Stratosphere	2530
5.5.10. A Case Study of Biomass Burning: The 1997 Wildfires in Southeast Asia	2530
5.5.11. Results of Calculations: Gaseous and Particulate Emissions from the Fires in Kalimantan and Sumatra, Indonesia, Augus	2531
5.5.12. The Impact of the Southeastern Asia Fires on the Composition and Chemistry of the Atmosphere	2532
5.5.12.1. Modeling O3 and CO over Indonesia	2532
5.5.12.2. Measurements over Indonesia	2533
5.5.12.3. Measurements between Singapore and Japan	2533
5.5.12.4. Measurements over Hawaii	2533
References	2533
Chapter 5.6: Mass-Independent Isotopic Composition of Terrestrial and Extraterrestrial Materials	2535
5.6.1. General Introduction	2535
5.6.2. Applications of Mass-Independent Isotopic Effects	2536
5.6.3. Isotopic Anomalies in Extraterrestrial Atmospheres a	2541
5.6.3.1. Physical Chemistry of Mass-Independent Isotope Effects	2542
5.6.4. Atmospheric Observations of Mass-Independent Isotopic Compositions	2544
5.6.4.1. Stratospheric and Tropospheric Ozone	2544
5.6.4.2. Stratospheric Carbon Dioxide	2545
5.6.5. Atmospheric Aerosol Sulfate: Present Earth's Atmosphere	2546
5.6.6. Mass-Independent Oxygen Isotopic Composition of Paleosulfates	2547
5.6.7. Atmospheric Mass-Independent Molecular Oxygen	2549
5.6.8. The Atmospheric Aerosol Nitrate and the Nitrogen Cycle	2549
5.6.9. Mass-Independent Oxygen Isotopic Compositions in Solids to Reflect Atmospheric Change: Earth and Mars	2550
5.6.10. Sulfur in the Earth's Earliest Atmosphere: The Rise of Oxygen	2553
5.6.11. Sulfur Isotopic Fractionation Processes in other Solar System Objects	2555
5.6.12. Concluding Comments	2555
Acknowledgments	2556
References	2556
Chapter 5.7: The Stable Isotopic Composition of Atmospheric CO2	2563
5.7.1. Introduction	2563
5.7.2. Methodology and Terminology	2564
5.7.3. delta13C in Atmospheric CO2	2566
5.7.3.1. Fossil Fuel Input	2569
5.7.3.2. Exchange with the Ocean	2570
5.7.3.3. Ocean Biology	2570
5.7.3.4. Atmosphere-Ocean Disequilibrium	2571
5.7.3.5. Photosynthetic CO2 Uptake on Land	2572
5.7.3.6. CO2 Release in Respiration	2575
5.7.3.7. The Land Disequilibrium	2576
5.7.3.8. Ecosystem Discrimination	2576
5.7.3.9. Incorporating Isotopes in Flux Measurements	2579
5.7.4. delta18O in CO2	2579
5.7.4.1. The Soil Component	2581
5.7.4.2. The Leaf Component	2582
5.7.4.3. The Minor Components	2584
5.7.4.3.1. The ocean component	2584
5.7.4.3.2. Anthropogenic emissions	2584
5.7.4.3.3. Troposphere-stratosphere exchange	2585
5.7.4.4. Spatial and Temporal Patterns	2585
5.7.5. Clumped Isotopes	2587
5.7.5.1. Clumped Isotopes in Atmospheric CO2	2588
5.7.5.1.1. Delta47 in combustion and background air	2588
5.7.5.1.2. Seasonal variations in Delta47	2589
5.7.5.1.3. Delta47 in stratospheric CO2	2589
5.7.6. Concluding Remarks	2589
Acknowledgments	2590
References	2590
Chapter 5.8: Water Stable Isotopes: Atmospheric Composition and Applications in Polar Ice Core Studies	2597
5.8.1. Introduction	2598
5.8.2. Present-Day Observations	2601
5.8.2.1. Deuterium and Oxygen-18 in Precipitation	2601
5.8.2.2. Oxygen-17 and 17O-Excess	2602
5.8.2.3. Water Isotopes in the Atmosphere	2603
5.8.3. Physics of Water Isotopes	2605
5.8.3.1. Fractionation Processes	2605
5.8.3.2. Growth of Individual Elements	2606
5.8.3.3. Isotopic Processes in Clouds	2607
5.8.4. Modeling the Water Isotope Atmospheric Cycle	2609
5.8.4.1. Rayleigh-Type Models	2609
5.8.4.2. Isotopic Models of Higher Complexity	2610
5.8.4.3. Isotope Modeling with GCMs	2610
5.8.4.3.1. Early IGCMs	2611
5.8.4.3.2. Recent simulations	2612
5.8.4.3.3. Nudged and regional isotopic models	2615
5.8.5. Ice Core Isotopic Records	2617
5.8.6. The Conventional Approach for Interpreting Water Isotopes in Ice Cores	2621
5.8.7. Alternative Estimates of Temperature Changes in Greenland and Antarctica	2622
5.8.7.1. Greenland	2623
5.8.7.2. Antarctica	2624
5.8.8. What Do People Learn from GCMs?	2625
5.8.8.1. Influence of the Seasonality of Precipitation	2625
5.8.8.2. Estimating the Temporal Slope from IGCMs	2626
5.8.9. Influence of the Oceanic Source of Polar Precipitation	2629
5.8.10. Conclusion	2632
Acknowledgments	2633
References	2633
Chapter 5.9: Radiocarbon	2641
5.9.1. Introduction	2641
5.9.2. Production and Distribution of 14C	2641
5.9.3. Measurements of Radiocarbon	2641
5.9.4. Timescale Calibration	2642
5.9.4.1. Calibration Based on Tree Rings	2642
5.9.4.2. Calibration Based on Corals	2645
5.9.4.3. Other Calibration Schemes	2645
5.9.4.4. Cause of the Long-Term 14C Decline	2645
5.9.4.5. Change in Ocean Operation	2646
5.9.5. Radiocarbon and Solar Irradiance	2647
5.9.6. The `Bomb´ 14C Transient	2649
5.9.6.1. Radiocarbon as a Tracer for Ocean Uptake of Fossil Fuel CO2	2650
5.9.6.2. Ocean Uptake of 14CO2 and CO2	2650
5.9.6.3. Terrestrial Uptake of 14CO2 and CO2	2652
5.9.7. Future Applications	2653
References	2653
Chapter 5.10: Natural Radionuclides in the Atmosphere	2657
5.10.1. Introduction	2657
5.10.2. Radon and Its Daughters	2657
5.10.2.1. Flux of Radon from Soils to the Atmosphere	2657
5.10.2.2. Flux of Radon from the Oceans	2660
5.10.2.3. Distribution of Radon in the Atmosphere	2660
5.10.2.4. Short-Lived Daughters of 222Rn in the Atmosphere	2661
5.10.2.5. 210Pb and Its Progeny	2661
5.10.2.5.1. Distribution of 210Pb in the atmosphere	2661
5.10.2.5.2. Flux of 210Pb to the Earth's surface	2662
5.10.2.5.3. Residence time of 210Pb and associated species in the atmosphere	2663
5.10.2.5.4. Use of 210Pb as surrogate for other atmospheric components	2665
5.10.3. Cosmogenic Nuclides	2667
5.10.3.1. Atmospheric Production of Cosmogenic Nuclides	2667
5.10.3.2. 7Be and 10Be	2668
5.10.3.3. 35S and the Kinetics of SO2 Oxidation and Deposition	2668
5.10.3.4. Phosphorus Isotopes	2670
5.10.4. Coupled Lead-210 and Beryllium-7	2670
5.10.4.1. Temporal and Spatial Variation	2670
5.10.4.2. Application of the Coupled 7Be-210Pb System to Sources of Atmospheric Species	2671
References	2672
Chapter 5.11: Carbonaceous Particles: Source-Based Characterization of Their Formation, Composition, and Structures	2675
5.11.1. Introduction	2676
5.11.1.1. Classifying Types of Carbonaceous Particles by Source	2676
5.11.1.2. Four Categories of Carbonaceous Particles	2678
5.11.2. Carbonaceous Particles from Fossil Fuel Combustion	2681
5.11.2.1. FFC Carbonaceous Particle Formation	2682
5.11.2.2. FFC Carbonaceous Particle Chemical Composition	2683
5.11.2.3. FFC Carbonaceous Particle Structure	2684
5.11.3. Biofuel and Biomass Burning Carbonaceous Particles	2684
5.11.3.1. BBB Carbonaceous Particle Formation	2684
5.11.3.2. BBB Carbonaceous Particle Chemical Composition	2685
5.11.3.3. BBB Carbonaceous Particle Structure	2686
5.11.4. Carbonaceous Particles from Biogenic Vapor Fluxes	2687
5.11.4.1. BVF Carbonaceous Particle Formation	2687
5.11.4.2. BVF Carbonaceous Particle Chemical Composition	2687
5.11.4.3. BVF Carbonaceous Particle Structure	2689
5.11.5. Carbonaceous Particles from Mechanically Lofted Biological Componen	2689
5.11.5.1. MBC Carbonaceous Particle Formation	2689
5.11.5.2. MBC Carbonaceous Particle Chemical Composition	2690
5.11.5.3. MBC Carbonaceous Particle Structures	2691
5.11.6. Impacts of Carbonaceous Particle on the Earth System	2691
5.11.6.1. Physical Properties of Carbonaceous Particles	2691
5.11.6.2. Global and Regional Modeling of Current and Future Carbonaceous Particles	2692
Appendix A. Measurement Techniques for Carbonaceous Particles	2692
Acknowledgments	2694
References	2695
Chapter 5.12: Ocean-Derived Aerosol and Its Climate Impacts	2701
5.12.1. Introduction	2701
5.12.2. Ocean-Derived Aerosol Production Mechanisms	2701
5.12.3. Radiative Effects of Ocean-Derived Aerosol	2703
5.12.3.1. Aerosol Direct Effects	2703
5.12.3.2. Aerosol-Cloud Interactions	2703
5.12.4. Sources and Composition of Ocean-Derived CCN	2704
5.12.4.1. The Dimethylsulfide Source of Ocean-Derived CCN	2704
5.12.4.1.1. Production of DMS-derived CCN	2705
5.12.4.2. The Sea Spray Source of Ocean-Derived CCN	2706
5.12.4.2.1. Sea salt aerosol	2706
5.12.4.2.2. Organic aerosol	2706
5.12.5. The MBL CCN Budget	2709
5.12.5.1. Production Fluxes of Sea Spray Aerosol	2709
5.12.6. The CLAW Hypothesis	2711
5.12.7. Concluding Comments	2712
Acknowledgments	2712
References	2712
Chapter 5.13: Aerosol Hygroscopicity: Particle Water Content and Its Role in Atmospheric Processes	2715
5.13.1. Introduction	2716
5.13.2. Methods for the Measurement of Aerosol Water Contents	2717
5.13.2.1. Instruments Operating Below Water Saturation	2717
5.13.2.1.1. Approaches using microscopy	2718
5.13.2.1.2. Electrodynamic balance	2719
5.13.2.1.3. Humidified tandem differential mobility analyzers	2719
5.13.2.1.4. Optical humidified/dry measurements (f(RH))	2720
5.13.2.2. Instruments Operating Above Water Saturation	2722
5.13.2.3. Water Uptake by Adsorption	2723
5.13.3. Parameterizations of Aerosol Hygroscopicity	2724
5.13.3.1. Diameter Growth Factor (g(RH)) Fits	2724
5.13.3.2. The Hygroscopicity Parameter, kappa	2725
5.13.3.3. Fits for f(RH)	2726
5.13.3.4. Fits for Adsorbed Water Contents	2726
5.13.4. Laboratory Measurements for Selected Aerosol Types	2727
5.13.4.1. Measurements of Aerosol Water Contents	2727
5.13.4.1.1. Inorganic ionic species	2727
5.13.4.1.2. Organic species	2728
5.13.4.1.3. Multicomponent particles	2729
5.13.4.1.4. Dust	2730
5.13.4.1.5. Soot particles	2730
5.13.4.1.6. Biological particles	2733
5.13.4.2. Optical Measurements	2733
5.13.5. Observations of Aerosol Water Content and Atmospheric Implications	2734
5.13.5.1. g(RH) Observations	2734
5.13.5.2. CCN-Derived kappa Observations	2736
5.13.5.3. f(RH) Observations	2736
5.13.5.4. Atmospheric Implications	2738
Acknowledgments	2739
References	2739
Chapter 5.14: The Stable Isotopic Composition of Atmospheric O2	2747
5.14.1. Introduction	2747
5.14.2. Methodology and Terminology	2748
5.14.2.1. Abundance and Fractionation of Oxygen Isotopes	2748
5.14.2.1.1. Isotopic fractionation	2748
5.14.2.2. Relationships between Fractionations of 17O/16O and 18O/16O	2749
5.14.3. 18O/16O Ratios in Atmospheric O2	2750
5.14.3.1. The Dole Effect and Its Magnitude	2750
5.14.3.2. Processes Influencing the Dole Effect	2750
5.14.3.2.1. Biological O2 consumption	2750
5.14.3.2.2. Photosynthetic O2 production	2753
5.14.3.2.3. Hydrologic processes	2755
5.14.3.2.4. Stratospheric photochemical reactions	2756
5.14.3.3. Global Budgets of Processes Influencing the Dole Effect	2757
5.14.3.4. Temporal Variations in the Dole Effect	2758
5.14.4. Oxygen-17 and Oxygen-18 in Atmospheric O2	2760
5.14.4.1. Mass-Independent Fractionation and Biological Normalization	2760
5.14.4.2. Temporal Variations in 17O/16O and 18O/16O	2762
References	2764
Chapter 5.15: Studies of Recent Changes in Atmo	2769
5.15.1. Introduction	2769
5.15.2. Overview of the Large-Scale Varia	2770
5.15.2.1. Long-Term Trends	2770
5.15.2.2. Seasonal Cycles	2772
5.15.2.3. Atmospheric Potential Oxygen	2773
5.15.3. Measurement Methods	2773
5.15.4. O2-Based Global Carbon Budgets	2774
5.15.4.1. Budget Equations	2774
5.15.4.2. Updated Budget for Recent Deca	2775
5.15.4.3. Updated Budgets Discussion	2776
5.15.4.4. Oxidative Ratios of the Long-T	2777
5.15.4.5. Nitrogen Cycle Perturbations	2778
5.15.4.6. Ocean O2 and N2 Outgassing	2779
5.15.5. Seasonal Cycles in APO	2780
5.15.6. Interannual Variability in APO	2781
5.15.7. Interhemispheric Gradient in O2/N2 and APO	2782
5.15.8. Diurnal and Other Shorter-Term	2784
5.15.9. Future Outlook	2785
Acknowledgments	2786
References	2786
Chapter 5.16: Fluorine-Containing Greenhouse Gases	2789
5.16.1. Introduction	2789
5.16.2. Global Observations	2789
5.16.2.1. Surface-Based Observational Networks	2789
5.16.2.2. Instruments and Calibration	2791
5.16.2.3. Observed Mole Fractions and Trends	2792
5.16.2.3.1. Trends in Montreal Protocol gases and their replacements	2792
5.16.2.3.2. Trends in Kyoto Protocol gases	2792
5.16.3. Global Cycles	2793
5.16.3.1. Anthropogenic Sources, Atmospheric Circulation and Atmospheric Chemistry	2793
5.16.3.2. Flux Estimation Techniques Using Models and Observations	2795
5.16.3.3. Source, Sink, and Lifetime Estimates	2796
5.16.4. Environmental Impacts, Current Trends and Emission Policies	2797
5.16.4.1. Climate Forcing and the Montreal and Kyoto Protocols	2797
5.16.4.2. Ozone Destruction and Montreal Protocol	2798
5.16.5. Verification of Future National Emission Reports Using Observations	2798
5.16.6. Conclusions	2799
Acknowledgments	2799
References	2799
e9780080983004v6	2803
e9780080983004v7	3238
Front Cover	3238
Surface and Ground Water, Weathering and Soils	3241
Copyright	3242
In Memoriam	3243
Heinrich Dieter Holland (1927–2012)	3245
Karl Karekin Turekian (1927–2013)	3247
References	3249
Dedication	3251
Contents	3253
Executive Editors’ Foreword to the Second Edition	3255
Contributors	3259
Volume Editor’s Introduction	3261
Chapter 7.1: Soil Formation	3263
7.1.1. Introduction	3263
7.1.2. What Is Soil?	3263
7.1.3. Geographical Access to Soil Data	3264
7.1.4. Conceptual Partitioning of the Earth Surface	3265
7.1.4.1. Stable Landforms	3265
7.1.4.2. Erosional Landscapes	3271
7.1.5. The Human Dimension of Soil Formation	3274
7.1.5.1. Accelerated Soil Formation Under Agriculture	3277
7.1.6. Soil Geochemistry in Deserts	3280
7.1.7. Soil Formation on Mars	3283
7.1.8. Concluding Remarks	3287
References	3287
Chapter 7.2: Modeling Low-Temperature Geochemical Processes	3289
7.2.1. Introduction	3289
7.2.1.1. What Is a Model?	3290
7.2.2. Modeling Concepts and Definitions	3291
7.2.2.1. Modeling Concepts	3291
7.2.2.2. Modeling Definitions	3291
7.2.2.3. Inverse Modeling, Mass Balancing, and Mole Balancing	3291
7.2.3. Solving the Chemical Equilibrium Problem	3293
7.2.4. Historical Background to Geochemical Modeling	3294
7.2.5. The Problem of Activity Coefficients	3295
7.2.5.1. Activity Coefficients	3295
7.2.5.2. Saturation Indices	3296
7.2.6. Geochemical Databases	3296
7.2.6.1. Thermodynamic Databases	3297
7.2.6.2. Kinetic Databases	3298
7.2.6.3. Electrolyte Databases	3298
7.2.7. Geochemical Codes	3298
7.2.7.1. USGS Codes	3298
7.2.7.2. LLNL/LBNL Codes	3299
7.2.7.3. Miami Code	3299
7.2.7.4. The Geochemist's Workbench™	3300
7.2.7.5. REDEQL–MINTEQ Codes	3300
7.2.7.6. Waterloo Codes	3301
7.2.7.7. Harvie–Møller–Weare Code	3301
7.2.7.8. FREZCHEM Code	3301
7.2.7.9. Windermere Humic Aqueous Model Codes	3301
7.2.7.10. Additional Codes	3302
7.2.8. Water–Rock Interactions	3303
7.2.8.1. Aqueous Speciation	3303
7.2.8.2. Sorption Reactions	3304
7.2.8.3. Aqueous Redox Kinetics and Microbial Growth	3304
7.2.8.4. Model Simulations of Mineral Reactions	3306
7.2.8.4.1. Which minerals reach solubility equilibrium?	3306
7.2.8.4.2. Calcite solubility	3308
7.2.8.4.3. Pyrite oxidation	3308
7.2.8.4.4. Pyrite oxidation with calcite dissolution and neutralization	3310
7.2.8.4.5. Seawater–groundwater mixing	3312
7.2.8.4.6. Madison regional limestone aquifer	3312
7.2.8.5. Reactive-Transport Modeling in Streams	3315
7.2.8.6. Reactive-Transport Modeling in Groundwater	3317
7.2.8.7. Geochemical Modeling of Catchments	3317
7.2.8.8. Evaporation of Seawater	3318
7.2.8.9. Reliability of Geochemical Model Simulations	3318
7.2.9. Final Comments	3320
Acknowledgments	3322
References	3322
Chapter 7.3: Reaction Kinetics of Primary Rock-Forming Minerals under Ambient Conditions	3331
7.3.1. Introduction	3331
7.3.2. Experimental Techniques for Dissolution Measurements	3334
7.3.2.1. Chemical Reactors	3334
7.3.2.2. Interpretation and Extrapolation of Rate Data	3335
7.3.3. Mechanisms of Dissolution	3338
7.3.3.1. Models for Dissolution Based on Surface Topography	3338
7.3.3.2. Carbonate Dissolution Mechanism	3338
7.3.3.3. Silicate and Oxide Dissolution Mechanisms	3339
7.3.3.3.1. Nonstoichiometric dissolution	3339
7.3.3.3.2. Surface complexation models	3341
7.3.3.3.3. Oelkers–Schott model	3344
7.3.3.3.4. Mechanism of dissolution of redox-sensitive silicates	3345
7.3.4. Surface Area	3345
7.3.4.1. BET and Geometric Surface Area	3345
7.3.4.2. Reactive Surface Area	3347
7.3.5. Rate Constants as a Function of Mineral Composition	3348
7.3.5.1. Silica	3349
7.3.5.2. Feldspars	3349
7.3.5.3. Nonframework Silicates	3349
7.3.5.4. Carbonates	3351
7.3.6. Temperature Dependence	3352
7.3.6.1. Activation Energy	3352
7.3.6.2. Temperature and the Effect of Solution Chemistry	3354
7.3.7. Chemistry of Dissolving Solutions	3354
7.3.7.1. Inorganic Species	3354
7.3.7.2. Dissolved Carbon Dioxide	3357
7.3.7.3. Ligand Effects	3358
7.3.7.3.1. Models of ligand-promoted dissolution	3358
7.3.7.3.2. Ligand-promoted dissolution of individual minerals	3359
7.3.7.3.3. Complex ligands	3360
7.3.8. Chemical Affinity	3360
7.3.8.1. Rate Laws Linear in ∆G near Equilibrium	3360
7.3.8.2. Rate Laws Nonlinear in ∆G near Equilibrium	3361
7.3.8.3. Models Based on Surface Topography	3363
7.3.9. Duration of Dissolution	3365
7.3.10. Conclusion	3366
Acknowledgments	3367
References	3367
Chapter 7.4: Natural Weathering Rates of Silicate Minerals	3377
7.4.1. Introduction	3378
7.4.2. Defining Natural Weathering Rates	3379
7.4.3. Mass Changes Related to Chemical Weathering	3380
7.4.3.1. Bulk Compositional Changes in Regoliths	3381
7.4.3.1.1. Weathering indices	3381
7.4.3.1.2. Mass transfer	3383
7.4.3.1.3. Profile categories	3385
7.4.3.1.4. Time evolution of profiles	3386
7.4.3.1.5. Utilization of soil chronosequences	3387
7.4.3.1.6. Steady-state denudation and weathering profile development	3389
7.4.3.2. Changes Based on Solute Compositions	3390
7.4.3.2.1. Characterization of fluid transport	3390
7.4.3.2.2. Weathering based on solutes in soils	3391
7.4.3.2.3. Weathering based on solutes in groundwater	3392
7.4.3.2.4. Weathering based on surface water solutes	3393
7.4.4. Normalization of Weathering to Regolith Surface Area	3393
7.4.4.1. Definitions of Natural Surface Areas	3394
7.4.4.2. Measurements of Specific Surface Areas	3396
7.4.4.3. Surface Roughness	3397
7.4.5. Tabulations of Weathering Rates of Some Common Silicate Minerals	3397
7.4.5.1. Elemental Weathering Fluxes	3397
7.4.5.2. Mineral Weathering Fluxes	3397
7.4.5.3. Specific Mineral Weathering Rates	3398
7.4.6. Time as a Factor in Natural Weathering	3398
7.4.6.1. Comparison of Contemporary and Geologic Rates	3398
7.4.7. Factors Influencing Natural Weathering Rates	3402
7.4.7.1. Mineral Weatherability	3402
7.4.7.2. Solute Chemistry and Saturation States	3403
7.4.7.3. Coupling the Effect of Hydrology and Chemical Weathering	3405
7.4.7.3.1. Low permeability	3406
7.4.7.3.2. High permeability	3408
7.4.7.4. Role of Climate on Chemical Weathering	3409
7.4.7.4.1. Temperature	3409
7.4.7.4.2. Precipitation and recharge	3410
7.4.7.4.3. Coupling climate effects	3410
7.4.7.5. Role of Physical Weathering	3410
7.4.8. Summary	3412
References	3413
Chapter 7.5: Geochemical Weathering in Glacial and Proglacial Environments	3419
7.5.1. Introduction	3419
7.5.2. Basic Glaciology and Glacier Hydrology	3420
7.5.2.1. Glaciers, Ice Caps, and Ice Sheets	3421
7.5.2.1.1. Cold or warm ice at the bed?	3422
7.5.2.1.2. Sources of water and flow paths	3422
7.5.2.1.3. Rock:water ratios and rock-water contact times	3423
7.5.2.2. The Proglacial Zone	3423
7.5.2.2.1. Broad definition – zone of ice advance and retreat	3423
7.5.2.2.2. Permafrost	3424
7.5.2.2.3. Seasonal freezing	3424
7.5.2.2.4. Evapoconcentration	3424
7.5.3. Composition of Glacial Runoff	3424
7.5.3.1. General Features in Comparison with Global Riverine Runoff	3424
7.5.3.2. Relation to Lithology	3425
7.5.3.3. Chemical Erosion Rates	3425
7.5.3.4. pH, pCO2 and pO2	3425
7.5.3.5. 87Sr/86Sr Ratios	3425
7.5.3.6. Ge/Si Ratios	3425
7.5.3.7. δ18O, δ13CDIC, δ34S, and δ18O–SO4	3427
7.5.3.8. Nutrients	3428
7.5.4. Geochemical Weathering Reactions in Glaciated Terrain	3428
7.5.4.1. Trace Reactive Bedrock Components are Solubilized	3428
7.5.4.2. Carbonate and Silicate Hydrolysis	3428
7.5.4.3. Cation Exchange	3428
7.5.4.4. Carbonate and Silicate Dissolution – Sources of CO2 and Strong Acids	3428
7.5.4.5. Sulfide Oxidation – Using O2 and Fe(III)	3428
7.5.4.6. Oxidation of Bedrock Organic Matter, Sulfate Reduction, and Onward to Methanogenesis&DEL i	3429
7.5.4.7. Nutrients from Glacial Flour	3429
7.5.4.8. Other Lithologies	3430
7.5.4.9. Little Necessity for Atmospheric CO2	3430
7.5.5. Geochemical Weathering Reactions in the Proglacial Zone	3430
7.5.5.1. Similarities with Subglacial Environments	3430
7.5.5.2. Evapoconcentration and Freeze Concentration	3430
7.5.5.3. Ingress of Water from Channels into the Proglacial Zone	3430
7.5.5.4. Enhancement of Glacial Solute Fluxes	3431
7.5.6. Composition of Subglacial Waters Beneath Antarctica	3431
7.5.7. Concluding Remarks	3433
References	3433
Chapter 7.6: Chemical Weathering Rates, CO2 Consumption, and Control Parameters Deduced from the Chemical Composition of Rivers	3437
7.6.1. Introduction	3437
7.6.2. Definition of Chemical Weathering	3439
7.6.3. Calculation of CWRs from Field Data	3439
7.6.3.1. The Vegetation Compartment	3441
7.6.3.2. Role of Atmospheric Deposition	3441
7.6.4. Parameters Controlling CWRs	3442
7.6.5. Control Parameters Deduced from the Chemical Composition of Rivers	3443
7.6.5.1. Field Studies on Small Watersheds	3443
7.6.5.1.1. Effect of lithology	3443
7.6.5.1.2. Effect of climate (temperature, runoff)	3446
7.6.5.1.3. The role of mechanical erosion	3447
7.6.5.1.4. Role of organic matter	3448
7.6.5.2. Field Studies on Large Watersheds	3450
7.6.5.2.1. The direct method	3450
7.6.5.2.2. The inversion method	3451
7.6.6. Conclusion	3452
References	3453
Chapter 7.7: Trace Elements in River Waters	3457
7.7.1. Introduction	3457
7.7.2. Natural Abundances of Trace Elements in River Water	3458
7.7.2.1. Range of Concentrations of Trace Elements in River Waters	3469
7.7.2.2. Crustal Concentrations versus Dissolved Concentrations in Rivers	3469
7.7.2.3. Correlations between Elements	3471
7.7.2.4. Temporal Variability	3472
7.7.2.5. Conservative Behavior of Trace Elements in River Systems	3473
7.7.2.6. Transport of Elements	3473
7.7.3. Sources of Trace Elements in Aquatic Systems	3474
7.7.3.1. Rock Weathering	3474
7.7.3.2. Atmosphere	3476
7.7.3.3. Other Anthropogenic Contributions	3476
7.7.4. Aqueous Speciation	3477
7.7.5. The ``Colloidal World´´	3479
7.7.5.1. Nature of the Colloids	3479
7.7.5.2. Ultrafiltration of Colloids and Speciation of Trace Elements in Organic-rich Rivers	3480
7.7.5.3. The Nonorganic Colloidal Pool	3482
7.7.5.4. Fractionation of REEs in Rivers	3483
7.7.5.5. Colloid Dynamics	3485
7.7.6. Interaction of Trace Elements with Solid Phases	3486
7.7.6.1. Equilibrium Solubility of Trace Elements	3486
7.7.6.2. Reactions on Surfaces	3487
7.7.6.3. Experimental Adsorption Studies	3487
7.7.6.4. Adsorption on Hydrous Oxides in River Systems	3488
7.7.6.5. The Sorption of REEs: Competition between Aqueous and Surface Complexation	3489
7.7.6.6. Importance of Adsorption Processes in Large River Systems	3490
7.7.6.7. Anion Adsorption in Aquatic Systems	3491
7.7.6.8. Adsorption and Organic Matter	3491
7.7.6.9. Particle Dynamics	3492
7.7.7. Conclusion	3493
Acknowledgments	3494
References	3494
Chapter 7.8: Dissolved Organic Matter in Freshwaters	3499
7.8.1. Introduction	3499
7.8.1.1. Terminology	3499
7.8.1.2. Analytical Measurements	3500
7.8.1.3. The Major Areas of Research Interest	3500
7.8.2. Inventories and Fluxes	3501
7.8.2.1. Estimates of Carbon Fluxes – 1970s	3501
7.8.2.2. Estimates of Carbon Fluxes – 1980s	3502
7.8.2.3. Estimates of Carbon Fluxes – 1990s and 2000s	3502
7.8.3. Chemical and Biological Interactions	3503
7.8.3.1. DOM and the Acid–Base Chemistry of Freshwaters	3503
7.8.3.2. DOM and UV–Visible Radiation	3504
7.8.3.3. DOM and Chemical Speciation of Trace Metal Cations	3505
7.8.3.4. DOM and Biological Activity of Trace Metal Cations	3506
7.8.3.5. Bioavailability of DOM	3506
7.8.3.6. DOM and Disinfection By-Products	3507
7.8.4. Chemical Properties	3507
7.8.4.1. Shapiro's Yellow Organic Acids	3508
7.8.4.2. Isolation and Fractionation of DOM	3508
7.8.4.2.1. Isolation and fractionation by XAD resins	3508
7.8.4.2.2. Isolation and fractionation by membranes	3510
7.8.4.3. Average Molecular Weights	3511
7.8.4.3.1. Molecular weight distributions and averages	3511
7.8.4.3.2. Colligative and noncolligative methods	3512
7.8.4.3.3. Statistical summary of average molecular weights	3512
7.8.4.3.4. Mass spectrometric analysis of molecular weight distributions	3514
7.8.4.4. Elemental Composition	3514
7.8.4.4.1. Mass percentages of carbon, hydrogen, nitrogen, oxygen, and sulfur	3514
7.8.4.4.2. Atomic ratios	3516
7.8.4.4.3. Average oxidation state of organic carbon	3517
7.8.4.4.4. Unsaturation and aromaticity	3517
7.8.4.5. Acidic Functional Groups	3517
7.8.4.5.1. Indirect titration methods	3517
7.8.4.5.2. Direct titration methods	3519
7.8.4.5.3. Carboxyl and phenolic contents of DOM	3519
7.8.4.6. Carbon Distribution from 13C NMR Spectrometry	3520
7.8.4.6.1. Processing source data	3520
7.8.4.6.2. Statistical summary of 13C NMR results	3520
7.8.4.7. Biomolecules in DOM	3520
7.8.4.7.1. Amino acids	3522
7.8.4.7.2. Sugars	3522
7.8.4.7.3. Lignin-derived phenols	3524
7.8.4.8. Overall Summary of the Chemical Properties of DOM	3526
7.8.5. Summary and Conclusions	3528
References	3529
Chapter 7.9: Environmental Isotope Applications in Hydrologic Studies	3535
7.9.1. Introduction	3536
7.9.1.1. Environmental Isotopes as Tracers	3536
7.9.1.2. Isotope Fundamentals	3537
7.9.1.2.1. Basic principles	3537
7.9.1.2.2. Isotope fractionation	3537
7.9.1.2.3. Rayleigh fractionation	3538
7.9.1.2.4. Terminology	3538
7.9.1.3. Causes of Isotopic Variation	3539
7.9.1.3.1. Isotope fractionations during phase changes	3539
7.9.1.3.2. Mixing of waters and/or solutes	3539
7.9.1.3.3. Geochemical and biological reactions	3540
7.9.2. Water Sources, Ages, and Cycling	3541
7.9.2.1. Deuterium and Oxygen-18	3541
7.9.2.1.1. Basic principles	3541
7.9.2.1.2. Precipitation	3541
7.9.2.1.3. Shallow groundwaters	3542
7.9.2.1.4. Deep groundwaters and paleorecharge	3543
7.9.2.1.5. Surface waters	3543
7.9.2.2. Tritium	3545
7.9.2.2.1. Basic principles	3545
7.9.2.2.2. Applications to hydrologic studies	3545
7.9.2.3. Determination of Runoff Mechanisms	3546
7.9.2.3.1. Mixing models	3546
7.9.2.3.2. Isotope hydrograph separation	3546
7.9.2.3.2.1. Two-component mixing models	3547
7.9.2.3.2.2. Three-component mixing models	3547
7.9.2.3.3. Temporal and spatial variability in end-members	3549
7.9.2.3.3.1. The ‘event’ water component	3549
7.9.2.3.3.2. The ‘pre-event’ groundwater component	3550
7.9.2.3.3.3. The soil water component	3550
7.9.2.4. Estimation of MRT	3551
7.9.3. Solute Isotope Hydrology and Biogeochemistry	3552
7.9.3.1. Carbon	3552
7.9.3.1.1. Carbon isotope fundamentals	3553
7.9.3.1.2. δ13C of soil CO2 and DIC	3553
7.9.3.1.3. Tracing sources of carbonate alkalinity in rivers	3554
7.9.3.1.4. Tracing sources of carbonate alkalinity in catchments	3556
7.9.3.1.5. Carbon-14	3557
7.9.3.1.6. Sources of DOC	3557
7.9.3.2. Nitrogen	3558
7.9.3.2.1. Nitrogen isotope fundamentals	3558
7.9.3.2.2. Oxygen isotope fundamentals	3559
7.9.3.2.3. Tracing atmospheric sources of nitrate	3559
7.9.3.2.3.1. Using δ15N	3559
7.9.3.2.3.2. Using δ18O	3561
7.9.3.2.3.3. Using δ17O (or ∆17O)	3561
7.9.3.2.4. Fertilizer and animal waste sources of N	3562
7.9.3.2.5. Soil sources of N	3563
7.9.3.2.6. Processes affecting the δ15N of nitrate	3563
7.9.3.2.6.1. N-fixation	3563
7.9.3.2.6.2. Assimilation	3563
7.9.3.2.6.3. Mineralization	3564
7.9.3.2.6.4. Nitrification	3564
7.9.3.2.6.5. Volatilization	3564
7.9.3.2.6.6. Denitrification	3564
7.9.3.2.7. Processes affecting the δ18O of nitrate	3565
7.9.3.2.7.1. Assimilation	3565
7.9.3.2.7.2. Nitrification	3565
7.9.3.2.7.3. Denitrification	3566
7.9.3.2.8. Nitrate isotope applications to hydrologic studies	3566
7.9.3.2.9. Small catchment studies	3567
7.9.3.2.10. Large river studies	3568
7.9.3.2.11. Subsurface waters	3568
7.9.3.3. Sulfur	3569
7.9.3.3.1. Sulfur isotope fundamentals	3570
7.9.3.3.2. Oxygen isotopes of sulfate	3571
7.9.3.3.3. Tracing atmospheric deposition of sulfate	3571
7.9.3.3.3.1. Using δ34S and δ18O	3571
7.9.3.3.3.2. Using δ17O (or ∆17O)	3572
7.9.3.3.3.3. Using Sulfur-35	3572
7.9.3.3.4. Sulfate in catchment surface waters	3573
7.9.3.3.5. Sulfate in groundwater	3573
7.9.3.4. Phosphorus	3574
7.9.3.4.1. Analytical methods	3574
7.9.3.4.2. Factors controlling δ18OPO4 in aquatic ecosystems	3575
7.9.3.4.3. Oxygen isotopic compositions of phosphate sources	3575
7.9.3.4.3.1. δ18O of phosphate fertilizers	3575
7.9.3.4.3.2. δ18O of WWTP phosphate	3575
7.9.3.4.3.3. δ18O of soil phosphate	3576
7.9.3.4.3.4. δ18O of organic phosphate	3576
7.9.3.4.4. Application studies in aquatic ecosystems	3576
7.9.4. Use of a Multi-Isotope Approach	3577
7.9.4.1. Determination of Flowpaths and Reaction Paths	3577
7.9.4.2. Multi-Isotope Studies of Hot Spots and Hot Moments	3578
7.9.4.2.1. Isoscapes of nitrate isotope data	3578
7.9.4.2.2. Organic matter isotopes	3579
7.9.5. Summary and Conclusions	3579
Acknowledgments	3580
References	3580
Chapter 7.10: Metal Stable Isotopes in Weathering and Hydrology	3591
7.10.1. Introduction	3591
7.10.2. Essential Background Information	3592
7.10.2.1. Metal Stable Isotope Fractionation Processes	3592
7.10.2.2. Instrumentation	3593
7.10.2.2.1. Data: Acquisition, reduction, and accuracy	3594
7.10.3. Li, Mg, Ca, and Fe Stable Isotope Signals in the Environment	3595
7.10.3.1. Lithium	3596
7.10.3.2. Magnesium	3598
7.10.3.3. Calcium	3602
7.10.3.4. Iron	3605
7.10.4. Frontier Metal Stable Isotope Systems	3609
7.10.4.1. Strontium	3610
7.10.4.2. Copper	3610
7.10.4.3. Zinc	3611
7.10.4.4. Chromium	3613
7.10.5. Directions Forward	3614
7.10.5.1. Other Potential Metal Stable Isotope Tracers: The Logical Next Steps	3615
7.10.5.2. Getting the Handle on Isotope Fractionation Factors	3616
7.10.5.3. Developing Robust Multitracer Approaches	3616
References	3617
Chapter 7.11: Groundwater Dating and Residence-Time Measurements	3623
7.11.1. Introduction	3624
7.11.2. Nature of Groundwater Flow Systems	3624
7.11.2.1. Driving Forces	3624
7.11.2.2. Topographic Control on Flow	3624
7.11.2.3. Hydraulic Conductivity and Its Variability	3625
7.11.2.4. Scales of Flow Systems	3625
7.11.2.4.1. Vadose-zone scale	3625
7.11.2.4.2. Local scale	3625
7.11.2.4.3. Aquifer scale	3625
7.11.2.4.4. Regional scale	3626
7.11.2.5. Sources of Solutes at Various Scales	3626
7.11.2.5.1. Meteoric (recharge)	3626
7.11.2.5.2. Weathering	3627
7.11.2.5.3. Diagenetic	3627
7.11.2.5.4. Connate	3627
7.11.2.5.5. `Basement waters´	3627
7.11.3. Solute Transport in Subsurface Water	3627
7.11.3.1. Fundamental Transport Processes	3628
7.11.3.1.1. Advection	3628
7.11.3.1.2. Diffusion	3628
7.11.3.1.3. Dispersion	3628
7.11.3.2. Advection–Dispersion Equation	3628
7.11.3.3. Interaction between Hydrogeological Heterogeneity and Transport	3629
7.11.3.3.1. Small-scale transport and effective dispersion	3629
7.11.3.3.2. Large-scale transport and mixing	3629
7.11.3.4. Groundwater Dating and the Concept of `Groundwater Age´	3629
7.11.4. Summary of Groundwater Age Tracers	3630
7.11.4.1. Introduction	3630
7.11.4.2. Radionuclides for Age Tracing of Subsurface Water	3630
7.11.4.2.1. Argon-37	3630
7.11.4.2.2. Sulfur-35	3631
7.11.4.2.3. Krypton-85	3631
7.11.4.2.4. Tritium	3631
7.11.4.2.5. Silicon-32	3633
7.11.4.2.6. Argon-39	3633
7.11.4.2.7. Carbon-14	3633
7.11.4.2.8. Krypton-81	3634
7.11.4.2.9. Chlorine-36	3634
7.11.4.2.10. Iodine-129	3635
7.11.4.3. Stable, Transient Tracers	3635
7.11.4.3.1. Chlorofluorocarbons and sulfur hexafluoride	3635
7.11.4.3.2. Atmospheric noble gases and stable isotopes	3635
7.11.4.3.3. Nonatmospheric noble gases	3636
7.11.5. Lessons from Applying Geochemical Age Tracers to Subsurface Flow and Transport	3637
7.11.5.1. Introduction	3637
7.11.5.2. Approaches	3638
7.11.5.2.1. Direct groundwater age estimation	3638
7.11.5.2.2. Modeling techniques: analytical versus numerical	3638
7.11.5.2.3. Identification of sources and sinks of a particular tracer	3639
7.11.5.2.4. Defining boundary conditions (modeling approach)	3639
7.11.6. Tracers at the Regional Scale	3639
7.11.6.1. Introduction	3639
7.11.6.2. Examples of Applications	3640
7.11.6.2.1. Noble-gas isotopes – Paris Basin	3640
7.11.6.2.2. Great Artesian Basin – noble-gas isotopes, 36Cl, and 81Kr	3642
7.11.6.2.3. Implications at the regional scale	3644
7.11.7. Tracers at the Aquifer Scale	3645
7.11.7.1. Introduction	3645
7.11.7.2. Carrizo Aquifer	3646
7.11.7.3. Implications at the Aquifer Scale	3648
7.11.8. Tracers at the Local Scale	3649
7.11.8.1. Introduction	3649
7.11.8.2. 3H/3He, CFC-11, CFC-12, 85Kr – Delmarva Peninsula	3650
7.11.8.3. Implications at the Local Scale	3653
7.11.9. Tracers in Vadose Zones	3653
7.11.10. Conclusions	3657
References	3657
Chapter 7.12: Cosmogenic Nuclides in Weathering and Erosion	3663
7.12.1. Introduction	3664
7.12.1.1. Definitions and Nomenclature	3664
7.12.1.2. Quantifying Weathering and Erosion	3664
7.12.1.2.1. Quantifying physical erosion rates	3665
7.12.1.2.2. Quantifying chemical erosion rates	3665
7.12.1.2.3. The advent of cosmogenic nuclide methods	3665
7.12.2. Cosmogenic Nuclide Systematics at Earth's Surface	3666
7.12.2.1. Cosmic Rays	3666
7.12.2.2. Cosmogenic Nuclide Production	3666
7.12.2.3. Cosmogenic Nuclide Production Profiles	3667
7.12.3. Using Cosmogenic Nuclides to Determine Rates of Surface Lowering and Denudation	3668
7.12.3.1. No Erosion (Surface Exposure Dating)	3668
7.12.3.1.1. Theory	3668
7.12.3.1.2. Examples	3669
7.12.3.1.2.1. Dating strath terraces	3669
7.12.3.1.2.2. Dating glacial moraines	3669
7.12.3.2. Rock Erosion	3670
7.12.3.2.1. Theory	3670
7.12.3.2.1.1. Steady erosion	3670
7.12.3.2.1.2. Complications due to unsteady denudation	3671
7.12.3.2.2. Examples	3671
7.12.3.2.2.1. Denudation of bedrock surfaces	3671
7.12.3.2.2.1. Rock erosion under soil cover	3672
7.12.3.3. Cosmogenic Nuclides in Vertically Mixed Soils	3673
7.12.3.3.1. Theory	3673
7.12.3.3.1.1. Exposure dating of vertically mixed sediment	3674
7.12.3.3.1.2. Denudation rates in vertically mixed soils	3674
7.12.3.3.1.3. Complications due to saprolite weathering and quartz enrichment	3675
7.12.3.3.2. Examples	3676
7.12.3.3.2.1. Exposure dating marine terraces	3676
7.12.3.4. Spatially Averaged Denudation Rates	3677
7.12.3.4.1. Theory	3677
7.12.3.4.1.1. Complications	3678
7.12.3.4.2. Examples	3678
7.12.3.4.2.1. Test of the method: comparing cosmogenic rates to absolute erosion rates	3678
7.12.3.4.2.2. Transient versus dynamic equilibrium landscapes	3679
7.12.4. Chemical Erosion Inferred from Cosmogenic Nuclides	3681
7.12.4.1. Chemical Erosion from Physically Stable Soils	3681
7.12.4.1.1. Theory	3681
7.12.4.1.1.1. Complications	3682
7.12.4.1.2. Example	3683
7.12.4.1.2.1. Chemical erosion rates of glacial moraines	3683
7.12.4.2. Chemical Erosion Rates of Soil Along a Physically Eroding Slope	3684
7.12.4.2.1. Theory	3684
7.12.4.1.2.1.1. Complications	3684
7.12.4.2.2. Example	3685
7.12.4.2.2.1. Chemical erosion rates on a hillslope in Australia	3685
7.12.4.3. Chemical Erosion Rates of Soils and Landscapes	3686
7.12.4.3.1. Theory	3686
7.12.4.3.1.1. Complications	3688
7.12.4.3.2. Examples	3689
7.12.4.3.2.1. Test of the mass balance approach	3689
7.12.4.3.2.2. Chemical erosion as a function of altitude	3689
7.12.4.3.2.3. Quantifying how chemical and physical erosion interrelate	3690
7.12.4.3.2.4. Climatic effects on chemical erosion rates	3691
7.12.5. Summary	3693
References	3695
Chapter 7.13: Geochemistry of Saline Lakes	3699
7.13.1. Introduction	3699
7.13.2. Origin and Occurrence	3699
7.13.3. Environmental Context	3701
7.13.3.1. Hydrology	3701
7.13.3.2. Climate	3702
7.13.3.3. Geology	3703
7.13.4. Compositional Controls	3704
7.13.4.1. Major Solutes	3704
7.13.4.2. Stable Isotopes	3705
7.13.5. Evaporative Brine Evolution	3706
7.13.6. Examples of Saline Lake Systems	3712
7.13.6.1. Chloride – Great Salt Lake	3718
7.13.6.2. Carbonate – East Africa	3719
7.13.6.3. Sulfate – Northern Great Plains, North America	3720
7.13.6.4. Mixed Anions – Death Valley	3721
7.13.6.5. Acid Lakes – Australia	3723
