The Oceans and Marine Geochemistry: Treatise on Geochemistry, Volume 6 (Treatise on Geochemistry)

The oceans are vitally important to an understanding of how the Earth works as an integrated system because its chemical composition records transfer of elements through the Earth’s geochemical reservoirs as well as defining how physical, biological and chemical processes combine to influence issues as diverse as climate change and the capacity of the oceans to remove toxic metals. Much modern marine geochemistry aims to link and integrate studies of the modern oceans with work using proxies to define how ocean chemistry and the ocean/atmospheric system has changed through time on a number of different timescales. Special focus in such work is the carbon cycle and its link to changes in greenhouse gases in the atmosphere. Volume 6 covers all the important topics needed for such an integrated approach, ranging from the contemporary ocean composition, transport processes in the ocean, paleoclimatology and paleo-oceanography from marine deposits, to the evolution of seawater composition. Treatise on Geochemistry......Page 2 Executive Editor's Foreword......Page 3 Nomenclature......Page 6 Composition of Seawater......Page 7 Causes of Major Components Not Being Conservative......Page 8 Pressure–Volume–Temperature Properties......Page 9 Application to other Natural Waters......Page 10 Carbonic Acid Equilibria in Seawater......Page 11 Solubility of Fe(III) in Seawater......Page 14 Kinetic Process in Seawater......Page 15 Oxidation of Fe(II) with O2......Page 16 Oxidation of Cu(I) with O2......Page 17 Modeling the Ionic Interactions in Seawater and other Natural Waters......Page 18 Physical-Chemical Properties......Page 19 Estimating Activity Coefficients......Page 20 Acknowledgments......Page 21 References......Page 22 Introduction......Page 27 Concentrations......Page 28 Distributions......Page 31 Rivers......Page 36 Atmosphere......Page 37 Active Biological Uptake in the Surface Waters......Page 39 Passive Scavenging......Page 41 Recycling within the Water Column......Page 43 Complexation with Organic Ligands......Page 44 Copper......Page 45 Iron......Page 46 Zinc......Page 47 References......Page 48 6.03 Gases in Seawater......Page 52 Introduction......Page 53 Air--Sea Gas Exchange Models......Page 54 Laboratory Studies of Air–Water Gas Exchange......Page 57 Field Studies of Air--Sea Gas Transfer......Page 61 Parametrizations of Air–Sea Gas Transfer......Page 64 Remote Sensing and Estimation of Transfer Velocity......Page 65 Introduction......Page 66 The Oceans as a Source of Gases to the Atmosphere......Page 67 The Oceans as a Source and a Sink of Volatile Compounds......Page 74 The Oceans as a Sink for Atmospheric Gases......Page 76 References......Page 78 6.04 The Biological Pump......Page 85 Description of the Biological Pump......Page 86 Photosynthesis and Nutrient Uptake......Page 88 Flocculation and Sinking......Page 90 Particle Decomposition and Repackaging......Page 92 Dissolved Organic Matter......Page 93 Macronutrients......Page 94 Trace Elements......Page 98 Measurement of New Production......Page 101 Measurement of Particle Flux......Page 102 Altering the Efficiency of the Biological Pump......Page 104 Response to Increased CO2......Page 107 Carbon Sequestration via Ocean Fertilization and the Biological Pump......Page 108 References......Page 109 Introduction: The Scope of Marine Bioinorganic Chemistry......Page 114 Concentrations......Page 115 Uptake......Page 117 Trace Element Storage......Page 122 The Biochemical Functions of Trace Elements in the Uptake and Transformations of Nutrients......Page 123 Trace Metals and the Marine Carbon Cycle......Page 124 Trace Metals and the Nitrogen Cycle......Page 127 Iron......Page 129 Manganese......Page 132 Zinc, Cobalt, and Cadmium......Page 133 Copper......Page 137 Nickel......Page 138 Paleoceanographic Aspects......Page 139 Acknowledgments......Page 140 References......Page 141 Introduction......Page 145 Reservoirs......Page 146 Fluxes......Page 148 Background......Page 149 Terrestrial Organic Matter in River Systems......Page 150 Quantitative Importance of Terrigenous Organic Carbon in Marine Sediments......Page 152 Background......Page 154 High Molecular Weight Dissolved Organic Matter: Biopolymers or Geopolymers?......Page 155 Gel Polymers and the Cycling of High Molecular Weight Dissolved Organic Matter......Page 