7.13.7. Economic Minerals in Saline Lakes	3724
7.13.8. Summary	3724
References	3725
Chapter 7.14: Deep Fluids in Sedimentary Basins	3733
7.14.1. Introduction	3734
7.14.2. Field and Laboratory Methods	3735
7.14.2.1. Water from Gas Wells	3736
7.14.2.2. Information from Wire-Line Logs	3737
7.14.3. Chemical Composition of Subsurface Waters	3737
7.14.3.1. Water Salinity	3737
7.14.3.1.1. Origin of elevated salinities	3737
7.14.3.1.1.1. Subaerial evaporation of seawater	3737
7.14.3.1.1.2. Subsurface dissolution of evaporites	3737
7.14.3.1.1.3. Marine aerosols: brines from rainwater	3737
7.14.3.1.1.4. Freezing	3737
7.14.3.1.1.5. Boiling	3738
7.14.3.1.2. Controls on salinity	3739
7.14.3.1.3. The role of formation waters in crustal cycling	3739
7.14.3.2. Major Cations	3739
7.14.3.2.1. Dissolved aluminum	3741
7.14.3.2.2. Water pH	3741
7.14.3.2.3. Dissolved silica	3743
7.14.3.2.4. Boron	3743
7.14.3.3. Water–Rock Reactions Controlling Cation Concentrations	3744
7.14.3.3.1. Cation geothermometry	3744
7.14.3.4. Major Anions	3745
7.14.3.4.1. Chloride and bromide	3745
7.14.3.4.2. Iodide	3746
7.14.3.4.3. Fluoride	3746
7.14.3.4.4. Inorganic carbon species	3747
7.14.3.4.5. Sulfate	3747
7.14.3.5. Reactive Organic Species	3747
7.14.3.5.1. Monocarboxylic acid anions	3747
7.14.3.5.2. Dicarboxylic acid anions	3748
7.14.3.5.3. Other reactive organic species	3748
7.14.3.5.4. Origin of major reactive species	3749
7.14.4. Isotopic Composition of Water	3749
7.14.4.1. Formation Waters Derived from Holocene Meteoric Water	3750
7.14.4.2. Formation Waters from `Old´ Meteoric Water	3750
7.14.4.3. Formation Waters of Connate Marine Origin	3750
7.14.4.4. Bittern Connate Water in Evaporites	3752
7.14.4.5. Brines from Mixing of Different Waters	3752
7.14.4.6. Do the Compositions of Basinal Brines Reflect Secular Variations in Seawater Chemistry?	3753
7.14.5. Isotopic Composition of Solutes	3754
7.14.5.1. Boron Isotopes	3754
7.14.5.2. Lithium Isotopes	3754
7.14.5.3. Carbon Isotopes	3755
7.14.5.4. Sulfur Isotopes	3755
7.14.5.5. Chlorine Isotopes	3756
7.14.5.6. Bromine Isotopes	3756
7.14.5.7. Strontium Isotopes	3756
7.14.5.8. Radioactive Isotopes and Age Dating	3756
7.14.6. Basinal Brines as Ore-Forming Fluids	3757
7.14.6.1. Metal-Rich Brines	3757
7.14.6.2. Solubilization of Heavy Metals	3757
7.14.6.3. Bisulfide Complexing	3757
7.14.6.4. Organic Complexing	3758
7.14.6.5. Chloride Complexing	3758
7.14.6.6. Geochemical Modeling of Ore Fluids	3758
7.14.6.7. Fluoride	3759
7.14.6.8. Barium and Strontium	3759
7.14.7. Dissolved Gases	3759
7.14.7.1. Methane	3759
7.14.7.2. Carbon Dioxide	3760
7.14.7.2.1. Storage of CO2 in sedimentary basins	3760
7.14.7.2.2. Storage of CO2 in the Frio Formation	3761
7.14.7.2.3. Potential impacts and risks of geologic storage of CO2	3764
7.14.7.3. Hydrogen Sulfide	3767
7.14.7.4. Noble Gases	3767
7.14.8. The Influence of Geologic Membranes	3768
7.14.9. Summary and Conclusions	3769
Acknowledgments	3769
References	3770
Chapter 7.15: Deep Fluids in the Continents	3779
7.15.1. Introduction	3780
7.15.1.1. The Crystalline Rock Environment	3780
7.15.1.1.1. The rocks	3780
7.15.1.1.2. Structural and geomechanical characteristics	3780
7.15.1.1.3. Hydrogeology	3781
7.15.2. Field Sampling Methods	3782
7.15.3. Chemistry and Isotopic Composition of Groundwaters from Crystalline Environments	3783
7.15.3.1. Trends in Major Ions and the Stable Isotopes of Water	3783
7.15.3.1.1. Bicarbonate and depth	3783
7.15.3.1.2. Sulfate and depth	3783
7.15.3.1.3. Chloride and depth	3789
7.15.3.1.4. Bromide and depth	3789
7.15.3.1.5. Fluoride	3789
7.15.3.1.6. Strontium and depth	3789
7.15.3.1.7. Oxygen-18 and depth	3789
7.15.3.1.8. Oxygen-18 and deuterium	3789
7.15.3.2. Strontium Isotopes	3790
7.15.3.3. Boron Isotopes	3792
7.15.3.4. Stable Chlorine Isotopes (37/35)	3792
7.15.3.5. Stable Bromine Isotopes (81/79)	3793
7.15.4. Gases from Crystalline Environments	3793
7.15.5. The Origin and Evolution of Fluids in Crystalline Environments	3794
7.15.5.1. The Origin of Salinity: The Influence of the Rock	3795
7.15.5.1.1. Halogen-bearing mineral and fluid inclusions	3795
7.15.5.1.2. The role of water/rock interaction	3796
7.15.5.1.3. Mineral/fluid reactions	3797
7.15.5.1.4. The role of strontium isotopes and water/rock interaction	3798
7.15.5.2. The Origin of Salinity: Fluids from External Sources	3800
7.15.5.2.1. Sources and concentration mechanisms for fluids from external sources	3800
7.15.5.2.1.1. Evaporation of surface waters	3800
7.15.5.2.1.2. Freezing of surface and subsurface waters	3801
7.15.5.2.2. Emplacement of fluids into crystalline rocks	3801
7.15.5.2.3. Major ions and stable isotopes	3802
7.15.5.2.4. Evidence for external sources from B, Sr, and Li isotopes	3802
7.15.5.3. Examples of Multiple Sources of Salinity	3803
7.15.5.3.1. Potential mixing of freeze-out fluids, shield brines, and the influence of gas hydr	3803
7.15.5.3.2. Stable chlorine isotope data from the Canadian and Fennoscandian Shields	3804
7.15.5.3.3. Interpreting Ca/Na versus Br/Cl trends for data from crystalline environments	3806
7.15.6. Examples from Research Sites Found in Crystalline Environments	3807
7.15.6.1. Groundwater Composition and Saline Fluids in the Lac du Bonnet Granite Batholith, Manitoba, Canada	3808
7.15.6.2. Groundwater Composition at the Palmottu Site in Finland	3809
7.15.6.3. Groundwater Composition and Hydrogeochemical Aspects of the Äspö Site, Sweden	3811
7.15.6.4. The KTB (Continental Deep Drilling Project of Germany)	3812
7.15.6.5. Hydrogeological and Hydrogeochemical Investigations in the Outokumpu Deep Drill Hole in Finlan	3813
7.15.6.6. The Hydrogeology and Geochemistry of the Kola Superdeep Well	3815
7.15.7. Summary and Conclusions	3816
References	3816
e9780080983004v8	3825
Front Cover	3825
The Oceans and Marine Geochemistry	3828
Copyright	3829
In Memoriam	3830
Heinrich Dieter Holland (1927–2012)	3832
Karl Karekin Turekian (1927–2013)	3834
References	3836
Dedication	3838
Contents	3840
Executive Editors’ Foreword to the Second Edition	3842
Contributors	3846
Volume Editor’s Introduction	3848
References	3850
Chapter 8.1: Physico-Chemical Controls on Seawater	3852
8.1.1. Composition of Seawater	3852
8.1.2. Thermodynamic Properties of Seawater	3853
8.1.3. Thermodynamic Equilibria in Seawater	3855
8.1.3.1. The Carbonate System in Seawater	3855
8.1.3.2. Other Ionic Equilibrium Processes	3856
8.1.4. Kinetic Processes in Seawater	3857
8.1.5. Modeling the Ionic Interactions in Natural Waters	3857
8.1.5.1. Estimating Activity Coefficients	3857
8.1.5.2. Estimating Physical-Chemical Properties	3858
8.1.6. Effect of Ocean Acidification	3859
Acknowledgments	3865
References	3865
Chapter 8.2: Controls of Trace Metals in Seawater	3870
8.2.1. Introduction	3870
8.2.1.1. Concentrations	3871
8.2.1.2. Distributions	3874
8.2.1.2.1. Conservative-type distributions	3874
8.2.1.2.2. Nutrient-type distributions	3875
8.2.1.2.3. Scavenged-type distributions	3876
8.2.1.2.4. Hybrid distributions	3876
8.2.1.2.5. Mixed distributions	3877
8.2.1.2.6. Data emerging from the GEOTRACES program	3878
8.2.2. External Inputs of Trace Metals to the Oceans	3880
8.2.2.1. Rivers	3880
8.2.2.2. Benthic Inputs	3881
8.2.2.3. Atmosphere	3881
8.2.2.4. Hydrothermal	3884
8.2.3. Removal Processes	3886
8.2.3.1. Active Biological Uptake in the Surface Waters	3886
8.2.3.1.1. Lessons from laboratory studies	3886
8.2.3.1.2. Non-Redfieldian assimilation	3887
8.2.3.2. Passive Scavenging	3888
8.2.3.2.1. Adsorption/desorption processes	3888
8.2.3.2.2. Lessons from radionuclides	3888
8.2.4. Internal Recycling	3890
8.2.4.1. Recycling within the Water Column	3890
8.2.4.2. Recycling at the Sediment/Seawater Interface	3890
8.2.5. Complexation with Organic Ligands	3891
8.2.5.1. Copper	3892
8.2.5.2. Iron	3893
8.2.5.3. Zinc	3894
8.2.5.4. Summary of Speciation	3894
8.2.6. Future Directions	3895
8.2.6.1. The Use of Trace Element Isotopes	3895
8.2.6.2. Ocean Acidification	3895
References	3896
Relevant Websites	3902
Chapter 8.3: Air-Sea Exchange of Marine Trace Gases	3904
8.3.1. Introduction	3905
8.3.2. Gas Exchange Processes and Parameterizations	3905
8.3.2.1. Gas Flux Theory	3905
8.3.2.1.1. Mass boundary layers at the interface	3905
8.3.2.1.2. Turbulent forcing: wind speed-based parameterizations of transfer velocity	3906
8.3.2.1.3. Interfacial models and the Schmidt number exponent on the water side	3907
8.3.2.1.4. Air-side transfer	3908
8.3.2.2. Processes Driving Gas Exchange	3908
8.3.2.2.1. The effect of wind	3908
8.3.2.2.2. The effect of waves	3908
8.3.2.2.3. The effect of bubbles and sea spray	3909
8.3.2.2.4. Heat and water fluxes	3910
8.3.2.2.5. The effect of surface films	3911
8.3.2.2.6. Chemical enhancement	3912
8.3.2.2.7. Biological effects	3912
8.3.2.3. Wind Speed Parameterizations	3913
8.3.2.3.1. Global 14C constraint	3913
8.3.2.3.2. Local-scale natural tracer experiments	3914
8.3.2.3.2.1. Radon-deficit technique	3914
8.3.2.3.2.2. Noble gas technique	3914
8.3.2.3.2.3. Biogenic gas mass balance	3915
8.3.2.3.3. Deliberate tracer experiments	3915
8.3.2.3.4. Direct flux measurements	3916
8.3.2.3.5. NOAA/COARE	3917
8.3.2.3.6. Reconciling observations	3918
8.3.2.3.7. Remote sensing of kw	3919
8.3.2.3.8. Air-side transfer velocity	3920
8.3.2.4. Estimating Trace Gas Fluxes in Biogeochemical Studies	3920
8.3.2.4.1. Gas-specific effects on transfer	3920
8.3.2.4.2. Selection of wind speed parameterization	3921
8.3.2.4.3. Averaging and interpolation/extrapolation	3922
8.3.2.4.4. Uncertainty in estimates	3923
8.3.2.5. Future Developments	3923
8.3.3. The Cycling of Trace Gases Across the Air-Sea Interface	3923
8.3.3.1. Greenhouse Gases	3924
8.3.3.1.1. Carbon dioxide	3924
8.3.3.1.2. Methane	3925
8.3.3.1.3. Nitrous oxide	3925
8.3.3.1.4. Ozone	3925
8.3.3.1.5. Carbon monoxide	3926
8.3.3.2. Nitrogen-Containing Gases	3926
8.3.3.2.1. Ammonia and methylamines	3926
8.3.3.2.2. Alkyl nitrates	3926
8.3.3.2.3. Hydrogen cyanide and methyl cyanide	3927
8.3.3.3. Sulfur-Containing Gases	3927
8.3.3.3.1. Dimethyl sulfide	3927
8.3.3.3.2. Methyl mercaptan	3930
8.3.3.3.3. Carbonyl sulfide	3930
8.3.3.3.4. Carbon disulfide	3930
8.3.3.3.5. Hydrogen sulfide	3930
8.3.3.3.6. Sulfur dioxide	3930
8.3.3.4. Nonmethane Hydrocarbons	3930
8.3.3.5. Oxygenated Volatile Organic Compounds	3931
8.3.3.6. Organohalogens	3931
8.3.3.6.1. The mono-organohalogens: methyl, ethyl, and propyl iodide&INS id=	3931
8.3.3.6.2. The di-organohalogens: diiodomethane, chloroiodomethane, bromoiodomethane,&	3933
8.3.3.6.3. The tri-organohalogens: bromoform and chloroform	3933
8.3.3.7. Miscellaneous Gases	3934
8.3.3.7.1. Chlorofluorocarbons	3934
8.3.3.7.2. Synthetic organic compounds	3934
8.3.3.7.3. Mercury	3934
8.3.3.7.4. Selenium and polonium	3934
8.3.3.7.5. Hydrogen	3935
8.3.4. Effects of Climate Change on Marine Trace Gases	3935
8.3.4.1. Effect on Air-Sea Gas Transfer	3935
8.3.4.2. Effect on Dissolved Gas Concentrations	3935
8.3.4.2.1. Carbon dioxide	3935
8.3.4.2.2. Dimethyl sulfide	3935
8.3.4.2.3. Other gases	3935
References	3936
Chapter 8.4: The Biological Pump	3944
List of Symbols	3945
8.4.1. Introduction	3945
8.4.2. Description of the Biological Pump	3946
8.4.2.1. Photosynthesis and the Incorporation of Nutrients and Trace Elements into Biogenic Materials	3947
8.4.2.1.1. Levels of primary production	3948
8.4.2.1.2. Patterns in time and space	3948
8.4.2.1.3. Nutrient limitation	3949
8.4.2.2. Formation of Sinking Particles	3949
8.4.2.2.1. Marine snow	3949
8.4.2.2.2. Aggregation and exopolymers	3949
8.4.2.2.3. Role of zooplankton	3950
8.4.2.2.3.1. Mucus feeding structures	3950
8.4.2.2.3.2. Fecal pellets	3950
8.4.2.3. Transport of Material to Depth	3950
8.4.2.3.1. The flux of POC	3950
8.4.2.3.1.1. Controls on particle sinking velocities	3951
8.4.2.3.2. Diel vertical migration of zooplankton	3951
8.4.2.4. Particle Decomposition, Fragmentation, and Repackaging	3951
8.4.2.4.1. Impacts of zooplankton	3953
8.4.2.4.2. Impact of bacteria	3953
8.4.2.5. Sedimentation and Burial	3954
8.4.2.6. Dissolved Organic Matter, the Microbial Loop, and the Microbial Carbon Pump	3954
8.4.2.7. New, Export, and Regenerated Production	3955
8.4.2.8. The Ballast Hypothesis	3955
8.4.3. Impact of the Biological Pum	3955
8.4.3.1. Carbon	3955
8.4.3.2. Nitrogen	3956
8.4.3.2.1. Nitrogen fixation versus denitrification	3956
8.4.3.3. Phosphorus	3957
8.4.3.4. Silicon	3957
8.4.3.4.1. The impact of the appearance of the diatoms on the marine silica cycle	3957
8.4.3.4.2. Excessive pumping of silicon	3958
8.4.4. Quantifying the Biological Pump	3958
8.4.4.1. Measurement of New Production and Export Production	3959
8.4.4.2. Measurement of Particle Flux	3959
8.4.4.2.1. Sediment traps	3959
8.4.4.2.2. Particle-reactive nuclides	3960
8.4.4.2.3. Oxygen utilization rates	3960
8.4.5. The Efficiency of the Biological Pump	3961
8.4.5.1. Definition of the Efficiency of the Biological Pump	3961
8.4.5.2. Geographic Variability in the Efficiency of the Biological Pump	3961
8.4.5.3. Altering the Efficiency of the Biological Pump	3962
8.4.5.3.1. Fertilization with micronutrients in HNLC areas	3962
8.4.5.3.2. Translocation of nutrients	3963
8.4.5.3.3. Changes in community composition	3963
8.4.5.3.4. Effects of the calcium carbonate counter-pump	3963
8.4.5.3.5. Enhancing particle transport	3964
8.4.5.3.6. Carbon overconsumption	3964
8.4.5.3.7. The C:N:P ratios of sinking material	3964
8.4.6. The Biological Pump in the Immediate Future	3965
References	3966
Chapter 8.5: Marine Bioinorganic Chemistry: The Role of Trace Metals in the Oceanic Cycles of Major Nutrients	3974
8.5.1. Introduction: The Scope of Marine Bioinorganic Chemistry	3974
8.5.2. Trace Metals in Marine Microorganisms	3975
8.5.2.1. Concentrations	3975
8.5.2.2. Uptake	3977
8.5.2.3. Trace Element Storage	3982
8.5.3. The Biochemical Functions of Trace Elements in the Uptake and Transformations of Nutrients	3982
8.5.3.1. Trace Metals and the Marine Carbon Cycle	3983
8.5.3.1.1. Light reaction of photosynthesis	3983
8.5.3.1.2. Dark reaction of photosynthesis	3983
8.5.3.1.3. Carbon concentrating mechanisms	3984
8.5.3.1.4. Respiration	3986
8.5.3.2. Trace Metals and the Nitrogen Cycle	3986
8.5.3.2.1. Acquisition of fixed nitrogen by phytoplankton	3986
8.5.3.2.2. N2 fixation and the nitrogen cycle	3987
8.5.3.3. Phosphorus Uptake	3987
8.5.3.4. Silicon Uptake	3988
8.5.4. Effects of Trace Metals on Marine Biogeochemical Cycles	3988
8.5.4.1. Iron	3988
8.5.4.1.1. Iron and growth rates	3988
8.5.4.1.2. Iron uptake	3990
8.5.4.1.3. Iron and electron transfer	3990
8.5.4.1.4. Iron and nitrogen acquisition	3990
8.5.4.2. Manganese	3990
8.5.4.3. Zinc, Cobalt, and Cadmium	3991
8.5.4.4. Copper	3994
8.5.4.5. Nickel	3996
8.5.5. Epilogue	3997
8.5.5.1. Paleoceanographic Aspects	3997
8.5.5.2. A View to the Future	3997
Acknowledgments	3998
References	3998
Chapter 8.6: Organic Matter in the Contemporary Ocean	4002
8.6.1. Introduction	4002
8.6.2. Reservoirs and Fluxes	4003
8.6.2.1. Reservoirs	4003
8.6.2.2. Fluxes	4004
8.6.2.2.1. Terrigenous OM fluxes to the oceans	4004
8.6.2.2.1.1. Riverine fluxes	4004
8.6.2.2.1.2. Eolian fluxes	4005
8.6.2.2.2. Water-column fluxes and the burial of OC in sedimen	4005
8.6.3. The Nature and Fate of TOC Delivered to the Oceans	4005
8.6.3.1. Background	4005
8.6.3.2. Terrestrial OM in River Systems	4006
8.6.3.3. Quantitative Importance of TOC in Marine Sediments	4008
8.6.3.3.1. Black carbon	4010
8.6.4. Origin, Cycling, Composition, and Fate of DOC in the Ocean	4011
8.6.4.1. Background	4011
8.6.4.2. Transport and Cycling of DOC in the Ocean	4011
8.6.4.3. Recalcitrant DOC	4013
8.6.4.4. The Composition of Semilabile HMW DOM: Biopolymers or Geopolymers?	4014
8.6.4.4.1. Acylpolysaccharides as major components of HMW DOM	4015
8.6.4.4.2. Proteins in HMW DOM	4018
8.6.4.4.3. Gel polymers and the cycling of HMW DOM	4018
8.6.4.5. Labile DOC and the Microbial Loop	4019
8.6.5. Emerging Perspectives on OM Preservation	4022
8.6.5.1. Background	4022
8.6.5.2. Compositional Transformations Associated with Sedimentation and Burial of OM	4022
8.6.5.3. Controls on OM Preservation	4025
8.6.5.3.1. Physical protection	4026
8.6.5.3.2. Role of oxygen	4027
8.6.5.3.3. Chemical protection	4029
8.6.5.3.3.1. Intrinsically refractory biomolecules	4029
8.6.5.3.3.2. Formation of organosulfur compounds	4029
8.6.6. Microbial OM Production and Processing: New Insights	4030
8.6.6.1. Background	4030
8.6.6.2. Planktonic Archaea	4031
8.6.6.3. Anaerobic Oxidation of Methane	4031
8.6.7. Summary and Future Research Directions	4032
Acknowledgments	4034
References	4034
Chapter 8.7: Hydrothermal Processes	4042
8.7.1. Introduction	4043
8.7.1.1. What Is Hydrothermal Circulation?	4043
8.7.1.2. Where Does Hydrothermal Circulation Occur?	4045
8.7.1.3. Why Should Hydrothermal Fluxes Be Considered Important?	4046
8.7.1.4. Outline Structure for Rest of this Chapter	4047
8.7.2. Vent-Fluid Geochemistry	4048
8.7.2.1. Why Are Vent-Fluid Compositions of Interest?	4048
8.7.2.2. Processes Affecting Vent-Fluid Compositions	4048
8.7.2.3. Compositions of Hydrothermal Vent Fluids	4052
8.7.2.3.1. Major element chemistry	4052
8.7.2.3.2. Trace element and isotope chemistry	4053
8.7.2.3.3. Gas chemistry of hydrothermal fluids	4054
8.7.2.3.4. Organic geochemistry of hydrothermal vent fluids	4055
8.7.2.4. Geographic Variations in Vent-Fluid Compositions	4056
8.7.2.4.1. Basalt-hosted hydrothermal systems	4056
8.7.2.4.2. Ultramafic-hosted systems	4058
8.7.2.4.3. Back-arc systems	4059
8.7.2.5. Temporal Variability in Vent-Fluid Compositions	4061
8.7.2.5.1. Temporal variability	4061
8.7.2.5.2. Effect on flux estimates	4062
8.7.3. The Net Impact of Hydrothermal Activity	4063
8.7.4. Near-Vent Deposits	4064
8.7.4.1. Alteration and Mineralization of the Upper Ocean Crust	4064
8.7.4.2. Near-Vent Hydrothermal Deposits	4064
8.7.5. Hydrothermal Plume Processes	4066
8.7.5.1. Dynamics of Hydrothermal Plumes	4066
8.7.5.2. Modification of Gross Geochemical Fluxes	4067
8.7.5.2.1. Dissolved noble gases	4067
8.7.5.2.2. Dissolved reduced gases (H2S, H2, and CH4)	4068
8.7.5.2.3. Fe and Mn geochemistry in hydrothermal plumes	4068
8.7.5.2.4. Coprecipitation and uptake with Fe in buoyant and nonbuoyant plumes	4071
8.7.5.2.5. Hydrothermal scavenging by Fe oxyhydroxides	4071
8.7.5.3. Physical Controls on Dispersing Plumes	4072
8.7.5.4. Biogeochemical Cycling in Hydrothermal Plumes	4073
8.7.5.5. Impact of Hydrothermal Plumes on Ocean Geochemical Cycles	4074
8.7.6. Hydrothermal Sediments	4075
8.7.6.1. Near-Vent Sediments	4075
8.7.6.2. Deposition from Hydrothermal Plumes	4075
8.7.6.3. Hydrothermal Sediments in Paleoceanography	4076
8.7.6.4. Hydrothermal Sediments and Boundary Scavenging	4076
8.7.7. Conclusion	4076
8.7.7.1. What Are the Integrated Fluxes of Hydrothermal Heat and Mass from a Single Vent System to the Surrounding Ocean?	4077
8.7.7.2. What Role Does Protolith Composition Play in Hydrothermal Vent-Fluid Chemistry?	4077
8.7.7.3. What Is the Impact of Seafloor Hydrothermal Venting on Global Ocean Biogeochemical Budgets?	4077
Remembrance	4077
References	4078
Chapter 8.8: Tracers of Ocean Mixing	4086
8.8.1. Introduction	4086
8.8.2. Theoretical Framework 1: Advection–Diffusion Equations	4088
8.8.3. The Nature of Oceanic Mixing	4089
8.8.3.1. Diapycnal Mixing in the Ocean	4090
8.8.3.2. Isopycnal Mixing in the Ocean:	4091
8.8.4. Theoretical Framework 2: Tracer Ages	4091
8.8.4.1. Radiometric Dating	4092
8.8.4.2. Transient Concentration Dating	4093
8.8.5. Theoretical Framework 3: Diagnostic Methods	4094
8.8.5.1. Optimum Multiparameter Analysis	4094
8.8.5.2. Transit Time Distributions	4095
8.8.5.3. Tracer Contour Inverse Analysis	4096
8.8.6. Steady-State Tracers	4097
8.8.6.1. Radiocarbon	4097
8.8.6.2. Radon-222	4098
8.8.6.3. Radium	4098
8.8.6.4. Argon-39	4099
8.8.6.5. Dissolved Noble Gas Saturation Anomalies	4099
8.8.7. Transient Tracers	4100
8.8.8. Tracer Age Dating	4103
8.8.9. Tracer Release Exp	4104
8.8.10. Concluding Remarks	4104
References	4105
Chapter 8.9: Chemical Tracers of Particle Transport	4110
8.9.1. Particle Transport and Ocean Biogeochemistry	4110
8.9.2. Tracers of Particle Transport	4111
8.9.3. Transfer from Solution to Particles (Scavenging)	4111
8.9.4. Colloidal Intermediaries	4113
8.9.4.1. Development of the Colloidal Pumping Hypothesis	4113
8.9.4.2. Important Features of Colloids	4114
8.9.4.3. Evidence for Coagulation of Colloids and of Colloidal Thorium (and other Metals)	4115
8.9.4.4. Rate Constants for Colloid Coagulation	4115
8.9.4.5. Limitations and Questions	4117
8.9.5. Export of Particles from Surface Ocean Waters	4117
8.9.5.1. Scavenging Rates and Particle Flux	4117
8.9.5.2. Export Flux of POC	4118
8.9.5.3. Non-Steady-State Conditions and Advected Fluxes	4118
8.9.5.4. Limitations and Prospects	4119
8.9.6. Particle Dynamics and Regeneration of Labile Particles	4120
8.9.6.1. Particle Dynamics, Fluxes, and Regeneration	4120
8.9.6.2. Conceptual Models of Aggregation and Disaggregation	4120
8.9.6.3. Strategies to Evaluate Rate Constants	4121
8.9.7. Lateral Redistribution of Sediments	4123
8.9.7.1. Focusing and Winnowing of Sediments	4123
8.9.7.2. Lead-210	4124
8.9.7.3. Thorium-230	4124
8.9.7.4. Helium-3	4126
8.9.8. Summary	4128
References	4128
Chapter 8.10: Biological Fluxes in the Ocean and Atmospheric pCO2	4132
8.10.1. Introduction	4132
8.10.2. How Atmospheric CO2 is Affected by the Biological Pump	4133
8.10.2.1. By Internal Rearrangement of the Chemis	4133
8.10.2.2. Changes to the Mean Chemical State of the Ocean	4134
8.10.3. Visions of the Biological Pump in the Ocean	4135
8.10.3.1. Global Rate of Carbon Export from the Euphotic Zone	4135
8.10.3.1.1. Sediment traps	4135
8.10.3.1.2. Bottles	4135
8.10.3.1.3. Ocean carbon cycle GCMs	4135
8.10.3.2. Organic Carbon Sinking Depth	4135
8.10.3.2.1. Observations	4135
8.10.3.2.2. Theory	4136
8.10.3.2.2.1. Zooplankton	4136
8.10.3.2.2.2. Aggregation	4136
8.10.3.2.2.3. Ballast	4137
8.10.3.2.2.4. Water column dissolution	4137
8.10.3.3. The CaCO3 Pump	4137
8.10.3.4. The SiO2 Pump	4138
8.10.4. How the Biological Pump Could Change	4139
8.10.4.1. Iron	4139
8.10.4.2. pH	4140
8.10.4.3. Transparent Exopolymers	4140
8.10.4.4. Climate Change Impacts	4140
8.10.4.5. Global Nutrient Inventories	4140
8.10.5. Conclusion	4141
References	4141
Chapter 8.11: Sedimentary Diagenesis, Depositional Environments, and Benthic Fluxes	4144
8.11.1. Introduction	4144
8.11.1.1. Early Diagenesis and the Global Sedimentary Cycle	4144
8.11.1.2. General Classes of Conceptual Models	4145
8.11.1.3. Diagenetic Regimes and Depositional Environments	4145
8.11.2. Diagenetic Oxidation-Reduction Reactions	4149
8.11.2.1. Biogeochemical Redox Reaction Sequence	4149
8.11.2.1.1. Coupled stoichiometric relations	4150
8.11.2.1.2. Pore water solutes as reaction indicators	4151
8.11.2.2. Reaction Rates and Kinetics	4151
8.11.2.3. Sedimentary Redox Reaction Patterns	4152
8.11.2.3.1. Redox oscillation	4154
8.11.2.3.2. Microenvironmental heterogeneity	4154
8.11.3. Diagenetic Transport Processes	4155
8.11.3.1. Diffusive Transport	4155
8.11.3.2. Advective Transport	4156
8.11.4. Diagenetic Transport-Reaction Models	4156
8.11.4.1. General Mass Balance Relations and Reference Frames	4156
8.11.4.2. Simplification of Diagenetic Models	4157
8.11.4.2.1. Characteristic scaling and steady state	4157
8.11.5. Patterns in Boundary Conditions and Reaction Balances	4158
8.11.5.1. Spatial Patterns in Sediment Accumulation and Biogenic Transport	4158
8.11.5.2. Spatial Patterns in Reactive Corg Delivery and Magnitudes of Benthic Fluxes	4159
8.11.5.3. Global Patterns in the Scaling of Redox Reactions	4160
8.11.5.4. Sedimentary Record of Diagenetic Reaction Dominance and Balances	4160
8.11.5.5. Temporal Patterns in Boundary Conditions and the Scaling of Reactions	4162
8.11.6. Corg Burial and Preservation: Reactants and Diagenetic Regime	4164
8.11.6.1. Patterns in Corg Distributions and Particle Associations	4164
8.11.6.2. Corg Preservation: O2, Accumulation Rates, and Diagenetic Regimes	4166
8.11.7. Carbonate Mineral Dissolution-Alteration-Preservation	4168
8.11.7.1. Coupling of Redox Reactions and Carbonate Diagenesis	4168
8.11.7.2. Carbonate Mineral Equilibria and Saturation States	4168
8.11.7.3. Kinetics of Biogenic Carbonate Dissolution in Sediments	4169
8.11.7.4. Shallow Water Carbonate Dissol	4171
8.11.7.5. Dissolution of Carbonate in Deep-Sea Deposits and Internal Reaction Patterns	4172
8.11.7.6. Benthic Alkalinity Fluxes	4172
8.11.8. Biogenic Silica and Reverse Weathering	4175
8.11.8.1. Patterns in Biogenic SiO2 Distributions	4175
8.11.8.2. Diagenetic Fates, Equilibria, and Dissolution Reaction Kinetics of Biogenic SiO2	4175
8.11.8.3. Authigenic Silicate Formation and Reverse Weathering	4177
8.11.9. Future Directions	4179
Acknowledgments	4179
References	4180
Chapter 8.12: Geochronometry of Marine Deposits	4186
8.12.1. Introduction	4186
8.12.2. Principles	4186
8.12.2.1. Radioactive Geochronometry	4186
8.12.2.2. Secondary Stratigraphic Procedures	4187
8.12.3. Radioactive Systems Used in Marine Geochronometry	4187
8.12.3.1. Radiocarbon	4187
8.12.3.2. Uranium and Thorium Decay Chain Nuclides	4187
8.12.3.3. Cosmogenic Nuclides	4187
8.12.3.4. Potassium-Argon	4188
8.12.4. Coastal Deposits	4188
8.12.4.1. Applicable Methods and Requirements	4188
8.12.4.2. Unbioturbated Deposits	4188
8.12.4.3. Bioturbated Deposits	4189
8.12.5. Deep-Sea Sediments	4190
8.12.5.1. Radiocarbon	4190
8.12.5.2. 230Th and 231Pa	4191
8.12.5.2.1. The basic theory	4191
8.12.5.2.2. The underlying assumptions	4192
8.12.5.2.3. Applications	4192
8.12.5.2.4. Problems of erosion and focusing	4193
8.12.5.3. 10Be	4193
8.12.5.4. 3He	4194
8.12.5.5. Volcanic Layers	4195
8.12.5.6. Extension of Dating Techniques	4195
8.12.5.6.1. The Milankovitch cycles and chronology	4195
8.12.5.6.2. Oxygen and carbon isotopes in carbonate tests	4195
8.12.5.6.3. Magnetic-reversal stratigraphy	4196
8.12.5.6.4. Element accumulation: Titanium and cobalt	4196
8.12.6. Ferromanganese Deposits	4197
8.12.6.1. Applicable Methods	4197
8.12.6.2. The Underlying Assumptions	4197
8.12.6.3. Applications	4197
8.12.7. Corals	4198
8.12.8. Methods Not Depending on Radioactive Decay	4200
8.12.8.1. Amino Acid Racemization	4200
8.12.8.2. Thermoluminescence	4200
Acknowledgments	4201
References	4201
Chapter 8.13: Geochemical Evidence for Quaternary Sea-Level Changes	4206
8.13.1. Introduction	4206
8.13.2. Methods of Sea-Level Reconstruction	4206
8.13.2.1. Methods of Direct Sea-Level Reconstruction	4207
8.13.2.2. Methods of Sea-Level Reconstruction from Oxygen Isotope Measurements	4207
8.13.3. History and Current State of Direct Sea-Level Reconstruction	4209
8.13.3.1. 230Th and 231Pa Dating: Current Status and Historical Overview	4209
8.13.3.2. 230Th and 231Pa Dating: Theory	4210
8.13.3.3. Tests of Dating Assumptions	4211
8.13.3.4. Sources of Error in Age	4212
8.13.3.5. Open-System 230Th Dating	4214
8.13.3.6. Current Status of Direct Sea-Level Reconstruction: The Past 500 ky	4214
8.13.4. History and Current State of Sea-Level Determinations from Oxygen Isotope Measurements	4219
8.13.4.1. History of Marine Oxygen Isotope Measurements and Sea Level	4219
8.13.4.2. Comparison of Direct Sea-Level and Benthic Foram Records	4219
8.13.4.3. 18O/16O-Based Sea-Level Records	4219
8.13.5. Causes of Sea-Level Change and Future Work	4220
References	4221
Chapter 8.14: Elemental and Isotopic Proxies of Past Ocean Temperatures	4224
8.14.1. Introduction	4224
8.14.2. A Brief History of Early Research on Geochemical Proxies of Temperature	4225
8.14.3. Oxygen Isotopes as a Paleotemperature Proxy in Foraminifera	4226
8.14.3.1. Background	4226
8.14.3.2. Paleotemperature Equations	4227
8.14.3.3. Secondary Effects and Diagenesis	4227
8.14.3.4. Results on Quaternary Timescales	4228
8.14.3.5. Results for the Neogene, Paleogene, and Earlier Periods	4228
8.14.3.6. Summary of Outstanding Research Issues	4228
8.14.4. Oxygen Isotopes as a Climate Proxy in Reef Corals	4229
8.14.4.1. Background	4229
8.14.4.2. Paleotemperature Equations	4229
8.14.4.3. Secondary Effects and Diagenesis	4229
8.14.4.4. Results on Historical Timescales	4230
8.14.4.5. Results on Late Quaternary Timescales	4230
8.14.4.6. Summary of Outstanding Research Issues	4231
8.14.5. Oxygen Isotopes as a Climate Proxy in other Marine Biogenic Phases	4231
8.14.6. Clumped Oxygen Isotopes	4231
8.14.7. Magnesium as a Paleotemperature Proxy in Foraminifera	4231
8.14.7.1. Background and History	4231
8.14.7.2. Calibration and Paleotemperature Equations	4232
8.14.7.3. Effect of Dissolution	4233
8.14.7.4. Other Secondary Effects on Mg/Ca	4234
8.14.7.5. Results over the Last Few Millennia	4235
8.14.7.6. Results on Quaternary Timescales	4235
8.14.7.7. Results for the Neogene, Paleogene, and Beyond	4237
8.14.7.8. Summary of Outstanding Research Issues	4237
8.14.8. Magnesium as a Paleotemperature Proxy in Ostracoda	4238
8.14.9. Strontium as a Climate Proxy in Corals	4238
8.14.9.1. Background	4238
8.14.9.2. Paleotemperature Equations	4238
8.14.9.3. Secondary Effects and Diagenesis	4239
8.14.9.4. Results on Historical Timescales	4240
8.14.9.5. Results on Geological Timescales	4240
8.14.9.6. Summary of Outstanding Research Issues	4241
8.14.10. Magnesium and Uranium in Corals as Paleotemperature Proxies	4241
8.14.11. Calcium Isotopes as a Paleotemperature Proxy	4241
8.14.12. Conclusions	4241
Acknowledgments	4242
References	4242
Chapter 8.15: Alkenone Paleotemperature Determinations	4250
8.15.1. Introduction	4250
8.15.2. Systematics and Detection	4252
8.15.3. Occurrence of Alkenones in Marine Waters and Sediments	4254
8.15.3.1. Genetic and Evolutionary Aspects of Alkenone Production	4255
8.15.4. Function	4256
8.15.5. Ecological Controls on Alkenone Production and Downward Flux	4257
8.15.5.1. Effects of Water Column Recycling and Sediment Diagenesis on the Alkenone Unsaturation Index	4260
8.15.6. Calibration of Uk37 Index to Temperature	4262
8.15.6.1. Culture Calibrations	4263
8.15.6.2. Particles	4264
8.15.6.2.1. Sediment traps	4265
8.15.6.3. Core Tops	4265
8.15.7. Synthesis of Calibration	4267
8.15.8. Paleotemperature Studies Using the Alkenone Method	4268
8.15.8.1. Holocene High-Resolution Studies	4268
8.15.8.2. Millennial-Scale Events of the Late Pleistocene and Last Glacial Termination	4269
8.15.8.3. Marine Temperatures During the LGM	4270
8.15.8.4. SST Records of the Late Pleistocene Ice Age Cycles	4273
8.15.8.5. SST before the Late Pleistocene	4274
8.15.8.6. Comparison with other Proxies: delta18O	4274
8.15.8.7. Comparison with other Proxies: Microfossils	4275
8.15.8.8. Comparison with other Proxies: Mg/Ca	4276
8.15.8.9. Comparison with other Proxies: TEX86 and other Glycerol Dialkyl Glycerol Tetraethers Indice	4277
8.15.8.10. Intercomparison of SST Proxies: Some Generalities	4277
8.15.9. Conclusions	4277
References	4278
Chapter 8.16: Tracers of Past Ocean Circulation	4286
8.16.1. Introduction	4286
8.16.2. Nutrient Water Mass Tracers	4287
8.16.2.1. Carbon Isotopes	4287
8.16.2.1.1. Controls on delta13C of oceanic carbon	4287
8.16.2.1.2. Carbon isotope ratios in benthic foraminifera	4288
8.16.2.2. Cadmium in Benthic Foraminifera	4289
8.16.2.2.1. Cd in seawater	4289
8.16.2.2.2. Cd/Ca in foraminifera	4290
8.16.2.3. Ba/Ca	4291
8.16.2.4. Zn/Ca	4291
8.16.2.5. Silicon Isotopes	4291
8.16.3. Conservative Water Mass Tracers	4291
8.16.3.1. Mg/Ca in Benthic Foraminifera	4291
8.16.3.2. Pore Water Chemistry	4291
8.16.3.3. Oxygen Isotopes in Benthic Foraminifera	4292
8.16.3.4. Clumped Isotopes	4292
8.16.3.5. Carbon Isotope Air-Sea Exchange Signature	4292
8.16.4. Neodymium Isotope Ratios	4293
8.16.5. Circulation Rate Tracers	4293
8.16.5.1. Radiocarbon	4293
8.16.5.2. 231Pa/230Th Ratio	4294
8.16.5.3. Geostrophic Shear Estimates from delta18O in Benthic Foraminifera	4294
8.16.6. Nongeochemical Tracers of Past Ocean Circulation	4294
8.16.7. Ocean Circulation during the LGM	4295
8.16.8. Conclusions	4299
References	4299
Chapter 8.17: Long-lived Isotopic Tracers in Oceanography, Paleoceanography, and Ice-sheet Dynamics	4304
8.17.1. Introduction	4304
8.17.2. Long-lived Isotopic Tracers and Their Applications	4304
8.17.3. Systematics of Long-lived Isotope Systems in the Earth	4305
8.17.3.1. Early Applications to the Oceans	4307
8.17.4. Neodymuim Isotopes in the Oceans	4308
8.17.4.1. REEs in Seawater	4308
8.17.4.2. Neodymium-isotope Ratios in Seawater	4309
8.17.4.3. Where does Seawater Neodymium Come From?	4313
8.17.4.4. Neodymium Isotopes as Water-mass Tracers	4314
8.17.4.5. The ``Nd Paradox´´	4316
8.17.4.6. Implications of Nd Isotopes and Concentrations in Seawater	4319
8.17.5. Applications to Paleoclimate	4320
8.17.5.1. Radiogenic Isotopes in Authigenic Ferromanganese Oxides	4320
8.17.5.2. Long-term Time Series in Fe-Mn Crusts	4322
8.17.5.3. Hf-Nd Isotope Trends in the Oceans	4323
8.17.6. Long-lived Radiogenic Tracers and Ice-sheet Dynamics	4324
8.17.6.1. Heinrich Events	4325
8.17.6.2. K/Ar ages of Heinrich Event Detritus	4325
8.17.6.3. Nd-Sr-Pb Isotopes in Terrigenous Sediments	4325
8.17.6.4. Isotopic and Geochronologic Measurements on Individual Mineral Grains	4327
8.17.6.5. Contrasting Provenance of H3 and H6	4327
8.17.6.6. Summary of Geochemical Provenance Analysis of Heinrich Layers	4328
8.17.6.7. Trough Mouth Fans as Archives of Major IRD Sources	4328
8.17.6.8. 40Ar/39Ar Hornblende Evidence for History of the Laurentide Ice Sheet During the Last Glacial Cycle	4329
8.17.7. Final Thoughts	4331
Acknowledgments	4331
References	4331
Chapter 8.18: The Biological Pump in the Past	4336
8.18.1. Introduction	4336
8.18.2. Concepts	4340
8.18.2.1. Aqueous Carbon Chemistry	4340
8.18.2.2. Soft-Tissue versus Carbonate Pump	4341
8.18.2.3. Low- versus High-Latitude Ocean	4343
8.18.2.4. Southern Ocean versus North Atlantic	4346
8.18.3. Tools	4348
8.18.3.1. Surface Ocean Biogeochemistry	4348
8.18.3.1.1. Nutrient status	4349
8.18.3.1.2. Export production	4350
8.18.3.2. Ocean Ventilation	4351
8.18.3.2.1. Water mass distribution	4351
8.18.3.2.2. Rates of ocean overturning and ventilation	4352
8.18.3.3. Integrative Constraints on the Biological Pump	4353
8.18.3.3.1. Carbon isotope distribution of the ocean and atmosphere	4353
8.18.3.3.2. Deep-ocean oxygen content	4353
8.18.3.3.3. Carbon chemistry and boron	4354
8.18.4. Observations	4355
8.18.4.1. 800 000 Year Perspective	4355
8.18.4.2. Deglacial Perspective	4357
References	4359
Chapter 8.19: The Oceanic CaCO3 Cycle	4370
8.19.1. Introduction	4370
8.19.2. The Contemporary Marine CaCO3 Cycle	4370
8.19.2.1. Formation and Transport Pathways of CaCO3	4372
8.19.2.2. Destruction and Dissolution of CaCO3	4373
8.19.3. Oceanic Distribution and Present-Day Changes in the Seawater CO2-Carbonic Acid System Due to Human Activities	4376
8.19.3.1. CO2 Gradients within and across Ocean Basins	4376
8.19.3.2. Surface Uptake of Anthropogenic CO2 and Future Projections	4377
8.19.3.3. Changes in Distribution of Omega and Shoaling of the CaCO3 Saturation Horizon	4379
8.19.4. Implications of Anthropogenic Ocean Acidification to the Marine CaCO3 Cycle	4379
8.19.4.1. Formation of CaCO3	4379
8.19.4.2. Destruction and Dissolution of CaCO3	4383
8.19.4.3. Feedbacks to Atmospheric CO2 and the Earth Climate System	4384
8.19.5. A Brief Commentary on Past Alterations to the Marine CaCO3 Cycle and Analogies to the Present Perturbation	4385
8.19.5.1. Calcite and Aragonite Seas	4385
8.19.5.2. Glacial to Interglacial Periods	4386
8.19.5.3. Paleocene Eocene Thermal Maximum	4387
8.19.5.4. Volcanic Vent Systems	4387
8.19.6. Back to the Future: Summary of Past and Present Clues on the Future CaCO3 Cycle	4387
Acknowledgments	4388
References	4388
Chapter 8.20: Records of Cenozoic Ocean Chemistry	4394
8.20.1. Introduction	4394
8.20.2. Cenozoic Deep-Sea Stable Isotope Record	4395
8.20.2.1. Oxygen Isotopes and Climate	4395
8.20.2.2. Carbon Isotopes and Ocean Carbon Chemistry	4398
8.20.3. The Marine Strontium and Osmium Isotope Records	4399
8.20.3.1. Globally Integrated Records of Inputs to the Ocean	4399
8.20.3.2. Osmium-Strontium Decoupling	4400
8.20.3.2.1. Decoupled riverine fluxes of strontium and osmium?	4401
8.20.3.2.2. Decoupled unradiogenic fluxes?	4401
8.20.3.3. Reconstructing Seawater Isotope Composition from Sediments	4401
8.20.3.4. Cenozoic Strontium and Osmium Isotope Records	4402
8.20.3.4.1. Overview of the Cenozoic marine strontium isotope record	4402
8.20.3.4.2. Overview of the Cenozoic marine osmium isotope record	4403
8.20.3.4.3. Significance of uplift and weathering of the Himalayan-Tibetan Plateau (HTP)	4404
8.20.3.4.4. Glaciation and the marine strontium and osmium isotope records	4405
8.20.3.5. Variations in the Strontium and Osmium Isotope Composition of Riverine Input	4406
8.20.3.6. Osmium and Strontium Isotopes as Chemical Weathering Proxies	4407
8.20.4. Mg/Ca Records from Benthic Foraminifera	4408
8.20.4.1. Coupling Benthic Foraminiferal Mg/Ca and Oxygen Isotope Records	4408
8.20.4.2. Calibration of the Mg/Ca Thermometer	4408
8.20.4.3. Cenozoic Benthic Foraminiferal Mg/Ca Records	4410
8.20.4.4. Changing Seawater Mg/Ca Ratio	4411
8.20.5. Boron Isotopes, Paleo-pH, and Atmospheric CO2	4411
8.20.5.1. The pH Dependence of Boron Isotope Fractionation	4411
8.20.5.2. Boron Partitioning into Calcite	4412
8.20.5.3. Paleo-pH and Atmospheric CO2 Reconstruction	4413
8.20.5.4. Outstanding Questions about Paleo-pH Reconstructions	4414
8.20.6. Closing Synthesis: Does Orogenesis Lead to Cooling?	4415
References	4416
Chapter 8.21: The Geologic History of Seawater	4420
8.21.1. Introduction	4420
8.21.2. The Hadean (4.5-4.0 Ga)	4421
8.21.3. The Archean (4.0-2.5 Ga)	4422
8.21.3.1. The Paleoarchean (4.0-3.7 Ga)	4422
8.21.3.2. The Mesoarchean (3.7-3.0 Ga)	4423
8.21.3.3. The Neoarchean (3.0-2.5 Ga)	4424
8.21.4. The Proterozoic (2.5-0.542 Ga)	4427
8.21.4.1. The Early and Middle Paleoproterozoic (2.5-1.8 Ga)	4428
8.21.4.2. The Late Paleoproterozoic and Mesoproterozoic (1.8-1.0 Ga)	4430
8.21.4.3. The Early and Middle Neoproterozoic (1.0-0.635 Ga)	4434
8.21.4.4. The Ediacaran Period (0.635-0.542 Ga)	4439
8.21.5. The Phanerozoic (0.542 Ga-Present)	4442
8.21.5.1. Evidence from Marine Evaporites	4442
8.21.5.2. Fluid Inclusions in Marine Halites	4443
8.21.5.3. The Analysis of Unevaporated Seawater in Fluid Inclusions	4446
8.21.5.4. Br- Concentration in Halite	4446
8.21.5.5. The Mineralogy of Marine Oölites and Carbonate Cements	4447
8.21.5.6. Mg2+/Ca2+ and Sr2+/Ca2+ Ratios of Marine Shell-Building Organisms (Echinoderms, Rudists, and Foraminifera)	4448
8.21.5.7. Seawater Mg2+/Ca2+ Ratio and the Carbonate Mineralogy of Shell-Building Organisms	4449
8.21.5.8. Seawater Mg2+/Ca2+ Ratio and Shell-Building Organisms: Experimental Results	4450
8.21.5.9. Models of Phanerozoic Seawater Chemistry	4451
8.21.5.10. The Isotopic Composition of Strontium in Marine Carbonates	4454
8.21.5.11. The Isotopic Composition of Sulfur in Seawater	4456
8.21.5.12. The Isotopic Composition of Calcium in Seawater	4460
8.21.6. Summary	4460
Acknowledgments	4462
References	4462
e9780080983004v9	4474
Front Cover	4474
Sediments, Diagenesis, and Sedimentary Rocks	4477
Copyright	4478
In Memoriam	4479
Heinrich Dieter Holland (1927–2012)	4481
Karl Karekin Turekian (1927–2013)	4483
References	4485
Dedication	4487
Contents	4489
Executive Editors’ Foreword to the Second Edition	4491
Contributors	4495
Volume Editors' Introduction	4497
References	4505
Chapter 9.1: Chemical Composition and Mineralogy of Marine Sediments	4507
9.1.1. Introduction	4507
9.1.2. Pelagic Sediments	4510
9.1.2.1. Equatorial Pacific	4512
9.1.2.2. South Pacific	4513
9.1.2.3. Central Indian Basin	4515
9.1.3. Ferromanganese Nodules and Crusts	4517
9.1.3.1. Equatorial Pacific Nodules	4520
9.1.3.2. Seamount Ferromanganese Crusts from the Central Pacific	4522
9.1.4. Metalliferous Ridge and Basal Sediments	4524
9.1.4.1. Metalliferous Ridge Sediments	4527
9.1.4.2. Metalliferous Basal Sediments	4528
9.1.5. Marine Phosphorites	4528
9.1.6. Conclusions	4532
References	4535
Chapter 9.2: The Recycling of Biogenic Material at the Sea Floor	4539
9.2.1. Introduction	4539
9.2.2. Pore Water Sampling and Profiling	4540
9.2.3. Organic Matter Decomposition in Sediments	4542
9.2.3.1. Electron Acceptors for Sedimentary Organic Matter Oxidation	4542
9.2.3.2. The Stoichiometry of Sedimentary Organic Matter Decomposition	4547
9.2.3.2.1. Pelagic sediments	4548
9.2.3.2.2. Continental margin sediments	4549
9.2.3.3. The Depth Distribution of Organic Matter Oxidation in the Sediment Column	4550
9.2.3.4. The Response Time for Organic Matter Oxidation	4552
9.2.3.5. The Burial of Organic Matter in Marine Sediments	4553
9.2.3.6. Benthic Organic Matter Cycling and Marine Geochemical Cycles	4554
9.2.4. Particle Mixing in Surface Sediments: Bioturbation	4554
9.2.5. CaCO3 Dissolution in Sediments	4556
9.2.5.1. Metabolic Dissolution in Sediments Above the Calcite Lysocline	4556
9.2.5.2. Metabolic Dissolution and the Kinetics of Organic Matter Oxidation	4558
9.2.5.3. CaCO3 Dissolution in Sediments on the Continental Slope and Rise	4559
9.2.5.4. Dissolution in Carbonate-Rich Sediments on the Continental Shelf	4559
9.2.6. Silica Cycling in Sediments	4559
9.2.6.1. Dissolved Silica Profiles in Pore Waters	4559
9.2.6.2. Preservation Efficiency	4560
9.2.6.3. Summary: Silica in Pore Waters and Sediments	4562
9.2.7. Conclusions	4562
References	4563
Chapter 9.3: Formation and Diagenesis of Carbonate Sediments	4567
9.3.1. Introduction	4568
9.3.2. Physical Geochemistry of Carbonate Minerals	4569
9.3.2.1. Preliminary Remarks	4569
9.3.2.2. Carbonic Acid System and Basic Solution Equilibria	4569
9.3.2.3. Major Marine Carbonate Phases	4571
9.3.2.3.1. Magnesian calcite	4572
9.3.2.3.2. Dolomite and related phases	4574
9.3.2.3.3. Aragonite and other related carbonates	4575
9.3.3. Surface Reactions: Review of Theory	4575
9.3.3.1. Preliminary Remarks	4575
9.3.3.2. General Rate Equations	4576
9.3.3.2.1. Crystal growth	4578
9.3.3.2.2. Crystal dissolution	4580
9.3.3.2.3. Reaction rate and cation/anion ratios	4582
9.3.4. New Directions, New Insights	4583
9.3.4.1. Preliminary Remarks	4583
9.3.4.2. Structure of the Cleavage Surface	4583
9.3.4.3. Detail Rate Measurements by Surface Microscopy	4585
9.3.4.3.1. Atomic force microscopy	4585
9.3.4.3.2. Vertical scanning interferometry	4585
9.3.4.4. Growth Measurements	4586
9.3.4.4.1. Saturation state	4586
9.3.4.4.2. Impurities and growth inhibition	4587
9.3.4.4.3. Beyond BCF	4588
9.3.4.5. Dissolution Measurements	4588
9.3.4.5.1. Baseline rates	4589
9.3.4.5.2. Etch-pit morphology and significance	4589
9.3.4.5.3. Dissolution inhibitors	4589
9.3.4.5.4. Magnesite and dolomite dissolution	4590
9.3.4.6. Rate Control by `Indifferent´ Electrolytes	4590
9.3.4.7. Rate Control by Dissolved Ratio of Lattice Ions	4591
9.3.4.8. Concluding Remarks	4592
9.3.5. Sources and Diagenesis of Deep-Sea Carbonates	4592
9.3.5.1. Sources and Sedimentation	4592
9.3.5.2. Distribution of CaCO3 in Deep-Sea Sediments	4593
9.3.5.3. CaCO3 Diagenesis in Deep-Sea Sediments	4594
9.3.5.3.1. General relations	4594
9.3.5.3.2. Early diagenetic processes in deep-sea sediments	4594
9.3.6. Sources and Diagenesis of Shoal-Water Carbonate-Rich Sediments	4596
9.3.6.1. Sources of Shoal-Water Carbonates	4596
9.3.6.1.1. General considerations	4596
9.3.6.1.2. Sources of carbonate muds	4596
9.3.6.1.3. Formation of carbonate sands	4597
9.3.6.2. Early Marine Diagenesis of Shoal-Water Carbonate-Rich Sediments	4597
9.3.6.2.1. Pore-water chemistry	4597
9.3.6.2.2. Precipitation `of early´ carbonate cements	4598
9.3.6.2.3. Dissolution of carbonates	4600
9.3.6.2.4. Carbonate diagenesis associated with reefs	4600
9.3.6.2.5. Early dolomite formation	4601
References	4601
Chapter 9.4: The Diagenesis of Biogenic Silica: Chemical Transformations Occurring in the Water Column, Seabed, and Crust	4609
9.4.1. Introduction	4609
9.4.2. The Precipitation of Biogenic Silica	4610
9.4.3. The Physical Properties of Biogenic Silica	4610
9.4.4. Changes in Biogenic Silica Chemistry Occurring in the Water Column	4611
9.4.5. Diagenesis of Biogenic Silica in the Upper Meter of the Seabed	4612
9.4.5.1. Modeling Biogenic Silica Distributions and Pore-Water Silicate Concentrations	4612
9.4.5.2. Transformation of Biogenic Silica to Authigenic Clay Minerals	4613
9.4.5.3. Preservation of Biogenic Silica in the Seabed	4613
9.4.6. Silica Diagenesis on Timescales of Millions of Years	4614
9.4.6.1. Formation of Opal-CT and Chert	4614
9.4.6.2. Geological Settings for Chert Formation	4616
Acknowledgments	4616
References	4616
Chapter 9.5: Formation and Geochemistry of Precambrian Cherts	4619
9.5.1. Introduction	4619
9.5.1.1. Definition and Importance	4620
9.5.1.2. Fundamental Difference Between Precambrian and Phanerozoic Chert	4621
9.5.1.3. Aspects of Inorganic Geochemistry of Silica	4622
9.5.1.4. Possible Association of Chert and Evaporite	4623
9.5.2. Neoproterozoic and Mesoproterozoic Environments of Chert Formation	4623
9.5.3. Chert of Late Archean and Paleoproterozoic Iron Formation	4624
9.5.3.1. Chert of Lake Superior-Type Iron Formation	4626
9.5.3.2. The End of Major Cherty Iron Formation Deposition	4627
9.5.3.3. Chert of the Transvaal Supergroup and Hamersley Group	4627
9.5.4. Archean Chert and Cherty Iron Formation	4628
9.5.5. Stable Isotopes and Rare Earth Elements in Precambrian Chert and Cherty Iron Formation	4629
9.5.5.1. Silicon Isotope Systematics	4629
9.5.5.2. Raleigh-Type Fractionation of Silicon Isotopes	4630
9.5.5.3. Silicon Isotopic Studies in Early Archean Chert and Temporal Changes in δ30Si	4631
9.5.5.4. Oxygen Isotope Systematics	4634
9.5.5.5. Preservation of the Oxygen Isotope Record in Precambrian Chert	4635
9.5.5.6. Oxygen Isotope Composition of Seawater	4636
9.5.5.7. Hydrogen Isotopes in Precambrian Chert	4637
9.5.5.8. Iron Isotope Systematics	4638
9.5.5.9. Iron and Silicon Isotope Studies of Early Paleoproterozoic Iron Formation	4638
9.5.5.10. Rare Earth Elements as Indicators of Depositional Environments of Cherts and Cherty Iron Formation	4639
9.5.6. Conclusions	4640
Acknowledgments	4641
References	4641
Chapter 9.6: Geochemistry of Fine-Grained, Organic Carbon-Rich Facies	4647
9.6.1. Introduction	4647
9.6.2. Conceptual Model: Processes	4648
9.6.2.1. Detrital Flux	4649
9.6.2.2. Biogenic Flux	4650
9.6.2.3. Authigenic Flux	4651
9.6.2.4. Carbon Cycle and Climate Feedback	4652
9.6.3. Conceptual Model: Proxies	4653
9.6.3.1. Limitations of Proxy Data	4653
9.6.3.2. Detrital Proxies	4654
9.6.3.2.1. Physical methods	4654
9.6.3.2.2. Elemental proxies	4655
9.6.3.3. Biogenic Proxies	4655
9.6.3.3.1. Organic matter sources	4655
9.6.3.3.2. Stable carbon isotopes of organic matter (delta13C)	4656
9.6.3.3.3. Elemental ratios	4656
9.6.3.3.4. Biomarkers	4656
9.6.3.3.5. Accumulation rates	4657
9.6.3.4. Authigenic Proxies	4657
9.6.3.4.1. C-S relationships	4657
9.6.3.4.2. Sulfur isotope relationships	4658
9.6.3.4.3. Iron	4660
9.6.3.4.4. Trace metals	4661
9.6.4. Geochemical Case Studies of Fine-Grained, Organic Carbon-Rich Sediments and Sedimentary Rocks	4663
9.6.4.1. Modern Anoxic Environments of OM Burial: The Black Sea and Cariaco Basin	4663
9.6.4.2. Cretaceous Western Interior Basin	4665
9.6.4.3. Devonian Appalachian Basin	4671
9.6.4.4. Recent Precambrian Advances	4674
9.6.5. Discussion: A Unified View of the Geochemistry of Fine-Grained Organic Carbon-Rich Sediments and Sedim	4674
9.6.5.1. Applicability of the Model	4675
9.6.5.2. Detrital Fluxes and Bulk Sedimentation	4675
9.6.5.3. Productivity and Nutrients	4675
9.6.5.4. Productivity and C Isotope Records	4675
9.6.5.5. Mo, Fe, and Redox Control	4675
9.6.5.6. Elemental Ratios versus Accumulation Rates	4676
9.6.5.7. Future Prospects	4676
Acknowledgments	4676
References	4676
Chapter 9.7: Late Diagenesis and Mass Transfer in Sandstone-Shale Sequences	4687
9.7.1. Introduction	4687
9.7.2. The Realm of `Late Diagenesis´	4688
9.7.3. Elemental Mobility at the Grain Scale	4688
9.7.3.1. Physical Processes	4688
9.7.3.1.1. Compaction	4688
9.7.3.1.2. Fracturing	4689
9.7.3.2. Chemical Processes in Late Diagenesis	4689
9.7.3.2.1. Dissolution	4689
9.7.3.2.2. Cementation	4691
9.7.3.2.3. Replacement	4691
9.7.4. Volumetrically Significant Processes of Late Diagenesis	4692
9.7.4.1. Detrital Feldspar Dissolution and Replacement	4692
9.7.4.2. Dissolution of Detrital Quartz (Pressure Solution)	4696
9.7.4.3. Dissolution of Detrital Carbonate	4697
9.7.4.4. Illitization	4697
9.7.4.5. Quartz Cement	4698
9.7.4.6. Authigenic Calcite	4699
9.7.4.7. Kaolinite and Chlorite	4701
9.7.4.8. Minor Cement and Replacement Phases	4701
9.7.4.9. Summary: Massive Reorganization by Fluid-Mediated Reactions	4702
9.7.5. Whole-Rock Elemental Data and Larger-Scale Elemental Mobility	4703
9.7.5.1. SiO2	4703
9.7.5.2. CaO (and CO2)	4704
9.7.5.3. K2O	4704
9.7.6. Fluid Flow	4704
9.7.7. Reverse Weathering and Concluding Comments	4704
Acknowledgments	4705
References	4705
Chapter 9.8: Coal Formation and Geochemistry	4713
9.8.1. Introduction	4713
9.8.2. Coal Formation	4714
9.8.2.1. Peat Formation and Early Diagenesis	4714
9.8.2.2. Coalification, Early Stage (Lignite, Brown Coal)	4719
9.8.2.3. Coalification, Late Stage (Subbituminous, Bituminous, Anthracite)	4721
9.8.3. Coal Rank	4721
9.8.4. Structure of Coal	4722
9.8.5. Hydrocarbons from Coal	4723
9.8.5.1. Liquid Hydrocarbons (Oil)	4723
9.8.5.2. Natural Gas	4724
9.8.6. Inorganic Geochemistry of Coal	4726
9.8.6.1. Abundance of Elements	4726
9.8.6.2. Mineralogy	4728
9.8.6.3. Modes of Occurrence	4729
9.8.7. Geochemistry of Coal Utilization	4731
9.8.8. Economic Potential of Metals from Coal	4731
9.8.9. Inorganics in Coal as Indicators of Depositional Environments	4731
9.8.10. Environmental Impacts	4732
9.8.10.1. Coal Combustion	4732
9.8.10.1.1. Sulfur emissions	4732
9.8.10.1.2. Nitrogen emissions	4732
9.8.10.1.3. Carbon dioxide emissions	4733
9.8.10.1.4. Emission of particulates	4733
9.8.10.1.5. Emission of trace elements	4733
9.8.10.1.6. Emission of organic compounds	4733
9.8.10.2. Environmental Impacts of Mining and Disposal of Coal Wastes	4733
9.8.10.3. Disposal of Solid Wastes from Coal Utilization	4733
9.8.10.4. Human Health	4733
9.8.11. Conclusions	4734
References	4735
Chapter 9.9: Formation and Geochemistry of Oil and Gas	4739
9.9.1. Introduction	4739
9.9.2. The Early Steps in Oil and Gas Formation: Where Does It All Begin?	4739
9.9.3. Insoluble Organic Material - Kerogen	4741
9.9.4. Soluble Organic Material	4744
9.9.4.1. Source	4746
9.9.4.2. Depositional Environments	4747
9.9.4.3. Maturity	4750
9.9.4.4. Biodegradation	4753
9.9.4.5. Age Dating	4754
9.9.4.6. Migration	4754
9.9.5. Geochemistry and Sequence Stratigraphy	4755
9.9.5.1. Lowstand System Tract	4755
9.9.5.2. Transgressive System Tract	4755
9.9.5.3. Condensed Section	4755
9.9.5.4. Highstand System Tract	4756
9.9.6. Fluid Inclusions	4757
9.9.7. Reservoir Geochemistry	4757
9.9.8. Basin Modeling	4759
9.9.9. Natural Gas	4763
9.9.10. Surface Prospecting	4765
9.9.11. Summary	4766
References	4766
Chapter 9.10: The Sedimentary Sulfur System: Biogeochemistry and Evolution through Geologic Time	4773
9.10.1. Introduction	4774
9.10.2. Sulfur in Sediments	4775
9.10.2.1. Forms of Sulfur in Sediments and Sedimentary Rocks	4776
9.10.2.1.1. Dissolved reduced sulfur species in sedimentary sulfide systems	4777
9.10.2.1.2. Iron sulfide minerals in sedimentary sulfide systems	4778
9.10.2.1.2.1. Iron(II) monosulfide: mackinawite	4778
9.10.2.1.2.2. Iron thiospinel, greigite	4779
9.10.2.1.2.3. Pyrite, FeS2p	4780
9.10.2.1.2.4. Cubic FeSc	4780
9.10.2.1.2.5. Troilite (FeSt) and the pyrrhotite group	4781
9.10.2.1.2.6. Smythite, rhombohedral Fe1-xSs	4781
9.10.2.1.2.7. Marcasite, orthorhombic FeS2m	4781
9.10.2.2. Distribution of Iron Sulfides in Sediments	4782
9.10.2.2.1. Observations of iron sulfide minerals in sediments	4782
9.10.2.2.2. Distribution of iron sulfide minerals in sediments	4783
9.10.3. Pyrite Formation in Sediments	4783
9.10.3.1. Thermodynamics of Sedimentary Pyrite Formation	4783
9.10.3.2. Mechanisms of Pyrite Formation	4785
9.10.3.3. Kinetics of Sedimentary Pyrite Formation	4786
9.10.4. Other Forms of Sulfur in Sediments	4787
9.10.4.1. Distribution of S8 in Sediments	4787
9.10.4.2. Sulfur in Suboxic Sedimentary Systems	4788
9.10.5. Reactive Iron	4789
9.10.5.1. The Nature of Nonsulfide Fe in Sediments	4789
9.10.5.2. Degree of Pyritization	4791
9.10.5.3. The Reactive Iron Shuttle	4791
9.10.5.4. Iron Isotopic Fractionation in Sulfidic Sediments	4792
9.10.5.5. Secular Variations in the Iron Isotopic Composition of Sedimentary Pyrite	4793
9.10.6. Microbial Ecology	4793
9.10.6.1. Microbial Sulfur Transformations	4793
9.10.6.2. Microbial Sulfate Reduction	4794
9.10.6.3. Microbiological Sulfate Reduction Rates (SRR)	4796
9.10.6.4. Iron Sulfides in Microorganisms	4796
9.10.6.5. Molecular Phylogeny of Sulfur Microorganisms in Sediments	4797
9.10.6.6. Syntrophy in the Sedimentary Sulfur System	4797
9.10.6.7. Microbial Sulfide Oxidation in Sediments	4798
9.10.6.8. Sulfur Disproportionating Organisms	4799
9.10.6.9. Microbial Stratigraphy: Biofilms and Microbial Mats	4799
9.10.6.10. Global Distribution of Sulfate-Reducing Microorganisms	4800
9.10.7. Evolution of the Sulfur Biome	4802
9.10.7.1. Sulfur Isotopic Fractionation by Microbial Sulfate Reduction	4802
9.10.7.2. Oxygen Isotope Fractionation During Sulfate Reduction and Sulfide Oxidation	4803
9.10.7.3. Microbial Disproportionation of Intermediate Sulfur Compounds	4803
9.10.7.4. Evolution of the Sulfur Biome from Sedimentary Sulfur Stable Isotope Geochemistry	4803
9.10.7.5. Carbon Isotopes	4804
9.10.7.6. Molecular Fossils: Sedimentary Biomarkers for Ancient Sulfur Microbes	4805
9.10.7.7. Molecular Biological Probes of the Evolution of the Sulfur Biome	4805
9.10.8. Euxinic Systems	4806
9.10.8.1. Oceanic Euxinic Conditions	4806
9.10.8.2. Sulfide Distribution in Natural Waters	4807
9.10.8.3. Proxies for Euxinia	4807
9.10.8.3.1. Sediment S/Corg ratios	4807
9.10.8.3.2. Biogenic silica	4808
9.10.8.3.3. Degree of pyritization	4808
9.10.8.3.4. Degree of sulfidation	4808
9.10.8.3.5. Reactive Fe content (FeHR)	4808
9.10.8.3.6. Pyrite framboid size	4809
9.10.8.3.7. Organic carbon:phosphate ratios, Corg/P	4809
9.10.8.3.8. Trace elements	4809
9.10.8.4. Sulfur Stable Isotopes in Euxinic Sediments	4809
9.10.8.5. Molybdenum Isotopes	4810
9.10.8.6. Other Stable Isotopes	4810
9.10.8.7. Biomarker Proxies	4811
9.10.9. The Geochemistry of Sulfidic Sedimentary Rocks	4811
9.10.9.1. Black Shales over the Last 200 Ma	4812
9.10.9.2. Paleozoic Black Shales	4813
9.10.9.3. Distribution of Black Shales in the Proterozoic	4814
9.10.9.4. Archean Sulfidic Sediments	4816
9.10.10. Geochemical Evolution of Sulfur-Based Sediments	4817
9.10.10.1. Mass-Independent Fractionation (MIF) of Sulfur Isotopes	4817
9.10.10.2. Sulfur-Rich Sediments and the History of Oceanic Oxygen	4818
9.10.10.3. The History of Marine Sulfate Concentration	4819
9.10.10.4. Variations in the Geochemistry of Sulfur-Rich Sediments through Geologic Time	4820
Acknowledgments	4821
References	4821
Chapter 9.11: Manganiferous Sediments, Rocks, and Ores	4833
9.11.1. Chemical Fundamentals	4833
9.11.2. Distribution of Manganese in Rocks and Natural Waters	4837
9.11.3. Common Manganese Minerals	4838
9.11.4. Composition of Manganese Accumulations	4840
9.11.5. Behavior of Manganese in Igneous Settings, Especially Mid-Ocean Ridge Vents	4843
9.11.6. Behavior of Manganese in Sedimentation	4845
9.11.6.1. Manganese Nodules and Crusts in Modern Sediments	4845
9.11.6.2. Manganese Carbonates in Modern Sediments	4845
9.11.7. Two Models of Sedimentary Manganese Mineralization	4846
9.11.8. Behavior in Soils and Weathering	4848
9.11.8.1. Manganese in Uncontaminated Soils	4848
9.11.8.2. Manganese in Soils Affected by Mining and Smelting	4850
9.11.9. Manganese through Geologic Time	4850
9.11.10. Conclusions	4851
References	4851
Chapter 9.12: Green Clay Minerals	4857
9.12.1. What Are We Looking At?	4857
9.12.1.1. The Cycle of Transformation	4858
9.12.1.2. Geologic Conditions of Green Clay Stability	4858
9.12.2. Description of Green Clay Minerals	4859
9.12.2.1. Potassic Green Clays (Mica-Based Structures)	4859
9.12.2.1.1. Glauconites	4859
9.12.2.1.2. Celadonite	4861
9.12.2.1.3. Summary of potassic green clays	4863
9.12.2.2. Ferrous, Green Clays	4863
9.12.2.2.1. Occurrence of berthiérine and verdine minerals	4863
9.12.2.2.2. Chamosite	4866
9.12.3. Nonchlorite, Nonmicaceous Green Clay Minerals	4866
9.12.3.1. Nontronite	4866
9.12.3.2. Talc	4867
9.12.4. Geochemical Origin of Green Clays	4867
9.12.4.1. Shallow Ocean Bottom, Marine Green Clays - Glauconite and Berthiérine	4867
9.12.4.2. Alteration Environments	4868
9.12.4.3. Diagenesis Reactions	4868
9.12.5. General Reflections	4869
References	4869
Chapter 9.13: Chronometry of Sediments and Sedimentary Rocks	4871
9.13.1. Introduction	4871
9.13.2. Chronometry Based on the Fossil Record - First Steps	4871
9.13.3. Refinements in Chronometry Using Fossils	4875
9.13.4. Oil Recovery in California Using Fossil-Based Chronometry	4877
9.13.5. Principles of Chorology: The Science of the Distribution of Organisms	4878
9.13.6. Constraints on Chronometry Imposed by Chorology	4882
9.13.7. Radiochronometry	4885
9.13.8. Magnetic Field Polarity and Chronometry	4886
9.13.9. Orbital Chronometry	4887
9.13.9.1. Aurichorology - The Golden Spikes and Global Statotype Section and Points	4888
9.13.10. Terminologies	4889
9.13.11. Summary	4889
References	4890
Chapter 9.14: The Geochemistry of Mass Extinction	4891
9.14.1. Introduction	4891
9.14.2. Isotope Records of the Major Mass Extinctions	4892
9.14.2.1. Carbon Isotope Record	4892
9.14.2.2. Sulfur Isotope Record	4892
9.14.2.3. Strontium Isotope Record	4893
9.14.2.4. Oxygen Isotope Record	4894
9.14.3. Interpreting the Geochemical Records of Mass Extinction	4894
9.14.3.1. Late Ordovician	4894
9.14.3.2. Late Devonian	4897
9.14.3.3. Permian-Triassic	4897
9.14.3.4. Triassic-Jurassic	4898
9.14.3.5. Cretaceous-Tertiary	4898
9.14.4. Summary with Extensions	4899
9.14.4.1. Paleozoic Suffocation	4899
9.14.4.2. Mesozoic Menace	4900
Acknowledgments	4901
References	4901
Chapter 9.15: Evolution of Sedimentary Rocks	4905
9.15.1. Introduction	4905
9.15.2. The Earth System	4906
9.15.2.1. Population Dynamics	4906
9.15.3. Generation and Recycling of the Oceanic and Continental Crust	4907
9.15.4. Global Tectonic Realms and Their Recycling Rates	4908
9.15.5. Present-Day Sedimentary Shell	4909
9.15.6. Tectonic Settings and Their Sedimentary Packages	4910
9.15.7. Petrology, Mineralogy, and Major Element Composition of Clastic Sediments	4911
9.15.7.1. Provenance	4911
9.15.7.2. Transport Sorting	4912
9.15.7.3. Sedimentary Recycling	4913
9.15.8. Trace Element and Isotopic Composition of Clastic Sediments	4913
9.15.9. Secular Evolution of Clastic Sediments	4914
9.15.9.1. Tectonic Settings and Lithology	4914
9.15.9.2. Chemistry	4914
9.15.9.3. Isotopes	4916
9.15.10. Sedimentary Recycling	4917
9.15.11. Ocean/Atmosphere System	4917
9.15.11.1. The Chemical Composition of Ancient Ocean	4918
9.15.11.2. Isotopic Evolution of Ancient Oceans	4919
9.15.11.2.1. Strontium isotopes	4919
9.15.11.2.2. Osmium isotopes	4922
9.15.11.2.3. Sulfur isotopes	4922
9.15.11.2.4. Carbon isotopes	4924
9.15.11.2.5. Oxygen isotopes	4927
9.15.11.2.6. Isotope tracers in developmental stages	4929
9.15.12. Major Trends in the Evolution of Sediments during Geologic History	4929
9.15.12.1. Overall Pattern of Lithologic Types	4929
9.15.12.2. Phanerozoic Carbonate Rocks	4930
9.15.12.2.1. Mass-age distribution and recycling rates	4930
9.15.12.2.2. Dolomite/calcite ratios	4932
9.15.12.2.3. Ooids and ironstones	4934
9.15.12.2.4. Calcareous shelly fossils	4935
9.15.12.2.5. The carbonate cycle in the ocean	4936
9.15.12.3. Geochemical Implications of the Phanerozoic Carbonate Record	4936
Acknowledgment	4937
References	4937
Chapter 9.16: Stable Isotopes in the Sedimentary Record	4943
9.16.1. Introduction	4943
9.16.2. Isotopic Concentration Units and Fractionation	4947
9.16.3. Hydrogen and Oxygen Isotopes in the Water Cycle	4948
9.16.4. Hydrogen and Oxygen Fractionation in Clays, Water, and Carbonates	4951
9.16.4.1. Illite and Kaolinite Reactions with Water	4952
9.16.4.2. Other Clay-Water Reactions	4953
9.16.4.3. δ18O in Carbonates	4955
9.16.5. Calcium Isotopes in Seawater and Carbonates	4956
9.16.6. Carbon Isotopes in Carbonates and Organic Matter	4959
9.16.6.1. Storage of Carbonates and Organic Matter	4960
9.16.6.2. Long-Term Trends of Carbonate Sediments	4962
9.16.7. Nitrogen Isotopes in Sedimentary Environment	4965
9.16.7.1. Specific Analytical Aspects	4966
9.16.7.2. N in the Mantle and Igneous Environment	4966
9.16.7.3. N in Sedimentary Rocks	4968
9.16.7.4. N in Oceanic Sediments and Particulate Matter	4968
9.16.7.5. Anthropogenic Effects	4970
9.16.8. Sulfur Isotopes in Sedimentary Sulfate and Sulfide	4971
9.16.9. Boron Isotopes at the Earth's Surface	4973
9.16.9.1. Ocean Water	4974
9.16.9.2. Ground- and River Waters	4975
9.16.9.3. Oceanic Sediments	4976
9.16.9.4. Clay Mineral-Water Exchange	4976
9.16.10. 40Ar in the Clay Fraction of Sediments	4977
9.16.10.1. 40Ar in Clay Diagenesis	4977
9.16.10.2. Clay Particle Size and K-Ar Apparent Age	4978
9.16.10.3. 40Ar Loss in Thermal Events	4981
9.16.10.4. 40Ar Flux from Sediments	4981
Acknowledgments	4983
References	4983
Chapter 9.17: Geochemistry of Evaporites and Evolution of Seawater	4989
9.17.1. Introduction	4990
9.17.2. Definition of Evaporites	4990
9.17.3. Brines and Evaporites	4990
9.17.4. Environment of Evaporite Deposition	4991
9.17.4.1. Evaporation	4992
9.17.4.2. Freezing	4992
9.17.4.3. Brine (Evaporating Waters)	4993
9.17.4.4. Salinity	4993
9.17.4.5. Temperature	4994
9.17.4.6. Heliothermal Effect	4995
9.17.4.7. pH	4995
9.17.5. Seawater as a Salt Source for Evaporites	4995
9.17.6. Evaporite and Saline Minerals	4996
9.17.7. Model of Marginal Marine Evaporite Basin	4997
9.17.7.1. Conceptual Model of the Basin	4998
9.17.7.2. Quantitative Model of the Basin	5001
9.17.8. Mode of Evaporite Deposition	5002
9.17.9. Primary and Secondary Evaporites	5004
9.17.10. Evaporation of Seawater - Experimental Approach	5005
9.17.11. Crystallization Sequence before K–Mg Salt Precipitation	5005
9.17.11.1. Early Salinity Rise - Calcium Carbonate Precipitation	5005
9.17.11.2. Gypsum Crystallization Field	5007
9.17.11.3. Halite Crystallization Field	5007
9.17.12. Crystallization Sequence of K–Mg Salts	5009
9.17.12.1. Natural Crystallization	5009
9.17.12.2. Theoretical Crystallization Paths	5010
9.17.13. Isotopic Effects in Evaporating Seawater Brines and Evaporite Salts	5011
9.17.14. Usiglio Sequence - A Summary	5011
9.17.15. Principles and Record of Chemical Evolution of Evaporating Seawater	5011
9.17.15.1. Principle of the Chemical Divide for Seawater	5011
9.17.15.2. Jänecke Diagrams	5013
9.17.15.3. Spencer Triangle	5014
9.17.16. Evaporation of Seawater - Remarks on Theoretical Approaches	5015
9.17.17. Sulfate Deficiency in Ancient K-Mg Evaporites	5015
9.17.17.1. Sulfate Deficiency as the Secondary Feature	5017
9.17.17.2. Sulfate Deficiency as a Record of Ancient Seawater Composition	5019
9.17.18. Ancient Ocean Chemistry Interpreted from Evaporites	5020
9.17.18.1. Implications from Evaporite Mineralogy and from Usiglio Sequence	5020
9.17.18.2. Implications of Primary Evaporite Minerals (Excluding Implications from Fluid Inclusions)	5022
9.17.19. Recognition of Ancient Marine Evaporites	5022
9.17.19.1. Sedimentological Criteria	5023
9.17.19.2. Mineralogical Criteria	5023
9.17.19.3. Geochemical Criteria	5023
9.17.20. Fluid Inclusions Reveal the Composition of Ancient Brines	5024
9.17.20.1. Criteria for Seawater Recognition in Halite Fluid Inclusions	5025
9.17.20.2. Reconstruction of Ancient Seawater Composition from Halite Fluid Inclusions	5026
9.17.21. Ancient Ocean Chemistry from Halite Fluid Inclusions - Summary and Comments	5029
9.17.22. Salinity of Ancient Oceans	5036
9.17.23. Evaporite Deposition through Time	5037
9.17.23.1. Late Ediacaran-Phanerozoic Marine Evaporites	5038
9.17.23.2. Precambrian (Pre-Ediacaran) Marine Evaporites	5042
9.17.23.3. Nonmarine Evaporites in Precambrian	5050
9.17.23.4. Pseudomorphs after Evaporite Minerals in Precambrian	5050
9.17.24. Significance of Evaporites in the Earth History	5052
9.17.24.1. Paleogeographic Indicators	5052
9.17.24.2. Seals for Hydrocarbons and More (Evaporites and Hydrocarbons)	5052
9.17.24.3. Halotectonics	5053
9.17.24.4. Diagenesis and Metamorphism of Evaporites	5053
9.17.25. Summary	5053
Acknowledgments	5054
References	5054
Chapter 9.18: Iron Formations: Their Origins and Implications for Ancient Seawater Chemistry	5067
9.18.1. Introduction	5068
9.18.2. Definition of IF	5069
9.18.3. Mineralogy of IF	5072
9.18.3.1. Precursor Sediments	5074
9.18.3.1.1. Secular trend in Fe mineralogy of GIFs	5075
9.18.4. Depositional Setting and Sequence-Stratigraphic Framework	5075
9.18.4.1. Basin-Type Control on IF Deposition	5077
9.18.4.2. Sedimentation Rates	5078
9.18.5. IF: A Proxy for Ancient Seawater Composition	5079
9.18.5.1. Trace Elements	5079
9.18.5.1.1. Rare earth elements	5079
9.18.5.1.2. Phosphorus	5080
9.18.5.1.3. Nickel	5083
9.18.5.1.4. Chromium	5083
9.18.5.2. Stable Isotope Studies of IF	5085
9.18.5.2.1. Traditional light stable isotopes	5085
9.18.5.2.2. Nontraditional stable isotopes	5087
9.18.5.2.2.1. Fe isotopes	5087
9.18.5.2.2.2. Chromium isotopes	5089
9.18.5.2.2.3. Silicon isotopes in chert and IF bands	5089
9.18.6. Perspective from the Modern Iron Cycle	5090
9.18.6.1. Hydrothermal Pulses of Si Synchronous with Fe Addition to Seawater	5092
9.18.6.2. Oxidation Mechanism: Biological versus Nonbiological	5092
9.18.6.2.1. Oxidation of Fe(II) by cyanobacterial O2	5094
9.18.6.2.2. Metabolic Fe(II) oxidation	5094
9.18.6.2.3. Ultraviolet photooxidation of Fe(II)	5095
9.18.7. Secular Trends for Exhalites, IFs, and VMS Deposits	5095
9.18.7.1. Relationships among Mantle Plumes, IF	5095
9.18.7.2. Secular Patterns in Precambrian VMS-Related Exhalites	5097
9.18.7.3. Secular Patterns in Sedimentary Iron Deposits	5098
9.18.7.3.1. Eoarchean IFs	5098
9.18.7.3.2. Paleoarchean IFs	5098
9.18.7.3.3. Neoarchean to Mesoarchean IFs	5098
9.18.7.3.4. Neoarchean IFs	5099
9.18.7.3.5. IFs deposited after the GOE and before 1.93Ga	5099
9.18.7.3.6. C.1.93-1.85Ga IFs coeval with large VMS de	5100
9.18.7.3.7. Proterozoic age gap in major IF deposition	5102
9.18.7.3.8. Neoproterozoic manganese deposits and IFs	5103
9.18.7.3.9. Phanerozoic ironstones, anoxic events, and VMS deposits	5104
9.18.8. Controls on IF Deposition	5106
9.18.8.1. Influence of Hydrothermal Processes on Ocean Composition and Organic Productivity	5108
9.18.8.2. Implications for Atmospheric Oxidation	5111
9.18.9. Euxinic Conditions Induced by Shift in Dissolved Fe/S Ratio of Seawater due to Iron Oxidation	5111
9.18.10. Research Perspectives and Future Directions	5112
Appendix 1. Precambrian Banded Iron Formations, Granular Iron Formations, and Rapitan-Type Iron Formationsa	5113
Appendix 2. Exhalites Associated with Precambrian Deep-Water (Cu-Rich) Volcanogenic Massive Sulfide Depositsa	5120
References	5123
Chapter 9.19: Bedded Barite Deposits: Environments of Deposition, Styles of Mineralization, and Tectonic Settings	5135
9.19.1. Introduction	5135
9.19.1.1. Modern Deposits of Massive Barite	5136
9.19.1.2. Ancient Deposits of Massive Barite	5137
9.19.1.3. Setting I. Continental Rifts (e.g., Red Dog)	5138
9.19.1.3.1. Regional setting	5139
9.19.1.3.2. Mudstone host	5140
9.19.1.3.3. Volcanic rocks	5141
9.19.1.3.4. Mineralization	5141
9.19.1.3.5. Fluid flow	5143
9.19.1.4. Setting II. Transtensional Basins (e.g., California Borderland)	5144
9.19.1.4.1. Regional setting	5144
9.19.1.4.2. Mudstone host	5145
9.19.1.4.3. Volcanic rocks	5146
9.19.1.4.4. Mineralization	5147
9.19.1.4.5. Fluid flow	5148
9.19.1.5. Setting III. Accretionary Prisms (e.g., Arkansas)	5150
9.19.1.5.1. Regional setting	5150
9.19.1.5.2. Mudstone host	5150
9.19.1.5.3. Volcanic rocks	5151
9.19.1.5.4. Mineralization	5152
9.19.1.5.5. Fluid flow	5153
9.19.2. Comparisons	5154
9.19.2.1. Environments of Deposition	5155
9.19.2.2. Mineralization	5155
9.19.2.3. Tectonic Setting	5155
9.19.3. The Nevada Barites: A Test Case	5155
9.19.3.1. Host Strata	5155
9.19.3.2. Mineralization	5156
9.19.3.3. Tectonic Setting	5157
9.19.4. Summary	5157
Acknowledgments	5159
References	5159
e9780080983004v10	5163
Front Cover	5163
Biogeochemistry	5166
Copyright	5167
In Memoriam	5168
Heinrich Dieter Holland (1927–2012)	5170
Karl Karekin Turekian (1927–2013)	5172
References	5174
Dedication	5176
Contents	5178
Executive Editors’ Foreword to the Second Edition	5180
Contributors	5184
Volume Editors’ Introduction	5186
References	5188
Chapter 10.1: The Early History of Life	5190
10.1.1. Introduction	5191
10.1.1.1. Strangeness and Familiarity - the Youth of the Earth	5191
10.1.1.2. Evidence in Rocks, Moon, Planets, and Meteorites - the Sources of Information	5191
10.1.1.3. Reading the Palimpsests – Using Evidence from the Modern Earth and Biology to Reconstruct the Ancestors and their Home	5192
10.1.1.4. Modeling - The Problem of Taking Fragments of Evidence and Rebuilding the Childhood of the Planet	5192
10.1.1.5. What Does a Planet Need to be Habitable?	5193
10.1.1.6. The Power of Biology: The Infinite Improbability Drive	5193
10.1.2. The Chaotian and Hadean (~4.56–4.0 Ga Ago)	5194
10.1.2.1. Definition of the Chaotian	5194
10.1.2.2. Definition of the Hadean	5194
10.1.2.3. Building a Habitable Planet	5194
10.1.2.4. The Hadean Geological Record	5196
10.1.2.5. When and Where Did Life Start?	5197
10.1.3. The Archean (~4-2.5Ga Ago)	5197
10.1.3.1. Definition of Archean	5197
10.1.3.2. The Archean Record	5198
10.1.3.2.1. Greenland	5198
10.1.3.2.2. Barberton	5198
10.1.3.2.3. Western Australia	5198
10.1.3.2.4. Steep Rock, Ontario, and Pongola, South Africa	5199
10.1.3.2.5. Belingwe	5200
10.1.4. The Functioning of the Earth System in the Archean	5201
10.1.4.1. The Physical State of the Archean Planet	5201
10.1.4.2. The Surface Environment	5202
10.1.5. Life: Early Setting and Impact on the Environment	5203
10.1.5.1. Origin of Life	5203
10.1.5.2. RNA World	5204
10.1.5.3. Hydrothermal World	5204
10.1.5.4. LUCA - The Last Common Ancestor	5204
10.1.5.5. A Hyperthermophile Heritage?	5208
10.1.5.6. Metabolic Strategies	5209
10.1.6. The Early Biomes	5210
10.1.6.1. Location of Early Biomes	5210
10.1.6.2. Methanogenesis: Impact on the Environment	5210
10.1.6.3. Prephotosynthetic Ecology	5211
10.1.6.4. Geological Settings of the Early Biomes	5212
10.1.7. The Evolution of Photosynthesis	5213
10.1.7.1. The Chain of Photosynthesis	5213
10.1.7.2. The Rubisco Fingerprint	5214
10.1.7.3. The Evolutionary Chain	5215
10.1.7.4. Anoxygenic Photosynthesis	5216
10.1.7.5. Oxygenic Photosynthesis	5217
10.1.7.6. Archean Oxygen	5218
10.1.8. Mud-Stirrers: Origin and Impact of the Eucarya	5219
10.1.8.1. The Ancestry of the Eucarya	5219
10.1.8.2. The Last Eukaryote Common Ancestor: Possible Settings for the Eukaryote Endosymbiotic Event	5221
10.1.8.3. Water and Mud Stirring - Consequences	5222
10.1.9. The breath of Life: The Impact of Life on the Ocean/Atmosphere System	5223
10.1.9.1. The Breath of Life	5223
10.1.9.2. Oxygen and Carbon Dioxide	5223
10.1.9.3. Nitrogen and Fixed Nitrogen	5224
10.1.9.4. Methane	5225
10.1.9.5. Sulfur and Biology	5225
10.1.10. Feedback from the Biosphere to the Physical State of the Planet	5225
Acknowledgments	5226
References	5226
Chapter 10.2: Evolution of Metabolism	5232
10.2.1. Introduction	5232
10.2.2. The Domains of Life	5232
10.2.3. Life and Rocks	5233
10.2.4. Mechanisms for Energy Conservation	5233
10.2.5. Extant Patterns of Metabolism	5235
10.2.5.1. Kinds of Phototrophs	5236
10.2.5.2. Lithotrophic Energy Sources	5237
10.2.5.3. Carbon Sources for Life	5237
10.2.5.4. Fermentative and Respiratory Metabolism	5238
10.2.6. Reconstructing the Evolution of Metabolism	5239
10.2.6.1. Approaches Employing Genomics and Molecular Genetics	5239