160 Background......Page 162 Compositional Transformations Associated with Sedimentation and Burial of Organic Matter......Page 163 Controls on Organic Matter Preservation......Page 165 Background......Page 170 Planktonic Archea......Page 171 Anaerobic Methane Oxidation......Page 172 Summary and Future Research Directions......Page 173 Acknowledgments......Page 174 References......Page 175 6.07 Hydrothermal Processes......Page 181 What is Hydrothermal Circulation?......Page 182 Where Does Hydrothermal Circulation Occur?......Page 184 Why Should Hydrothermal Fluxes Be Considered Important?......Page 186 Why are Vent-fluid Compositions of Interest?......Page 187 Processes Affecting Vent-fluid Compositions......Page 188 Compositions of Hydrothermal Vent Fluids......Page 194 Geographic Variations in Vent-fluid Compositions......Page 198 Temporal Variability in Vent-fluid Compositions......Page 200 The Net Impact of Hydrothermal Activity......Page 202 Alteration and Mineralization of the Upper Ocean Crust......Page 203 Near-vent Hydrothermal Deposits......Page 204 Dynamics of Hydrothermal Plumes......Page 205 Modification of Gross Geochemical Fluxes......Page 207 Physical Controls on Dispersing Plumes......Page 211 Biogeochemical Interactions in Dispersing Hydrothermal Plumes......Page 212 Hydrothermal Sediments......Page 213 Deposition from Hydrothermal Plumes......Page 214 Hydrothermal Sediments in Paleoceanography......Page 215 References......Page 216 Introduction......Page 223 Theoretical Framework 1: The Advection--Diffusion Equation......Page 225 The Nature of Oceanic Mixing......Page 227 Isopycnal Mixing in the Ocean......Page 228 Theoretical Framework 2: Tracer Ages......Page 229 Radiometric Dating......Page 230 Transient Concentration Dating......Page 232 Theoretical Framework 3: Optimum Multiparameter Analysis and Tracer Age Spectra......Page 233 Radiocarbon......Page 235 Radium......Page 236 Transient Tracers......Page 237 Tracer Release Experiments......Page 241 Concluding Remarks......Page 242 References......Page 243 Nomenclature......Page 247 Tracers of Particle Transport......Page 248 Transfer from Solution to Particles (Scavenging)......Page 249 Important Features of Colloids......Page 252 Rate Constants for Colloid Coagulation......Page 253 Scavenging Rates and Particle Flux......Page 255 Export Flux of POC......Page 256 Non-steady-state Conditions and Advected Fluxes......Page 257 Limitations and Prospects......Page 258 Conceptual Models of Aggregation and Disaggregation......Page 259 Strategies to Evaluate Rate Constants......Page 260 Lead-210......Page 263 Thorium-230......Page 264 Helium-3......Page 267 Summary......Page 268 References......Page 269 Introduction......Page 274 The Organic Carbon Biological Pump......Page 275 CaCO3 Production and Export......Page 276 SiO2 Production and Export......Page 277 Geochemical Signature of the Biological Pump......Page 278 Direct Atmospheric pCO2 Signature of the Biological Pump......Page 280 Controls of Mean Ocean Chemistry......Page 281 References......Page 286 Introduction......Page 291 The Pillars of Organic Matter Diagenesis......Page 292 Organic Matter Diagenesis Down the Redox Progression......Page 295 Factors Controlling Organic Matter Degradation......Page 299 Diagenesis and Preservation of Calcium Carbonate......Page 302 Mechanisms Controlling CaCO3 Burial: Thermodynamics......Page 303 Mechanism of CaCO3 Dissolution: Kinetics......Page 305 Diagenesis and Preservation of Silica......Page 309 Controls on the H4SiO4 Concentration in Sediment Pore Waters: Kinetics......Page 310 The Importance of Aluminum and the Rebirth of ‘‘Reverse Weathering’’......Page 311 Appendix A......Page 313 References......Page 314 6.12 Geochronometry of Marine Deposits......Page 318 Radiocarbon......Page 319 Cosmogenic Nuclides......Page 320 Unbioturbated Deposits......Page 321 Bioturbated Deposits......Page 322 Radiocarbon......Page 323 230Th and 231Pa......Page 325 10Be......Page 327 Volcanic Layers......Page 328 Extension of Dating Techniques......Page 329 The Underlying Assumptions......Page 331 Corals......Page 332 Amino Acid Racemization......Page 334 References......Page 335 Introduction......Page 339 Methods of Sea-level Reconstruction from Oxygen Isotope Measurements......Page 340 230Th and 231Pa Dating: Current Status and Historical Overview......Page 342 230Th and 231Pa Dating: Theory......Page 344 Tests of