10.2.6.2. Approaches Employing Geochemical and Geophysical Methods	5240
10.2.6.2.1. Physical fossils	5240
10.2.6.2.2. Signature molecules	5241
10.2.6.2.3. Inorganic chemistry of sediments	5241
10.2.6.2.4. Stable isotope fractionation	5242
10.2.6.2.5. Carbon isotopes	5242
10.2.6.2.6. Sulfur isotopes	5244
10.2.6.2.7. Nitrogen isotopes	5244
10.2.6.2.8. Iron isotopes	5244
10.2.7. Overview	5245
References	5246
Chapter 10.3: Sedimentary Hydrocarbons, Biomarkers for Early Life	5250
10.3.1. Introduction	5250
10.3.2. Biomarkers as Molecular Fossils	5251
10.3.2.1. The Fate of Dead Biomass: Diagenesis, Catagenesis, and Metagenesis	5251
10.3.2.2. Compound-Specific Stable Isotopes	5253
10.3.3. Thermal Stability and Maturity of Biomarkers	5253
10.3.3.1. Biomarkers as Maturity Indicators	5253
10.3.3.2. The Survival of Biomarkers with Increasing Temperature and Time	5254
10.3.4. Experimental Approaches to Biomarker and Kerogen Analysis	5256
10.3.5. Discussion of Biomarkers by Hydrocarbon Class	5257
10.3.5.1. Advantages and Limitations of the Biomarker Approach	5257
10.3.5.2. n-Alkanes, Algaenans, and other Polymethylenic Biopolymers	5257
10.3.5.3. Methyl and Ethyl Alkanes	5259
10.3.5.4. Alkyl Cyclohexanes and Cyclopentanes	5260
10.3.5.5. Isoprenoids	5260
10.3.5.6. Carotenoids	5263
10.3.5.6.1. Aromatic carotenoids and arylisoprenoids	5264
10.3.5.6.2. Bacterioruberin	5267
10.3.5.7. Chlorophylls and Maleimides	5267
10.3.5.8. Sesquiterpanes (C15) and Diterpanes (C20)	5268
10.3.5.9. Cheilanthanes and other Tricyclic Polyprenoids	5270
10.3.5.10. Hopanoids and other Pentacyclic Triterpanes	5270
10.3.5.11. Steroid Hydrocarbons	5273
10.3.6. Reconstruction of Ancient Biospheres: Biomarkers for the Three Domains of Life	5276
10.3.6.1. Bacteria	5276
10.3.6.1.1. Hopanoids as biomarkers for bacteria	5276
10.3.6.1.2. Cyanobacteria	5276
10.3.6.1.3. Methanotrophs, methylotrophs, and acetic acid bacteria	5276
10.3.6.1.4. Phototrophic sulfur bacteria	5276
10.3.6.2. Archaea	5277
10.3.6.2.1. Methanogens	5277
10.3.6.2.2. Biomarkers and ecology at marine methane seeps	5277
10.3.6.2.3. Halobacteria	5278
10.3.6.2.4. Marine Crenarchaeota	5278
10.3.6.3. Eukarya	5278
10.3.7. Biomarkers as Environmental Indicators	5278
10.3.7.1. Marine versus Lacustrine Conditions	5278
10.3.7.2. Hypersaline Conditions	5279
10.3.7.3. Anoxic and Euxinic Conditions	5280
10.3.7.4. Carbonates versus Clay-rich Sediments	5280
10.3.7.5. Paleotemperature and Paleolatitude Biomarkers	5281
10.3.8. Age Diagnostic Biomarkers	5281
10.3.9. Biomarkers in Precambrian Rocks	5281
10.3.9.1. Biomarkers in the Proterozoic (0.54-2.5 Ga)	5281
10.3.9.2. Biomarkers Extracted from Archean Rocks (>2.5 Ga)	5282
10.3.10. Outlook	5283
Acknowledgments	5283
References	5283
Chapter 10.4: Biomineralization	5294
10.4.1. Introduction	5295
10.4.1.1. Outline of the Chapter	5295
10.4.1.2. Definitions and General Background on Biomineralization	5296
10.4.2. Biominerals	5297
10.4.2.1. Calcium Carbonates	5297
10.4.2.1.1. Calcite	5297
10.4.2.1.2. Aragonite	5297
10.4.2.1.3. Vaterite	5299
10.4.2.2. Silica	5300
10.4.2.2.1. Opal	5300
10.4.2.3. Bioapatite	5301
10.4.2.4. Iron Oxides and Hydroxides	5303
10.4.2.4.1. Magnetite	5303
10.4.3. Examples of Biomineralization	5304
10.4.3.1. Introduction	5304
10.4.3.2. Sulfur Biomineralization	5305
10.4.3.2.1. Sulfur oxidizers	5305
10.4.3.2.2. Sulfate reducers	5305
10.4.3.2.3. Formation of elemental sulfur	5305
10.4.3.2.4. Sulfate biomineralization	5306
10.4.3.3. Iron Biomineralization	5306
10.4.3.3.1. Roles of iron in archaea and bacteria	5306
10.4.3.3.2. Bacterial iron mineral formation	5306
10.4.3.3.3. Magnetotactic bacteria	5307
10.4.3.4. Carbonate Biomineralization	5307
10.4.3.4.1. Cyanobacteria	5309
10.4.3.4.2. Cnidaria (coelenterates)	5310
10.4.3.4.2.1. Corals	5310
10.4.3.4.2.2. Other taxa that biomineralize	5310
10.4.3.4.3. Coccoliths	5311
10.4.3.4.3.1. E. huxleyi: Intracellular calcification	5311
10.4.3.4.4. Foraminifera	5311
10.4.3.4.5. Echinoids	5313
10.4.3.4.6. Mollusks	5314
10.4.3.4.6.1. Bivalves	5314
10.4.3.4.6.2. Bivalve shell architecture	5314
10.4.3.4.6.3. Chitons	5314
10.4.3.4.6.4. Teeth of chitons	5316
10.4.3.4.7. Arthropods	5316
10.4.3.4.7.1. Crustacea exoskeleton: The carapace	5317
10.4.3.4.7.2. Gastroliths	5317
10.4.3.5. Silica Biomineralization	5317
10.4.3.5.1. Radiolarians	5318
10.4.3.5.2. Diatoms	5319
10.4.3.5.3. Sponges	5321
10.4.3.5.4. Plant biominerals	5323
10.4.3.5.4.1. Silica in plants	5323
10.4.3.5.5. Phytoliths: Indicators of the environment and paleoenvironment	5327
10.4.3.5.5.1. Radiocarbon dating using plant biominerals	5329
10.4.3.5.5.2. Stable isotope investigations on plant biominerals	5329
10.4.3.5.6. Bones and bone tissues	5329
10.4.3.5.6.1. Biomineralization of bone: The bone morphogenic unit	5329
10.4.3.5.6.2. Bone cells and products: Collagen	5332
10.4.3.5.6.3. Matrix-mediated biomineralization and other possibilities	5333
10.4.3.5.6.4. Analyses of the bone	5335
10.4.3.5.7. Cartilage	5335
10.4.3.5.7.1. Biomineralization of cartilage	5337
10.4.3.5.8. Antlers	5337
10.4.3.5.9. Teeth	5337
10.4.3.5.9.1. Introduction	5337
10.4.3.5.9.2. Tooth biology and mineralogy	5339
10.4.3.5.10. Otoliths	5341
10.4.4. Summary: Why Biomineralize?	5341
10.4.4.1. Physical or Macrobiomineralization Contributions	5341
10.4.4.1.1. Defense and protection through biomineralization	5343
10.4.4.2. Chemical or Microbiomineralization Contributions	5343
Acknowledgments	5344
References	5344
Chapter 10.5: Biogeochemistry of Primary Production in the Sea	5352
10.5.1. Introduction	5352
10.5.1.1. The Two Carbon Cycles	5353
10.5.1.2. A Primer on Redox Chemistry	5353
10.5.2. Chemoautotrophy	5353
10.5.3. Photoautotrophy	5354
10.5.3.1. Selective Forces in the Evolution of Photoautotrophy	5354
10.5.3.2. Selective Pressure in the Evolution of Oxygenic Photosynthesis	5355
10.5.4. Primary Productivity by Photoautotrophs	5355
10.5.4.1. What Are Photoautotrophs?	5356
10.5.4.1.1. The red and green lineages	5357
10.5.4.2. Estimating Chlorophyll Biomass	5357
10.5.4.2.1. Satellite-based algorithms for ocean color retrievals	5357
10.5.4.3. Estimating Net Primary Production	5359
10.5.4.3.1. Global models of net primary production for the ocean	5359
10.5.4.4. Quantum Efficiency of NPP	5360
10.5.4.4.1. Comparing efficiencies for oceanic and terrestrial primary production	5360
10.5.5. Export, New, and `True New` Production	5361
10.5.5.1. Steady State Versus Transient State	5362
10.5.5.2. Climate Change and the Transient State	5362
10.5.6. Nutrient Fluxes	5363
10.5.6.1. The Redfield Ratio	5363
10.5.7. Nitrification	5363
10.5.7.1. Carbon Burial	5364
10.5.7.2. Carbon Isotope Fractionation in Organic Matter and Carbonates	5364
10.5.7.3. Balance Between Net Primary Production and Losses	5364
10.5.7.4. Carbon Burial in the Contemporary Ocean	5364
10.5.7.5. Carbon Burial in the Precambrian Ocean	5366
10.5.8. Limiting Macronutrients	5366
10.5.8.1. The Two Concepts of Limitation	5366
10.5.9. The Evolution of the Nitrogen Cycle	5366
10.5.10. Functional Groups	5367
10.5.10.1. Siliceous Organisms	5368
10.5.10.2. Calcium Carbonate Precipitation	5369
10.5.10.3. Vacuoles	5369
10.5.11. High-Nutrient, Low-Chlorophyll Regions: Iron Limitation	5370
10.5.12. Glacial-Interglacial Changes in the Biological CO2 Pump	5370
10.5.13. Iron Stimulation of Nutrient Utilization	5371
10.5.14. Linking Iron to N2 Fixation	5371
10.5.15. Other Trace-Element Controls on NPP	5371
10.5.16. Concluding Remarks	5373
Acknowledgments	5373
References	5373
Chapter 10.6: Biogeochemical Interactions Governing Terrestrial Net Primary Production	5378
10.6.1. Introduction	5379
10.6.2. General Constraints on NPP	5379
10.6.2.1. What is NPP?	5379
10.6.2.2. Physiological Controls over NPP	5380
10.6.2.3. Environmental Controls over NPP	5381
10.6.2.4. Species Controls over NPP	5384
10.6.3. Limitations to Leaf-Level Carbon Gain	5384
10.6.3.1. The Basic Recipe for Carbon Gain	5384
10.6.3.2. CO2 Limitation	5384
10.6.3.3. Light Limitation	5385
10.6.3.4. Nitrogen Limitation	5385
10.6.3.5. Water Limitation	5386
10.6.4. Stand-Level Carbon Gain	5386
10.6.4.1. Spatial Scaling of GPP	5386
10.6.4.2. Temporal Scaling of GPP	5387
10.6.5. Respiration	5388
10.6.6. Allocation of NPP	5390
10.6.7. Tissue Turnover	5390
10.6.8. Global Patterns of Biomass and NPP	5390
10.6.9. Nutrient Use	5391
10.6.10. Balancing Nutrient Limitation	5392
10.6.10.1. Nutrient Requirements	5392
10.6.10.2. Limitation by Different Nutrients	5392
10.6.10.3. Stoichiometry of NPP	5393
10.6.10.4. Uncoupling Mechanisms	5394
10.6.10.4.1. Litterfall and leaching inputs	5394
10.6.10.4.2. Nutrient mineralization	5395
10.6.10.4.3. Nutrient availability	5396
10.6.10.4.4. Element interactions	5396
10.6.10.4.5. Plant uptake	5396
10.6.10.5. Recoupling Mechanisms	5397
10.6.11. Community-Level Adjustments	5398
10.6.12. Species Effects on Interactive Controls	5398
10.6.12.1. Species Effects on Resources	5398
10.6.12.1.1. Decomposition and nitrogen mineralization	5398
10.6.12.1.2. Water dynamics	5399
10.6.12.2. Species Effects on Climate	5399
10.6.12.3. Species Effects on Disturbance	5400
10.6.13. Species Interactions and Ecosystem Processes	5400
10.6.14. Summary	5400
Acknowledgments	5401
References	5401
Chapter 10.7: Biogeochemistry of Decomposition and Detrital Processing	5406
10.7.1. Introduction	5406
10.7.2. Composition of Decomposer Resources	5407
10.7.2.1. Plant Litter	5408
10.7.2.2. Roots	5409
10.7.2.3. Secondary Resources	5410
10.7.2.4. Soil Organic Matter	5410
10.7.2.5. Summary	5411
10.7.3. The Decomposer Organisms	5411
10.7.3.1. Functional Ecology	5412
10.7.3.2. Soil Microorganisms	5412
10.7.3.3. Soil Fauna	5415
10.7.3.4. Interactions	5418
10.7.4. Methods for Studying Decomposition	5419
10.7.4.1. Litter Techniques	5419
10.7.4.2. SOM Techniques	5420
10.7.5. Detrital Processing	5421
10.7.5.1. Time Course of Litter Decomposition	5421
10.7.5.2. Comminution	5424
10.7.5.3. Leaching	5424
10.7.5.4. Catabolism	5426
10.7.5.5. Change in Nutrient Status	5430
10.7.5.6. Priming Effect on Native SOM	5432
10.7.6. Humification	5432
10.7.6.1. Selective Preservation	5433
10.7.6.2. Condensation Models	5433
10.7.7. Control of Decomposition and Stabilization	5434
10.7.7.1. Decomposer Organisms	5435
10.7.7.2. Resource Quality	5437
10.7.7.3. Soil Characteristics	5441
10.7.7.4. Climate	5445
10.7.7.5. Multiple Constraints	5451
10.7.8. Modeling Approaches	5451
10.7.9. Conclusions	5453
References	5454
Chapter 10.8: Anaerobic Metabolism: Linkages to Trace Gases and Aerobic Processes	5462
10.8.1. Overview of Life in the Absence of O2	5463
10.8.1.1. Introduction	5463
10.8.1.2. Overview of Anaerobic Metabolism	5464
10.8.1.3. Anaerobic-Aerobic Interface Habitats	5465
10.8.1.4. Syntax of Metabolism	5466
10.8.2. Autotrophic Metabolism	5466
10.8.2.1. Phototroph (Photolithoautotrophy) Diversity and Metabolism	5466
10.8.2.2. Chemotroph (Chemolithoautotrophy) Diversity and Metabolism	5468
10.8.2.3. Pathways of CO2 Fixation	5469
10.8.3. Decomposition and Fermentation	5469
10.8.3.1. Polymer Degradation	5469
10.8.3.1.1. Polysaccharides	5470
10.8.3.1.2. Lignin	5471
10.8.3.2. Fermentation	5471
10.8.3.2.1. Acetogenesis	5472
10.8.3.2.2. Syntrophy and interspecies hydrogen transfer	5472
10.8.4. Methane	5475
10.8.4.1. Methane in the Environment	5475
10.8.4.2. Methanogen Diversity and Metabolism	5476
10.8.4.3. Regulation of Methanogenesis	5477
10.8.4.3.1. O2 and oxidant inhibition	5477
10.8.4.3.2. Nutrients and pH	5477
10.8.4.3.3. Temperature	5477
10.8.4.3.4. Carbon quantity and quality	5478
10.8.4.3.5. Plants as carbon sources	5479
10.8.4.4. Contributions of Acetotrophy versus Hydrogenotrophy	5480
10.8.4.4.1. Organic carbon availability	5480
10.8.4.4.2. Temperature	5482
10.8.4.5. Anaerobic Methane Oxidation	5483
10.8.4.6. Aerobic Methane Oxidation	5485
10.8.4.6.1. Methanotroph diversity	5485
10.8.4.6.2. Regulation of methanotrophy	5486
10.8.4.6.3. Methane oxidation efficiency	5487
10.8.4.7. Wetland Methane Emissions and Global Change	5488
10.8.5. Nitrogen	5489
10.8.5.1. Nitrogen in the Environment	5489
10.8.5.2. Nitrogen Fixation	5491
10.8.5.3. Respiratory Denitrification	5491
10.8.5.3.1. Denitrifier diversity and metabolism	5491
10.8.5.3.2. Regulation of denitrification	5492
10.8.5.3.3. Nitrification-denitrification coupling	5494
10.8.5.3.4. Animals and plants	5494
10.8.5.3.5. N2O and NO fluxes	5495
10.8.5.4. Dissimilatory Nitrate Reduction to Ammonium (DNRA)	5495
10.8.5.4.1. Physiology and diversity of DNRA bacteria	5495
10.8.5.4.2. DNRA versus denitrification	5496
10.8.5.5. Alternative Pathways to N2 Production	5497
10.8.5.5.1. Anammox	5497
10.8.5.5.2. Nitrifier denitrification	5499
10.8.5.5.3. Abiotic and autotrophic denitrification	5499
10.8.6. Iron and Manganese	5500
10.8.6.1. Iron and Manganese in the Environment	5501
10.8.6.2. Iron and Manganese Geochemistry	5501
10.8.6.3. Microbial Reduction of Iron and Manganese	5501
10.8.6.3.1. Metabolic diversity in Fe(III)- and Mn(IV)-reducing organisms	5502
10.8.6.3.2. Physical mechanisms for accessing oxides	5502
10.8.6.4. Factors that Regulate Fe(III) Reduction	5503
10.8.6.4.1. Electron shuttling compounds	5503
10.8.6.4.2. Fe(lll) chelators	5504
10.8.6.4.3. Mineral reactivity	5504
10.8.6.4.4. Abiotic versus biotic reduction	5505
10.8.6.4.5. Separating enzymatic and nonenzymatic Fe(lll) reduction	5506
10.8.6.4.6. Fe(III) reduction in ecosystems	5506
10.8.6.5. Microbial Oxidation of Iron and Manganese	5507
10.8.6.5.1. Energetics of Fe(ll) and Mn(ll) oxidation	5507
10.8.6.5.2. Anaerobic Fe(ll) oxidation	5507
10.8.6.5.3. Aerobic Fe(ll) oxidation	5508
10.8.6.6. Iron Cycling	5509
10.8.7. Sulfur	5509
10.8.7.1. Sulfur Geochemistry	5510
10.8.7.2. Microbial Reduction of Sulfate	5510
10.8.7.2.1. Overview of sulfate reduction	5510
10.8.7.2.2. Metabolic diversity	5511
10.8.7.3. Taxonomic Considerations	5513
10.8.7.4. Sulfate-Reducing Populations	5514
10.8.7.5. Factors Regulating Sulfate Reduction Activity	5514
10.8.7.5.1. Sulfate-reducing activity	5514
10.8.7.5.2. Temperature	5515
10.8.7.5.3. Carbon	5515
10.8.7.5.4. Sulfate and molecular oxygen concentrations	5515
10.8.7.6. Microbial Reduction of Sulfur	5516
10.8.7.7. Disproportionation	5516
10.8.7.8. Sulfur Gases	5517
10.8.7.8.1. Hydrogen sulfide	5517
10.8.7.8.2. Methylsulfides	5517
10.8.7.8.3. Carbonyl sulfide and carbon disulfide	5519
10.8.7.9. Microbial Oxidation of Sulfur	5519
10.8.7.9.1. Colorless sulfur bacteria	5520
10.8.7.9.2. Single-cell colorless sulfur bacteria	5520
10.8.7.9.3. Filamentous colorless sulfur bacteria	5521
10.8.7.9.4. Anoxyphototrophic bacteria	5521
10.8.7.9.5. Ecological aspects of sulfide oxidation	5522
10.8.8. Coupled Anaerobic Element Cycles	5522
10.8.8.1. Evidence of Competitive Interactions	5522
10.8.8.2. Mechanisms of Competition	5522
10.8.8.3. Exceptions	5523
10.8.8.4. Noncompetitive Interactions	5524
10.8.8.5. Contributions to Carbon Metabolis	5524
10.8.8.6. Concluding Remarks	5524
Acknowledgments	5524
References	5525
Chapter 10.9: The Geologic History of the Carbon Cycle	5550
10.9.1. Introduction	5550
10.9.2. Modes of Carbon-Cycle Change	5551
10.9.2.1. The Carbon Cycle over Geologic Timescales	5551
10.9.2.1.1. The ``carbon dioxide´´ carbon cycle	5551
10.9.2.1.2. The ``methane´´ carbon subcycle	5554
10.9.2.2. Timescales of Carbon-cycle Change	5557
10.9.3. The Quaternary Record of Carbon-Cycle Change	5558
10.9.3.1. Analysis of CO2 and CH4 in Ice Cores	5558
10.9.3.2. Holocene Carbon-cycle Variations	5562
10.9.3.3. Glacial/interglacial Carbon-cycle Variations	5566
10.9.3.3.1. Carbon-cycle influences on glacial/interglacial climate	5566
10.9.3.3.2. Climate influences on glacial/interglacial carbon cycling	5568
10.9.3.3.3. Carbon/climate interactions at glacial terminations	5571
10.9.4. The Phanerozoic Record of Carbon-Cycle Change	5572
10.9.4.1. Mechanisms of Gradual Geologic Carbon-cycle Change	5573
10.9.4.1.1. The carbonate weathering-sedimentation cycle	5573
10.9.4.1.2. The silicate-carbonate weathering-decarbonation cycle	5573
10.9.4.1.3. The organic carbon production-consumption-oxidation cycle	5574
10.9.4.2. Model Simulations of Gradual Geologic Carbon-cycle Change	5576
10.9.4.3. Geologic Evidence for Phanerozoic Atmospheric CO2 Concentrations	5576
10.9.4.4. Abrupt Carbon-cycle Change	5578
10.9.5. The Precambrian Record of Carbon-Cycle Change	5579
10.9.6. Conclusions	5580
Acknowledgments	5580
References	5580
Chapter 10.10: The Contemporary Carbon Cycle	5588
10.10.1. Introduction	5589
10.10.2. Major Reservoirs and Natural Fluxes of Carbon	5589
10.10.2.1. Reservoirs	5589
10.10.2.1.1. The atmosphere	5589
10.10.2.1.2. Terrestrial ecosystems: vegetation and soils	5590
10.10.2.1.3. The oceans	5591
10.10.2.1.4. Fossil fuels	5591
10.10.2.2. The Natural Flows of Carbon	5592
10.10.2.2.1. Between land and atmosphere	5592
10.10.2.2.2. Between oceans and atmosphere	5594
10.10.2.2.3. Between land and oceans	5594
10.10.3. Changes in the Stocks and Fluxes of Carbon as a Result of Human Activities	5595
10.10.3.1. Changes over the Period 1850-2008	5595
10.10.3.1.1. Emissions of carbon from combustion of fossil fuels	5595
10.10.3.1.2. The increase in atmospheric carbon dioxide	5596
10.10.3.1.3. Net uptake of carbon by the oceans	5597
10.10.3.1.3.1. Ocean carbon models	5598
10.10.3.1.4. Land: net exchange of carbon between terrestrial ecosystems and the atmosphere	5598
10.10.3.1.5. Land: changes in land use	5598
10.10.3.1.6. Land: the residual carbon sink	5601
10.10.3.2. Changes over the Period 1980-2008	5602
10.10.3.2.1. The global carbon budget	5602
10.10.3.2.1.1. Sources and sinks inferred from inverse modeling with atmospheric transport models and atmospheric concentrat...	5602
10.10.3.2.1.2. Terrestrial sources and sinks of carbon from land-use change	5604
10.10.3.2.2. Regional distribution of sources and sinks of carbon: the northern mid-latitudes	5604
10.10.3.2.2.1. Inferring changes in terrestrial carbon storage from analysis of forest inventories	5605
10.10.3.2.3. Regional distribution of sources and sinks of carbon: the tropics	5606
10.10.3.2.3.1. Forest inventories	5606
10.10.3.2.3.2. Direct measurement of CO2 flux	5607
10.10.3.2.4. Summary: synthesis of the results of different methods	5607
10.10.4. Mechanisms Thought to be Responsible for Current Terrestrial Carbon Sink	5608
10.10.4.1. Physiological or Metabolic Responses to Environmental Change	5609
10.10.4.1.1. CO2 fertilization	5609
10.10.4.1.2. Nitrogen fertilization	5610
10.10.4.1.3. Atmospheric chemistry	5610
10.10.4.1.4. Climatic variability and climatic change	5611
10.10.4.1.5. Synergies among physiological `mechanisms´	5612
10.10.4.1.6. Terrestrial carbon models	5612
10.10.4.2. Structural, Demographic, and Disturbance Mechanisms	5613
10.10.4.3. Which Terrestrial Mechanisms Are Most Important?	5613
10.10.4.4. Other Possible Explanations for the Residual Terrestrial Carbon Sink	5613
10.10.4.4.1. Aquatic transport: erosion and redeposition of carbon	5614
10.10.4.4.2. Woody encroachment	5614
10.10.4.4.3. Emissions from draining and burning of peatlands	5614
10.10.5. The Future	5614
10.10.5.1. Natural Feedbacks	5614
10.10.5.1.1. The airborne fraction	5615
10.10.5.1.2. How will the magnitude of the current terrestrial sink change in the future?	5615
10.10.5.1.3. How will the oceanic uptake of carbon change in the future?	5616
10.10.5.1.3.1. Physical and chemical mechanisms	5616
10.10.5.1.3.1.1. The buffer factor	5616
10.10.5.1.3.1.2. Warming	5616
10.10.5.1.3.1.3. Vertical mixing and stratification	5617
10.10.5.1.3.1.4. Rate of CO2 emissions	5617
10.10.5.1.3.2. Biological feedback/processes	5617
10.10.5.1.3.2.1. Addition of nutrients limiting primary production	5617
10.10.5.1.3.2.2. Enhanced utilization of nutrients	5617
10.10.5.1.3.2.3. Changes in the elemental ratios of organic matter in the ocean	5617
10.10.5.1.3.2.4. Increases in the organic carbon/carbonate ratio of export production	5617
10.10.5.2. Deliberate Sequestering of Carbon (or Reduction of Emissions)	5618
10.10.5.2.1. Terrestrial	5618
10.10.5.2.2. Oceanic	5618
10.10.5.2.3. Geologic	5618
10.10.6. Conclusion	5618
References	5619
Chapter 10.11: The Global Oxygen Cycle	5626
10.11.1. Introduction	5628
10.11.2. Distribution of O2 among Earth Surface Reservoirs	5628
10.11.2.1. The Atmosphere	5628
10.11.2.2. The Oceans	5628
10.11.2.3. Freshwater Environments	5631
10.11.2.4. Soils and Groundwaters	5631
10.11.3. Mechanisms of O2 Production	5632
10.11.3.1. Photosynthesis	5632
10.11.3.2. Photolysis of Water	5633
10.11.4. Mechanisms of O2 Consumption	5634
10.11.4.1. Aerobic Respiration	5634
10.11.4.2. Photorespiration	5634
10.11.4.3. C1 Metabolism	5634
10.11.4.4. Inorganic Metabolism	5635
10.11.4.5. Macroscale Patterns of Aerobic Respiration	5635
10.11.4.6. Volcanic Gases	5636
10.11.4.7. Mineral Oxidation	5636
10.11.4.8. Hydrothermal Vents	5636
10.11.4.9. Fe and S Oxidation at the Oxic&ndas	5636
10.11.4.10. Abiotic Organic Matter Oxidati	5637
10.11.5. Global O2 Budgets	5637
10.11.6. Atmospheric O2 Throughout Earth History	5637
10.11.6.1. Early Models	5637
10.11.6.2. The Archean	5639
10.11.6.2.1. Constraints on the O2 content of the Archean atmosphere	5639
10.11.6.2.2. The evolution of oxygenic photosynthesis	5640
10.11.6.2.3. Carbon isotope effects associated with photosynthesis	5642
10.11.6.2.4. Evidence for oxygenic photosynthesis in the late Archean	5643
10.11.6.3. The Proterozoic Atmosphere	5643
10.11.6.3.1. The Great Oxidation Event	5643
10.11.6.3.2. Survival strategies on the earliest oxygenated Earth	5646
10.11.6.3.3. Atmospheric O2 during the Mesoproterozoic	5646
10.11.6.3.4. Neoproterozoic atmospheric O2	5647
10.11.6.4. Phanerozoic Atmospheric O2	5649
10.11.6.4.1. Constraints on Phanerozoic O2 variation	5649
10.11.6.4.2. Evidence for variations in Phanerozoic O2	5649
10.11.6.4.3. Numerical models of Phanerozoic atmospheric O2	5651
10.11.7. Conclusions	5658
References	5659
Chapter 10.12: The Global Nitrogen Cycle	5664
10.12.1. Introduction	5664
10.12.2. Biogeochemical Reactions	5666
10.12.2.1. The Initial Reaction: Nr Creation	5666
10.12.2.2. Atmosphere	5666
10.12.2.2.1. Inorganic reduced N	5667
10.12.2.2.2. Inorganic oxidized N	5667
10.12.2.2.3. Reduced organic N	5668
10.12.2.2.4. Oxidized organic N	5668
10.12.2.3. Biosphere	5668
10.12.2.3.1. Nitrogen fixation	5668
10.12.2.3.2. Ammonia assimilation	5668
10.12.2.3.3. Nitrification	5668
10.12.2.3.4. Assimilatory nitrate reduction	5668
10.12.2.3.5. Ammonification	5668
10.12.2.3.6. Denitrification	5668
10.12.2.3.7. Anammox	5669
10.12.3. N Reservoirs and Their Exchanges	5669
10.12.3.1. Land to Atmosphere	5669
10.12.3.2. Ocean to Atmosphere	5669
10.12.3.3. Atmosphere to Surface	5669
10.12.3.4. Land to Ocean	5669
10.12.3.5. Continent to Continent - Commerce	5669
10.12.4. Nr Creation	5669
10.12.4.1. Introduction	5669
10.12.4.2. Lightning	5669
10.12.4.3. Terrestrial BNF	5670
10.12.4.4. Anthropogenic	5670
10.12.4.4.1. Introduction	5670
10.12.4.4.2. Food production	5671
10.12.4.4.3. Energy production	5672
10.12.4.5. Anthropogenic Nr Creation Rates from 1860 to 2005	5672
10.12.5. Global Terrestrial N Budgets	5672
10.12.5.1. Introduction	5672
10.12.5.2. Nr Creation	5674
10.12.5.3. Nr Distribution	5674
10.12.5.4. Nr Conversion to N2	5675
10.12.6. Global Marine N Budget	5676
10.12.7. Regional N Budgets	5678
10.12.8. Consequences	5679
10.12.8.1. Introduction	5679
10.12.8.2. Atmosphere	5680
10.12.8.3. Terrestrial Ecosystems	5680
10.12.8.4. Aquatic Ecosystems	5681
10.12.9. Future	5682
10.12.10. Societal Responses	5682
10.12.11. Summary	5685
Acknowledgments	5685
References	5685
Chapter 10.13: The Global Phosphorus Cycle	5688
10.13.1. Introduction	5688
10.13.2. The Global Phosphorus Cycle: Overview	5689
10.13.2.1. The Terrestrial Phosphorus Cycle	5689
10.13.2.2. Transport of Phosphorus from Continents to the Ocean	5692
10.13.2.2.1. Human impacts on the global phosphorus cycle	5693
10.13.2.3. The Marine Phosphorus Cycle	5693
10.13.3. Phosphorus Biogeochemistry and Cycling: Current Research	5694
10.13.3.1. Phosphorus Cycling in Terrestrial Ecosystems and Soils	5694
10.13.3.2. Phosphorus Cycling in Terrestrial Aquatic Systems: Lakes, Rivers, and Estuaries	5695
10.13.3.2.1. Biogeochemistry and cycling of phosphorus in lakes	5695
10.13.3.2.2. Biogeochemistry and cycling of phosphorus in rivers and estuaries	5696
10.13.3.2.3. Submarine groundwater discharge of phosphorus to the ocean	5698
10.13.3.3. Biogeochemistry and Cycling of Phosphorus in the Modern Ocean	5699
10.13.3.3.1. Phosphorus in the oceanic water column: Composition and cycling	5699
10.13.3.3.1.1. Dissolved inorganic phosphorus	5699
10.13.3.3.1.2. Dissolved organic phosphorus	5700
10.13.3.3.1.3. Water column particulate P	5704
10.13.3.3.1.3.1. Water column C:P ratios	5704
10.13.3.3.1.3.2. Application of 31P-NMR to water column particulate matter	5704
10.13.3.3.1.3.3. Cosmogenic 32P and 33P as tracers of phosphorus cycling in surface waters	5705
10.13.3.3.1.4. Oxygen isotopes of phosphate in seawater	5706
10.13.3.3.1.5. Phosphorus limitation of marine primary photosynthetic production	5707
10.13.3.3.2. Phosphorus burial and the marine phosphorus budget	5710
10.13.3.3.2.1. Historical perspective	5710
10.13.3.3.2.2. Diagenesis and burial of phosphorus in marine sediments	5711
10.13.3.3.2.2.1. Sedimentary organic phosphorus: composition and reactivity	5714
10.13.3.3.2.2.2. Authigenic CFA: modern phosphorites	5715
10.13.3.3.2.2.3. Disseminated authigenic CFA	5717
10.13.3.3.2.2.4. Experimental studies of authigenic apatite precipitation	5723
10.13.3.3.2.2.5. Other authigenic phosphate minerals	5724
10.13.3.3.2.2.6. Sedimentary organic carbon to organic phosphorus [(C:P)org] ratios	5725
10.13.3.3.2.2.7. Coupled iron-phosphorus cycling	5729
10.13.3.3.3. Benthic return flux of phosphorus from the seabed	5731
10.13.3.3.4. The oceanic residence time of phosphorus	5732
10.13.3.4. Phosphorus Cycling Over Long, Geologic Timescales	5733
10.13.3.4.1. The role of tectonics in the global phosphorus cycle	5733
10.13.3.4.2. Links to other biogeochemical cycles on long, geologic timescales	5733
10.13.3.4.2.1. The nutrient-CO2 connection	5733
10.13.3.4.2.2. The phosphorus-iron-o&	5734
10.13.3.4.3. Phosphorus in paleoceanography: P burial as a proxy for weathering, paleoproductivity, and climate change	5735
10.13.3.4.4. Ancient phosphorites	5736
10.13.4. Summary	5736
References	5736
Chapter 10.14: The Global Sulfur Cycle	5748
10.14.1. Elementary Issues	5749
10.14.1.1. History	5749
10.14.1.2. Isotopes	5749
10.14.1.3. Allotropes	5750
10.14.1.4. Vapor Pressure	5750
10.14.1.5. Chemistry	5750
10.14.2. Abundance of Sulfur and Early History	5752
10.14.2.1. Sulfur in the Cosmos	5753
10.14.2.2. Condensation, Accretion, and Evolution	5753
10.14.2.3. Sulfur on the Early Earth	5754
10.14.3. Occurrence of Sulfur	5755
10.14.3.1. Elemental Sulfur	5755
10.14.3.2. Sulfides	5755
10.14.3.3. Evaporites	5755
10.14.3.4. The Geological History of Sulfur	5755
10.14.3.5. Utilization and Extraction of Sulfur Minerals	5756
10.14.4. Chemistry of Volcanogenic Sulfur	5757
10.14.4.1. Deep-Sea Vents	5757
10.14.4.1.1. Chemistry of volcanogenic sulfur	5757
10.14.4.2. Aerial Emissions	5757
10.14.4.3. Fumaroles	5758
10.14.4.4. Crater Lakes	5758
10.14.4.5. Impacts of Emissions on Local Environments	5758
10.14.5. Biochemistry of Sulfur	5759
10.14.5.1. Origin of Life	5759
10.14.5.2. Sulfur Biomolecules	5759
10.14.5.3. Uptake of Sulfur	5760
10.14.6. Sulfur in Seawater	5760
10.14.6.1. Sulfate	5760
10.14.6.2. Hydrogen Sulfide	5761
10.14.6.3. OCS and Carbon Disulfide	5761
10.14.6.4. Organosulfides	5761
10.14.6.5. Coastal Marshes	5763
10.14.7. Surface and Groundwaters	5763
10.14.8. Marine Sediments	5764
10.14.9. Soils and Vegetation	5765
10.14.10. Troposphere	5766
10.14.10.1. Atmospheric Budget of Sulfur Compounds	5766
10.14.10.2. Hydrogen Sulfide	5767
10.14.10.3. Carbonyl Sulfide	5767
10.14.10.4. Carbon Disulfide	5768
10.14.10.5. Dimethyl Sulfide	5768
10.14.10.6. DMSO and Methanesulfonic Acid	5769
10.14.10.7. Sulfur	5769
10.14.10.8. Sulfur Dioxide	5769
10.14.10.9. Aerosol Sulfates and Climate	5771
10.14.10.10. Deposition	5771
10.14.11. Anthropogenic Impacts on the Sulfur Cycle	5772
10.14.11.1. Combustion Emissions	5772
10.14.11.2. Organosulfur Gases	5772
10.14.11.3. Acid Rain	5773
10.14.11.4. Water and Soil Pollutants	5773
10.14.11.5. Coastal Pollution	5774
10.14.12. Sulfur in Upper Atmospheres	5774
10.14.12.1. Radiation Balance and Sulfate Particles	5774
10.14.12.2. Ozone	5775
10.14.12.3. Aircraft	5775
10.14.13. Planets and Moons	5776
10.14.13.1. Venus	5776
10.14.13.2. Jupiter	5776
10.14.13.3. Io	5776
10.14.13.4. Europa	5776
10.14.14. Conclusions	5777
References	5777
Chapter 10.15: Plankton Respiration, Net Community Production and the Organic Carbon Cycle in the Oceanic Water Column	5782
10.15.1. Introduction	5782
10.15.2. Biogeochemical Background	5783
10.15.3. Biochemical Background	5784
10.15.4. Measurement of Respiration Rates	5785
10.15.4.1. Measurement of the Rate of Concentration Change of a Reactant or Product	5785
10.15.4.2. Measurements of the ETS	5785
10.15.4.3. Other Biological Approaches	5786
10.15.5. First Order Overall Global Organic Budget of the Oceans	5786
10.15.6. Distribution of Respiration within the Oceans	5787
10.15.6.1. Respiration in the Epipelagic Zone	5788
10.15.6.2. Assessment of the Output of Organic Material from the Euphotic Zone	5793
10.15.6.3. Consumption of Organic Material Within the Dark Zone of the Ocean	5794
10.15.7. Distribution of Respiration within the Community	5797
10.15.8. Summary	5799
References	5800
Chapter 10.16: Respiration in Terrestrial Ecosystems	5802
10.16.1. Introduction	5804
10.16.1.1. Photosynthesis and Respiration	5805
10.16.1.2. A Definition of Respiration	5805
10.16.1.3. Objectives and Outline	5806
10.16.2. Cellular Respiration	5806
10.16.2.1. Carbon Metabolism in Respiration	5806
10.16.2.1.1. Glycolysis	5806
10.16.2.1.2. Tricarboxylic acid cycle	5807
10.16.2.2. The Mitochondrial Electron Transport Chain and Oxidative Phosphorylation	5807
10.16.2.3. Daytime Foliar Respiration	5809
10.16.2.4. Fermentation	5809
10.16.2.5. Alternative Microbial Terminal Electron Acceptors	5809
10.16.2.5.1. Nitrate and sulfate reduction	5809
10.16.2.5.2. Methanogenesis	5810
10.16.2.5.3. Methane oxidation	5810
10.16.3. Whole-Plant Respiration	5810
10.16.3.1. Sinks for Respiratory Energy: Growth, Maintenance, and Transport	5810
10.16.3.2. Nonphosphorylating Respiration	5811
10.16.3.3. Contribution of the Alternative, Nonphosphorylating Pathway to Respiration in Roots and Leaves	5812
10.16.3.4. Effects of Some Environmental Conditions on Plant Respiration	5813
10.16.3.5. Plant Respiration and Photosynthesis	5815
10.16.3.5.1. The RA/GPP of plants and in terrestrial ecosystems	5815
10.16.3.5.2. Environmental effects on plant RA/GPP	5815
10.16.3.5.3. Forest RA/GPP during stand development	5818
10.16.4. Animal Respiration	5819
10.16.4.1. Respiration of Individual Animals	5819
10.16.4.2. Animal Respiration in Terrestrial Ecosystems	5819
10.16.4.3. Respiration by Humans and Domestic Farm Animals	5820
10.16.4.4. Methane Production by Terrestrial Animals	5821
10.16.4.4.1. Methane production by wild vertebrates	5821
10.16.4.4.2. Methane production by termites and other terrestrial arthropods	5821
10.16.4.4.3. Methane production by domestic animals	5821
10.16.5. Respiration of Terrestrial Ecosystems	5822
10.16.5.1. Soil Respiration	5822
10.16.5.1.1. Soil CO2 efflux and soil respiration	5822
10.16.5.1.2. Temporal variations in soil CO2 efflux	5823
10.16.5.1.3. Annual soil respiration within terrestrial ecosystems	5823
10.16.5.1.4. Sources of soil-derived CO2	5824
10.16.5.1.4.1. Decomposer contributions to soil respiration	5825
10.16.5.1.4.2. Root contributions to soil respiration	5825
10.16.5.1.4.3. Soil methane oxidation	5826
10.16.5.1.4.4. Soil denitrification	5826
10.16.5.1.4.5. Abiotic CO2 production within soils	5827
10.16.5.1.5. Effects of environmental factors on microbial and soil respiration	5828
10.16.5.1.5.1. Soil organic carbon and climate change	5828
10.16.5.1.5.2. Temperature and soil carbon mineralization	5828
10.16.5.1.5.3. Soil moisture and soil carbon mineralization	5829
10.16.5.2. Net Ecosystem Exchange of Carbon Dioxide	5829
10.16.6. Global Terrestrial Ecosystem Respiration	5830
References	5831
e9780080983004v11	5839
Front Cover	5839
Environmental Geochemistry	5842
Copyright	5843
In Memoriam	5844
Heinrich Dieter Holland (1927–2012)	5846
Karl Karekin Turekian (1927–2013)	5848
References	5850
Dedication	5852
Contents	5854
Executive editors’ Foreword to the Second Edition	5856
Contributors	5860
Volume editor’s Introduction	5862
References	5863
Chapter 11.1: Groundwater and Air Contamination: Risk, Toxicity, Exposure Assessment, Policy, and Regulation	5864
11.1.1. Introduction	5864
11.1.2. Principles, Definitions, and Perspectives of Hazardous Waste Risk Assessments	5865
11.1.2.1. Definitions of Hazard and Risk	5865
11.1.2.2. Typical Risks Encountered – Natural and Anthropogenic	5865
11.1.2.3. Risks Associated with Contaminated Sites and Groundwater	5865
11.1.3. Regulatory and Policy Basis for Risk Assessment	5865
11.1.3.1. Examples of Contaminated Sites and Potential Risk Exposure Pathways	5865
11.1.3.2. Risk-Based Nature of CERCLA	5866
11.1.3.3. Risk-Based Corrective Actions	5866
11.1.3.4. Use of Applicable or Relevant and Appropriate Requirements	5867
11.1.3.5. Limited Uses of Absolute Standards	5867
11.1.4. The Risk Assessment Process	5867
11.1.4.1. Sources, Pathways, and Receptors: The Fundamental Algorithm for Risk Assessments	5867
11.1.4.2. The Four-Step Risk Assessment Process	5868
11.1.5. Hazard Identification	5868
11.1.5.1. Determining Contaminant Identity, Concentration, and Distribution	5868
11.1.5.2. Contaminant Surrogate Analysis	5868
11.1.6. Exposure Assessment	5869
11.1.6.1. Potential Exposure Pathways	5869
11.1.6.2. Estimating Exposure Concentrations	5869
11.1.6.3. Identifying Potentially Exposed Populations	5869
11.1.6.4. Estimating Chemical Intake	5869
11.1.7. Toxicity Assessment	5870
11.1.7.1. Overview of Human Health Toxicology	5870
11.1.7.1.1. Classification of toxic responses	5871
11.1.7.1.2. Quantifying reversible toxic effects	5871
11.1.7.2. Quantifying Noncarcinogenic Risk: Reference Dosages	5871
11.1.7.2.1. The no observed adverse effect level	5871
11.1.7.2.2. Acceptable daily intakes and reference doses	5871
11.1.7.3. Quantifying Carcinogenic Risk: Slope Factors	5872
11.1.8. Risk Characterization	5873
11.1.8.1. Determination of Noncarcinogenic Risk	5873
11.1.8.2. Determination of Carcinogenic Risk	5873
11.1.9. Sources of Uncertainties in Risk Assessment	5873
11.1.9.1. Source Characterization	5873
11.1.9.2. Lack of Available Data	5874
11.1.9.3. Exposure Assessment Models and Methods	5874
11.1.9.4. Quality of Toxicological Data	5874
11.1.9.5. Evaluating Uncertainty	5874
11.1.10. Risk Management and Risk Communication	5874
References	5875
Chapter 11.2: Arsenic and Selenium	5876
11.2.1. Introduction	5877
11.2.2. Sampling	5879
11.2.2.1. Rocks, Soils, and Sediments	5879
11.2.2.2. Water	5879
11.2.2.2.1. Techniques	5879
11.2.2.2.2. Filtered or unfiltered samples	5880
11.2.2.2.3. Sample preservation and redox stability	5880
11.2.3. Analytical Methods	5881
11.2.3.1. Arsenic	5881
11.2.3.1.1. Total arsenic in aqueous samples	5881
11.2.3.1.1.1. Laboratory methods	5881
11.2.3.1.1.2. Field-test kits	5882
11.2.3.1.2. Total arsenic in solid samples	5882
11.2.3.1.3. Arsenic speciation	5882
11.2.3.1.3.1. Aqueous speciation	5882
11.2.3.1.3.2. Solid-phase speciation	5882
11.2.3.1.3.3. EPA TCLP test	5883
11.2.3.2. Selenium	5883
11.2.3.2.1. Total selenium in aqueous samples	5883
11.2.3.2.1.1. Pretreatment to destroy organic matter	5883
11.2.3.2.1.2. Laboratory methods	5883
11.2.3.2.2. Selenium in solid samples	5884
11.2.3.2.3. Selenium speciation	5884
11.2.3.3. Quality Control and Standard Reference Materials	5884
11.2.4. Abundance and Forms of Arsenic in the Natural Environment	5885
11.2.4.1. Abundance in Rocks, Soils, and Sediments	5885
11.2.4.2. National and International Standards for Drinking Water	5885
11.2.4.3. Abundance and Distribution in Natural Waters	5886
11.2.4.3.1. Atmospheric precipitation	5886
11.2.4.3.2. River water	5887
11.2.4.3.3. Lake water	5887
11.2.4.3.4. Seawater and estuaries	5888
11.2.4.3.5. Groundwater	5888
11.2.4.3.6. Sediment pore water	5889
11.2.4.3.7. Acid mine drainage	5889
11.2.4.4. Arsenic Species in Natural Waters	5890
11.2.4.4.1. Inorganic species	5890
11.2.4.4.2. Organic species	5891
11.2.4.4.3. Observed speciation in different water types	5891
11.2.4.5. Microbial Controls	5892
11.2.5. Pathways and Behavior of Arsenic in the Natural Environment	5892
11.2.5.1. Release from Primary Minerals	5893
11.2.5.1.1. Examples of mining-related arsenic problems	5893
11.2.5.1.2. Modern practice in mine-waste stabilization	5894
11.2.5.2. Role of Secondary Minerals	5894
11.2.5.2.1. The importance of arsenic cycling and diagenesis	5894
11.2.5.2.2. Redox behavior	5894
11.2.5.3. Adsorption of Arsenic by Oxides and Clays	5895
11.2.5.4. Arsenic Transport	5896
11.2.5.5. Impact of Changing Environmental Conditions	5896
11.2.5.5.1. Release of arsenic at high pH	5896
11.2.5.5.2. Release of arsenic on reduction	5896
11.2.5.6. Case Studies	5896
11.2.5.6.1. The Bengal Basin, Bangladesh, and India	5896
11.2.5.6.2. Chaco-Pampean Plain, Argentina	5898
11.2.5.6.3. Eastern Wisconsin, USA	5900
11.2.6. Abundance and Forms of Selenium in the Natural Environment	5901
11.2.6.1. Abundance in Rocks, Soils, and Sediments	5901
11.2.6.2. National and International Standards in Drinking Water	5903
11.2.6.3. Abundance and Distribution in Natural Waters	5903
11.2.6.3.1. Atmospheric precipitation	5904
11.2.6.3.2. River and lake water	5904
11.2.6.3.3. Seawater and estuaries	5904
11.2.6.3.4. Groundwater	5904
11.2.6.3.5. Sediment pore water	5905
11.2.6.3.6. Mine drainage	5905
11.2.6.4. Selenium Species in Water, Sediment, and Soil	5905
11.2.7. Pathways and Behavior of Selenium in the Natural Environment	5906
11.2.7.1. Release from Primary Minerals	5906
11.2.7.2. Adsorption of Selenium by Oxides and Clays	5906
11.2.7.3. Selenium Transport	5907
11.2.7.3.1. Global fluxes	5907
11.2.7.3.2. Selenium fluxes in air	5907
11.2.7.3.3. Soil–water–plant relationships	5908
11.2.7.4. Case Studies	5909
11.2.7.4.1. Kesterson Reservoir, USA	5909
11.2.7.4.2. Enshi, China	5909
11.2.7.4.3. Soan-Sakesar Valley, Pakistan	5910
11.2.7.4.4. Selenium deficiency, China	5911
11.2.8. Concluding Remarks	5911
Acknowledgments	5912
References	5912
Chapter 11.3: Heavy Metals in the Environment – Historical Trends	5922
11.3.1. Introduction	5922
11.3.1.1. Metals: Pb, Zn, Cd, Cr, Cu, Ni	5922
11.3.1.2. Sources of Metals	5923
11.3.1.2.1. Natural	5923
11.3.1.2.2. Anthropogenic	5923
11.3.1.3. Source and Pathways	5924
11.3.2. Occurrence, Speciation, and Phase Associations	5924
11.3.2.1. Geochemical Properties and Major Solute Species	5924
11.3.2.1.1. Lead	5924
11.3.2.1.2. Zinc	5926
11.3.2.1.3. Cadmium	5926
11.3.2.1.4. Chromium	5927
11.3.2.1.5. Copper	5927
11.3.2.1.6. Nickel	5928
11.3.2.2. Occurrence in Rocks, Soils, Sediments,Anthropogenic Materials	5928
11.3.2.3. Geochemical Phase Associations in Soils and Sediments	5929
11.3.3. Atmospheric Emissions of Metals and Geochemical Cycles	5932
11.3.3.1. Historical Heavy Metal Fluxes to the Atmosphere	5933
11.3.3.2. Perturbed Heavy Metal Cycles	5934
11.3.3.3. Global Emissions of Heavy Metals	5934
11.3.3.4. US Emissions of Heavy Metals	5935
11.3.3.4.1. Lead	5935
11.3.3.4.2. Zinc	5936
11.3.3.4.3. Cadmium	5936
11.3.4. Historical Metal Trends Reconstructed from Sediment Cores	5937
11.3.4.1. Paleolimnological Approach	5937
11.3.4.2. Age Dating	5940
11.3.4.3. Selected Reconstructed Metal Trends	5940
11.3.4.3.1. Lead and leaded gasoline: consequence of the clean air act	5940
11.3.4.3.2. Zinc from rubber tire wear	5942
11.3.4.3.3. Metal processing and metal trends in sediment cores	5943
11.3.4.3.4. Reduction in power plant emissions of heavy metals: clean air act amendments and the use of low sulfur coal	5944
11.3.4.3.5. European lacustrine records of heavy metal pollution	5946
References	5949
Chapter 11.4: Geochemistry of Mercury in the Environment	5954
11.4.1. Introduction	5954
11.4.1.1. The Global Mercury Cycle	5956
11.4.2. Fundamental Geochemistry	5958
11.4.2.1. Solid Earth Abundance and Distribution	5958
11.4.2.2. Isotopic Distributions	5959
11.4.2.3. Minable Deposits	5959
11.4.2.4. Occurrence of Mercury in Fossil Fuels	5959
11.4.3. Sources of Mercury to the Environment	5960
11.4.3.1. Volcanic Mercury Emissions	5960
11.4.3.2. Mercury Input to the Oceans via Submarine Volcanism	5963
11.4.3.3. Low-Temperature Volatilization	5963
11.4.3.4. Anthropogenic Sources	5964
11.4.3.5. Mining	5965
11.4.3.6. Biomass Burning, Soil and Oceanic Evasion – Mixed Sources	5965
11.4.3.7. Watersheds and Legacy Mercury	5966
11.4.4. Atmospheric Cycling and Chemistry of Mercury	5966
11.4.5. Aquatic Biogeochemistry of Mercury	5970
11.4.5.1. Environmental Mercury Methylation	5972
11.4.5.1.1. Nearshore regions	5973
11.4.5.1.2. Open-ocean mercury cycling	5974
11.4.5.1.3. Open-ocean mercury profiles	5975
11.4.6. Removal of Mercury from the Surficial Cycle	5977
11.4.7. Models of the Global Cycle	5979
11.4.8. Developments in Studying Mercury in the Environment on a Variety of Scales	5981
11.4.8.1. Acid Rain and Mercury Synergy in Lakes	5981
11.4.8.2. METAALICUS	5981
11.4.8.3. Fractionation of Mercury Isotopes	5981
11.4.8.4. Tracing Atmospheric Mercury with 210Pb and Br	5982
11.4.8.5. Mercury and Organic Matter Interactions	5983
11.4.9. Summary	5983
Acknowledgments	5983
References	5983
Chapter 11.5: The Geochemistry of Acid Mine Drainage	5994
11.5.1. Introduction	5995
11.5.1.1. Scale of the Problem	5995
11.5.1.2. Overview of the Mining Process and Sources of Low-Quality Drainage	5995
11.5.1.3. Sources of Low-Quality Drainage	5995
11.5.1.3.1. Mine workings	5995
11.5.1.3.2. Open-pits	5996
11.5.1.3.3. Waste rock	5996
11.5.1.3.4. Mill tailings	5996
11.5.1.3.5. Wastes from extractive metallurgy operations	5996
11.5.2. Mineralogy of Ore Deposits	5997
11.5.2.1. Coal Deposits	5997
11.5.2.2. Base-Metal Deposits	5998
11.5.2.3. Precious-Metal Deposits	5999
11.5.2.4. Uranium Deposits	5999
11.5.2.5. Diamond Deposits	6000
11.5.2.6. Other Deposits	6000
11.5.3. Sulfide Oxidation and the Generation of Oxidation Products	6000
11.5.3.1. Sulfide-Mineral Oxidation	6001
11.5.3.1.1. Pyrite oxidation	6001
11.5.3.1.1.1. Chemical oxidation by Fe3+ and O2	6001
11.5.3.1.2. Pyrrhotite oxidation	6002
11.5.3.1.2.1. Chemical oxidation by O2 and Fe3	6003
11.5.3.1.2.2. Nonoxidative mechanism	6003
11.5.3.1.3. Oxidation of other metal sulfides	6003
11.5.3.1.3.1. Sphalerite	6003
11.5.3.1.3.2. Galena and chalcopyrite	6003
11.5.3.1.3.3. Mercury sulfides	6004
11.5.3.1.4. Oxidation of arsenic sulfides	6004
11.5.3.2. Bacteria and Sulfide-Mineral Oxidation	6005
11.5.3.2.1. Mechanisms of sulfide-mineral dissolution and the role of microorganisms	6005
11.5.3.2.2. Biodiversity of iron- and sulfur-oxidizing acidophilic microorganisms	6007
11.5.3.2.2.1. Acidophilic bacteria and archaea that oxidize sulfur	6009
11.5.3.2.2.2. Acidophilic bacteria and archaea that oxidize both iron and sulfur	6010
11.5.4. Acid-Neutralization Mechanisms at Mine Sites	6010
11.5.4.1. Mechanisms of Acid Neutralization	6010
11.5.4.1.1. Carbonate-mineral dissolution	6011
11.5.4.1.2. Dissolution of hydroxide minerals	6012
11.5.4.1.3. Dissolution of silicate minerals	6012
11.5.4.1.4. Development of pH-buffering sequences	6013
11.5.5. Geochemistry and Mineralogy of Secondary Minerals	6013
11.5.5.1. Soluble Sulfates: Iron Minerals	6013
11.5.5.2. Soluble Sulfates: Other Elements	6013
11.5.5.3. Less Soluble Sulfate Minerals	6014
11.5.5.4. Metal Oxides and Hydroxides	6015
11.5.5.5. Carbonate Minerals	6016
11.5.5.6. Arsenic Oxides	6016
11.5.5.7. Phosphates	6017
11.5.5.8. Secondary Sulfides	6017
11.5.5.9. Role of Microorganisms in the Formation and Dissolution of Secondary Minerals	6018
11.5.6. AMD in Mines and Mine Wastes	6021
11.5.6.1. Underground Workings	6021
11.5.6.2. Open-Pits	6022
11.5.6.3. Waste-Rock Piles	6024
11.5.6.4. Coal-Mine Spoils	6026
11.5.6.5. Tailings Impoundments	6027
11.5.7. Bioaccumulation and Toxicity of Oxidation Products	6030
11.5.7.1. Uptake and Bioaccumulation	6030
11.5.7.2. Toxicity of Oxidation Products	6031
11.5.7.3. Assessment of Toxicity	6031
11.5.7.3.1. Predictive models	6031
11.5.7.3.2. Biologic sensors	6032
11.5.7.3.3. Molecular tools	6032
11.5.8. Methods of Prediction	6032
11.5.8.1. Laboratory Static Procedures	6032
11.5.8.2. Mineralogical Prediction	6033
11.5.8.3. Laboratory Dynamic Procedures	6034
11.5.8.4. Geochemical Models	6034
11.5.8.4.1. Geochemical modeling approaches	6034
11.5.8.4.2. Application of geochemical speciation mass-transfer models	6035
11.5.8.5. Reactive-Transport Models	6036
11.5.9. Approaches for Remediation and Prevention	6036
11.5.9.1. Collection and Treatment	6037
11.5.9.2. Controls on Sulfide Oxidation	6037
11.5.9.2.1. Physical barriers	6037
11.5.9.2.1.1. Subaqueous disposal	6037
11.5.9.2.1.2. Dry covers	6038
11.5.9.2.1.3. Synthetic covers	6038
11.5.9.2.1.4. Oxygen-consuming materials	6038
11.5.9.2.2. Chemical treatments	6039
11.5.9.2.3. Bactericides	6039
11.5.9.3. Passive Remediation Techniques	6039
11.5.9.3.1. Types of passive systems	6039
11.5.9.3.2. Anaerobic bioreactors	6039
11.5.9.3.3. Constructed wetlands	6040
11.5.9.3.4. Permeable reactive barriers	6040
11.5.9.3.5. Other in situ techniques	6041
11.5.10. Summary and Conclusions	6042
References	6042
Chapter 11.6: Radioactivity, Geochemistry, and Health	6054
11.6.1. Introduction	6055
11.6.1.1. Approach and Outline of Chapter	6055
11.6.1.2. Previous Reviews and Scope of the Chapter	6055
11.6.2. Radioactive Processes and Sources	6056
11.6.2.1. Radioactive Processes	6056
11.6.2.2. Overview of Radioactive Sources and Exposure	6058
11.6.2.2.1. Natural sources of radioactivity	6058
11.6.2.2.2. Nuclear waste	6058
11.6.2.2.3. Sites of radioactive environmental contamination	6059
11.6.2.2.4. Exposure to background and anthropogenic sources of radioactivity	6059
11.6.3. Radionuclide Geochemistry: Principles and Methods	6059
11.6.3.1. Aqueous Speciation and Solubility	6060
11.6.3.1.1. Experimental studies	6060
11.6.3.1.2. Aqueous speciation and solubility models	6060
11.6.3.2. Sorption	6060
11.6.3.2.1. Experimental studies	6060
11.6.3.2.2. Sorption models	6061
11.6.3.2.3. Reactive transport models	6062
11.6.3.3. Colloids	6063
11.6.3.3.1. Introduction	6063
11.6.3.3.2. Microbial and humic colloids	6063
11.6.3.3.3. Models for transport of radionuclides by colloids	6064
11.6.4. Environmental Radioactivity and Health Effects Relevant to Drinking Water, the Nuclear Fuel Cycle, and Nuclear Weap	6064
11.6.4.1. Radium in Groundwater	6065
11.6.4.1.1. Geological occurrence	6065
11.6.4.1.2. Geochemical controls on Ra concentrations	6066
11.6.4.1.3. Isotopic ratios	6066
11.6.4.1.3.1. 228Ra/226Ra ratios	6066
11.6.4.1.3.2. 224Ra/228Ra ARs	6067
11.6.4.1.4. Radium removal and generation of TENORM	6067
11.6.4.1.5. Health effects owing to radium exposure	6068
11.6.4.2. Uranium and Other Actinides [An(III), An(IV), An(V), An(VI)]	6069
11.6.4.2.1. General trends in speciation, solubility, and sorption of the actinides	6069
11.6.4.2.1.1. Oxidation state	6069
11.6.4.2.1.2. Complexation and solubility	6070
11.6.4.2.1.3. Actinide sorption	6070
11.6.4.2.2. Behavior of uranium in the environment and impacts on human health	6072
11.6.4.2.2.1. Radiochemical, geochemical, and biogeochemical properties of uranium	6072
11.6.4.2.2.2. Environmental distribution of uranium	6074
11.6.4.2.2.2.1. Overview: relationship between geochemical properties and distribution	6074
11.6.4.2.2.2.2. Air	6074
11.6.4.2.2.2.3. Rocks and soils	6075
11.6.4.2.2.2.4. Water: background concentration levels	6075
11.6.4.2.2.2.5. Water concentrations at contaminated sites	6075
11.6.4.2.2.3. Uranium exposure and human health	6076
11.6.4.2.2.3.1. Exposure pathways	6076
11.6.4.2.2.3.2. Environmental toxicology and epidemiology of uranium	6076
11.6.4.2.2.4. Application: uranium contamination from mining	6077
11.6.4.2.2.4.1. Overview of mining, processing, and disposal	6077
11.6.4.2.2.4.2. Uranium mill tailings: introduction	6077
11.6.4.2.2.4.3. Geochemistry of mill tailings	6078
11.6.4.2.2.4.3.1. Mineralogy of tailings	6078
11.6.4.2.2.4.3.2. Geochemistry of aqueous contamination from mill tailings	6078
11.6.4.2.2.4.3.3. Bacterial processes	6079
11.6.4.2.2.4.3.4. Long-term behavior of mill tailings:&/I	6079
11.6.4.2.2.4.4. ISR of Uranium	6080
11.6.4.2.2.4.4.1. General description	6080
11.6.4.2.2.4.4.2. Choice of leaching solution	6080
11.6.4.2.2.4.4.3. Processing	6080
11.6.4.2.2.4.4.4. Site restoration	6081
11.6.4.2.2.4.4.5. Environmental issues	6081
11.6.4.2.2.4.4.6. Case histories	6082
11.6.4.2.2.4.4.7. Current controversies	6083
11.6.4.2.2.4.4.8. NA for ISR sites	6083
11.6.4.2.2.4.5. Remediation of uranium-contaminated sites	6084
11.6.4.2.2.4.5.1. Permeable reactive barriers	6084
11.6.4.2.2.4.5.2. Bioremediation	6085
11.6.4.2.2.4.5.3. Monitored natural attenuation	6085
11.6.4.2.3. Actinides and nuclear waste disposal	6086
11.6.4.2.3.1. Speciation, solubility, and sorption of actinides in nuclear waste repository environments	6087
11.6.4.2.3.1.1. Americium	6087
11.6.4.2.3.1.2. Thorium	6088
11.6.4.2.3.1.3. Neptunium	6088
11.6.4.2.3.1.4. Plutonium	6090
11.6.4.2.3.1.5. Uranium	6091
11.6.4.2.3.1.6. Actinide sorption by uranium wastes	6092
11.6.4.2.3.2. Geochemical models in risk assessment for	6092
11.6.4.3. Fission Products	6093
11.6.4.3.1. Introduction	6093
11.6.4.3.2. Geochemistry of fission products	6093
11.6.4.3.2.1. 90Sr	6093
11.6.4.3.2.2. 137Cs	6094
11.6.4.3.2.3. 99Tc	6094
11.6.4.3.2.4. 129I	6094
11.6.4.3.3. Application: the Chernobyl reactor accident	6095
11.6.4.3.3.1. Introduction	6095
11.6.4.3.3.2. Geochemical behavior	6095
11.6.4.3.3.3. Environmental epidemiology	6096
11.6.4.3.4. Application: contamination from weapons production at Chelyabins	6096
11.6.4.3.4.1. Chelyabinsk complex	6096
11.6.4.3.4.2. Environmental epidemiology	6097
11.6.5. Summary	6097
Appendix A. Radioactivity and Human Health	6098
Basis for Health Effects from Radiation: Interactions between Io	6099
Equivalent Dose and Biokinetics	6099
Dosimetry and Environmental Exposure	6100
Linear Nonthreshold Dose–Response Curve	6100
Epidemiological Studies of the Effects of Radiation	6101
Populations Living Near Nuclear Power Plants	6101
Survivors of Atomic Bomb Blasts at Hiroshima and Nagasaki	6102
Regulating Radionuclide Releases to the Environment and Exposures to the Public	6102
US Regulations	6103
European Regulations	6103
Appendix B Health Effects of Uranium	6103
Absorption	6103
Distribution	6104
Toxicity	6104
Carcinogencity	6104
Environmental Health Regulations	6105
Acknowledgments	6105
References	6105
Chapter 11.7: The Environmental and Medical Geochemistry of Potentially Hazardous Materials Produced by Disasters	6120
11.7.1. Introduction	6121
11.7.2. Potentially Hazardous Materials Produced by Disasters	6121
11.7.3. Medical Geochemistry – A Review and Update	6123
11.7.3.1. Factors Influencing the Health Effects of Disaster Materials	6128
11.7.3.2. Interdisciplinary Methods Used to Study the Health Effects of Disaster Materials	6129
11.7.4. Sampling, Analytical, and Remote Sensing Methods Applied to Disaster Materials	6130
11.7.4.1. Spatially Extensive Sampling in Rapid Response and over the Long Term	6130
11.7.4.2. Safety during Sampling	6130
11.7.4.3. Sampling Methods for Deposits of Solid Samples	6130
11.7.4.4. Sampling Methods for Airborne Particulate Matter and other Aerosols	6131
11.7.4.5. Field Analytical Methods for Solids	6131
11.7.4.6. Sampling and Field Analysis Methods for Waters	6131
11.7.4.7. Processing and Preparation of Solid DM for Lab Analysis	6131
11.7.4.8. Laboratory Methods for the Analysis of Disaster Materials	6132
11.7.4.9. Remote Sensing Methods for Identification and Mapping of Disaster Materials	6133
11.7.5. Volcanic Eruptions and Volcanic Degassing	6133
11.7.5.1. Volcanic Gases, Vog, and Laze	6133
11.7.5.2. Crater Lake Gas Eruption Disasters – Lake Nyos as an Example	6134
11.7.5.3. Volcanic Ash	6134
11.7.6. Landslides, Debris Flows, and Lahars	6136
11.7.6.1. Landslides and Debris Flows Sourced in Ultramafic Rocks	6137
11.7.6.2. Landslides and Debris Flows Sourced in Sulfide-Rich Rocks	6137
11.7.6.3. Volcanic Lahars	6137
11.7.6.4. Pathogens in Dusts from Earthquake-Generated Landslides	6138
11.7.7. Hurricanes, Extreme Storms, and Floods – Katrina as an Exam	6138
11.7.7.1. An Overview of DM Produced by Hurricanes, Extreme Storms, and Floods	6138
11.7.7.2. Hurricane Katrina Floodwaters, Flood Sediments, and Molds	6138
11.7.8. Wildfires at the Wildland–Urban Interface	6141
11.7.8.1. Types of Ash Produced by Wildfires	6142
11.7.8.2. Ash, Debris, and Burned Soil Characteristics of Potential Environmental or Health Concern	6142
11.7.8.3. Potential Environmental and Health Concerns of Wildfire Ash	6144
11.7.9. Mud and Waters from the Lusi Mud Eruption, East Java, Indonesia	6145
11.7.10. Failures of Mill Tailings or Mineral-Processing Waste Impoundments	6146
11.7.10.1. Mine Waste and Mill Tailings Impoundment Failures, Marinduque Island, Philippines	6146
11.7.10.2. Mill Tailings Impoundment Failure, Aznalcóllar Mine, Spain	6148
11.7.10.3. Cyanide Processing Impoundment Failures – Baia Mare, Romania, as an Example	6149
11.7.10.4. Red Mud Spill from Bauxite Processing, Hungary	6150
11.7.10.5. General Insights Regarding Environmental and Health Impacts of Mineral-Processing Impound	6151
11.7.11. Failures of Coal Slurry or Coal Fly Ash Impoundments	6151
11.7.11.1. Coal Slurry Impoundment Failures	6152
11.7.11.2. Coal Fly Ash Impoundment Failures	6152
11.7.12. Building Collapse – The World Trade Center as an Example	6154
11.7.13. Disaster Preparedness	6159
11.7.14. Summary	6161
Acknowledgments	6161
References	6161
Chapter 11.8: Eutrophication of Freshwater Systems	6168
11.8.1. Introduction	6169
11.8.1.1. Importance and Structure of Water	6169
11.8.1.2. Movement over and through Land	6170
11.8.1.3. Implications for Overloading the System	6170
11.8.2. Nutrient Cycles in Aquatic Ecosys	6170
11.8.2.1. Phosphorus	6171
11.8.2.2. Nitrogen	6172
11.8.3. Aquatic Ecosystem Structure	6174
11.8.3.1. Nutrient Input Patterns	6174
11.8.3.2. Lotic Systems	6174
11.8.3.2.1. Determining order	6175
11.8.3.2.2. Runoff, discharge, and loading rates	6175
11.8.3.3. Wetlands	6176
11.8.3.4. Lentic Systems	6176
11.8.3.4.1. Temperature and mixing	6177
11.8.3.4.2. Light, turbidity, and primary productivity	6177
11.8.3.4.3. Nutrient ratios and phytoplankton dynamics	6178
11.8.4. Eutrophication	6180
11.8.4.1. Ecological Succession versus Eutr	6180
11.8.4.2. Natural Eutrophication	6180
11.8.4.3. Cultural Eutrophication	6180
11.8.4.4. Conditions that Affect Eutrophication	6180
11.8.4.4.1. Dissolved organic carbon	6180
11.8.4.4.2. Salinity	6181
11.8.4.4.3. Fire	6181
11.8.4.4.4. Drought	6181
11.8.5. Two Case Studies in Eutrophicatio	6182
11.8.5.1. A Point-Source-Impacted Deep Water Lake	6182
11.8.5.2. A Nonpoint-Source-Impacted Shallow Water Lake	6183
11.8.6. Future Opportunities	6184
11.8.6.1. Management	6184
11.8.6.2. Monitoring	6184
11.8.7. Conclusions	6185
References	6185
Chapter 11.9: Salinization and Saline Environments	6188
11.9.1. Introduction	6190
11.9.2. River Salinization	6192
11.9.3. Lake Salinization	6199
11.9.4. Groundwater Salinization	6201
11.9.4.1. Seawater Intrusion and Saltwater Displacement in Coastal Aquifers	6201
11.9.4.2. Mixing with External Saline Waters in Noncoastal Areas	6205
11.9.4.3. Salinization of Shallow Groundwater in River Basins	6207
11.9.4.4. Salinization of Nonrenewable Groundwater	6208
11.9.5. Salinization of Dryland Environment	6209
11.9.6. Anthropogenic Salinization	6211
11.9.6.1. Urban Environment and Wastewater Salinization	6211
11.9.6.2. Deicing and Salinization	6213
11.9.6.3. Agricultural Drainage and the Unsaturated Zone	6213
11.9.7. Salinity and the Occurrence of Health-Related Contaminants	6215
11.9.7.1. Fluoride and Salinity	6216
11.9.7.2. Oxyanions and Salinity	6216
11.9.7.2.1. Arsenic	6216
11.9.7.2.2. Selenium	6217
11.9.7.2.3. Boron	6217
11.9.7.3. Naturally Occurring Radionuclides and Salinity	6219
11.9.7.4. Trihalomethanes and Salinity	6219
11.9.7.5. Salinity and Toxic Algae Bloom	6220
11.9.8. Elucidating the Sources of Salinity	6221
11.9.9. Remediation and the Chemical Composition of Desalination	6226
Acknowledgments	6230
References	6230
Chapter 11.10: Acid Rain – Acidification and Recovery	6242
11.10.1. Introduction	6243
11.10.2. What Is Acidification?	6245
11.10.3. Long-Term Acidification	6246
11.10.3.1. Has Long-Term Acidification Occurred?	6246
11.10.3.2. What Controls Long-Term Acidification?	6247
11.10.4. Short-Term and Episodic Acidification	6249
11.10.5. Drivers of Short-Term and Episodic Acidification	6250
11.10.5.1. High Discharge from Snowmelt and Rain	6250
11.10.5.2. Pulsed Release of SO4 and NO3 from Soils	6250
11.10.5.3. Marine Aerosols	6250
11.10.5.4. Organic Acidity	6251
11.10.5.5. Dilution	6251
11.10.5.6. In-Lake Processes Affecting pH and ANC	6251
11.10.6. Effects of Acidification	6252
11.10.6.1. Release of Al and other Elements	6252
11.10.6.2. Nutrient Availability	6253
11.10.7. Effects of a Changing Physical Climate on Acidification	6255
11.10.7.1. NO3	6256
11.10.7.2. SO4	6256
11.10.7.3. CO2	6256
11.10.7.4. Organic Acids	6257
11.10.7.5. Evaporation/Hydrology	6257
11.10.7.6. Marine Aerosols	6257
11.10.7.7. Biological Feedbacks	6258
11.10.8. Acidification Trajectories through Recent Time	6258
11.10.9. Longitudinal Acidification	6259
11.10.10. Some Areas with Recently or Potentially Acidified Soft Waters	6260
11.10.10.1. Eastern Canada	6260
11.10.10.2. Eastern United States	6260
11.10.10.3. British Isles	6260
11.10.10.4. Scandinavia	6261
11.10.10.5. Continental Europe	6261
11.10.10.6. South America	6261
11.10.10.7. Eastern Asia	6262
11.10.11. Experimental Acidification and Deacidification of LowANC Systems	6262
11.10.11.1. Experimental Acidification of Lakes	6262
11.10.11.2. Experimental Acidification of Wetlands	6262
11.10.11.3. Experimental Acidification of Terrestrial Ecosystems	6262
11.10.11.4. Experimental Acidification of Streams	6263
11.10.12. Remediation of Acidity	6264
11.10.12.1. Ca Additions	6264
11.10.12.2. Nutrient Additions to Eliminate Excess NO3	6264
11.10.12.3. Land Use	6264
11.10.12.3.1. Deforestation	6264
11.10.12.3.2. Afforestation	6265
11.10.13. Chemical Modeling of Acidification of Soft Water Systems	6265
11.10.13.1. SteadyState Models	6265
11.10.13.2. Dynamic Models	6266
11.10.14. Chemical Recovery from Anthropogenic Acidification	6266
Acknowledgments	6269
References	6270
Chapter 11.11: Tropospheric Ozone and Photochemical Smog	6278
11.11.1. Introduction	6279
11.11.2. General Description of Photochemical Smog	6279
11.11.2.1. Primary and Secondary Pollutants	6279
11.11.2.2. Ozone	6280
11.11.2.2.1. Urban ozone	6280
11.11.2.2.2. Regional pollution events and long-distance transport	6280
11.11.2.2.3. Ozone and the global troposphere	6281
11.11.2.2.4. Ozone precursors: NOx, CO, and volatile organics	6282
11.11.2.2.5. Impact of biogenics	6283
11.11.2.3. Particulates	6283
11.11.2.4. Environmental and Health Impacts	6285
11.11.2.5. Long-Term Trends in Ozone and Particulates	6287
11.11.3. Photochemistry of Ozone and Particulates	6287
11.11.3.1. Ozone	6287
11.11.3.1.1. Ozone formation	6287
11.11.3.1.2. Odd hydrogen radicals	6288
11.11.3.1.3. O3, NO, and NO2	6288
11.11.3.1.4. O3– NOx–VOC sensitivity and OH	6289
11.11.3.1.5. Ozone formation in the remote troposphere	6290
11.11.3.1.6. Ozone production efficiency	6290
11.11.3.2. Chemistry of Aerosols	6291
11.11.3.3. Ozone–Aerosol Interactions	6292
11.11.4. Meteorological Aspects of Photochemical Smog	6292
11.11.4.1. Dynamics	6292
11.11.4.2. Ozone and Temperature	6294
11.11.5. New Directions: Evaluation Based on Ambient Measurements	6294
Acknowledgments	6297
References	6297
Chapter 11.12: Volatile Hydrocarbons and Fuel Oxygenates	6302
11.12.1. Introduction	6302
11.12.1.1. Scope of the Problem	6302
11.12.1.2. Petroleum Chemical Composition	6305
11.12.1.2.1. Crude oil	6305
11.12.1.2.2. Fuels	6307
11.12.1.2.3. Fuel oxygenates	6307
11.12.1.2.4. Solvents, lubricants, and petrochemical feedstocks	6309
11.12.1.3. Ecological Concerns and Human Exposure Pathways	6309
11.12.2. The Petroleum Industry	6311
11.12.2.1. Petroleum Exploration, Production, and Processing	6311
11.12.2.2. Petroleum Transportation and Storage	6312
11.12.2.3. Petroleum Usage	6313
11.12.2.4. Disposal of Petroleum Wastes	6314
11.12.3. Environmental Transport Processes	6314
11.12.3.1. Phase Partitioning	6314
11.12.3.2. Physical Transport	6320
11.12.4. Transformation Processes	6320
11.12.4.1. Abiotic Transformation	6321
11.12.4.2. Biotic Transformation	6321
11.12.4.2.1. Aerobic processes	6322
11.12.4.2.2. Anaerobic processes	6324
11.12.4.2.3. Fuel hydrocarbon and oxygenate mixtures	6328
11.12.5. Environmental Restoration	6329
11.12.5.1. Natural Attenuation Processes	6329
11.12.5.2. Engineered or Enhanced Remediation	6332
11.12.5.3. Innovative Tools to Assess Remediation	6332
11.12.6. Challenges	6335
Acknowledgments	6336
References	6336
Chapter 11.13: High Molecular Weight Petrogenic and Pyrogenic Hydrocarbons in Aquatic Environments	6344
11.13.1. Introduction	6344
11.13.2. Scope of Review	6345
11.13.3. Sources	6346
11.13.3.1. Petrogenic Hydrocarbons	6346
11.13.3.2. Pyrogenic Sources of HMW Hydrocarbons	6349
11.13.4. Pathways	6352
11.13.5. Fate	6354
11.13.5.1. Sorption	6355
11.13.5.2. Volatilization	6356
11.13.5.3. Water Dissolution and Solubility	6357
11.13.5.4. Photochemical Reactions	6358
11.13.5.5. Biodegradation	6358
11.13.6. Carbon Isotope Geochemistry	6360
11.13.6.1. Carbon Isotope Variations in PAH Sources	6361
11.13.6.1.1. Pyrogenesis	6361
11.13.6.1.2. Pedogenesis	6362
11.13.6.2. Weathering and Isotopic Composition	6363
11.13.6.3. Isotopic Source Apportionment of PAHs in St. John's Harbor: An Example	6364
11.13.7. Synthesis	6367
Acknowledgments	6368
References	6368
Chapter 11.14: Biogeochemistry of Halogenated Hydrocarbons	6374
11.14.1. Introduction	6374
11.14.2. Global Transport and Distribution of Halogenated Organic Compounds	6374
11.14.2.1. Persistent Organic Pollutants	6375
11.14.2.1.1. Global distribution mechanisms	6375
11.14.2.1.2. Contaminant classification	6376
11.14.2.2. Biogenic Pollutants and Anthropogenic Non-POPs	6376
11.14.3. Sources and Environmental Fluxes	6377
11.14.3.1. Adsorbable Organic Halogens	6377
11.14.3.2. Alkyl Halides	6378
11.14.3.3. Aryl Halides	6379
11.14.4. Chemical Controls on Reactivity	6380
11.14.4.1. Phase Partitioning	6380
11.14.4.2. Reaction Energetics	6381
11.14.5. Microbial Biogeochemistry and Bioavailability	6382
11.14.5.1. Ecological Considerations	6382
11.14.5.2. Matrix Interactions	6383
11.14.6. Environmental Reactivity	6384
11.14.6.1. Microbial Reactivity	6384
11.14.6.2. Surface-Mediated Reactivity	6386
11.14.6.3. Organic-Matter-Mediated Reactivity	6387
11.14.6.4. Predictive Models: Structure–Reactivity Relationships	6388
11.14.7. Implications for Environmental Cycling of Halogenated Hydrocarbons	6389
11.14.8. Knowledge Gaps and Fertile Areas for Future Research	6392
Acknowledgments	6393
References	6393
Chapter 11.15: The Geochemistry of Pesticides	6398
11.15.1. Introduction	6399
11.15.1.1. Previous Reviews of Pesticide Geochemistry	6399
11.15.1.2. Scope of This Review	6399
11.15.1.3. Biological Effects of Pesticide Compounds	6399
11.15.1.4. Variations in Pesticide Use over Time and Space	6400
11.15.1.5. Environmental Distributions in Relation to Use	6400
11.15.1.6. Overview of Persistence in the Hydrologic System	6402
11.15.2. Partitioning among Environmental Matrices	6403
11.15.2.1. Partitioning between Soils, Sediments, and Natural Waters	6403
11.15.2.2. Partitioning between Aquatic Biota and Natural Waters	6406
11.15.2.3. Partitioning between Earth's Surface and the Atmosphere	6406
11.15.2.3.1. Movement between air and natural waters	6406
11.15.2.3.2. Movement between air, soil, and plant surfaces	6407
11.15.3. Transformations	6408
11.15.3.1. Photochemical Transformations	6409
11.15.3.2. Neutral Reactions	6410
11.15.3.3. Electron-Transfer Reactions	6411
11.15.3.4. Governing Factors	6413
11.15.3.4.1. Reactant concentrations	6413
11.15.3.4.2. Structure and properties of the pesticide substrate	6414
11.15.3.4.3. Structure and properties of other reactants	6416
11.15.3.4.4. Physical factors	6418
11.15.3.4.5. Geochemical environment	6420
11.15.3.5. Effects of Transformations on Environmental Transport and Fate	6424
11.15.3.6. Occurrence of Pesticide Transformation Products in the Hydrologic System	6425
11.15.4. The Future	6425
Acknowledgments	6427
References	6428
Chapter 11.16: The Biogeochemistry of Contaminant Groundwater Plumes Arising from Waste Disposal Facilities	6436
11.16.1. Introduction	6436
11.16.2. Source and Leachate Composition	6437
11.16.3. Spreading of Pollutants in Groundwater	6438
11.16.4. Biogeochemistry of Landfill Leachate Plumes	6439
11.16.4.1. Redox Environments and Redox Buffering	6439
11.16.4.2. Microbial Activity and Redox Processes	6442
11.16.5. Overview of Processes Controlling Fate of Landfill Leachate Compounds	6443
11.16.5.1. Dissolved Organic Matter, Inorganic Macrocomponents, and Heavy Metals	6445
11.16.5.1.1. Dissolved organic carbon	6445
11.16.5.1.2. Inorganic macrocomponents	6445
11.16.5.1.3. Heavy metals	6445
11.16.5.2. Xenobiotic Organic Compounds	6445
11.16.6. Norman Landfill (United States)	6447
11.16.6.1. Source, Geology, and Hydrogeology	6447
11.16.6.2. Landfill Leachate Plume	6447
11.16.6.2.1. Biogeochemistry of the plume	6447
11.16.6.2.2. Availability of electron acceptors	6452
11.16.6.2.3. Fate of XOCs	6453
11.16.7. Grindsted Landfill Site (DK)	6454
11.16.7.1. Source, Geology, and Hydrogeology	6454
11.16.7.2. Landfill Leachate Plume	6456
11.16.8. Monitored Natural Attenuation	6462
11.16.9. Future Challenges	6463
References	6464
e9780080983004v12	6469
Front Cover	6469
Organic Geochemistry	6472
Copyright	6473
In Memoriam	6474
Heinrich Dieter Holland (1927–2012)	6476
Karl Karekin Turekian (1927–2013)	6478
Dedication	6482
Contents	6484
Executive Editors’ Foreword to the Second Edition	6486
Contributors	6490
Volume Editors’ Introduction	6492
Introduction	6492
Chapter 12.1: Organic Geochemistry of Meteorites	6494
12.1.1. Meteorites and Their Carbon	6494
12.1.2. Classification of Carbonaceous Chondrites	6495
12.1.3. Stable Isotopes and Carbonaceous Chondrites	6495
12.1.4. The Organic Compounds in Carbonaceous Chondrites	6497
12.1.5. Carboxylic Acids	6497
12.1.5.1. Short-Chain Monocarboxylic Acids	6497
12.1.5.2. Long-Chain Monocarboxylic Acids	6499
12.1.5.3. Hydroxycarboxylic Acids	6499
12.1.5.4. Dicarboxylic Acids	6499
12.1.5.5. Aromatic Carboxylic Acids	6500
12.1.5.6. Stable Isotopes and Carboxylic Acids	6500
12.1.6. Amino Acids	6501
12.1.6.1. Free Amino Acids	6501
12.1.6.2. Enantiomeric Excesses	6503
12.1.6.3. Origin of Enantiomeric Excess	6504
12.1.6.4. Amino Acid Precursors	6504
12.1.6.5. Stable Isotopes and Amino Acids	6505
12.1.7. Amines and Amides	6506
12.1.8. Aliphatic Hydrocarbons	6506
12.1.8.1. Short-Chain Alkanes	6506
12.1.8.2. Normal Alkanes	6506
12.1.8.3. Stable Isotopes and Short-Chain Alkanes	6507
12.1.8.4. Stable Isotopes and Normal Alkanes	6508
12.1.9. Aromatic Hydrocarbons	6508
12.1.9.1. Solvent and Thermal Extracts	6508
12.1.9.2. Laser Mass Spectrometry	6509
12.1.9.3. Stable Isotopes and Aromatic Hydrocarbons	6509
12.1.10. Nucleic Acid Bases and Other Nitrogen Heterocycles	6510
12.1.11. Alcohols, Polyhydroxylated Compounds, and Carbonyls	6511
12.1.12. Sulfonic and Phosphonic Acids	6512
12.1.12.1. Chemical Structures	6512
12.1.12.2. Stable Isotopes and Sulfonic and Phosphonic Acids	6512
12.1.13. Organohalogens	6512
12.1.14. Macromolecular Material	6512
12.1.14.1. Aliphatic and Aromatic Units	6512
12.1.14.2. Oxygen-Containing Units	6513
12.1.14.3. Sulfur-Containing Units	6514
12.1.14.4. Nitrogen-Containing Units	6514
12.1.14.5. Radicals	6514
12.1.14.6. Stable Isotopes and the Macromolecular Material	6514
12.1.14.7. Variations Within and Between Macromolecular Materials	6515
12.1.15. Microvesicles and Nanoglobules	6516
12.1.16. Organic-Inorganic Relationships	6518
12.1.17. Source Environments	6518
References	6519
Chapter 12.2: Organic Geochemical Signatures of Early Life on Earth	6526
12.2.1. Introduction	6526
12.2.2. Eoarchean (4.0-3.6Ga) Biological Remnants?	6526
12.2.3. The Post-3.5Ga Sedimentary Record of Stable Carbon Isotopes	6527
12.2.4. The Record of Organic Carbon Burial	6528
12.2.5. The Composition of Buried Organic Matter	6530
12.2.6. Visible Structures with Organic Affinities	6533
12.2.6.1. Organic-Walled Microfossils	6533
12.2.6.2. Fossil Microbial Mats, Textures, and Trace Fossils	6534
12.2.6.3. Stromatolites	6534
12.2.7. Summary and Prospects	6535
Acknowledgments	6536
References	6536
Chapter 12.3: The Analysis and Application of Biomarkers	6540
12.3.1. Introduction	6540
12.3.2. Biomarkers and Environments	6542
12.3.2.1. Introduction	6542
12.3.2.2. Hopanoids	6546
12.3.2.3. Steranes	6547
12.3.2.4. Marine/Lacustrine Environments	6548
12.3.2.5. Marine Environments	6548
12.3.2.6. Lacustrine Environments	6549
12.3.2.7. Terrigenous Environments	6549
12.3.2.7.1. Steranes	6549
12.3.2.7.2. n-Alkanes	6549
12.3.2.7.3. Diterpenoids	6550
12.3.2.7.4. Triterpenoids	6550
12.3.2.8. Biomarkers for Specific Environmental Conditions	6551
12.3.2.8.1. Photic zone euxinia	6551
12.3.2.8.2. Purple sulfur bacteria	6551
12.3.2.8.3. Green sulfur bacteria	6552
12.3.2.8.4. Archaea	6554
12.3.2.8.5. Glycerol dialkyl glycerol tetraethers	6554
12.3.2.8.6. TEX86 and other GDGT-based palaeotemperature proxies	6556
12.3.2.8.7. Halophilic archaea	6556
12.3.3. Age-Diagnostic Biomarkers	6557
12.3.3.1. n-Alkanes	6557
12.3.3.2. Evolution of the Land Plants in the Late Devonian	6557
12.3.3.3. Evolution of Flowering Plants in the Cretaceous	6557
12.3.3.4. Botryococcanes in Tertiary Lakes	6558
12.3.3.5. Evolution of Demospongiae in the Latest Neoproterozoic	6558
12.3.3.6. Evolution of Dinoflagellates in the Late Mesozoic	6558
12.3.3.7. Evolution of Diatoms in the Jurassic	6558
12.3.3.8. Age-Diagnostic Steranes	6559
12.3.4. Biomarkers of Fungi	6559
12.3.5. Biomarkers and Extinction Events	6559
12.3.5.1. Permian/Triassic	6559
12.3.5.2. Triassic/Jurassic	6560
12.3.5.3. The Palaeocene-Eocene Thermal Maximum	6561
12.3.6. Analytical Approaches	6561
12.3.6.1. Analytical Pyrolysis	6561
12.3.6.2. Laser Micropyrolysis GC-MS	6562
12.3.6.3. Catalysed HyPy	6562
12.3.6.4. Stable Isotope Analysis	6562
12.3.6.5. Comprehensive Two-Dimensional Gas Chromatography (GCxGC)	6563
12.3.6.6. Time-of-Flight Secondary Ion Mass Spectrometry	6563
12.3.7. Summary	6563
Acknowledgments	6563
References	6563
Chapter 12.4: Hydrogen Isotope Signatures in the Lipids of Phytoplankton	6572
12.4.1. Introduction	6572
12.4.2. The Effect of δDwater on δDlipid	6573
12.4.3. The Effect of Biosynthesis on δDlipid	6575
12.4.4. The Effect of Species on δDlipid	6576
12.4.5. The Effect of Salinity on δDlipid	6576
12.4.6. The Effect of Temperature on δDlipid	6580
12.4.7. The Effect of Growth Rate on δDlipid	6582
12.4.7.1. Substrate-Limited Growth Rate Effects	6582
12.4.7.2. Light-Limited Growth Rate Effects	6585
12.4.8. Summary and Conclusions	6585
Acknowledgments	6585
References	6585
Chapter 12.4: 13C/12C Signatures in Plants and Algae	6588
12.5.1. Introduction	6588
12.5.2. The Term ‘Isotopic Fractionation’	6589
12.5.3. Isotopic Fractionation in Plants and Algae	6592
12.5.3.1. Outline	6592
12.5.3.2. δ13C of Source Carbon	6592
12.5.3.3. Isotopic Fractionation During Photosynthesis	6594
12.5.3.3.1. Outline	6594