Dating Assumptions......Page 345 Sources of Error in Age......Page 347 Current Status of Direct Sea-level Reconstruction: The Past 500 kyr......Page 348 Comparison of Direct Sea-level and Benthic Foram Records......Page 354 18’O/16’O-based Sea-level Records......Page 355 Causes of Sea-Level Change and Future Work......Page 356 References......Page 357 6.14 Elemental and Isotopic Proxies of Past Ocean Temperatures......Page 361 A Brief History of Early Research on Geochemical Proxies of Temperature......Page 362 Paleotemperature Equations......Page 364 Secondary Effects and Diagenesis......Page 365 Background......Page 366 Secondary Effects and Diagenesis......Page 367 Results on Historical Timescales......Page 368 Summary of Outstanding Research Issues......Page 369 Background and History......Page 370 Calibration and Paleotemperature Equations......Page 371 Effect of Dissolution......Page 372 Other Secondary Effects: Salinity, pH, Gametogenesis, and Changes in Seawater Mg/Ca......Page 373 Results on Quaternary Timescales......Page 374 Results for the Neogene......Page 375 Magnesium as Paleotemperature Proxies in Ostracoda......Page 376 Paleotemperature Equations......Page 377 Secondary Effects and Diagenesis......Page 378 Results on Historical Timescales......Page 379 Magnesium and Uranium in Corals as Paleotemperature Proxies......Page 380 References......Page 381 Introduction......Page 387 Systematics and Detection......Page 389 Occurrence of Alkenones in Marine Waters and Sediments......Page 392 Genetic and Evolutionary Aspects of Alkenone Production......Page 394 Function......Page 395 Ecological Controls on Alkenone Production and Downward Flux......Page 396 Effects of Water-column Recycling and Sediment Diagenesis on the Alkenone Unsaturation Index......Page 400 Culture Calibrations......Page 403 Particulates......Page 405 Core Tops......Page 406 Synthesis of Calibration......Page 408 Paleotemperature Studies Using the Alkenone Method......Page 409 Holocene High-resolution Studies......Page 410 Millennial-scale Events of the Late Pleistocene and Last Glacial Termination......Page 411 Marine Temperatures during the LGM......Page 413 SST Records of the Late Pleistocene Ice Age Cycles......Page 416 SST before the Late Pleistocene......Page 417 Comparison with other Proxies: delta18O......Page 418 Comparison with other Proxies: Microfossils......Page 419 Comparison with other Proxies: Mg/Ca......Page 420 Conclusions......Page 421 References......Page 422 Introduction......Page 429 Carbon Isotopes......Page 430 Pore-water Chemistry......Page 435 Oxygen Isotopes in Benthic Foraminifera......Page 436 Radiocarbon......Page 437 Geostrophic Shear Estimates from delta18O in Benthic Foraminifera......Page 438 Ocean Circulation during the Last Glacial Maximum......Page 439 Conclusions......Page 443 References......Page 444 Introduction......Page 448 Systematics of Long-lived Isotope Systems in the Earth......Page 449 Early Applications to the Oceans......Page 451 REEs in Seawater......Page 453 Neodymium-isotope Ratios in Seawater......Page 454 Where does Seawater Neodymium Come From?......Page 457 Neodymium Isotopes as Water-mass Tracers......Page 460 The ‘‘Nd Paradox’’......Page 462 Radiogenic Isotopes in Authigenic Ferromanganese Oxides......Page 468 Long-term Time Series in Fe--Mn Crusts......Page 470 Nd–Sr–Pb Isotopes in Terrigenous Sediments......Page 472 Isotopic and Geochronologic Measurements on Individual Mineral Grains......Page 473 Trough Mouth Fans as Archives of Major IRD Sources......Page 474 40’Ar/39’Ar Hornblende Evidence for History of the Laurentide Ice Sheet During the Last Glacial Cycle......Page 476 Final Thoughts......Page 479 References......Page 480 Introduction......Page 485 Concepts......Page 490 Low- and Mid-latitude Ocean......Page 493 High-latitude Ocean......Page 497 Export Production......Page 503 Nutrient Status......Page 505 Integrative Constraints on the Biological Pump......Page 506 Low- and Mid-latitude Ocean......Page 508 High-latitude Ocean......Page 511 Summary and Current Opinion......Page 514 References......Page 516 Introduction......Page 523 Depth of Transition Zone......Page 524 Distribution of CO2-3 Ion in Today’s Deep Ocean......Page 525 Dissolution Mechanisms......Page 527 Dissolution in the Past......Page 531 Sediment-Based Proxies......Page 532 Shell Weights......Page 533 The Boron Isotope Paleo pH Method......Page 534 Zn/Cd