12.5.3.3.2. Terrestrial C3 plants	6594
12.5.3.3.3. Aquatic plants and algae	6596
12.5.3.3.4. Terrestrial C4 plants	6596
12.5.3.3.5. Terrestrial CAM plants	6596
12.5.3.3.6. Experimental values for	6597
12.5.3.3.7. Other factors	6597
12.5.3.4. Model for Isotopic Fractionation in Biosynthetic Products	6598
12.5.3.5. Sources of Carbon Atoms for Biosynthetic Products	6602
12.5.3.5.1. Outline	6602
12.5.3.5.2. Lipids	6602
12.5.3.5.3. Amino acids	6603
12.5.3.5.4. Chlorophylls	6607
12.5.3.5.5. Nucleic acid bases	6607
12.5.3.5.6. Lignin	6609
12.5.3.6. A Deeper Understanding of Isotopic Fractionation in Lipid Biosynthesis	6609
12.5.3.7. Topics for Further Study	6611
References	6612
Chapter 12.6: Dissolved Organic Matter in Aquatic Systems	6618
12.6.1. Introduction	6620
12.6.2. Inventory and Fluxes	6621
12.6.2.1. The Global Inventory	6621
12.6.2.2. Sources to the Ocean	6621
12.6.2.3. Turnover and Flux of Marine DOM	6622
12.6.2.4. What Happens to Terrigenous DOM?	6624
12.6.2.5. Global Distribution	6624
12.6.3. Bulk Chemical Properties	6626
12.6.3.1. Carbon Isotopes	6626
12.6.3.1.1. Stable carbon isotopes	6626
12.6.3.1.2. Radiocarbon	6626
12.6.3.2. Optical Properties	6627
12.6.3.2.1. Colored DOM	6627
12.6.3.2.2. Fluorescent DOM	6630
12.6.3.3. Nuclear Magnetic Resonance	6631
12.6.4. The Composition of DOM on an Individual Molecular Level	6633
12.6.4.1. Introduction	6633
12.6.4.2. Ultrahigh-Resolution Mass Spectrometry	6634
12.6.4.3. Interaction Among Individual Molecules	6638
12.6.4.4. Molecular Clues on the Source and Turnover of Marine DOM	6639
12.6.4.4.1. Introduction	6639
12.6.4.4.2. The fate of terrigenous DOM in the ocean	6639
12.6.4.4.3. A thermogenic component	6640
12.6.4.4.4. The microbial imprint	6640
12.6.5. Reasons Behind the Stability of DOM in the Deep Ocean	6641
12.6.6. Perspectives	6643
12.6.6.1. What Is the Substrate on Which Marine Microorganisms Grow?	6643
12.6.6.2. Why Do DOM Molecules Lose Their Physiological Function Over Time?	6643
12.6.6.3. Reading the Molecular Archive for Historic Reconstruction	6643
12.6.6.4. What Are the Organic Ligands of Essential Trace Metals?	6644
Acknowledgments	6644
References	6644
Chapter 12.7: Dynamics, Chemistry, and Preservation of Organic Matter in Soils	6650
12.7.1. Soil Organic Matter and Soil Functions	6651
12.7.2. Input and Quantity of SOM	6653
12.7.2.1. Amount of OM in Soils	6653
12.7.2.2. Plant and Microbial Input to SOM	6654
12.7.2.2.1. Aboveground input	6654
12.7.2.2.2. Belowground input	6655
12.7.2.3. Plant Compound Classes	6655
12.7.2.3.1. Cellulose	6656
12.7.2.3.2. Noncellulosic polysaccharides	6656
12.7.2.3.3. Lignin	6656
12.7.2.3.4. Tannins and other polyphenols	6656
12.7.2.3.5. Lipids	6656
12.7.2.3.6. Cutin and suberin	6657
12.7.2.3.7. N-, S-, and P-containing compounds	6657
12.7.2.3.8. Specific components of fungi and bacteria	6658
12.7.2.4. Charcoal	6660
12.7.3. Composition and Transformation of Organic Matter in Soils	6661
12.7.3.1. Bulk SOM Composition	6661
12.7.3.2. Organic Matter in Subsoils	6665
12.7.4. Turnover of SOM	6666
12.7.4.1. Pools and Models	6666
12.7.4.2. Assessing Mean Residence Times on the Bases of C Isotopic Composition	6667
12.7.4.2.1. δ13C abundance measurements as a tool for turnover assessment	6667
12.7.4.2.2. Δ14C abundance measurements as a tool for turnover assessment	6669
12.7.4.2.3. Turnover of OC in topsoils and subsoils	6669
12.7.5. Origin and Turnover of Specific Components in Soils	6670
12.7.5.1. Biomarkers for Plant-Derived C	6670
12.7.5.1.1. Lignins	6670
12.7.5.1.2. Tannins	6673
12.7.5.1.3. Aliphatic compounds	6673
12.7.5.1.4. Carbohydrates	6674
12.7.5.2. Biomarkers for Living Microbial Biomass	6674
12.7.5.2.1. Phospholipid fatty acids	6674
12.7.5.2.2. Ergosterol and others	6675
12.7.5.2.3. Glycerol dialkyl glycerol tetraethers	6675
12.7.5.3. Biomarkers for Dead Microbial Biomass	6675
12.7.5.3.1. Terpenoids	6675
12.7.5.3.2. Nitrogen-containing biomarkers	6675
12.7.5.4. Biomarkers for Off-Site Contributions to SOM	6676
12.7.5.4.1. Steroids and bile acids	6676
12.7.5.4.2. Benzene polycarboxylic acids	6676
12.7.5.5. Examples for Applications in Soil Science	6677
12.7.5.5.1. Changes in biomarker signature with prolonged arable cropping	6677
12.7.5.5.2. Biomarkers in particle-size fractions	6678
12.7.5.6. Turnover Rates of Different Biomarkers	6679
12.7.5.6.1. Biomarker-specific stable isotope analyses in artificial labeling experiments	6679
12.7.5.6.2. Biomarker-specific stable isotope analyses after C3/C4 vegetation change	6680
12.7.6. Soil-Specific Interactions of OM with the Mineral Phase	6682
12.7.6.1. Soil Architecture and Its Effects on C Turnover and Stabilization	6682
12.7.6.1.1. Accessibility/aggregation	6682
12.7.6.1.2. Organomineral interactions	6684
12.7.6.1.3. Types of C and N in organomineral associations	6684
12.7.6.1.4. Phyllosilicate clay minerals	6684
12.7.6.1.5. Pedogenic oxides	6685
12.7.6.1.6. Interactions with metal ions	6685
12.7.6.2. SOM Formation in Major Soil Types	6685
12.7.6.2.1. Chernozems	6686
12.7.6.2.2. Podzols	6687
12.7.6.2.3. Ferralsols	6689
12.7.6.2.4. Cryosols	6690
12.7.6.2.5. Andosols	6691
12.7.6.2.6. Man-made soils (Anthrosols)	6692
12.7.6.2.6.1. Paddy soils	6692
12.7.6.2.6.2. Terra preta	6694
12.7.7. Peculiarities	6695
References	6698
Chapter 12.8: Weathering of Organic Carbon	6710
12.8.1. Introduction	6710
12.8.2. Reservoirs and Fluxes in the Geochemical Carbon Cycle	6710
12.8.2.1. Rock Reservoirs of Carbon	6710
12.8.2.2. Addition of OM to the Rock Reservoir: OM Burial	6711
12.8.2.3. Removal of OM from the Rock Reservoir: Weathering, Erosion, and Oxidation	6712
12.8.3. Weathering of Kerogen	6713
12.8.3.1. Weathering of Kerogen in Black Shales	6713
12.8.3.1.1. Decreases in organic carbon content	6713
12.8.3.1.2. Changes in kerogen composition accompanying weathering	6714
12.8.3.1.3. Changes in bitumen composition during weathering	6717
12.8.3.2. Metals and Minerals During Shale Weathering	6717
12.8.3.3. Oxidative Weathering of OM-Rich Sediments	6718
12.8.3.4. Models of Shale Weathering	6719
12.8.4. Biodegradation of Sedimentary OM	6719
12.8.4.1. Direct Biodegradation of Kerogen and Coal	6719
12.8.4.2. Hydrocarbon Biodegradation During Weathering	6720
12.8.4.3. Biodegradation of Rock-Derived Hydrocarbons	6721
12.8.4.4. Fossil OM Biodegradation in the Subsurface	6721
12.8.5. Surficial Transport and Transformations of Fossil OM	6722
12.8.5.1. Kerogen Recycling Along Active Continental Margins	6722
12.8.5.2. River Transport and Transformations of Rock-Derived OM	6722
12.8.6. Model Estimates of Global Organic Carbon Weathering	6723
12.8.6.1. Models of the Geochemical Cycles of Carbon and Oxygen	6723
12.8.6.2. OC Loss Through Chemical Weathering of Sedimentary Rocks	6725
12.8.6.3. Global Re Fluxes: Constraints on OM Weathering	6727
12.8.7. Synthesis and Conclusions: Carbon Weathering in the Global Carbon Cycle	6727
References	6728
Chapter 12.9: Organic Carbon Cycling and the Lithosphere	6732
12.9.1. Introduction	6732
12.9.2. Carbon Content of the Continental Crust	6732
12.9.3. Isotopic Constraints on Crustal Carbon	6734
12.9.4. Cycling of Crustal Carbon	6735
12.9.5. Inconsistencies in Crustal-Sedimentary Carbon Budgets	6736
12.9.6. Carbon Cycling Under Reduced Atmospheric Oxygen Levels	6738
12.9.7. Conclusions	6740
References	6741
Chapter 12.10: Organic Nitrogen: Sources, Fates, and Chemistry	6744
12.10.1. Introduction	6744
12.10.2. Nitrogen Assimilation and Isotopic Effects	6745
12.10.2.1. Background	6745
12.10.2.2. Nitrogen Assimilation Processes by Autotrophs	6746
12.10.2.3. Nitrogen Isotopic Fractionation Associated with Autotrophic Nitrogen Assimilation	6747
12.10.2.4. Nitrification and Denitrification	6749
12.10.2.5. Applications to Oceanic Systems	6750
12.10.3. Cellular Nitrogenous Compounds and Isotope Effects	6751
12.10.3.1. Background	6751
12.10.3.2. Amino Acids and Proteins	6752
12.10.3.3. Nucleobases and Nucleic Acids	6755
12.10.3.4. Chlorophylls	6756
12.10.3.5. Other Tetrapyrroles	6758
12.10.3.6. Other Nitrogenous Compounds	6759
12.10.4. Organic Nitrogen in Sediments and Its Application to Paleoenvironmental Reconstructions	6760
12.10.4.1. Background	6760
12.10.4.2. Degradations of Proteins and Amino Acids and Isotopic Effects on Bulk Organic Nitrogen	6761
12.10.4.3. Chlorins	6763
12.10.4.4. Alkyl Porphyrins	6765
12.10.4.5. Maleimides	6768
12.10.4.6. Other Nitrogenous Compounds	6769
12.10.5. Related Topics	6770
12.10.5.1. Ecological and Archaeological Applications	6770
12.10.5.2. Recent Advances in Enantiomer-Specific Nitrogen Isotope Analysis of Amino Acids	6771
12.10.5.3. Extraterrestrial Nitrogenous Compounds	6772
12.10.6. Conclusions	6775
Acknowledgments	6775
References	6775
Chapter 12.11: Lipidomics for Geochemistry	6784
12.11.1. Introduction	6784
12.11.2. Lipid Biosynthetic Pathways	6785
12.11.2.1. Acetogenic Lipids	6785
12.11.2.2. Isoprenoids - MVA Pathway	6788
12.11.2.3. Isoprenoids - MEP Pathway	6789
12.11.2.4. Ether and Ester Linkages to Glycerol - Bacteria and Eukaryotes	6790
12.11.2.5. Diethers and Tetraethers of Archaea	6793
12.11.2.6. Glycerol Membrane Lipids: Final Comments	6795
12.11.2.7. Polar Head Groups	6795
12.11.2.8. Linear Polyprenes	6801
12.11.2.9. Hopanoids	6801
12.11.2.10. Steroids	6802
12.11.2.11. Ladderanes	6803
12.11.2.12. Long-Chain Alkenones	6805
12.11.2.13. Highly Branched Isoprenoids of Diatoms	6805
12.11.3. Case Studies and Approaches to Lipidomics	6806
12.11.3.1. Examples Using Bacterial Genetics	6807
12.11.3.1.1. Role of squalene-hopene cyclase in the synthesis of hopanoid lipids	6808
12.11.3.1.2. Synthesis of A-ring methylated bacteriohopanepolyols	6809
12.11.3.1.3. Synthesis of hopanoid C5 side chains	6810
12.11.3.2. Examples Using Genomic Data from Characterized Species	6810
12.11.3.2.1. Bacteria capable of sterol biosynthesis	6811
12.11.3.2.2. Anaerobes capable of synthesizing hopanoids	6811
12.11.3.2.3. The distribution of phosphatidylcholine in bacteria	6812
12.11.3.2.4. Hypotheses about synthesis of ladderane lipids	6812
12.11.3.3. Examples Using Environmental Metagenomics and Functional Genomics	6813
12.11.3.3.1. Functional gene surveys - environmental shc genes	6813
12.11.3.3.2. General metagenomic surveys - hopanoid synthesis genes	6814
12.11.3.3.3. General metagenomic surveys - other lipid biosynthetic pathways	6815
12.11.3.4. Examples Using Experimental Biochemical Approaches	6817
12.11.3.4.1. Synthesis of botryococcene	6817
12.11.3.4.2. Multifunctional 2,3-oxidosqualene cyclases in plants	6817
12.11.3.5. Examples Using SSU rRNA Combined with Taxonomic Specificity of Biomarkers	6818
12.11.3.5.1. Paleorecord of alkenone-producing haptophyte algae	6819
12.11.3.5.2. Highly branched isoprenoids of diatoms	6819
12.11.4. Conclusions	6820
Acknowledgments	6820
References	6820
Chapter 12.12: Mineral Matrices and Organic Matter	6830
12.12.1. Introduction	6831
12.12.2. Evidence for Organic Matter Association with Minerals	6833
12.12.2.1. Correlations with Grain Size and Mineral-Specific Surface Area	6833
12.12.2.2. Why Do Organic Matter and Minerals Stick Together?	6833
12.12.2.2.1. Sorption	6834
12.12.2.2.1.1. Ligand exchange	6834
12.12.2.2.1.2. Ion exchange	6834
12.12.2.2.1.3. Cation bridging	6834
12.12.2.2.1.4. Van der Waals forces	6834
12.12.2.2.1.5. Hydrogen bonding	6834
12.12.2.2.1.6. Hydrophobic interactions	6834
12.12.2.2.1.7. Multimode sorption	6835
12.12.2.2.1.8. Intercalation	6836
12.12.2.2.2. Occlusion by biomineralization	6836
12.12.2.2.3. Secondary architectures: aggregation	6836
12.12.2.2.4. The role of mineral surface area and geometry	6839
12.12.3. Impact on Organic Matter	6839
12.12.3.1. Compositional Variations Among Different Mineral Associations	6839
12.12.3.2. Organic Matter Stabilization and Destabilization	6840
12.12.3.2.1. Abiotic and biotic roles of minerals in organic matter decay	6840
12.12.3.2.2. Minerals as organic matter stabilizers	6840
12.12.3.2.3. Does mineralogy influence protection?	6842
12.12.3.3. Crosscutting Themes	6843
12.12.3.3.1. Microbial roles	6843
12.12.3.3.2. Oxygen effects on bulk organic matter persistence	6844
12.12.3.3.3. Physical disturbance	6845
12.12.4. Future Directions	6846
12.12.5. Conclusion	6847
Acknowledgments	6847
References	6847
Chapter 12.13: Biomarker-Based Inferences of Past Climate: The Alkenone pCO2 Proxy	6854
12.13.1. Introduction	6854
12.13.2. The Alkenone CO2 Proxy	6854
12.13.2.1. Roots of the Methodology	6854
12.13.2.2. Models of Algal Carbon Isotope Fractionation Assuming Diffusive Carbon Transport	6855
12.13.2.3. Development of the Alkenone-CO2 Proxy	6857
12.13.2.4. The Calibration of `b´ and Estimates of εf	6858
12.13.3. CO2 Reconstructions, Uncertainties, and Complications	6859
12.13.3.1. The Influence of Growth Rate and Irradiance	6861
12.13.3.1.1. Dilute cultures and mesocosm experiments	6861
12.13.3.1.2. Ocean and surface sediment data	6862
12.13.3.1.3. The case against growth rate as the dominant influence on εp37:2	6862
12.13.3.2. Consideration of Cell Geometry Changes on Long-Term εp37:2 Records	6863
12.13.4. Active Transport and the Case Against the Diffusive Model of Carbon Uptake	6865
12.13.4.1. Models for Active Carbon Uptake	6866
12.13.5. Summary	6867
References	6868
Chapter 12.14: Biomarker-Based Inferences of Past Climate: The TEX86 Paleotemperature Proxy	6872
12.14.1. Introduction	6872
12.14.2. History and Systematics	6872
12.14.3. Detection and Analysis of GDGTs	6874
12.14.4. Ecology of the Thaumarchaeota and Implications for TEX86	6874
12.14.5. Preservation of GDGT Lipids in Sediments	6877
12.14.6. Calibration of TEX86 to Temperature	6877
12.14.6.1. Mesocosm Calibrations	6877
12.14.6.2. Surface-Sediment Calibrations	6878
12.14.7. Conclusion	6883
References	6884
Chapter 12.15: Biomarkers for Terrestrial Plants and Climate	6888
12.15.1. Higher Plants Biomarkers	6888
12.15.1.1. n-Alkyl Compounds in Plant Cuticle	6888
12.15.1.1.1. n-Alkane concentrations in leaves of vascular plants	6889
12.15.1.1.2. n-Alkane distributions: average chain length	6889
12.15.1.1.3. n-Alkane distributions: carbon preference index	6891
12.15.1.1.4. Alkyl compounds and aliphatic carbon preservation	6891
12.15.1.1.5. Other sources for n-alkyl compounds	6892
12.15.1.2. Terpenoids	6892
12.15.1.3. Macromolecular Components of Vascular Plants: Lignin and Related Structures	6894
12.15.2. Soil and Lake Microbial Lipids and Proxies for Terrestrial Paleoclimate	6895
12.15.3. Carbon Isotope Signatures of Vegetation and Climate	6896
12.15.3.1. Carbon Isotopic Compositions of C3 Plants	6897
12.15.3.1.1. Sensitivity of C3 photosynthetic isotope fractionation to water	6897
12.15.3.1.2. Sun exposure, growth rates, and the canopy effect	6898
12.15.3.1.3. Atmospheric CO2 concentrations and plant delta13C &INS id	6898
12.15.3.1.4. Fractionation and atmospheric CO2 concentration	6899
12.15.3.2. Carbon Isotopic Composition of C4 Plants	6899
12.15.3.3. C4 Evolution, Ecosystems, and Past Climates	6899
12.15.3.4. Woodland-Grassland Ecosystems and C3/C4 Mixing Models	6900
12.15.4. Lipid-Leaf Fractionation Factors	6900
12.15.5. Transport and Preservation in Soils, Lakes, and Marine Sediments	6901
12.15.5.1. Transport Means and Depositional Setting	6901
12.15.5.2. The Impact of Fire on Aeolian Inputs	6901
12.15.5.3. Catchment and Landscape Dynamics: Hydrology, Topography, Vegetation, and Erosion	6902
12.15.5.4. Soil and Shelf Residence Time	6902
12.15.6. Terrestrial Biomarkers and Isotopes: Research Outlook	6902
Acknowledgments	6902
References	6902
e9780080983004v13	6910
Front Cover	6910
Geochemistry of Mineral Depsoits	6913
Copyright	6914
IN MEMORIAM	6915
HEINRICH DIETER HOLLAND (1927–2012)	6917
KARL KAREKIN TUREKIAN (1927–2013)	6919
DEDICATION	6923
CONTENTS	6925
EXECUTIVE EDITORS’ FOREWORD TO THE SECOND EDITION	6927
CONTRIBUTORS	6931
VOLUME EDITOR’S INTRODUCTION	6933
Chapter 13.1: Fluids and Ore Formation in the Earths Crust	6937
13.1.1. Ore Deposits and Crustal Geochemistry	6938
13.1.1.1. Ores, Mineral Deposits, and Crustal Composition	6938
13.1.1.2. Economic Aspects: Deposit Assessment, Grade, and Resources and Reserves	6938
13.1.1.3. Extreme Metal Enrichment: A Rare Conjunction of Common Processes	6940
13.1.2. Magmatic Ore Formation	6941
13.1.3. Ore-Forming Hydrothermal Processes	6944
13.1.3.1. Physical Aspects of Hydrothermal Metal Enrichment	6945
13.1.3.1.1. Energy sources driving fluid flow	6945
13.1.3.1.2. Fluid focusing and `structural control´	6946
13.1.3.1.3. Timescales of fluid flow and heat transfer	6946
13.1.3.2. Chemical Driving Forces for Hydrothermal Metal Enrichment	6947
13.1.3.2.1. Rock buffering and fluid-chemical master variables	6947
13.1.3.2.2. Sulfide solubility and base-metal content of crustal fluids	6948
13.1.3.2.3. Example: Hydrothermal redistribution of gold	6950
13.1.3.3. Metal Source Regions versus Ore Deposition Sites	6951
13.1.3.3.1. Source region characteristics	6951
13.1.3.3.2. Ore deposition and wall-rock alteration	6951
13.1.4. Hydrothermal Ore Formation in Sedimentary Basins	6952
13.1.5. Hydrothermal Ore Systems in the Oceanic Realm	6953
13.1.6. Magmatic-Hydrothermal Ore Systems	6953
13.1.6.1. Melt Generation, Magma Storage, and Ascent	6953
13.1.6.2. Fluid Exsolution and Element Transfer from Melt to Fluid	6955
13.1.6.3. Fluid Cooling, Decompression, and Phase Separation	6955
13.1.6.4. Fluid Evolution Paths at the Porphyry to Epithermal Transition	6956
13.1.6.5. Wall-Rock Alteration and Ore Mineral Precipitation	6957
13.1.7. Ore Formation at the Earth's Surface	6958
13.1.8. Back to the Future: Global Mineral Resources	6959
Acknowledgments	6959
References	6959
Chapter 13.2: The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids	6965
13.2.1. Introduction	6965
13.2.1.1. Compositions of Ore-Forming Fluids	6966
13.2.2. Hydrothermal Ore Solution Chemistry - The Main Dissolved Components	6969
13.2.2.1 Water Solvent at Hydrothermal Conditions	6969
13.2.2.2 NaCl – The Main Dissolved Electrolyte Component	6971
13.2.2.3 Ion Hydration, Association, and Water Activity	6971
13.2.2.4 Weak Acid/Base Equilibria in Hydrothermal Systems	6972
13.2.3. Mineral Solubility in Water and Salt Solutions at High Temperature and Pressure	6973
13.2.4. Ore Metal Transport and Deposition	6976
13.2.4.1. Ore Fluids with Liquid-Like Densities	6976
13.2.4.1.1. Ligands in hydrothermal ore solutions	6976
13.2.4.1.2. Metal chloride complexing	6977
13.2.4.1.3. Complexing with other halide ligands	6978
13.2.4.1.4. Metal complexes with hydroxide and other oxygen electron donor ligands	6979
13.2.4.1.5. Complexing with hydrosulfide/sulfide ligands	6981
13.2.4.1.6. Thioanions	6982
13.2.4.1.7. Complexing with other sulfur-containing ligands	6983
13.2.4.1.8. Other complexing ligands	6984
13.2.4.1.9. Ore fluids with gas-like density	6984
13.2.5. Epilogue	6986
Acknowledgments	6986
References	6986
Chapter 13.3: Stable Isotope Geochemistry of Mineral Deposits	6995
13.3.1. Introduction	6995
13.3.2. Fundamental Aspects of Stable Isotope Geochemistry	6995
13.3.3. Stable Isotope Systematics	6996
13.3.3.1. Delta Notation	6996
13.3.3.2. Fractionation Equations	6996
13.3.3.3. Reservoir Effects and Mass Balance Calculations	6997
13.3.3.4. Water/Rock Ratio	6998
13.3.4. Analytical Methods	6998
13.3.5. Ore Deposit Types	6998
13.3.5.1. Magmatic Sulfide and PGE Deposits	6998
13.3.5.2. Porphyry Deposits	6999
13.3.5.3. Skarn Deposits	7001
13.3.5.4. Volcanogenic Massive Sulfide Deposits	7004
13.3.5.5. Sedimentary-Exhalative and Mississippi Valley-Type Deposits	7011
13.3.5.6. Precious-Metal Deposits: Epithermal, Carlin-Type, and Orogenic Au	7013
13.3.5.7. Banded Iron Formation	7014
13.3.6. Summary and Conclusions	7016
Acknowledgments	7018
References	7018
Chapter 13.4: Dating and Tracing the History of Ore Formation	7023
13.4.1. A Holistic Approach to Ore Geology	7024
13.4.1.1. What We Know	7024
13.4.1.2. Critical and Compromising Gaps	7025
13.4.1.3. Meaningful Results	7025
13.4.1.4. Meaningful Models	7026
13.4.2. The Fourth Dimension - Time	7026
13.4.2.1. The Transcendence of Time	7026
13.4.2.2. Time Ties that Bind	7027
13.4.3. Radiometric Clocks	7027
13.4.3.1. What Geologic Clocks Measure	7027
13.4.3.2. How Radiometric Clocks Work	7028
13.4.3.2.1. Ages through single mineral clocks	7029
13.4.3.2.2. Ages through isochrons	7030
13.4.3.2.3. Conditions for isotopic closure	7030
13.4.3.2.3.1. Thermal dependence	7031
13.4.3.2.3.2. Chemical dependence	7032
13.4.4. Radiometric Clocks for Ore Geology	7033
13.4.4.1 U–Th–Pb (Uranium–Thorium–Lead)	7033
13.4.4.1.1. Zircon (ZrSiO4)	7033
13.4.4.1.2. Monazite (Ce, LREE, Th, U, Ca)PO4	7034
13.4.4.1.3. Uraninite (UO2)	7034
13.4.4.2. Pb-Pb (Lead-Lead)	7034
13.4.4.3. Pt-Os (Platinum-Osmium)	7036
13.4.4.4. Rb-Sr (Rubidium-Strontium)	7036
13.4.4.5. 40Ar/39Ar (Argon-Argon)	7036
13.4.4.6. Sm-Nd (Samarium-Neodymium)	7037
13.4.5 Rhenium–Osmium – A Clock for Sulfides	7037
13.4.5.1. Where We Find Re and Os	7037
13.4.5.2. Historical Background	7037
13.4.5.2.1. Sample-spike equilibration	7037
13.4.5.2.2 Negative TIMS	7037
13.4.5.2.3. An interlaboratory age standard	7038
13.4.5.2.4. Half-life hurdles - the 187Re decay constant	7038
13.4.5.2.5. Stoichiometry of Os standards	7038
13.4.5.3. The Last Steps for the First Chronometer for Ore Deposition	7039
13.4.5.3.1. Comparison of Re-Os ages with other ages	7039
13.4.5.3.2. Lack of effect of alteration on Re-Os systematics	7039
13.4.5.3.3. Parent-daughter decoupling conundrum in molybdenite	7039
13.4.5.3.4. Revival of model ages for geochronometry	7040
13.4.5.4. Molybdenite Dating of a Young Porphyry Cu-(Mo) Deposit in Chile	7040
13.4.5.4.1. Full circle back to the field	7043
13.4.5.5. Molybdenite Dating of an Old Porphyry Cu-(Mo) Deposit in Northern Sweden	7044
13.4.5.6. Low Level, Highly Radiogenic (LLHR) Sul	7045
13.4.6. Re-Os in Nonsulfides	7046
13.4.6.1. Chromite (FeCr2O4)	7046
13.4.6.2. Magnetite (Fe3O4)	7047
13.4.6.3. Native Gold	7047
13.4.7. A Clock for Metal Release and Migration from Hydrocarbon Maturation	7047
13.4.8. Future of Dating for Ore Geology and Mineral Exploration	7048
Acknowledgments	7049
References	7049
Chapter 13.5: Fluid Inclusions in Hydrothermal Ore Deposits	7055
13.5.1. Introduction	7056
13.5.2. Mississippi Valley-Type Deposits	7056
13.5.2.1. Composition of MVT Fluids	7057
13.5.2.1.1. Major cations	7057
13.5.2.1.2. Ore metals	7057
13.5.2.2. MVT Fluid Sources	7058
13.5.3. Volcanogenic Massive Sulfide (VMS) Deposits	7058
13.5.3.1. General Fluid Characteristics	7058
13.5.3.2. Composition of VMS Fluids	7058
13.5.3.3. VMS Fluid Sources	7059
13.5.4. Epithermal Gold and Silver Deposits	7059
13.5.4.1. Overall Temperature and Salinity Ranges of Epithermal Fluids	7060
13.5.4.2. Compositional Variations of Epithermal Fluids	7060
13.5.4.2.1. Sulfidation state	7060
13.5.4.2.2. Correlation between metals in ore and fluid salinity	7060
13.5.4.2.3. Volatiles	7061
13.5.4.2.4. Depth of formation	7061
13.5.4.2.5. Source of mineralizing fluids	7061
13.5.5. Porphyry Cu Deposits	7062
13.5.5.1. Homogenization Temperature and Salinity Data	7062
13.5.5.1.1. Variation in Th and salinity with alteration and mineralization	7063
13.5.5.2. Compositions of Individual Fluid Inclusions	7064
13.5.5.2.1. Copper content of ore fluids	7064
13.5.5.3. Depth and Pressure of Ore Formation	7065
13.5.6. Porphyry Mo Deposits	7065
13.5.6.1. Homogenization Temperature and Salinity Data	7065
13.5.6.2. Depth and Pressure of Ore Formation	7066
13.5.6.3. Source of Metals in Porphyry Mo Deposits	7066
13.5.7. Porphyry Sn-W Deposits	7066
13.5.7.1. General Fluid Characteristics	7066
13.5.7.2. Fluid Composition	7067
13.5.7.3. Fluid Source	7067
13.5.7.4. Precipitation Mechanism	7067
13.5.8. Skarn Deposits	7068
13.5.8.1. Homogenization Temperature and Salinity Data	7068
13.5.8.2. Sources of Fluids	7069
13.5.8.3. Pressures and Depths of Mineralization	7069
13.5.9. Carlin-Type Au Deposits	7069
13.5.9.1. Homogenization Temperature, Salinity, and Volatile Data	7070
13.5.9.2. Pressure and Depth of Formation	7070
13.5.9.3. Source of Mineralizing Fluids	7070
13.5.10. Orogenic Gold Deposits	7070
13.5.10.1. Compositional and Microthermometric Data	7070
13.5.10.2. Compositions of Orogenic Gold Fluids	7070
13.5.10.2.1. Major ions	7071
13.5.10.2.2. Volatile components	7071
13.5.10.3. Evidence of Immiscibility	7072
13.5.10.4. Depths of Formation	7072
13.5.10.5. Sources of Mineralizing Fluids	7072
13.5.11. Concluding Remarks and Future Directions	7073
Acknowledgments	7073
References	7073
Chapter 13.6: Melt Inclusions	7079
13.6.1. Introduction	7079
13.6.2. Formation of Melt Inclusions	7080
13.6.3. Postentrapment Changes in Melt Inclusions	7081
13.6.4. Analytical Techniques	7084
13.6.4.1. Melt-Inclusion Rehomogenization	7084
13.6.4.2. Electron Microprobe Analysis	7085
13.6.4.3. Secondary Ion Mass Spectrometry	7086
13.6.4.4. Laser Ablation ICP-MS	7086
13.6.4.5. Spectroscopic Techniques	7087
13.6.5. Information Obtainable from Melt Inclusions	7087
13.6.5.1. Coexistence with other Phases	7087
13.6.5.1.1. Immiscibility between silicate melt and aqueous fluid	7089
13.6.5.1.2. Immiscibility between silicate melt and salt melts	7089
13.6.5.1.3. Silicate melt-silicate melt immiscibil	7090
13.6.5.2. Concentration of Volatiles	7091
13.6.5.3. Constraints on P-T-X Conditions	7091
13.6.5.4. Concentrations of Ore Metals	7094
13.6.5.5. Melt Evolution during Magma Chamber Processes	7094
13.6.5.6. Isotopic Information	7095
13.6.6. Melt Inclusions in Mineralized Systems	7095
13.6.6.1. Porphyry-Type Ore Deposits	7095
13.6.6.1.1. Porphyry Cu (-Au, Mo) Deposits	7095
13.6.6.1.2. Porphyry Mo deposits	7100
13.6.6.1.3. Porphyry Sn deposits	7100
13.6.6.2. Intrusion-Related Vein, Skarn, and Greisen Deposits	7101
13.6.6.2.1. Sn-W deposits	7101
13.6.6.2.2. Other intrusion-related ore deposits	7101
13.6.6.3. Magmatic Oxide and Sulfide Deposits	7102
13.6.6.4. Volcanogenic Massive Sulfide Deposits	7102
13.6.6.5. Pegmatites	7102
13.6.6.6. Alkali Complexes and Carbonatites	7103
13.6.7. Synthesis and Conclusions	7103
Acknowledgments	7104
References	7104
Chapter 13.7: Metamorphosed Hydrothermal Ore Deposits	7111
13.7.1. Introduction	7111
13.7.2. Characteristics of Metamorphosed Hydrothermal Ore Systems	7112
13.7.2.1. Terminology	7112
13.7.2.2. Hydrothermal Ore Deposits and Alteration Haloes	7112
13.7.2.3. Effects of Metamorphism on Ore and Host Rocks	7115
13.7.2.4. Lithological and Mineralogical Attributes of Metamorphosed Hydrothermal Systems	7116
13.7.2.4.1. Metaexhalite, metainhalite, and ironstone	7116
13.7.2.4.2. Hydrothermal alteration haloes	7117
13.7.2.4.3. Mineral compositions as indicators	7118
13.7.2.5. Remobilization and Melting as Agents of Chemical Transformation of Ore Systems	7118
13.7.2.5.1. Remobilization of preexisting ore bodies	7118
13.7.2.5.2. Melting of ore deposits	7118
13.7.3. Geochemical Techniques Used to Study Metamorphosed Ore Deposits	7119
13.7.3.1. Lithogeochemistry	7119
13.7.3.2. Metamorphic Fluids and Fluid Inclusion Studies	7119
13.7.3.3. Behavior of Light Stable Isotopes during Metamorphism	7121
13.7.3.3.1. Sulfur	7121
13.7.3.3.2. Boron	7122
13.7.3.3.3. Oxygen	7122
13.7.3.4. Behavior of Nontraditional Stable Isotopes during Metamorphism	7122
13.7.4. From Case Examples to Conceptual Models and Exploration Tools	7123
13.7.4.1. Vectoring to Ore through Metamorphic Petrology Applications	7123
13.7.4.1.1. Protolithology as an essential step of lithogeochemical exploration	7123
13.7.4.1.2. Chemographic approaches in the recognition of metamorphosed hydrothermal alteration	7123
13.7.4.1.3. Application to metaaluminous and peraluminous gneisses	7124
13.7.4.2. Knowledge, Knowledge Gaps, and the Importance of Geochemical Haloes	7125
13.7.5. Conclusions	7126
Acknowledgments	7126
References	7126
Chapter 13.8: Geochemistry of Magmatic Ore Deposits	7131
13.8.1. Introduction	7131
13.8.2. Trace Element Behavior	7132
13.8.3. Fertility of Primary Magmas	7133
13.8.4. Incompatible Element Deposits	7136
13.8.4.1. Rare-Element Granites, Syenites, and Pegmatites	7136
13.8.4.2. Carbonatite	7137
13.8.5. Compatible Lithophile Element Deposits	7138
13.8.5.1. Chromitite	7138
13.8.5.2. Stratiform Magnetitite	7140
13.8.5.3. Kiruna-Type Ores and Nelsonites	7140
13.8.5.4. Tellnes-Type Ti Deposits	7141
13.8.6. Magmatic Chalcophile Element Deposits	7141
13.8.6.1. Sulfide Liquid Immiscibility	7141
13.8.6.2. Sulfide Solubility	7141
13.8.6.3. Chalcophile Element Partitioning	7142
13.8.6.4. Sulfide Segregation	7142
13.8.6.5. Crystallization of Sulfide Magmas	7146
13.8.6.6. Precious Metal Sulfide Deposits	7147
13.8.6.6.1. Classification	7147
13.8.6.6.2. Offset reefs	7148
13.8.6.6.3. Unconformity-hosted reefs	7148
13.8.7. Conclusions	7150
Acknowledgments	7151
References	7151
Chapter 13.9: Sediment-Hosted Zinc-Lead Mineralization: Proce	7155
13.9.1. Introduction	7156
13.9.2. Sedimentary `Exhalative&INS id=	7157
13.9.2.1. Introduction	7157
13.9.2.2. Tectonostratigraphic Setting	7157
13.9.2.3. Structural Setting	7157
13.9.2.4. Mineralization	7158
13.9.2.5. Fluid Sources	7160
13.9.2.6. Metal and Sulfur Sources	7161
13.9.2.7. Secular Variation in the Abundance of SEDEX Deposits	7162
13.9.2.8. Fluid Flow Mechanism	7163
13.9.2.9. Genetic Model	7164
13.9.3. Mississippi Valley-Type Mineralization	7164
13.9.3.1. Introduction	7164
13.9.3.2. Tectonostratigraphic Setting	7165
13.9.3.3. Structural Setting	7165
13.9.3.4. Mineralization	7165
13.9.3.5. Fluid Sources	7166
13.9.3.6. Metal and Sulfur Sources	7167
13.9.3.7. Secular Variation in the Abundance of MVT Deposits	7168
13.9.3.8. Fluid Flow Mechanism	7169
13.9.3.9. Genetic Model	7170
13.9.4. Irish-Type Zn-Pb Mineralization: A Transitional Ore Type	7171
13.9.4.1. Introduction	7171
13.9.4.2. Tectonostratigraphic Setting	7172
13.9.4.3. Structural Setting	7174
13.9.4.4. Mineralization	7174
13.9.4.5. Fluid Sources	7175
13.9.4.6. Metal and Sulfur Sources	7176
13.9.4.7. Timing of Mineralization	7177
13.9.4.8. Fluid Flow Mechanism	7178
13.9.4.9. Genetic Model	7178
13.9.5. Discussion	7179
13.9.5.1. Irish Deposits as Carbonate-Replacement SEDEX Systems	7179
13.9.5.2. Key Factors in the Genesis of SEDEX Deposits	7179
13.9.5.3. Key Factors in the Genesis of MVT Deposits	7180
13.9.5.4. Outstanding Questions	7180
Acknowledgments	7180
References	7181
Chapter 13.10: Low-Temperature Sediment-Hosted Copper Deposits	7187
13.10.1. Introduction	7187
13.10.2. Geochemistry in the Genesis of SSC Minera	7188
13.10.2.1. Characteristics of SSCs	7188
13.10.2.2. A General Genetic Model for SSC Copper Deposition	7191
13.10.2.2.1. Early concepts	7191
13.10.2.2.2. A diagenetic explanation for SSCs	7191
13.10.2.3. Copper Solubility	7194
13.10.2.4. Solubilities of other Ore-Stage Metals	7196
13.10.2.5. Sources of Copper	7196
13.10.2.6. A Basin-Scale Genetic Model for SSCs	7198
13.10.3. Closely Related Sediment-Hosted Copper Deposits	7199
13.10.3.1. Redbed-Type Copper Deposits	7199
13.10.3.2. Volcanic-Associated Redbed Deposits	7200
13.10.4. Distantly Related Sediment-Hosted Deposit Types	7201
13.10.5. Concluding Remarks	7204
Acknowledgments	7204
References	7204
Chapter 13.11: Deep-Ocean Ferromanganese Crusts and Nodules	7209
13.11.1. Introduction	7209
13.11.1.1. Definitions and General Mechanisms of Formation	7209
13.11.1.2. Distribution	7210
13.11.1.3. Physical Properties	7211
13.11.1.4. Review of Nodule and Crust Compositions	7212
13.11.1.4.1. Mineralogy	7212
13.11.1.4.2. Chemical composition	7212
13.11.1.5. Age Dating	7216
13.11.2. New Considerations	7216
13.11.2.1. Concentrations of High-Tech Trace Metals in Nodules and Crusts	7216
13.11.2.1.1. High field-strength elements, Ti, Zr, Hf, Nb, and &	7216
13.11.2.1.2. Noble metals	7216
13.11.2.1.3. REEs and yttrium	7216
13.11.2.1.4. Vanadium, molybdenum, and tungsten	7217
13.11.2.1.5. Tellurium	7217
13.11.2.2. Mechanisms of Formation with Focus on High-Tech Metals	7217
13.11.2.3. Biomineralization as a Mechanism of Crust and Nodule Formation	7220
13.11.3. Paleoceanographic Records from Fe-Mn Crusts and Nodules	7221
13.11.4. Exploration, Technology, and Resource Considerations	7222
13.11.4.1. Mining Systems	7222
13.11.4.2. Resources	7222
13.11.4.3. Environmental Issues	7223
13.11.5. Future Directions	7224
Acknowledgments	7225
References	7225
Chapter 13.12: Geochemistry of a Marine Phosphate Deposit: A Signpost to Phosphogenesis	7229
13.12.1. Introduction	7229
13.12.2. Statement of the Problem	7229
13.12.3. The MPM: Local Setting	7231
13.12.4. Lithogenous Sediment Fraction	7234
13.12.5. Seawater-Derived Trace Elements	7236
13.12.5.1. Biogenous Trace Elements	7238
13.12.5.2. Hydrogenous Trace Elements	7238
13.12.5.3. A Circulation Model	7241
13.12.6. Rare Earth Elements	7242
13.12.7. Summary and Conclusions	7244
Acknowledgments	7245
References	7245
Chapter 13.13: Sedimentary Hosted Iron Ores	7249
13.13.1. Introduction	7249
13.13.2. Definition and Classification of Iron-Formation	7251
13.13.2.1. Precambrian Iron-Formation	7252
13.13.2.2. Occurrence and Distribution of Precambrian Iron-Formation	7253
13.13.2.3. BIF Ores	7254
13.13.2.4. Mineralogy	7255
13.13.2.5. Chemical Composition	7255
13.13.2.6. Beneficiation of BIF/GIF	7256
13.13.3. Enriched BIF-Hosted Iron Ores	7256
13.13.3.1. Residual BIF-Hosted Iron Ore	7257
13.13.3.2. Martite-Goethite BIF-Hosted Iron Ore	7257
13.13.3.3. Martite Microplaty Hematite BIF-Hosted Iron Ore	7258
13.13.3.3.1. Genetic models	7260
13.13.3.4. Weathering of Martite-Goethite and Hematite BIF-hosted Iron Ores	7265
13.13.3.5. Geochemistry of Martite-Goethite and Martite-microplaty Hematite Iron Ores	7267
13.13.3.5.1. Major and minor elements	7268
13.13.3.5.2. Rare earth elements	7268
13.13.3.6. Detrital Iron Deposits	7268
13.13.4. Ooidal Ironstones	7270
13.13.4.1. Introduction	7270
13.13.4.2. POI Genesis	7271
13.13.4.2.1. Marine ironstones	7271
13.13.4.2.2. Terrestrial ironstones	7273
13.13.4.3. Comparative Evaluation of POI-Derived Iron Ore Mineralogy and Composition	7275
13.13.4.4. Bog Iron Ores	7279
13.13.4.4.1. General occurrence setting and early utilization	7279
13.13.4.4.2. Bog iron ore exploitation	7279
13.13.4.4.3. Types of bog iron ores	7280
13.13.4.4.3.1. Lake ores	7280
13.13.4.4.3.1.1. Stream/spring bog ores	7280
13.13.4.4.3.2. Marsh or peat bog ores	7281
13.13.4.4.3.2.1. Blackband ironstones	7281
13.13.4.4.3.3. Bacterial association in bog ores	7281
13.13.4.4.3.4. Bog ore iron oxides - mineralogy	7283
13.13.5. Summary	7284
Acknowledgments	7285
References	7285
Chapter 13.14: Geochemistry of Porphyry Deposits	7293
13.14.1. Introduction	7293
13.14.2. Geology, Alteration, and Mineralization	7293
13.14.3. Tectonic Setting	7296
13.14.4. Igneous Petrogenesis	7296
13.14.5. Geochronology	7299
13.14.6. Lead Isotopes	7300
13.14.7. Fluid Inclusions	7302
13.14.8. Conventional Stable Isotopes	7303
13.14.8.1. Oxygen-Deuterium	7303
13.14.8.2. Sulfur	7303
13.14.8.3. Carbon-Oxygen	7306
13.14.9. Nontraditional Stable Isotopes	7306
13.14.9.1. Copper	7306
13.14.9.2. Molybdenum	7308
13.14.9.3. Iron	7309
13.14.9.4. Summary	7309
13.14.10. Ore-Forming Processes	7309
13.14.11. Exploration Model	7311
Acknowledgments	7312
References	7312
Chapter 13.15: Geochemistry of Hydrothermal Gold Deposits	7319
13.15.1. Introduction	7319
13.15.2. Epithermal Deposits	7320
13.15.2.1. Introduction	7320
13.15.2.2. Low-Sulfidation Epithermal Deposits	7321
13.15.2.2.1. Trace elements and mineral associations	7321
13.15.2.2.2. Ore fluid characteristics	7322
13.15.2.2.3. Hydrothermal alteration	7322
13.15.2.2.4. Geochemistry of the Midas LS deposit, Nevada	7323
13.15.2.3. High-Sulfidation Epithermal Ores	7326
13.15.2.3.1. Hydrothermal alteration	7326
13.15.2.3.2. Trace elements and mineral associations	7327
13.15.2.3.3. Ore-fluid composition	7328
13.15.2.3.4. Light-stable isotopes	7329
13.15.2.3.5. Reaction of volcanic gas condensate with quartz latite	7329
13.15.2.3.6. Ore deposition	7330
13.15.2.4. New Ideas about the Geochemistry of Epithermal Deposits	7333
13.15.3. Carlin-Type Gold Deposits	7334
13.15.3.1. Introduction	7334