Ratios......Page 536 Dissolution and Preservation Events......Page 537 Neutralization of Fossil Fuel CO2......Page 539 References......Page 541 Introduction......Page 544 Cenozoic Deep-sea Stable Isotope Record......Page 545 Oxygen Isotopes and Climate......Page 547 Carbon Isotopes and Ocean Carbon Chemistry......Page 549 Globally Integrated Records of Inputs to the Ocean......Page 550 Decoupled riverine fluxes of strontium and osmium?......Page 552 Reconstructing Seawater Isotope Composition from Sediments......Page 553 Overview of the Cenozoic marine strontium isotope record......Page 554 Overview of the Cenozoic marine osmium isotope record......Page 555 Significance of uplift and weathering of the Himalayan–Tibetan Plateau (HTP)......Page 556 Glaciation and the marine strontium and osmium isotope records......Page 558 Variations in the Strontium and Osmium Isotope Composition of Riverine Input......Page 559 Osmium and Strontium Isotopes as Chemical Weathering Proxies......Page 560 Coupling Benthic Foraminiferal Mg/Ca and Oxygen Isotope Records......Page 561 Cenozoic Benthic Foraminiferal Mg/Ca Records......Page 562 The pH Dependence of Boron Isotope Fractionation......Page 565 Boron Partitioning into Calcite......Page 566 Paleo-pH and Atmospheric CO2 Reconstruction......Page 567 Closing Synthesis: Does Orogenesis lead to Cooling?......Page 569 References......Page 570 Introduction......Page 575 The Hadean (4.5-4.0 Ga)......Page 576 The Isua Supracrustal Belt, Greenland......Page 577 The Mesoarchean Period (3.7-3.0 Ga)......Page 581 The Neoarchean (3.0--2.5 Ga)......Page 583 The Paleoproterozoic (2.5-1.8Ga)......Page 587 The Mesoproterozoic (1.8-1.2 Ga)......Page 591 The Neoproterozoic (1.2-0.54 Ga)......Page 593 Evidence from Marine Evaporites......Page 597 The Mineralogy of Marine Oolites......Page 598 The Magnesium Content of Foraminifera......Page 599 The Spencer--Hardie Model......Page 601 The Role of the Stand of Sea Level......Page 603 Trace Elements in Marine Carbonates......Page 604 The Isotopic Composition of Osmium in Seawater......Page 606 The Isotopic Composition of Sulfur and Carbon in Seawater......Page 607 A Brief Summary......Page 608 References......Page 610 Appendix 1. Periodic Table of the Elements......Page 618 Appendix 2. Table of Isotopes......Page 619 Appendix 3. The Geologic Timescale......Page 623 Appendix 4. Useful Values......Page 624 Back Cover......Page 625 "The oceans are vitally important to an understanding of how the Earth works as an integrated system because its chemical composition records transfer of elements through the Earth's geochemical reservoirs as well as defining how physical, biological and chemical processes combine to influence issues as diverse at climate change and the capacity of the oceans to remove toxic metals. Much modern marine geochemistry aims to link and integrate studies of the modern oceans with work using proxies to define how ocean chemistry and the ocean/atmosphere system has changed through time on a number of different timescales. A special focus in such work is the carbon cycle and its link to changes in greenhouse gases in the atmosphere. Volume 6 covers all the important topics needed for such an integrated approach, ranging from the contemporary ocean composition, transport processes in the ocean, paleoclimatology and paleoceanography from marine deposits, to the evolution of seawater composition."--Publisher The oceans are vitally important to an understanding of how the Earth works as an integrated system because its chemical composition records transfer of elements through the Earth's geochemical reservoirs as well as defining how physical, biological and chemical processes combine to influence issues as diverse as climate change and the capacity of the oceans to remove toxic metals. Much modern marine geochemistry aims to link and integrate studies of the modern oceans with work using proxies to define how ocean chemistry and the ocean/atmospheric system has changed through time on a number of different timescales. Special focus in such work is the carbon cycle and its link to changes in greenhouse gases in the atmosphere. This Volume covers all the important topics needed for such an integrated approach, ranging from the contemporary ocean composition, transport processes in the ocean, paleoclimatology and paleo-oceanography from marine deposits, to the evolution of seawater composition.