13.15.3.2. Age and Geologic Setting of CTD	7335
13.15.3.3. Ore and Gangue Minerals	7335
13.15.3.4. Geochemistry of Rocks and Pyrite	7336
13.15.3.5. Composition of Ore Fluids	7340
13.15.3.6. Carbonate Dissolution	7340
13.15.3.7. Ore Fluid Composition and Precipitation Mechanisms	7341
13.15.3.8. Element Substitution in Pyrite	7342
13.15.3.9. Source(s) of Ore Fluid Components	7343
13.15.4. Orogenic Gold Deposits	7345
13.15.4.1. Introduction	7345
13.15.4.1.1. General geologic setting and genetic model	7345
13.15.4.2. Geochemistry and Mineralogy of Alteration and Ores	7347
13.15.4.2.1. Ore mineral assemblages	7347
13.15.4.2.2. Wall rock alteration	7348
13.15.4.2.3. Geochemistry of ore-forming fluids	7349
13.15.4.2.4. PTX constraints on ore deposition	7351
13.15.4.3. Geochemistry of Type Examples	7352
13.15.4.3.1. Phanerozoic metasedimentary-hosted Muruntau	7352
13.15.4.3.2. Paleoproterozoic BIF-hosted Homestake	7353
13.15.4.3.3. Late Archean Greenstone-hosted Golden Mile	7354
13.15.5. Summary and Conclusions	7354
Acknowledgments	7355
References	7355
Chapter 13.16: Silver Vein Deposits	7361
13.16.1. Introduction	7361
13.16.2. Silver-Lead-Zinc Veins	7361
13.16.2.1. Cordilleran Vein Type Deposits	7361
13.16.2.2 Silver–Lead–Zinc Veins in Clastic Metasedimentary Terranes	7362
13.16.3 Five-Element (Ag–Ni–Co–As–Bi) Veins	7362
13.16.4 Epithermal Ag–Au and Ag–Base Metal Veins	7364
13.16.4.1. Low-Sulfidation Epithermal Deposi	7364
13.16.4.2. High-Sulfidation Epithermal Depo	7365
13.16.5. Silver-Bearing Veins Related to Tin Mineralization	7366
13.16.6. Silver-Bearing Veins Related to Skarn Mineralization	7366
13.16.7. Discussion	7366
Acknowledgments	7367
References	7367
Chapter 13.17: Geochemistry of Placer Gold - A Case Study of the Witwatersrand Deposits	7369
13.17.1. Introduction	7369
13.17.2. Chemical and Physical Properties of Gold	7369
13.17.3. Gold Abundances	7370
13.17.4. Gold Compounds and Minerals	7371
13.17.5. Aqueous Geochemistry of Gold at 25C	7371
13.17.6. Gold in Surficial Environments	7372
13.17.6.1. Gold Morphology in Placer Deposits	7372
13.17.6.2. Compositional Changes in the Surficial Environment	7373
13.17.6.3. Composition of Alluvial and Eluvial Gold Compared to Its Source Characteristics	7376
13.17.7. Witwatersrand Gold - A Case Study	7377
13.17.7.1. Introduction	7377
13.17.7.2. Geological Background	7377
13.17.7.3. Formation of the Ore Deposits	7380
13.17.7.4. Chemical Composition of Witwatersrand Gold	7381
13.17.7.4.1. The nature of the available data	7381
13.17.7.4.2 Variation of gold chemistry within the Central Rand Group	7384
13.17.7.4.2.1. Witwatersrand gold compositions at the deposit level - the km scale	7384
13.17.7.4.2.2 Witwatersrand gold compositions within individual mines/deposits – the km–10 m scale	7388
13.17.7.4.2.3. Witwatersrand gold compositions within individual hand specimens &nd	7388
13.17.7.4.2.4. Witwatersrand gold compositions within individual thin sections - the cm scale	7392
13.17.7.4.2.5. Witwatersrand gold compositions within individual gold grains - the micron scale	7392
13.17.7.5. The Origins of Witwatersrand Gold	7392
13.17.7.5.1. Gold chemistry and implications for the modified placer and hydrothermal models	7392
13.17.7.5.2. Potential gold source regions	7392
13.17.8. Conclusions	7394
Acknowledgments	7394
References	7394
Chapter 13.18: Volcanogenic Massive Sulfide Deposits	7399
13.18.1. Introduction	7399
13.18.2. Distribution, Abundance, and Classification	7401
13.18.3. Composition	7401
13.18.4. General Genetic Model	7403
13.18.5. Chemical Evolution of the Hydrothermal Fluids	7404
13.18.5.1. Fluid-Mineral Equilibria	7404
13.18.5.2. Metal Concentrations	7407
13.18.5.3. Role of Phase Separation	7408
13.18.5.4. Redox Controls on Ore Deposition	7409
13.18.6. Metal Zoning and Trace Element Geochemistry	7410
13.18.6.1. Metal Zoning	7410
13.18.6.2. Trace Element Geochemistry	7412
13.18.6.3. Sources of Trace Metals	7413
13.18.7. Nonsulfide Gangue Minerals	7414
13.18.8. Alteration Mineralogy and Geochemistry	7415
13.18.9. Chemical Sediments	7416
13.18.10. Sulfur Isotopes	7417
13.18.11. Oxygen, Hydrogen, and Carbon Isotopes	7418
13.18.12. Strontium and Lead Isotopes	7419
13.18.13. Conclusions	7419
Acknowledgments	7420
References	7421
Chapter 13.19: Uranium Ore Deposits	7425
13.19.1. Introduction	7425
13.19.2. The Need for Uranium	7426
13.19.3. Geochemistry of Uranium	7426
13.19.4. Uranium Deposits Through Time	7428
13.19.5. Deposit Types	7429
13.19.5.1. Unconformity-Related Deposits	7429
13.19.5.1.1. The Athabasca Basin	7430
13.19.5.1.2. The Kombolgie Basin	7433
13.19.5.1.3. Karku, Russia	7434
13.19.5.1.4. Otish Basin, Quebec	7434
13.19.5.2. Sandstone Uranium Deposits	7435
13.19.5.2.1. United States	7436
13.19.5.2.2. Africa	7437
13.19.5.2.3. Asia	7437
13.19.5.3. Vein Deposits	7438
13.19.5.3.1. Beaverlodge, Canada	7438
13.19.5.4. Metasomatic Deposits	7438
13.19.5.4.1. Na metasomatism-related deposits of	7439
13.19.5.4.2. Valhalla, Australia	7439
13.19.5.5. Breccia Complex Deposits	7439
13.19.5.6. Intrusive Deposits	7440
13.19.5.6.1. Alaskites	7440
13.19.5.6.2. Peralkaline systems	7441
13.19.5.6.2.1. The Ilmaussaq complex	7441
13.19.5.6.2.2. Bokan Mountain (United States)	7441
13.19.5.6.3. Peraluminous granites	7441
13.19.5.7. Volcanic-Associated Deposits	7442
13.19.5.7.1. Streltsovkoye caldera (Transbaikalia, Russia)	7442
13.19.5.7.2. Macusani, Peru	7443
13.19.5.8. Quartz-Pebble Conglomerate Deposits	7443
13.19.5.8.1. Blind River-Elliot Lake district	7443
13.19.5.8.2. The Witwatersrand Basin	7444
13.19.5.9. Surficial Uranium Deposits	7444
13.19.5.10. Collapse Breccia Pipe Deposits	7445
13.19.5.11. Phosphorite Deposits	7445
13.19.5.12. Black Shale and Seawater	7446
13.19.6. Synopsis	7446
Acknowledgments	7446
References	7446
Chapter 13.20: Iron Oxide(-Cu-Au-REE-P-Ag-U-Co) Systems	7451
13.20.1. Introduction	7451
13.20.1.1. Semantics and Postulated Origins	7452
13.20.2. Geologic Context for IOCG Systems	7453
13.20.2.1. Distribution in Space and Time	7453
13.20.2.2. Geologic Settings	7454
13.20.2.2.1. Association with igneous rocks (or lack thereof)	7454
13.20.2.2.2. Framework lithologies and paleoclimate	7455
13.20.3. Synopsis of Deposit Features	7455
13.20.3.1. Deposit Types	7455
13.20.3.1.1. Magnetite- and/or hematite-dominated deposits	7456
13.20.3.1.2. Fe oxide-poor Cu(-Au/Ag) deposits of proposed affinity to IOCG systems	7458
13.20.3.1.3. Possible modern analogues	7458
13.20.3.2. Grade, Size, and Form	7458
13.20.3.3. Ore Mineralogy and Paragenesis	7459
13.20.3.4. Minor Element Contents and Mineralogy: U-Th, REE, Co-Ni-V, Cl-F-Br, B	7460
13.20.4. Hydrothermal Alteration and System-scale Zoning	7461
13.20.4.1. Types of Hydrothermal Alteration	7461
13.20.4.1.1. Sodic to calcic alteration types	7461
13.20.4.1.2. Carbonate-hosted alteration: Skarn and Fe oxide replacement	7462
13.20.4.1.3. K-rich alteration: High-temperature and low-temperature types	7462
13.20.4.1.4. Hydrolytic (acid) alteration	7463
13.20.4.2. System- to Regional-Scale Spatial and Temporal Patterns	7463
13.20.4.3. Extent of Metasomatism and Comparison with Porphyry/Alkaline Cu Systems	7464
13.20.5. Petrologic and Geochemical Characteristics	7465
13.20.5.1. Conditions of Formation	7465
13.20.5.1.1. Depth	7465
13.20.5.1.2. Temperature	7466
13.20.5.1.3. Fluid inclusion compositions	7466
13.20.5.1.4. Oxidation state, sulfidation state, and total sulfur	7467
13.20.5.2. Tracer Studies and Sources of Components	7467
13.20.5.2.1. Light stable isotopes: H, O, S, C, and B	7468
13.20.5.2.2. Radiogenic isotopes: Sr, Nd, Pb, and Os	7469
13.20.5.2.3. Halogens and noble gases: Ratios and isotopes	7470
13.20.6. Summary of the IOCG Clan, Likely Origins, and the terrestrial Hydrothermal Environment	7470
13.20.6.1. Discussion of Genesis	7471
13.20.6.2. IOCG Systems and the Terrestrial Hydrothermal Environment	7472
Acknowledgments	7472
References	7472
Chapter 13.21: Geochemistry of the Rare-Earth Element, Nb, Ta, Hf, and Zr Deposits	7479
13.21.1. Introduction	7479
13.21.1.1. Uses of Rare Elements	7480
13.21.1.2. Rare-Element Mineralogy	7481
13.21.2. Geochemistry of Rare Elements	7481
13.21.2.1. Magmatic Behavior and Processes	7485
13.21.2.1.1. Concentrations of rare elements in magmatic rocks	7485
13.21.2.1.2. Partial melting and fractional crystallization	7485
13.21.2.1.3. Solubility of rare elements in carbonatite melts	7486
13.21.2.1.4. Solubility of rare elements in silicate melts	7486
13.21.2.1.5. Fluid-melt partitioning of rare elements	7487
13.21.2.2. Hydrothermal Behavior and Processes	7487
13.21.2.2.1. Concentrations of rare metals in natural fluids	7487
13.21.2.2.2. Aqueous complexation and mineral solubility	7488
13.21.2.2.2.1. Aqueous complexation of the REE	7488
13.21.2.2.2.2. Speciation calculations and REE transport in hydrothermal environments	7489
13.21.2.2.3. REE mineral solubility	7489
13.21.2.2.4. Zirconium	7490
13.21.2.2.5. Tantalum and niobium	7490
13.21.3. Deposit Characteristics	7490
13.21.3.1. Introduction	7490
13.21.3.2. Deposits in Alkaline Igneous Provinces	7490
13.21.3.2.1. Carbonatites and genetically related rocks	7490
13.21.3.2.2. Silicate-hosted deposits	7493
13.21.3.2.2.1. Khibiny and Lovozero	7493
13.21.3.2.2.2. Ilimaussaq	7493
13.21.3.2.2.3. Thor Lake (the Nechalacho deposit)	7494
13.21.3.2.2.4. Strange Lake	7494
13.21.3.3. Peraluminous Granite- and Pegmatite-Hosted Deposits	7495
13.21.3.3.1. Peraluminous granite-hosted deposits	7495
13.21.3.3.2. Peraluminous pegmatite-hosted deposits	7495
13.21.3.4. Supergene Deposits	7496
13.21.3.4.1. Saprolite deposits	7496
13.21.3.4.2. Laterite deposits	7496
13.21.3.4.3. Reworked laterite deposits	7496
13.21.3.4.4. Ion-adsorbed clay deposits	7496
13.21.3.5. Placer Deposits	7497
13.21.4. Genesis of HFSE Deposits	7497
13.21.4.1. Magmatic Controls of Carbonatite Deposits	7497
13.21.4.2. Hydrothermal Controls of Carbonatite Deposits	7498
13.21.4.3. Magmatic Controls of Alkaline Silicate Environments	7498
13.21.4.4. Hydrothermal Controls of Alkaline Silicate Environments	7499
13.21.4.5. Magmatic Controls of Peraluminous Environments	7499
13.21.4.6. Hydrothermal Controls of Peraluminous Environments	7500
13.21.5. Commonalities of Rare-Element Mineralization	7500
Acknowledgments	7500
References	7500
Relevant Websites	7504
Chapter 13.22: Geochemistry of Evaporite Ores in an Earth-Scale Climatic and Tectonic Framework	7505
13.22.1. Introduction	7505
13.22.2. Extractable Economic Salts (Excluding Halite and CaSO4 Salts)	7505
13.22.3. Sodium Carbonate (Soda-Ash: Trona)	7506
13.22.4. Sodium Sulfate (Salt-Cake)	7507
13.22.5. Borate and Lithium Occurrences	7509
13.22.6. Climatic and Tectonic Controls on Nonmarine Salts	7516
13.22.7. Potash Salts	7518
References	7527
Chapter 13.23: Gem Deposits	7531
13.23.1. Introduction	7531
13.23.2. Diamond	7532
13.23.2.1. Morphology	7532
13.23.2.2. Crystal Chemistry and Diamond Types	7532
13.23.2.3. Environment of Diamond Formation and Associated Inclusion Suites	7533
13.23.2.3.1. Diamond-forming reactions and mantle metasomatism	7533
13.23.2.3.2. Inclusion suites and diamond-forming environments	7533
13.23.2.3.3. Pressure and temperature constraints	7534
13.23.2.4. Stable Isotopes of Diamond and Diamond Inclusions	7535
13.23.2.5. Dating	7535
13.23.2.6. Model	7536
13.23.3. Ruby and Sapphire	7536
13.23.3.1. Introduction	7536
13.23.3.2. Distribution and Classification of Gem Corundum Deposits	7537
13.23.3.3. Recent Studies	7537
13.23.3.3.1. Gem corundum in marble	7538
13.23.3.3.2. Gem corundum in volcanic rocks	7538
13.23.3.3.3. Sapphire in lamprophyric dikes	7538
13.23.3.3.4. Metasomatic sapphire	7538
13.23.3.3.5. Gem corundum in placers	7538
13.23.3.4. Exploration	7539
13.23.4. Emerald	7539
13.23.4.1. Introduction	7539
13.23.4.2. The Crystal Chemistry of Beryl	7539
13.23.4.3. The Geochemistry of Be, Cr, and V	7542
13.23.4.4. Deposit Models	7542
13.23.4.4.1. Emerald deposits related to granitic intrusions	7542
13.23.4.4.2. The Colombian model	7543
13.23.4.4.3. Regional metamorphism and tectonometamorphic processes	7543
13.23.4.5. Genetic Classification	7545
13.23.4.6. Exploration	7546
13.23.5. Non-Emerald Gem Beryl	7547
13.23.6. Chrysoberyl	7547
13.23.7. Tanzanite	7549
13.23.8. Tsavorite	7549
13.23.9. Topaz	7550
13.23.10. Jade	7550
13.23.10.1. Introduction	7550
13.23.10.2. Jadeitite	7551
13.23.10.3. Nephrite	7551
Acknowledgments	7552
References	7552
Chapter 13.24: Exploration Geochemistry	7559
13.24.1. Introduction	7559
13.24.1.1. Role of Geochemistry in Mineral Exploration	7559
13.24.1.2. Geochemical Processes and Terrains	7559
13.24.2. The Primary Environment	7560
13.24.3. The Secondary Environment	7563
13.24.3.1. Weathering and Dispersion	7563
13.24.3.2. Arid and Deeply Weathered Terrains	7565
13.24.3.3. Transported Cover	7566
13.24.3.4. Glaciated Terrains	7569
13.24.3.5. Other Example Techniques	7571
13.24.3.5.1. Heavy indicator minerals	7571
13.24.3.5.2. Hydrogeochemistry	7571
13.24.3.5.3. Biogeochemistry	7574
13.24.3.5.4. Vapor and gas geochemistry	7574
13.24.4. Regional Geochemical Mapping	7575
13.24.5. Analysis	7577
13.24.6. Geochemical Data Interpretation	7580
Acknowledgments	7582
References	7582
e9780080983004v14	7587
Front Cover	7587
Archaeology and Anthropology	7590
Copyright	7592
In Memoriam	7594
Heinrich Dieter Holland (1927–2012)	7596
Karl Karekin Turekian (1927–2013)	7598
References	7600
Dedication	7602
Contents	7604
Executive Editors’ Foreword to the Second Edition	7606
Contributors	7610
Volume Editor’s Introduction	7612
References	7613
Chapter 14.1: K/Ar and 40Ar/39Ar Isotopic Dating Techniques as Applied to Young Volcanic Rocks, Particularly Those Associated with Hominin Lo	7614
14.1.1. Introduction	7614
14.1.2. Basis of the K/Ar and 40Ar/39Ar Dating Techniques	7614
14.1.3. Suitable Materials for Dating	7618
14.1.4. Size Limitations	7619
14.1.5. The Omo-Turkana Basin Sequence	7620
14.1.6. Results from Afar, Ethiopia	7625
14.1.7. Conclusions	7626
Acknowledgments	7627
References	7627
Chapter 14.2: Luminescence Dating Methods	7630
14.2.1. Luminescence Dating	7630
14.2.1.1. Introduction	7630
14.2.1.2. Production of Luminescence Signals	7631
14.2.1.3. Preparation of Samples	7633
14.2.1.4. Determining De	7634
14.2.1.5. Combining De Datasets	7635
14.2.1.6. Dose Rate Determination	7637
14.2.1.7. Problems	7638
14.2.1.8. Single-Grain Measurements	7639
14.2.2. Applications	7640
14.2.2.1. General Impact	7640
14.2.2.2. The MSA in Southern Africa	7640
14.2.2.3. The Aterian and Earlier Stone Industries in North Africa	7643
14.2.2.4. Human Arrival in Australia	7645
14.2.3. Summary	7645
Acknowledgments	7646
References	7646
Chapter 14.3: Radiocarbon: Calibration to Absolute Time Scale	7650
Glossary	7650
14.3.1. Introduction	7650
14.3.2. Variable Atmospheric 14C Content	7650
14.3.3. Radiocarbon Calibration Curve	7651
14.3.4. Calibration and Calibration Programs	7653
14.3.5. Calibration in Archaeological Studies	7653
References	7655
Chapter 14.4: Radiocarbon: Archaeological Applications	7658
14.4.1. Introduction	7658
14.4.2. Late Paleolithic	7658
14.4.3. Neolithic	7659
14.4.4. Development of Metal Use	7659
14.4.5. Bronze Age	7659
14.4.6. Iron Age	7660
14.4.7. Egyptian Chronologies	7660
14.4.8. New World Archaeology	7660
14.4.9. Australia	7661
14.4.10. Polynesia	7661
14.4.11. Chemistry	7662
14.4.12. Bone Dating	7662
14.4.13. Radiocarbon Dating of Art Works and Historical Objects	7662
14.4.14. Understanding Radiocarbon Dates	7663
14.4.14.1. The Significance of Radiocarbon Reservoir Effects	7664
14.4.14.2. Regional and Site-Specific Differences in Atmospheric 14C	7664
14.4.15. Bayesian Modeling	7664
References	7664
Chapter 14.5: The Molecular Clock	7668
14.5.1. Introduction	7668
14.5.2. Historical Overview	7668
14.5.3. A Numerical Example: The Chimp-Human Common Ancestor	7669
14.5.4. Difficulties with the Molecular Clock	7669
14.5.4.1. Uncertainties	7669
14.5.4.2. Purifying Selection	7670
14.5.4.3. Variation in Rates	7670
14.5.5. Coping with an Imperfect Clock	7671
14.5.5.1. Excluding Variant Lineages	7671
14.5.5.2. Relaxed Clocks	7672
14.5.6. Using Multiple Genes	7672
14.5.7. Conclusions	7673
References	7673
Chapter 14.6: Correlation: Volcanic Ash, Obsidian	7676
14.6.1. Introduction	7676
14.6.2. Some Relatively Common Types of Natural Glass and Their Compositions	7677
14.6.3. Field Occurrence	7679
14.6.4. Sample Preparation	7680
14.6.5. Analytical Techniques	7681
14.6.5.1. Electron Probe Microanalysis	7681
14.6.5.2. Laser Ablation, Inductively Coupled Plasma Mass Spectrometry	7681
14.6.5.3. X-Ray Fluorescence	7682
14.6.6. Handling Analyses	7682
14.6.6.1. Analyses of Individual Shards and	7682
14.6.6.2. Analyses of Bulk Samples	7683
14.6.7. Recalculation of Analyses	7683
14.6.8. Sets of Analyses	7684
14.6.8.1. Unimodal Ash Layers	7684
14.6.8.2. Bimodal Ash Layers	7685
14.6.8.3.Ash Layers with Linear Arrays of Analyses	7685
14.6.9. The Problem of Alkali Content	7687
14.6.10. Comparison of Analyses	7689
14.6.11. Examples of Uses of Volcanic Glass in Archaeological Studies	7689
14.6.11.1. Determining Sources of Obsidian	7689
14.6.11.2. Correlation of Archaeological Sites	7690
14.6.11.3. Primary Dates on Archaeological Material	7691
14.6.11.4. Indirect Dates and Climatic Information through Correlations to Marine Cores	7691
Acknowledgments	7692
References	7692
Chapter 14.7: Cosmogenic Nuclide Burial Dating in Archaeology and Paleoanthropology	7694
14.7.1. Introduction	7694
14.7.2. Cosmogenic Nuclides	7695
14.7.2.1. Cosmogenic Nuclide Production	7695
14.7.2.2. Production Rates at the Surface	7695
14.7.2.2.1. Latitude	7696
14.7.2.2.2. Altitude	7696
14.7.2.2.3. Time	7696
14.7.2.3. Production Rates at Depth	7696
14.7.2.3.1. Neutrons	7696
14.7.2.3.2. Muons	7696
14.7.2.3.2.1. Negative muon capture	7697
14.7.2.3.2.2. Fast muons	7697
14.7.2.4. Cosmogenic Nuclide Buildup in Rocks	7697
14.7.2.4.1. Exposure	7698
14.7.2.4.2. Erosion	7698
14.7.3. Burial Dating	7698
14.7.3.1. Burial Dating Theory	7699
14.7.3.2. Simple Burial Dating	7699
14.7.3.2.1. Example: Sima del Elefante, Atapuerca	7700
14.7.3.3. Min/Max Methods	7701
14.7.3.3.1. Example: Rietputs Formation, lower Vaal River	7702
14.7.3.4. Isochron Dating	7702
14.7.3.4.1. Example: Sundays River	7703
14.7.3.5. Uncertainties and limits of burial dating	7704
14.7.4. Applications to Archaeology and Paleoanthropology	7705
14.7.4.1. Simple Burial Dating: Zhoukoudian, China	7705
14.7.4.2. Min/Max Burial Dating: Rietputs Formation, South Africa	7706
14.7.4.3. Min/Max Burial Dating: Attirampakkam, India	7707
14.7.4.4. Problematic Burial Dates	7708
14.7.4.4.1. Sterkfontein, South Africa	7708
14.7.4.4.2. Luangwa Valley, Zambia	7708
14.7.5. Summary	7709
References	7709
Chapter 14.8: Marine Sediment Records of African Climate Change: Progress and Puzzles	7712
14.8.1. Introduction	7712
14.8.2. Marine Sediments as Recorders of Terrestrial Climate Change	7713
14.8.2.1. Eolian Dust Supply, Composition, and Grain Size	7713
14.8.2.2. River Runoff, Paleohydrology, and Vegetation Proxies	7716
14.8.3. Marine Sediment Records of African Paleoclimate: Progress and Puzzles	7718
14.8.3.1. Summary of North African Climate Evolution Since the Last Glacial Maximum	7718
14.8.3.2. Fidelity of Aridity Proxies: Dustiness or Gustiness?	7718
14.8.3.3. An Abrupt or Gradual End of the AHP near 5k	7719
14.8.4. Summary and Future Directions	7719
References	7720
Chapter 14.9: History of Water in the Middle East and North Africa	7722
14.9.1. Introduction	7722
14.9.1.1. Geographical Characteristics and Distribution of the Middle East and North Africa	7722
14.9.1.2. Present-Day Synoptic System in the Middle East	7723
14.9.1.3. Present-Day Synoptic System in North Africa	7724
14.9.2. Paleoclimate of the Middle East and Northeast Africa	7725
14.9.2.1. Paleoclimate of the Middle East and Northeast Africa Based on Deep Sea Sediments from the East	7725
14.9.2.2. Paleoclimate of the Middle East and North Africa Based on Speleothems and Lake Records	7727
14.9.2.2.1. Speleothems	7727
14.9.2.3. Eastern Mediterranean Speleothem Records	7728
14.9.2.4. Desert Speleothems	7729
14.9.2.4.1. Origin of rainfall for the desert speleothems	7731
14.9.2.4.2. The MIS 6/5 transition	7732
14.9.2.5. Arabian Speleothems	7732
14.9.2.5.1. Lakes	7733
14.9.2.6. Eastern Mediterranean and North African Lakes	7734
14.9.2.7. The Connection between `Wet´ Episodes in Northeast Africa-Middle East and H	7735
14.9.3. Conclusions	7736
References	7737
Chapter 14.10: The Carbon, Oxygen, and Clumped Isotopic Composition of Soil Carbonate in Archeology	7742
14.10.1. Introduction	7742
14.10.2. Paleosol Carbonate Recognition	7742
14.10.3. Limitations for Archeologists	7744
14.10.4. Seasonality of Formation and Isotopic Equilibrium	7744
14.10.5. Carbon Isotopes in Soil Carbonate	7745
14.10.5.1. Plants and Climate	7745
14.10.5.2. The Soil Diffusion Model	7745
14.10.5.3. Reconstructing the Fraction Woody Cover	7747
14.10.5.4. The Radiation of C4 Plants and Evolution of Hominids	7748
14.10.5.4.1. Phase I (>8.4Ma): A mainly C3 world	7750
14.10.5.4.2. Phase II (8.4-7Ma): C4 grasses appear	7750
14.10.5.4.3. Phase III (7-2.7Ma): Expansion of C4 grasses	7750
14.10.5.4.4. Phase IV (2.7Ma to present): Development of modern savannas in most of East Africa	7750
14.10.6. Clumped Isotopes in Soil Carbonate	7750
14.10.6.1. Principles and Methods	7750
14.10.6.2. Soil Temperature Considerations	7751
14.10.6.3. Examples of Use	7751
14.10.7. Oxygen in Soil Carbonate	7752
14.10.7.1. Temperature Effects	7752
14.10.7.2. Composition of Precipitation	7752
14.10.7.3. Soil Water Evaporation	7752
14.10.7.4. The Late Cenozoic Oxygen Isotope Shift	7753
14.10.8. Integrity of the Isotopic Record from Soil Carbonate	7753
14.10.9. Environmental Reconstruction on Short Timescales and Future Directions	7754
Acknowledgments	7754
References	7754
Chapter 14.11: Microanalytical Isotope Chemistry: Applications for Archaeology	7758
14.11.1. History of Micromilling Technology	7758
14.11.2. Applications of Micromilling Devices toward the Enhancement of Sampling Strategies and Derivation of High-Resolution Records	7760
14.11.2.1. Mollusks	7760
14.11.2.1.1. From seasonality of site occupation to seasonality of temperature	7760
14.11.2.2. Fish Otoliths	7760
14.11.2.3. Derivation of Seasonality of Temperature in Continental &INS id=	7761
14.11.2.4. Seasonality of Site Occupation	7763
14.11.2.5. Coral	7763
14.11.2.6. Speleothems	7763
14.11.2.7. Teeth	7764
14.11.2.8. Trees	7765
14.11.3. Future Advances and Directions	7766
14.11.4. Conclusions	7766
14.11.5. Partial List of Applications of Micromilling in Archaeology	7766
14.11.5.1. Mollusks	7766
14.11.5.2. Otoliths	7766
14.11.5.3. Bone	7766
14.11.5.4. Speleothems	7766
14.11.5.5. Teeth	7766
14.11.5.6. Hair	7766
Acknowledgments	7766
References	7767
Chapter 14.12: Stable Isotope Evidence for Hominin Environments in Africa	7770
14.12.1. Introduction	7771
14.12.2. Carbon Isotopes in Plants	7771
14.12.3. Ecology of Mixed C3 and C4 Ecosystems	7772
12.13.3.1. Isotopes and Shade: Quantification of Woody Cover	7772
14.12.3.2. Paleosols as Recorders of Paleoenvironments in African Hominin Sites	7774
14.12.4. Paleotemperature	7775
14.12.4.1. Temperature as a Variable in Human Evolution	7775
14.12.4.2. Paleotemperature from Delta47 in Paleosols	7775
14.12.5. Diet History of Mammals	7776
14.12.5.1. Isotopes Distinguish Between Grazing and Browsing	7776
14.12.5.2. Diet Histories of Nonprimates Associated with Hominins	7776
14.12.5.2.1. Overall faunal preferences	7776
14.12.5.3. Diets of Early Human Relatives	7777
14.12.6. Summary and Future Directions	7777
Acknowledgments	7779
References	7779
Chapter 14.13: Geochemistry of Ancient Metallurgy: Examples from Africa and Elsewhere	7782
14.13.1. Introduction	7782
14.13.2. Chemistry of Ancient Metallurgy	7784
14.13.3. Geochemistry Methods in Archaeometallurgy: Some Common Examples	7787
14.13.4. Geochemistry Applications in Ancient Metallurgy	7789
14.13.4.1. One of the Earliest Beginnings of Metallurgy in the World: The Case of the Balkans	7789
14.13.4.2. The Unresolved Case of the Earliest African Metallurgy: Contributions of Geochemistry	7790
14.13.4.3. Getting to Grips with the Full Ancient Metal Production Chain: Technology, Organization of Production, and Social	7791
14.13.4.4. Going Beyond System Generated Constraints in Ancient Metal Smelting	7793
14.13.4.5. Provenancing Artifacts Using NAA and Lead Isotope Analysis	7793
14.13.4.6. Reading Gender Specialization in Ancient Metallurgy: Contributions of Geochemistry	7795
14.13.4.7. Geochemistry for Conservation: Oranjemund Shipwreck	7797
14.13.5. Conclusion	7800
Acknowledgments	7800
References	7800
Chapter 14.14: Elemental and Isotopic Analysis of Ancient Ceramics and Glass	7804
14.14.1. Introduction	7804
14.14.2. Considerations on Archeological Ceramic Studies	7805
14.14.2.1. Pottery in Archeology	7805
14.14.2.2. Pottery and Provenance	7805
14.14.2.3. Pottery Analyses	7806
14.14.2.3.1. Ceramic petrography and mineralogy	7806
14.14.2.3.2. Chemical analysis of ceramics	7806
14.14.2.3.2.1. Analytical techniques and methodology	7806
14.14.2.3.2.2. A summary of useful elements in ceramic provenance studies	7806
14.14.2.3.2.2.1. Cr, Ni, and Co	7807
14.14.2.3.2.2.2. Zr (Hf)	7807
14.14.2.3.2.2.3. Y	7807
14.14.2.3.2.2.4. Ti	7807
14.14.2.3.2.2.5. Sr	7807
14.14.2.3.2.2.6. K, Rb	7807
14.14.2.3.2.2.7. Ba	7807
14.14.2.3.2.2.8. Fe	7807
14.14.2.3.2.2.9. Th (U)	7807
14.14.2.3.3. Data treatment in ceramic provenancing	7808
14.14.2.4. Case Studies in Pottery Analysis	7808
14.14.3. Considerations on Archeological Glass Analysis	7810
14.14.3.1. Glass in Archeology	7810
14.14.3.2. Glass and Provenance	7811
14.14.3.3. Glass Analyses	7813
14.14.3.3.1. Glass provenance and elemental analysis	7813
14.14.3.3.1.1. Glass flux types: sodium, potassium, magnesium, phosphorous	7813
14.14.3.3.1.2. Glass network former and stabilizer: silica, lime, alumina	7813
14.14.3.3.1.3. Glass colorants: antimony, manganese, copper, cobalt, tin, etc.	7813
14.14.3.3.1.4. Glass provenance: other minor and trace elements	7813
14.14.3.3.2. Glass provenance and isotopes	7814
14.14.3.3.2.1. Oxygen isotopes	7814
14.14.3.3.2.2. Lead isotopes	7814
14.14.3.3.2.3. Strontium isotopes	7815
14.14.3.3.2.4. Neodymium isotopes	7815
14.14.3.4. Case Study in Glass Analysis	7815
References	7816
Chapter 14.15: Synchrotron Methods: Color in Paints and Minerals	7822
14.15.1. Introduction	7823
14.15.1.1. Role of Color in Archaeology	7823
14.15.1.2. What Kind of Information Is Looked for When Searching for Investigating Color in Paints or Minerals?	7824
14.15.1.3. From the Color Cause of Ancient Materials to Archaeological Information	7824
14.15.1.4. Physical and Chemical Causes of Color Important in Terms of Archaeological Materials	7824
14.15.2. Studies of Ancient Pigments, Paints, and Minerals	7824
14.15.2.1. Definition of Pigments, Colorants, and Paints	7824
14.15.2.2. Relevant Archaeological and Historical Pigments	7824
14.15.2.3. Relevant Archaeological and Historical Minerals, Biominerals, Colored Stones, and Gemstones	7825
14.15.3. History of Their Study and Current Trends	7828
14.15.3.1. First Archaeometric Laboratory Studies	7828
14.15.3.2. General Approach for Studying Archaeomaterials	7830
14.15.3.3. Neutron Sources	7831
14.15.3.4. Ion Beam Analyses	7831
14.15.3.5. Current Trends	7831
14.15.4. Overview of Synchrotron-Based Method Used for the Study of Pigments, Paints, and Minerals	7831
14.15.4.1. Why Use Synchrotron-Based X-Ray Methods to Study Color of Archaeomaterials?	7831
14.15.4.2. Chemical Analysis	7832
14.15.4.3. Structural Investigations	7833
14.15.4.4. Molecular Studies	7834
14.15.4.5. Spectroscopic Studies	7834
14.15.4.6. Noninvasive Depth-Resolved Investigations	7836
14.15.4.7. Synchrotrons with Important Activities in the Field of CH Studies	7837
14.15.5. Case Studies	7837
14.15.5.1. Identification of Pigments and Minerals	7837
14.15.5.1.1. Black Paleolithic paints in the Lascaux cave (Dordogne): use of different Mn oxides with diffe	7837
14.15.5.1.2. Color shades investigated in Roman frescoes by SR-micro-XRD mapping	7839
14.15.5.1.3. Possible differentiation of different lead whites in successive paint layers of the Isenheim A	7839
14.15.5.1.4. Special Zn-containing pigments found in Indian miniature paintings long before European paintings:	7839
14.15.5.1.5. Color reconstruction of a hidden face painted by Vincent Van Gogh using fast macro-XRF mapping combined with mic	7841
14.15.5.2. Early Synthesis of Colored Matter in Ancient Civilizations	7841
14.15.5.2.1. Early chemical synthesis to manufacture ancient Egyptian make&	7841
14.15.5.2.2. Different production processes for two different synthetic pigments used in ancient Egypt	7843
14.15.5.2.3. Synthetic Chinese purple pigment (Han purple) used on Qin terracotta warriors: technology transfer from Egypt to	7844
14.15.5.2.4. A hybrid synthetic pigment with amazing stability over time: Maya blue in pre-Columbian Mesoamerica	7844
14.15.5.3. Study of Paint and Pigment Discoloration	7845
14.15.5.3.1. Hiding or discoloration of prehistoric paints in limestone caves (Large cave of Arcy-sur-Cure,	7845
14.15.5.3.2. From fossil bone to turquoise imitation	7846
14.15.5.3.3. Blackening of Pompeian wall paintings	7847
14.15.5.3.4. Discoloration of smalt used as pigment in paintings	7848
14.15.6. Conclusion and Trends	7848
References	7849
Chapter 14.16: Geochemical Methods of Establishing Provenance and Authenticity of Mediterranean Marbles	7854
14.16.1. Foreword	7854
14.16.2. Types of Fakes	7855
14.16.3. Determining Marble Provenance	7856
14.16.3.1. Analytical Techniques	7856
14.16.3.1.1. Stable isotope methodology	7857
14.16.3.1.2. Electron paramagnetic resonance/electron spin resonance	7857
14.16.3.1.3. A note on the use of CL in marbles	7859
14.16.3.2. Case Studies	7859
14.16.3.2.1. Excavations at Cyrene	7859
14.16.3.2.2. Cyrene revisited	7859
14.16.3.2.3. Deconstructing Antonia	7860
14.16.3.2.4. Aphrodite	7862
14.16.3.2.5. Aphrodite in the National Gallery of Art	7863
14.16.4. Testing Authenticity	7864
14.16.5. Summary	7864
References	7865
Chapter 14.17: Biblical Events and Environments - Authentification of Controversial Archaeological Artifacts	7868
14.17.1. Introduction	7868
14.17.1.1. Archaeological Forgery	7868
14.17.1.2. Patina	7869
14.17.1.3. Oxygen and Carbon Isotopic Composition	7869
14.17.2. The James Ossuary	7870
14.17.2.1. The Ossuary	7870
14.17.2.2. Authenticity Studies	7871
14.17.3. Jehoash Inscription	7874
14.17.3.1. The Tablet	7874
14.17.3.2. Authenticity Studies	7874
14.17.3.2.1. Petrography	7875
14.17.3.2.2. Oxygen isotopic composition	7875
14.17.4. The Ivory Pomegranate	7877
14.17.4.1. The Pomegranate	7877
14.17.4.2. Authenticity Study	7877
14.17.4.2.1. The inscription	7877
14.17.4.2.2. The patina	7878
14.17.4.2.2.1. Stable isotope analysis	7878
14.17.5. Iron Age Ostraca	7878
14.17.5.1. The ostraca	7878
14.17.5.2. Authenticity Examination	7879
14.17.5.2.1. Micromorphologic and petrographic examination	7879
14.17.5.2.2. Oxygen and carbon isotopic composition	7879
14.17.6. Dust	7881
14.17.7. Conclusions	7881
References	7882
Chapter 14.18: Trace Evidence: Glass, Paint, Soil, and Bone	7884
14.18.1. Introduction	7885
14.18.2. Elemental Analysis Techniques	7886
14.18.3. Man-Made Matrices	7887
14.18.3.1. Glass	7887
14.18.3.2. Elemental Analysis of Glass	7887
14.18.3.3. Paint	7887
14.18.3.4. Elemental Analysis of Paint	7887
14.18.4. Natural Matrices	7888
14.18.4.1. Soil	7888
14.18.4.2. Properties of Soil	7888
14.18.4.3. Soil Sampling and Sample Preparation	7888
14.18.4.4. Analysis of Soil	7889
14.18.4.5. Elemental Analysis of Soil	7889
14.18.4.6. Bones and Teeth	7890
14.18.4.7. Properties of Bone	7891
14.18.4.8. Bone Sampling and Sample Preparation	7891
14.18.4.9. Analysis of Bone	7891
14.18.4.10. Elemental Analysis of Bone	7892
14.18.5. Interpretation	7893
14.18.6. Conclusion	7894
References	7894
Chapter 14.19: Stable Isotopes in Forensics Applications	7898
14.19.1. Stable Isotope Geochemistry as a Science-Based Forensic Application	7899
14.19.1.1. Overview	7899
14.19.1.2. A Framework for Applying Stable Isotope Analysis in Forensic Investigations	7899
14.19.2. Nonspatial Applications of Stable Isotope Analysis	7900
14.19.2.1. Synthetic Drugs	7900
14.19.2.1.1. Amphetamine-type stimulants	7901
14.19.2.1.2. Performance-enhancing steroids	7901
14.19.2.2. Manufactured Explosives	7902
14.19.2.2.1. Peroxide-based explosives	7902
14.19.2.2.2. An industrial explosive: ammonium nitrate	7903
14.19.2.2.3. A militarygrade explosive: pentaerythritol tetranitrate	7904
14.19.2.3. Packaging Materials	7905
14.19.2.4. Crude Oils and Petroleum Products	7905
14.19.3. Spatial Applications of Stable Isotope Analysis	7905
14.19.3.1. Water Isotopes and the Isoscapes Foundational Approach	7906
14.19.3.2. Waters, Beverages, and the Isoscapes Potential	7907
14.19.4. Plant-Related Forensic Applications of Stable Isotope Analysis	7908
14.19.4.1. Economic Adulteration of Foods	7908
14.19.4.2. Food Origin Authentication	7910
14.19.4.3. Controlled Substances Produced from Plants	7911
14.19.4.3.1. Cocaine and heroin	7911
14.19.4.3.2. Marijuana	7912
14.19.4.4. Wood and other Plant Product Isotope Records	7913
14.19.4.4.1. Arson - isotopic comparisons	7913
14.19.4.4.2. Flavor compounds - adulteration detection	7913
14.19.4.4.3. Plant and wood products - geographical region of origin	7913
14.19.5. Human-Related Forensic Applications of Stable Isotope Analysis	7914
14.19.5.1. Dietary Patterns	7914
14.19.5.2. Spatial Patterns	7915
14.19.5.2.1. Body water, geography, and metabolism	7915
14.19.5.2.2. Carbonates and phosphates in teeth and bones	7915
14.19.5.2.3. Proteins in bone and hair	7916
14.19.5.3. Provenancing Unidentified Homicide Victims	7917
14.19.5.4. Human Diseases	7918
14.19.6. Animal-Related (Nonhuman) Forensic Applications of Stable Isotope Analysis	7918
14.19.6.1. Animal Migration and Movement	7918
14.19.6.2. Provenance of Trade Goods	7920
14.19.7. Archaeological and Gem Origin Investigations Utilizing Stable Isotope Analysis	7921
14.19.7.1. Sculpture Source: Monuments, Statues, and Artifacts	7921
14.19.7.2. Gem Origins	7922
14.19.7.2.1. Rubies and sapphires	7922
14.19.7.2.2. Emeralds	7922
14.19.7.2.3. Diamonds	7922
14.19.8. Isotope Geochemists as Contributors to the Forensic Sciences	7922
14.19.8.1. Addressing the Needs of the NRC Report	7922
14.19.8.2. Isotopes in the Courts	7923
14.19.8.3. Concluding Points	7923
References	7923
Chapter 14.20: Reconstructing Aquatic Resource Exploitation in Human Prehistory Using Lipid Biomarkers and Stable Isotopes	7932
14.20.1. Introduction	7932
14.20.2. Reconstructing Diet and Economy fr	7933
14.20.3. The Lipid Composition of Aquatic Fats and Oils	7934
14.20.4. Early Attempts to Detect Aquatic Lipids in the Archeological Record	7934
14.20.5. New Aquatic Resource Biomarkers	7935
14.20.5.1. Vicinal Dihydroxy Acids	7935
14.20.5.2. Isoprenoid Fatty Acids	7936
14.20.5.3. omega-(o-Alkylphenyl)alkanoic Acids	7936
14.20.6. Stable Isotope Proxies	7938
14.20.6.1. Carbon Isotopes	7938
14.20.6.2. Hydrogen Isotopes	7939
14.20.7. Experimental Approaches and Protocols	7939
14.20.7.1. Thermal Degradation Experiments to Demonstrate Formation of Novel Lipid Biomarkers During the Heating of Unsaturat	7939
14.20.7.2. High Sensitivity GC/MS Protocols for the Detection of Marine Lipid Biomarkers	7940
14.20.7.3. Determination of Compound-Specific delta13C and deltaD Values of Individual n-Alkanoic Acids of Marine Organism	7944
14.20.8. Detecting Evidence for Marine Product Processing in Prehistory Using Biomarker and Stable Isotope Proxies	7945
14.20.8.1. Southern Brazil	7945
14.20.8.2. South Africa	7946
14.20.8.3. Northern and Northwestern Europe	7947
14.20.8.4. The Arctic	7948
14.20.9. Conclusions	7948
Acknowledgments	7950
References	7950
Chapter 14.21: Investigating Ancient Diets Using Stable Isotopes in Bioapatites	7954
14.21.1. Introduction	7954
14.21.2. A Few Basics	7954
14.21.2.1. Isotopes	7954
14.21.2.2. Bioapatite	7955
14.21.3. Development of the Field	7955
14.21.3.1. Photosynthesis	7955
14.21.3.2. From Plants to Animals	7956
14.21.3.3. Enter Anthropology	7957
14.21.3.4. Apatite as a Recorder on Geological Timescales	7957
14.21.4. Practical Issues	7958
14.21.4.1. Sampling and Analysis via Acid Hydrolysis	7958
14.21.4.2. Diet-Tissue Relationships	7958
14.21.4.3. Signal Attenuation	7959
14.21.4.4. Coupling Apatite and Collagen - A	7960
14.21.5. Applications	7961
14.21.5.1. Anthropology	7961
14.21.5.1.1. Holocene archaeology	7961
14.21.5.1.2. Anthropology in the deeper past	7963
14.21.5.2. Paleontology and Paleoecology	7963
14.21.5.2.1. Carbon isotopes for paleodiet and p&	7963
14.21.5.2.2. Oxygen isotopes in mammalian e	7964
14.21.6. Conclusions	7964
References	7965
Chapter 14.22: Human Physiology in Relation to Isotopic Studies of Ancient and Modern Humans	7970
14.22.1. Introduction	7970
14.22.2. Molecular Constituents of Human T	7970
14.22.2.1. Amino Acids	7970
14.22.2.2. Proteins	7972
14.22.2.3. Lipids	7972
14.22.2.4. Methane	7972
14.22.2.5. Inorganic Species in Solution	7973
14.22.2.5.1. Processing of phosphate	7973
14.22.3. Tissues Preserved Postmortem	7974
14.22.3.1. Bone	7974
14.22.3.1.1. Composition and structure	7974
14.22.3.1.1.1. The mineral components of teeth and bone	7974
14.22.3.1.1.2. Collagen	7975
14.22.3.1.1.3. Noncollagenous proteins and other molecules	7976
14.22.3.1.2. Structure of bone	7976
14.22.3.1.3. Modeling and remodeling	7977
14.22.3.2. Teeth: Composition, Structure, and Ontogeny	7978
14.22.3.3. Hair	7979
14.22.3.4. Lipids	7979
14.22.4. Homeostasis, Mineral Stability	7979
14.22.4.1. Calcium Phosphate Saturation	7979
14.22.4.2. Osmoregulation, Water Stress	7980
14.22.5. Nutritional and Metabolic Diseases	7980
References	7980
Chapter 14.23: Hair as a Geochemical Recorder: Ancient to Modern	7984
14.23.1. Introduction	7984
14.23.1.1. Structure and Composition of Hair	7984
14.23.1.2. Hair Growth	7985
14.23.2. Survival of Hair in Archaeological and Forensic Contexts	7986
14.23.3. Studies of Isotope Ratios in Animal Hair	7988
14.23.3.1. Animal Hair from Controlled, Experimental Situations	7988
14.23.3.2. Animal Hair as an Environmental Sampling Tool	7989
14.23.4. Anthropological Studies on Modern and Historically Collected Hair	7992
14.23.5. Health and Medical Applications of Hair Analysis	7994
14.23.5.1. Human Dietary Preferences and Stable Isotope Ratios	7994
14.23.5.2. Use of Isotope Ratios to Investigate Nitrogen Balance during Pregnancy	7995
14.23.5.3. Investigation of Stable Isotope Ratios as a Means of Diagnosing Eating Disorders	7995
14.23.5.4. Trace Element Analysis of Human Hair as a Tool for Health Investigation	7996
14.23.6. Archaeological Hair	7996
14.23.6.1. The Americas	7997
14.23.6.2. The Nile Valley	7998
14.23.6.3. Other Regions	7998
14.23.7. Applications to Forensic Investigations	7998
14.23.7.1. Unidentified Human Remains	7998
14.23.7.2. Wildlife Forensics and Isotopic Analysis of Hair	7999
14.23.8. Geography and Temporal Dynamics in Hair Oxygen Isotope Ratios	7999
14.23.9. Future Directions	8001
References	8001
e9780080983004v15	8007
Front Cover	8007
Analytical Geochemistry/Inorganic Instrument Analysis	8010
Copyright	8011
In Memoriam	8012
Heinrich Dieter Holland (1927–2012)	8014
Karl Karekin Turekian (1927–2013)	8016
References	8018
Dedication	8020
Contents	8022
Executive Editors’ Foreword To The Second Edition	8024
Contributors	8028
Volume Editor’s Introduction	8030
The First Step: Sampling Strategies and Getting Ready for the Lab	8030
Uncertainties, Reference Materials, and Isotope Dilution	8030
Digesting and Preparing Samples in the Clean Lab	8031
Analyzing the Sample: Photons and Atomic Masses	8031
Measuring Photons	8032
Measuring Mass	8033
Analyzing the Planet: New Developments	8034
Chapter 15.1: Basic Considerations: Sampling, the Key for a Successful Applied Geochemical Survey for Mineral Exploration and Environ	8036
15.1.1. Introduction and Background Information	8036
15.1.2. Design of a Geochemical Sampling Campaign	8037
15.1.2.1. Desk Study	8037
15.1.2.2. Orientation Survey	8037
15.1.2.2.1. Orientation survey in mineral exploration	8037
15.1.2.2.2. Orientation survey in a contaminated land investigation	8038
15.1.2.3. Regional Geochemical Survey	8039
15.1.2.4. Follow-up Geochemical Survey	8040
15.1.2.5. Detailed Geochemical Survey	8040
15.1.2.5.1. Detailed rock or soil geochemical survey	8041
15.1.2.5.2. Detailed contaminated land investigation	8041
15.1.2.5.2.1. Systematic versus random sampling	8043
15.1.2.5.2.2. Square block sampling	8043
15.1.2.5.2.3. Composite versus spot sampling	8043
15.1.3. Randomization of Samples	8044
15.1.4. Quality Control - Duplicate Field Samples and Control Samples	8044
15.1.5. Sampling	8045
15.1.5.1. Stream Sediment Sampling	8045
15.1.5.1.1. Wet sieving	8047
15.1.5.1.2. Dry sieving	8047
15.1.5.1.3. Without sieving	8047
15.1.5.2. Overbank or Floodplain Sediment Sampling	8047
15.1.5.3. Stream and Ground-Water Sampling	8050
15.1.5.4. Rock Sampling	8052
15.1.5.5. Soil Sampling	8053
15.1.5.5.1. Soil sampling for mineral exploration	8053
15.1.5.5.2. Soil sampling for environmental investigations	8054
15.1.5.5.2.1. Urban soil sampling	8055
15.1.5.5.2.2. Soil sampling for contaminated land investigations	8057
15.1.5.6. House-Dust Sampling	8057
15.1.5.7. Attic-Dust Sampling	8058
15.1.5.8. Road Dust Sampling	8059
15.1.6. Sampling in the Laboratory	8059
15.1.7. Conclusions	8062
Acknowledgments	8062
References	8063
Chapter 15.2: Error Propagation	8068
15.2.1. Introduction	8068
15.2.2. Accuracy, Precision, and Types of Errors	8068
15.2.2.1. Accuracy and Precision	8068
15.2.2.2. Errors	8068
15.2.3. Statistical Treatment of Random Errors	8069
15.2.3.1. Mean and Standard Deviation	8069
15.2.3.2. Weighted Averages	8070
15.2.3.3. Variance, Covariance, and Correlated Errors	8070
15.2.4. Probability Distributions	8071
15.2.4.1. Normal/Gaussian Distribution	8071
15.2.4.1.1. Log-normal distribution	8072
15.2.4.2. Poisson Distribution	8072
15.2.5. Calibration Curves, Blank Standar	8073
15.2.5.1. Calibration Curves	8073
15.2.5.2. Blank Standard Deviation, Blank Standard	8073
15.2.6. Error Propagation	8075
15.2.6.1. Random Error Propagations	8075
15.2.6.2. Systematic Error Propagations	8076
15.2.5.3. Use of Least Squares to Estimate	8074
Acknowledgments	8077
References	8077
Chapter 15.3: Reference Materials in Geochemical and Environmental Research	8078
15.3.1. Introduction	8079
15.3.2. ISO Guidelines and IAG Certification Protocol	8079
15.3.3. Rock Reference Materials	8081
15.3.3.1. Preparation	8081
15.3.3.2. Frequently Used Rock Reference Materials	8082
15.3.3.2.1. USGS basalts and andesites	8083
15.3.3.2.2. Certified reference materials	8083
15.3.3.2.3. Reference materials from diverse providers	8084
15.3.3.2.4. Reference materials for platinum-group elements	8085
15.3.4. Environmental Reference Materials	8085
15.3.4.1. Soils and Sediments	8085
15.3.4.2. Dust and Air Particulates and Nanoparticles	8086
15.3.4.3. Water Reference Materials	8086
15.3.4.4. Biota	8086
15.3.5. Microanalytical Reference Materials	8086
15.3.5.1. Synthetic Reference Glasses	8087
15.3.5.1.1. NIST SRM reference glasses	8087
15.3.5.1.2. BAM-certified reference glasses	8087
15.3.5.1.3. USGS GS reference glasses	8087
15.3.5.2. Natural Reference Glasses	8091
15.3.5.2.1. Geologic USGS reference glasses	8091
15.3.5.2.2. Geologic MPI-DING reference glasses	8092
15.3.5.2.3. Geologic NRCG reference glasses	8092
15.3.5.3. Mineral Reference Materials	8092
15.3.5.3.1. Zircon	8092
15.3.5.3.2. Sulfide reference materials	8093
15.3.5.3.3. Other mineral reference materials	8093
15.3.6. Isotopic Reference Materials	8093
15.3.6.1. Radiogenic Isotopic Reference Materials	8093
15.3.6.1.1. Strontium isotopes	8093
15.3.6.1.2. Barium isotopes	8093
15.3.6.1.3. Cerium isotopes	8093
15.3.6.1.4. Neodymium isotopes	8094
15.3.6.1.5. Hafnium isotopes	8094
15.3.6.1.6. Osmium isotopes	8094
15.3.6.1.7. Lead isotopes	8094
15.3.6.2. Radioactive Isotopic Reference Materials	8094
15.3.6.2.1. Uranium isotopes	8095
15.3.6.2.2. Thorium isotopes	8095
15.3.6.3. Stable Isotopic Reference Materials	8095
15.3.6.3.1. Hydrogen isotopes	8095
15.3.6.3.2. Lithium isotopes	8097
15.3.6.3.3. Boron isotopes	8097
15.3.6.3.4. Carbon isotopes	8097
15.3.6.3.5. Nitrogen isotopes	8097
15.3.6.3.6. Oxygen isotopes	8097
15.3.6.3.7. Magnesium isotopes	8097
15.3.6.3.8. Silicon isotopes	8098
15.3.6.3.9. Sulfur isotopes	8098
15.3.6.3.10. Chlorine isotopes	8098
15.3.6.3.11. Calcium isotopes	8098
15.3.6.3.12. Titanium isotopes	8098
15.3.6.3.13. Vanadium isotopes	8098
15.3.6.3.14. Chromium isotopes	8098
15.3.6.3.15. Iron isotopes	8098
15.3.6.3.16. Nickel isotopes	8098
15.3.6.3.17. Copper isotopes	8099
15.3.6.3.18. Zinc isotopes	8099
15.3.6.3.19. Germanium isotopes	8099
15.3.6.3.20. Selenium isotopes	8099
15.3.6.3.21. Rubidium isotopes	8099
15.3.6.3.22. Strontium isotopes	8099
15.3.6.3.23. Zirconium isotopes	8099
15.3.6.3.24. Molybdenum isotopes	8099
15.3.6.3.25. Cadmium isotopes	8099
15.3.6.3.26. Silver isotopes	8099
15.3.6.3.27. Antimony isotopes	8099
15.3.6.3.28. Tungsten isotopes	8099
15.3.6.3.29. Rhenium isotopes	8100
15.3.6.3.30. Mercury isotopes	8100
15.3.6.3.31. Thallium isotopes	8100
15.3.7. GeoReM Database	8100
15.3.8. Successes and Needs	8100
Acknowledgments	8101
References	8101
Chapter 15.4: Application of Isotope Dilution in Geochemistry	8106
15.4.1. Introduction	8106
15.4.2. Applications of Isotope Dilution	8106
15.4.2.1. Determination of Accurate and Precise Element Concentrations	8106
15.4.2.2. `Double Spiking´ for IC Measurements	8107
15.4.3. Principles of Isotope Dilution	8107
15.4.3.1. Derivation of the Principal ID Equation	8107
15.4.3.2. Criteria for Spiking Samples	8109
15.4.3.3. The Optimum Spike-Sample Ratio	8109
15.4.3.4. Sources of Uncertainty in ID Measurements	8110
15.4.4. Applying Isotope Dilution	8111
15.4.4.1. Preparation and Calibration of Spikes	8111
15.4.4.2. Mixed Spikes Versus Single Spikes	8112
15.4.4.3. Simultaneous IC and ID: `Spike Stripping´	8113
15.4.5. Double and Triple Spiking	8115
15.4.6. Conclusions	8119
Acknowledgments	8120
References	8120
Chapter 15.5: Sample Digestion Methods	8122
15.5.1. Introduction	8122
15.5.2. General Considerations	8123
15.5.2.1. Mineral Acids	8123
15.5.2.1.1. Hydrofluoric acid	8123
15.5.2.1.2. Nitric acid	8123
15.5.2.1.3. Aqua regia	8123
15.5.2.1.4. Hydrochloric acid	8124
15.5.2.1.5. Perchloric acid	8124
15.5.2.1.6. Sulfuric acid	8124
15.5.2.1.7. Phosphoric acid	8124
15.5.2.2. Digestion Vessel Materials	8124
15.5.2.3. Contamination from the Digestion Process	8124
15.5.2.4. Assessing a Digestion Procedure	8125
15.5.3. Sample Digestion Methods	8126
15.5.3.1. Open Vessel Acid Digestions	8126
15.5.3.2. Closed Vessel Digestions	8127
15.5.3.3. Microwave Digestions	8128
15.5.3.4. Partial Dissolutions	8130
15.5.3.5. Dry Ashing Techniques	8130
15.5.3.6. Alkali Fusions	8132
15.5.3.6.1. Fusion with NaOH and KOH	8132
15.5.3.6.2. Sinter or fusion with Na2O2	8132
15.5.3.6.3. Fusion with LiBO2 and Li2B4O7	8133
15.5.3.6.4. Fusion with Na2CO3	8133
15.5.3.7. Fire Assays	8134
15.5.3.7.1. Lead fire assay	8134
15.5.3.7.2. Nickel fire assay	8134
15.5.3.8. Carius Tube and High-Pressure Asher (HPA-S)	8135
15.5.3.9. Direct Fusion of Rock Powder	8136
15.5.3.9.1. Flux-free fusion glasses	8137
15.5.3.9.2. Lithium-borate fusion glass	8137
15.5.4. Summary and Overview	8138
Acknowledgments	8138
References	8138
Chapter 15.6: Developments in Clean Lab Practices	8146
15.6.1. Introduction	8146
15.6.2. Detection and Quantification Limits	8148
15.6.2.1. Limit of Detection	8148
15.6.2.2. Procedural Blank	8149
15.6.3. Design of a Clean Room	8149
15.6.3.1. Materials	8150
15.6.3.2. Clean Air Supply	8150
15.6.3.3. Pure Water Supply	8150
15.6.4. Clean Lab Equipment, Labware&I	8151
15.6.4.1. Laminar Flow Boxes	8151
15.6.4.2. Labware	8151
15.6.4.3. Sub boiling Distillation of Reagents	8153
15.6.5. Examples of Low-Level Blank &I	8154
15.6.5.1. Uranium-Lead Zircon Dating	8154
15.6.5.2. Strontium Isotopic Analysis by Micromilling	8154
15.6.5.3. Palladium-Silver Analysis of Meteorites	8155
15.6.5.4. High-Field-Strength Elements and Tungsten	8155
15.6.5.5. Rhenium-Osmium Systematics	8155
15.6.5.6. Trace Element Contamination-Lithium Example	8156
15.6.6. Concluding Remarks	8156
Acknowledgments	8156
References	8156
Chapter 15.7: Basics of Ion Exchange Chromatography for Selected Geological Applications	8158
15.7.1. Introduction	8159
15.7.2. Basic Principles of Ion Chromatography	8159
15.7.2.1. Stationary Phase-Mobile Phase	8159
15.7.2.2. Structure of Ion Exchange Resins	8159
15.7.2.3. Ion Exchange Processes	8160
15.7.2.3.1. The equilibrium distribution coefficient (Kd)	8160
15.7.2.3.2. The batch method	8161
15.7.2.3.3. The column method	8161
15.7.2.3.4. Retention volume and retention time	8162
15.7.2.3.5. The ion exchange capacity of a resin	8162
15.7.2.3.6. The capacity factor	8163
15.7.2.3.7. Selectivity, separation factor, and selectivity coefficient: the efficiency of an ion exchange column to separate	8163
15.7.2.3.8. Minimizing peak broadening: van Deemter&INS id=	8163
15.7.3. Cation Exchange Versus Anion Exchange Chromatography	8164
15.7.3.1. Structure and Basic Functionality of Cation and Anion Exchange Resins	8164
15.7.3.2. Equilibrium Distribution Coefficients (Kd) for Cation and Anion Exchange Resins	8165
15.7.3.2.1. Equilibrium distribution coefficients for strong cation exchange resins	8165
15.7.3.2.2. Equilibrium distribution coefficients for strong anion exchange resins	8165
15.7.4. Applications of Anion and Cation Exchange Chromatography for Element Enrichment and Purification Prior to High-&INS i	8166
15.7.4.1. General Considerations for Chromatographic Ion Exchange Separation Procedures	8166
15.7.4.2. General Laboratory Procedure of Ion Exchange Separations	8173
15.7.4.3. The Setup of Ion Exchange Separation Methods: Calibration and Verification of Accuracy	8173
15.7.4.4. Procedural Blanks	8174
15.7.4.5. Selected Examples of Geological Applications Using Strong Cation or Anion Exchange Resin in Combina	8174
15.7.4.5.1. Lithium	8178
15.7.4.5.2. Chromium	8178
15.7.4.5.3. Iron	8178
15.7.4.5.4. Silver	8178
15.7.4.5.5. Neodymium	8179
15.7.5. Concluding Remarks	8179
References	8179
Chapter 15.8: Separation Methods Based on Liquid-Liquid Extraction, Extraction Chromatography, and Other Miscellaneous Solid Phase Extraction	8182
15.8.1. Introduction	8182
15.8.2. Separations by Liquid-Liquid Extraction	8183
15.8.2.1. General	8183
15.8.2.2. Experimental	8184
15.8.2.3. Some Examples of Geochemical Applications	8184
15.8.3. Extraction Chromatography	8186
15.8.3.1. General Principle	8186
15.8.3.2. Preparation of EXC Materials and Columns	8187
15.8.3.2.1. General	8187
15.8.3.2.2. EXC materials	8187
15.8.3.2.2.1. Inert support	8187
15.8.3.2.2.2. Loading of the stationary phase onto the inert support	8188
15.8.3.2.3. Column packing	8188
15.8.3.3. Examples of EXC Materials	8188
15.8.3.3.1. Sr resin	8188
15.8.3.3.2. Pb resin	8190
15.8.3.3.3. TRU resin	8190
15.8.3.3.4. RE resin	8190
15.8.3.3.5. TEVA resin	8192
15.8.3.3.6. UTEVA resin	8192
15.8.3.3.7. Actinide (DIPEX) resin	8192
15.8.3.3.8. Ln resin	8193
15.8.3.3.9. `DGA resins	8194
15.8.3.3.10. Miscellaneous, not marketed EXC materials	8194
15.8.3.3.10.1. BPHA resin	8194
15.8.3.3.10.2. DIBK resin	8194
15.8.3.4. Some Examples of Applications in Geochemistry and Cosmochemistry	8194
15.8.3.5. Advantages and Limitations of Extraction Chromatography	8197
15.8.3.5.1. Advantages	8197
15.8.3.5.2. Limitations	8200
Chapter 15.9: Principles of Atomic Spectroscopy	8206
15.9.1. Introduction and Terminology	8206
15.9.2. Some History	8206
15.9.3. Principles of Atomic Spectroscopy: Electromagnetic Radiation	8207
15.9.4. Origin of Atomic Spectra	8209
15.9.5. Analytical Applications of Atomic Spectroscopy	8210
15.9.5.1. Atomic Absorption	8210
15.9.5.2. Atomic Emission	8210
15.9.5.3. X-Ray Fluorescence	8211
15.9.5.4. Mass Spectrometry	8212
15.9.5.5. Mass Spectrometer Ion Source	8212
15.9.5.6. Mass Dispersion Devices	8213
15.9.5.6.1. Magnetic sector	8213
15.9.5.6.2. Quadrupole mass analyzer	8213
15.9.6. Characteristics of Analytical Atomic Spectrometry Instruments	8213
15.9.6.1. Atomic Absorption Spectrometry	8214
15.9.6.2. X-Ray Fluorescence Analysis	8214
15.9.6.3. Inductively Coupled Plasma-Atomic Emission Spectrometry	8214
15.9.6.4. Inductively Coupled Plasma-Mass Spectrometry	8215
References	8215
Chapter 15.10: x-Ray Fluorescence Spectroscopy for Geochemistry	8216
15.10.1. Principles	8217
15.10.1.1. Introduction	8217
15.10.1.2. x-Ray Generation	8217
15.10.1.3. Primary and Fluorescent x-Ray	8218
15.10.1.4. Excitation Energy	8218
15.10.1.5. x-Ray Absorption and Analytic Depth	8219
15.10.1.6. x-Ray Safety	8219
15.10.2. Instrumentation	8219
15.10.2.1. Measuring Systems	8219
15.10.2.1.1. Wavelength dispersive system	8219
15.10.2.1.2. Energy dispersive system	8220
15.10.2.1.3. Portable handheld device	8220
15.10.2.2. x-Ray Source	8220
15.10.2.3. x-Ray Detection	8220
15.10.2.4. x-Ray Filter	8221
15.10.2.5. Pulse-Height Analyzer	8221
15.10.2.6. Measuring Atmosphere	8221
15.10.2.7. Analyzing Crystal for WDS	8221
15.10.3. Sample Preparation	8221
15.10.3.1. Criteria of Specimen	8221
15.10.3.2. Direct Measurement	8222
15.10.3.3. Specimen with Sample Pulverization	8222
15.10.3.3.1. Sample pulverization	8222
15.10.3.3.2. Loose powder analyses	8223
15.10.3.3.3. Pressed powder pellet analyses	8223
15.10.3.3.4. Fused glass bead analyses	8223
15.10.3.4. Liquid Sample	8223
15.10.3.5. Contamination	8224
15.10.4. Qualitative Analysis	8224
15.10.4.1. x-Ray Spectrum	8224
15.10.4.2. Special Lines	8224
15.10.4.3. Spectral Interference	8224
15.10.4.4. Peak Identification	8224
15.10.5. Quantitative Analysis	8224
15.10.5.1. x-Ray Intensity	8224
15.10.5.1.1. Analytic line	8224
15.10.5.1.2. XRF intensity for determination	8225
15.10.5.1.3. Standardization for routine analysis	8225
15.10.5.1.4. x-Ray statistics	8225
15.10.5.2. Standardless Determination	8225
15.10.5.3. Determination with Calibration Standard	8225
15.10.5.3.1. Criteria of standard specimen	8225
15.10.5.3.2. Commercial standards	8226
15.10.5.3.3. Synthetic standards	8226
15.10.5.3.4. In-house standards	8226
15.10.5.3.5. Calibration curve	8226
15.10.5.4. Matrix Effect	8227
15.10.5.5. Matrix Corrections	8227
15.10.5.5.1. Standard addition	8227
15.10.5.5.2. Internal standard	8227
15.10.5.5.3. Correction with scattering x-rays	8227
15.10.5.5.4. Model calculations	8228
15.10.5.6. Validation	8228
15.10.5.7. Applications	8228
15.10.6. Further Techniques	8228
15.10.6.1. Total Reflection for Surface Analysis	8228
15.10.6.2. Chemical Shift for Chemical State Analysis	8228
References	8229
Chapter 15.11: Raman and Nuclear Resonant Spectroscopy in Geosciences	8230
15.8.4. Other Element-Specific SPE Materials	8201
15.8.4.1. A Few Selected Examples of Chelating Resins	8201
15.8.4.1.1. Boron-specific resin	8201
15.8.4.1.2. Precious elements specific resins	8201
15.8.4.1.3. Chelating resins for trace element separation from (sea-) water	8201
15.8.4.2. SPE Materials Based on Macrocyclic Ligands	8202
15.8.5. Suggestions for Future Trends	8202
References	8203
15.11.1. Introduction	8230
15.11.1.1. Interaction of Electromagnetic Waves and Matter	8231
15.11.1.2. General Raman and Nuclear Resonant Spectroscopy	8232
15.11.1.3. Electronic Structures and Crystal Field Theory	8232
15.11.2. Raman Spectroscopy	8233
15.11.2.1. Theory of Vibrational Properties of Molecules and Crystals	8233
15.11.2.2. Instrumentation for Raman Experiments	8234
15.11.2.2.1. Raman microprobe and mapping	8234
15.11.2.2.2. Raman spectroscopy in high P-T DAC	8235
15.11.2.2.3. Raman instrumentation for planetary e&/	8236
15.11.2.3. Raman Analyses of Planetary Materials	8236
15.11.2.3.1. Phase identification in natural and synthetic samples	8237
15.11.2.3.2. Raman microprobe study of meteorites and lunar samples	8237
15.11.2.3.3. Laboratory studies at high P-T	8237
15.11.3. Synchrotron MS and NRIXS	8238
15.11.3.1. Mössbauer Effect and MS	8239
15.11.3.1.1. Chemical shift	8239
15.11.3.1.2. Quadrupole splitting	8239
15.11.3.1.3. Magnetic hyperfine splitting	8239
15.11.3.1.4. Recoil-free fraction	8240
15.11.3.2. Mössbauer Instrumentation Using Conventional and Synchrotron Sources	8240
15.11.3.3. Nuclear Resonant Scattering Using Synchrotron Radiation	8240
15.11.3.4. Geophysical Applications	8242
15.11.3.4.1. Sound velocities of iron alloys by NRIXS	8243
15.11.3.4.2. Electronic spin and valence states by SMS	8243
15.11.4. Prospective Directions	8243
Acknowledgments	8244
References	8244
Chapter 15.12: Synchrotron x-Ray Spectroscopic Analysis	8248
15.12.1. Introduction	8248
15.12.2. High-Energy Synchrotrons	8248
15.12.3. Synchrotron Radiation Sources	8250
15.12.4. Synchrotron Beamlines	8251
15.12.5. XAFS Analysis	8252
15.12.6. XRM Analysis	8254
15.12.6.1. XRM Instrumentation	8255
15.12.6.2. XRF Microanalysis	8255
15.12.6.3. Micro-XAFS Analysis	8257
15.12.6.4. Micro-XRD Analysis	8260
15.12.7. Computed Microtomography	8260
15.12.8. Surface and Interface Methods	8262
15.12.9. Other Synchrotron Methods	8263
15.12.10. Future Directions	8263
Acknowledgments	8263
References	8263
Chapter 15.13: Transmission Electron Microscope-Based Spectroscopy	8266
Glossary	8266
15.13.1. Introduction	8266
15.13.2. TEM Design Considerations	8268
15.13.2.1. TEM or STEM	8268
15.13.2.2. Thermionic and Field Emission Electron Sources	8269
15.13.2.3. Energy Spread and Monochromators	8269
15.13.2.4. Operating Voltage	8269
15.13.3. Energy-Dispersive x-Ray Spectroscopy and Electron Energy-Loss Spectroscopy Instrumentation	8270
15.13.3.1. EDS Detectors	8270
15.13.3.2. Electron Energy-Loss Spectrometers	8270
15.13.4. Sample Preparation	8270
15.13.5. Energy-Dispersive x-Ray Spectroscopy Examples	8272
15.13.6. Electron Energy-Loss Spectroscopy Examples	8277
References	8279
Chapter 15.4: Laser-Induced Breakdown Spectroscopy	8280
15.14.1. Introduction and Overview	8280
15.14.2. The LIBS Analysis	8281
15.14.3. LIBS Fundamentals	8282
15.14.3.1. The Physics of LIBS	8282
15.14.3.2. Spatial Resolution	8287
15.14.3.3. The Chemistry of LIBS	8288
15.14.3.3.1. Quantitative LIBS	8288
15.14.3.3.2. Qualitative LIBS	8289
15.14.4. Laboratory, Field-Portable, and Standoff LIBS Analysis	8290
15.14.5. Example Applications of LIBS for Natural Material Analysis	8291
15.14.5.1. Minerals and Rocks	8291
15.14.5.2. Sediment and Soil Analysis	8293
15.14.5.3. Fluid Analysis	8295
15.14.5.4. Fluid Inclusion Analysis	8296
15.14.5.5. Material Analysis under Water	8297
15.14.5.6. Environmental Applications	8297
15.14.5.7. Archaeological Applications	8298
15.14.5.8. Extraterrestrial Analysis	8298
15.14.5.9. Isotopic Analysis by LIBS	8299
15.14.6. Statistical Signal Processing for LIBS	8299
15.14.7. Conclusions - The Path Forward	8301
Acknowledgments	8302
References	8302
Chapter 15.15: Nuclear Spectroscopy	8308
15.15.1. Introduction	8308
15.15.2. The Discovery of Radioactivity	8309
15.15.3. The Atomic Nucleus, Isotopes, and Radionuclides	8309
15.15.4. Radioactive Decay	8310
15.15.4.1. Modes of Radioactive Decay	8310
15.15.4.2. Radioactive Decay Law	8310
15.15.4.3. Units of Radioactivity	8311
15.15.4.4. Growth and Decay of Radioactive Products	8311
15.15.5. Nuclear Reactions	8312
15.15.5.1. The Reaction Process	8312
15.15.5.2. Compound Nucleus Formation	8313
15.15.5.3. Reaction Cross Sections	8313
15.15.5.4. Excitation Functions	8314
15.15.5.5. Growth of Radioactive Products During Irradiation	8314
15.15.6. Irradiation Sources	8314
15.15.6.1. Nuclear Reactors	8315
15.15.6.2. Neutron Generators	8316
15.15.6.3. Charged-Particle Accelerators	8316
15.15.6.4. Radioisotopic Sources	8316
15.15.7. Interactions Between Radiation and Matter	8316
15.15.7.1. Interaction of Heavy-Charged Particles with Matter	8316
15.15.7.2. Interaction of Electrons and Positrons with Matter	8317
15.15.7.3. Interaction of Gamma Rays with Matter	8317
15.15.7.4. Interaction of Neutrons with Matter	8318
15.15.8. Radiation Detection and Measurement	8318
15.15.8.1. General Properties of Detectors	8319
15.15.8.2. Scintillation Detectors	8319
15.15.8.3. Semiconductor Detectors	8320
15.15.8.4. Shielding and Compton Suppression	8320
15.15.9. Applications for Nuclear Spectroscopy	8321
15.15.9.1. Activation Analysis	8321
15.15.9.1.1. Preparation of samples and standards for activation analysis	8321
15.15.9.1.2. Irradiation and counting techniques	8322
15.15.9.1.3. Activation analysis with thermal neutrons	8322
15.15.9.1.4. Activation analysis with epithermal neutrons	8323
15.15.9.1.5. Activation analysis with fast neutrons	8323
15.15.9.1.6. Activation analysis using prompt gamma rays	8323
15.15.9.1.7. Activation analysis with charged-particle beams	8323
15.15.9.1.8. Activation analysis with high-energy photons	8324
15.15.9.1.9. Activation analysis with radiochemical separation	8324
15.15.9.1.10. Activation analysis with gamma-gamma coincidence	8324
15.15.9.2. Other Applications of Nuclear Spectroscopy	8325
References	8325
Chapter 15.16: Stable Isotope Techniques for Gas Source Mass Spectrometry	8326
15.16.1. Introduction	8326
15.16.2. Mass Spectrometers	8326
15.16.2.1. Inlet System	8327
15.16.2.1.1. Dual inlet	8327
15.16.2.1.2. Continuous flow inlet	8328
15.16.2.2. Ion Source	8330
15.16.2.3. Analyzer	8331
15.16.2.4. Collector Assembly	8332
15.16.3. Standardization	8333
15.16.4. Methods of Analysis	8334
15.16.4.1. Hydrogen	8334
15.16.4.1.1. Reduction methods	8335
15.16.4.1.2. Equilibration methods	8335
15.16.4.2. Carbon	8335
15.16.4.3. Nitrogen	8336
15.16.4.4. Oxygen	8336
15.16.4.5. Sulfur	8337
15.16.4.6. Chlorine	8338
15.16.5. Laser Absorption Spectrometry	8338
References	8340
Chapter 15.17: Inductively Coupled Plasma Mass Spectrometers	8344
15.17.1. Introduction	8346
15.17.2. Sample Preparation	8348
15.17.3. Sample Introduction and Ion Production	8349
15.17.4. Sampler/Skimmer Interface	8352
15.17.5. ICP-MS with Quadrupole Mass Spectrometers	8352
15.17.6. Spectral Overlaps in ICP-MS	8352
15.17.6.1. Elemental Ions	8353
15.17.6.2. Molecular Ions	8353
15.17.6.3. Doubly Charged Ions	8354
15.17.6.4. Recognizing that Spectral Overlaps Exist	8354
15.17.6.5. Preventing Errors in Reported Concentrations Due to Spectral Overlaps	8355
15.17.6.5.1. Choice of isotopes to measure	8355
15.17.6.5.2. Mathematical corrections: Elemental ions	8355
15.17.6.5.3. Mathematical corrections: Molecular ions	8355
15.17.6.5.4. Desolvation system to reduce solvent-related ion signals	8356
15.17.6.5.5. Modifying plasma conditions to reduce molecular ion signals: Addition of molecular gas to the plasma	8356
15.17.6.5.7. Chemical separation prior to analysis	8356
15.17.6.5.8. Kinetic energy discrimination using a collision/reaction cell	8356
15.17.6.5.9. Ion-molecule reactions using a collision/reaction cell	8357
15.17.6.5.6. Modifying plasma conditions to reduce signals from ions with high ionization energy: &INS id=	8356
15.17.7. Collision/Reaction Cells to Overcome Spectral Overlaps in ICP-Quadrupole MS	8357
15.17.7.1. Kinetic Energy Discrimination	8357
15.17.7.2. Ion-Molecule Reactions	8359
15.17.8. ICP-MS Instrument Designs with a Quadrupole Mass Analyzer	8359
15.17.9. ICP-Sector Field Mass Spectrometers	8360
15.17.9.1. ICP-SFMS with Sequential Detection	8360
15.17.10. ICP-MS Instruments with Simultaneous Detection of the Mass Spectrum	8365
15.17.10.1. ICP-Sector Field Mass Spectrometer with Simultaneous Imaging Detector	8365
15.17.10.2. ICP-Time of Flight Mass Spectrometer	8365
15.17.11. Multicollector Inductively Coupled Plasma Mass Spectrometers	8365
15.17.11.1. Spectral Overlaps	8367
15.17.11.2. Fixed or Variable Position Detectors	8367
15.17.11.3. Static and Dynamic Measurements	8367
15.17.11.4. Mass Discrimination (Mass Bias)	8368
15.17.11.4.1. Double or triple spike correction for mass bias	8368
15.17.11.4.2. Internal standardization using an analyte isotope pair that is constant in nature	8368
15.17.11.4.3. Internal standardization using a pair of isotopes of another element	8368
15.17.11.4.4. Internal standardization with isotopes of another element using a regression approach	8368
15.17.11.4.5. External standard sample standard bracketing	8369
15.17.11.4.6. Isotope ratio uncertainties	8369
15.17.11.5. Applications	8369
References	8369
Chapter 15.18: Thermal Ionization Mass Spectrometry	8372
15.18.1. Introduction	8372
15.18.2. Why TIMS Survives	8372
15.18.2.1. Strengths	8372
15.18.2.2. Weaknesses	8373
15.18.3. Thermal Ionization	8374
15.18.4. The Physical TIMS Instrument	8376
15.18.4.1. The Ion Source	8376
15.18.4.2. The Mass Analyzer	8377
15.18.4.3. Ion Detectors	8380
15.18.4.3.1. Faraday detectors	8380
15.18.4.3.2. Ion multipliers	8382
15.18.5. Measuring Isotope Ratios by TIMS	8384
15.18.5.1. Noise	8384
15.18.5.2. Time Variability of the Ion Beam	8384
15.18.5.3. Correcting for Amplifier and Faraday Cup Gains	8384
15.18.5.4. Fractionation Correction	8385
15.18.6. Conclusions and Future Prospects	8387
Acknowledgments	8388
References	8388
Chapter 15.19: Noble Gas Mass Spectrometry	8390
15.19.1. Introduction	8390
15.19.1.1. Noble Gases in Geochemistry and Cosmochemistry	8390
15.19.2. Characteristics of Noble Gas Mass Spectrometry	8391
15.19.3. Types of Samples, Noble Gas Extraction and Purification	8392
15.19.3.1. Solid Samples	8393
15.19.3.1.1. Total extraction of noble gases from solid samples	8394
15.19.3.1.2. Stepwise noble gas extraction from solid samples	8394
15.19.3.2. Liquid Samples	8395
15.19.3.3. Gaseous Samples	8395
15.19.3.4. Noble Gas Purification	8396
15.19.3.5. Separation of Noble Gases from Each Other	8397
15.19.3.6. Nitrogen Analysis by Static Mass Spectrometry	8397
15.19.4. Ionization, Mass Separation, and Ion Detection	8397
15.19.4.1. Ionization	8397
15.19.4.2. Mass Separation and Detection	8397
15.19.5. Calibration	8399
15.19.5.1. Spiking	8399
15.19.5.2. Peak-Height Comparison	8399
15.19.5.3. Standards	8400
15.19.5.4. The Isotopic Composition of Noble Gases in Air	8400
15.19.6. Blank and Interference Corrections	8402
15.19.6.1. Noble Gas Blanks	8402
15.19.6.2. Interference Corrections	8402
15.19.7. Mass Spectrometer Memory and Ion Pumping	8403
15.19.8. Outlook	8404
Acknowledgments	8405
References	8405
Chapter 15.20: Accelerator Mass Spectrometry	8410
15.20.1. Introduction	8410
15.20.2. The AMS Instrument	8410
15.20.3. Ion Source	8411
15.20.4. Injection Magnet and Bouncer	8412
15.20.5. Tandem Particle Accelerator and Stripper	8413
15.20.6. High-Energy Particle Analysis	8413
15.20.7. Particle Detection	8414
15.20.8. Development of Smaller Machines	8414
15.20.8.1. The 0.5-1MV `Small&INS i	8414
15.20.8.2. 200kV Machines	8415
15.20.8.3. The `Single-Stage&INS id=	8416
15.20.9. Conclusion	8416
References	8417
Chapter 15.21: Ion Microscopes and Microprobes	8420
15.21.1. Overview	8420
15.21.2. Primary Ion Beams	8421
15.21.2.1. Primary Ions	8421
15.21.2.2. Primary Column and Beam Characteristics	8422
15.21.3. Secondary Ions	8423
15.21.3.1. Ion Yields	8424
15.21.4. Mass Spectrometry	8424
15.21.4.1. History of Ion Microprobe Mass Spectrometers	8425
15.21.4.2. Nuclidic Mass Resolution	8425
15.21.4.3. Mass Spectra	8426
15.21.4.4. Energy Spectra	8426
15.21.5. Instrumentation	8427
15.21.5.1. Cameca Ion Microscopes (ims 7f and 1280 Series)	8427
15.21.5.2. Cameca NanoSIMS	8427
15.21.5.3. SHRIMP	8428
15.21.6. Measurement	8431
15.21.6.1. Detection	8431
15.21.6.2. Ion Counting	8431
15.21.6.3. 2D Detectors	8432
15.21.6.4. Faraday Cups	8432
15.21.6.5. Multiple Collection	8433
15.21.7. Chemical Analysis	8434
15.21.7.1. Volatile Abundance Measurements	8434
15.21.8. Stable Isotope Analysis	8435
15.21.8.1. Isotope Mass Fractionation	8435
15.21.8.2. Sulfur Isotope Analysis	8435
15.21.8.3. Oxygen Isotope Analysis	8436
15.21.8.4. Carbon and Nitrogen	8436
15.21.8.5. Lithium and Boron	8437
15.21.8.6. Hydrogen	8437
15.21.9. Radiogenic Isotopes	8437
15.21.9.1. U-Th-Pb Geochronology	8438
15.21.9.2. U-Th Disequilibrium	8439
15.21.9.3. 176Lu-176Hf in Zircon	8440
15.21.9.4. 40K-40Ca Measurements	8440
15.21.9.5. Short-Lived Radionuclides	8440
15.21.10. Isotopic Anomalies	8441
15.21.10.1. Refractory Inclusions	8441
15.21.10.2. Presolar Grains	8441
15.21.11. Future Developments and Issues	8442
References	8442
Chapter 15.22: Time-of-Flight Secondary Ion Mass Spectrometry, Secondary Neutral Mass Spectrometry, and Resonance Ionization Mass Spectrometry	8446
15.22.1. Introduction	8446
15.22.2. Time-of-Flight Secondary Ion Mass Spectrometry	8447
15.22.2.1. Technical Principles	8447
15.22.2.2. Sample Considerations	8448
15.22.2.3. Matrix Effects	8448
15.22.2.4. Data Analysis	8449
15.22.2.5. Quantification	8450
15.22.2.6. Some Neat Little Tricks	8450
15.22.2.7. Summary: Strengths and Weaknesses	8450
15.22.2.8. Applications: Inorganic Geochemistry	8451
15.22.2.8.1. TOF-SIMS in cosmochemistry	8451
15.22.2.8.2. TOF-SIMS in space	8451
15.22.3. Organic TOF-SIMS	8451
15.22.3.1. Applications: Organic Geochemistry	8452
15.22.3.1.1. TOF-SIMS in geomicrobiology	8452
15.22.3.1.2. TOF-SIMS in organic cosmochemistry	8452
15.22.4. New Developments of TOF-SIMS	8453
15.22.4.1. Combination with DC Primary Ion Beams	8453
15.22.5. Postionization	8454
15.22.5.1. Resonance Ionization Mass Spectrometers	8454
15.22.5.1.1. Noble gas resonance ionization mass spectrometers	8455
15.22.5.1.2. Sputter-initiated resonance ionization mass spectrometry - Resonant ionization of sputte	8456
15.22.5.2. Laser SNMS Applications	8456
15.22.5.2.1. Isotopic and elemental analysis	8456
15.22.5.3. Nonresonant Laser Postionization	8457
References	8457
Chapter 15.23: Laser Ablation ICP-MS and Laser Fluorination GS-MS	8460
15.23.1. Introduction	8460
15.23.2. Laser Processing	8460
15.23.2.1. Bandgap Energies of Solid Materials	8460
15.23.2.2. Laser Radiation and Photon-Substrate Coupling	8461
15.23.2.3. Stoichiometric Laser Sampling	8462
15.23.2.4. Commercial Laser Ablation Systems	8463
15.23.3. Laser Ablation ICP-MS Methodology	8464
15.23.3.1. Plasma Source Mass Spectrometry	8464
15.23.3.1.1. Quadrupole ICP-MS	8465
15.23.3.1.2. High-resolution ICP-MS	8466
15.23.3.1.3. Multicollector ICP-MS	8467
15.23.3.2. Quantitative LA-ICP-MS Analysis	8467
15.23.3.2.1. Spectral matrix effects	8467
15.23.3.2.2. Nonspectral matrix effects	8468
15.23.3.2.3. Laser-induced elemental fractionations	8469
15.23.3.2.4. Recent and future advances in LA-ICP-MS technology and applications	8470
15.23.4. Laser Fluorination Mass Spectr	8470
15.23.4.1. The Advent of Laser Fluorinati	8470
15.23.4.2. Fundamental LF-GS-MS	8471
15.23.4.3. Applications of Laser Fluorination M	8472
15.23.5. Conclusions	8472
References	8473
Chapter 15.24: Geoneutrino Detection	8478
15.24.1. Introduction	8478
15.24.2. Neutrino Physics	8478
15.24.2.1. Neutrinos in the Standard Model	8478
15.24.2.2. Neutrino Reactions	8480
15.24.3. Neutrino Detector Technologies	8482
15.24.3.1. Charge Collection	8482
15.24.3.2. Cherenkov Light	8482
15.24.3.3. Scintillation Light	8483
15.24.3.4. Liquid Scintillator Antineutrino Detector Design	8483
15.24.4. Existing and Planned Geoneutrino Detectors	8484
15.24.4.1. KamLAND	8484
15.24.4.2. Borexino	8485
15.24.4.3. SNO	8485
15.24.4.4. Future Geoneutrino Detectors	8485
15.24.5. Desired Future Developments	8486
15.24.5.1. Global Survey	8486
15.24.5.2. Directionality	8486
15.24.5.3. Detection of 40K Geoneutrinos	8487
15.24.6. Conclusions	8487
References	8487
e9780080983004v16	8490
Front Cover	8490
Indexes	8493
Copyright	8494
In Memoriam	8495
Heinrich Dieter Holland (1927–2012)	8497
Karl Karekin Turekian (1927–2013)	8499
References	8501
Volume Editors	8503
Contents	8511
Contents of All Volumes	8513
Contributors of All Volumes	8529
Index	8543

Treatise on Geochemistry

Additional Information

Book Details

Abstract

Table of Contents

Contact Us

Quick Navigation