CO2 in Seawater: Equilibrium, Kinetics, Isotopes -  D. Wolf-Gladrow,  R.E. Zeebe

CO2 in Seawater: Equilibrium, Kinetics, Isotopes (eBook)

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2001 | 1. Auflage
360 Seiten
Elsevier Science (Verlag)
978-0-08-052922-6 (ISBN)
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192,56 inkl. MwSt
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Carbon dioxide is the most important greenhouse gas after water vapor in the atmosphere of the earth. More than 98% of the carbon of the atmosphere-ocean system is stored in the oceans as dissolved inorganic carbon. The key for understanding critical processes of the marine carbon cycle is a sound knowledge of the seawater carbonate chemistry, including equilibrium and nonequilibrium properties as well as stable isotope fractionation.


Presenting the first coherent text describing equilibrium and nonequilibrium properties and stable isotope fractionation among the elements of the carbonate system. This volume presents an overview and a synthesis of these subjects which should be useful for graduate students and researchers in various fields such as biogeochemistry, chemical oceanography, paleoceanography, marine biology, marine chemistry, marine geology, and others.


The volume includes an introduction to the equilibrium properties of the carbonate system in which basic concepts such as equilibrium constants, alkalinity, pH scales, and buffering are discussed. It also deals with the nonequilibrium properties of the seawater carbonate chemistry. Whereas principle of chemical kinetics are recapitulated, reaction rates and relaxation times of the carbonate system are considered in details. The book also provides a general introduction to stable isotope fractionation and describes the partitioning of carbon, oxygen, and boron isotopes between the species of the carbonate system. The appendix contains formulas for the equilibrium constants of the carbonate system, mathematical expressions to calculate carbonate system parameters, answers to exercises and more.






Carbon dioxide is the most important greenhouse gas after water vapor in the atmosphere of the earth. More than 98% of the carbon of the atmosphere-ocean system is stored in the oceans as dissolved inorganic carbon. The key for understanding critical processes of the marine carbon cycle is a sound knowledge of the seawater carbonate chemistry, including equilibrium and nonequilibrium properties as well as stable isotope fractionation.Presenting the first coherent text describing equilibrium and nonequilibrium properties and stable isotope fractionation among the elements of the carbonate system. This volume presents an overview and a synthesis of these subjects which should be useful for graduate students and researchers in various fields such as biogeochemistry, chemical oceanography, paleoceanography, marine biology, marine chemistry, marine geology, and others.The volume includes an introduction to the equilibrium properties of the carbonate system in which basic concepts such as equilibrium constants, alkalinity, pH scales, and buffering are discussed. It also deals with the nonequilibrium properties of the seawater carbonate chemistry. Whereas principle of chemical kinetics are recapitulated, reaction rates and relaxation times of the carbonate system are considered in details. The book also provides a general introduction to stable isotope fractionation and describes the partitioning of carbon, oxygen, and boron isotopes between the species of the carbonate system. The appendix contains formulas for the equilibrium constants of the carbonate system, mathematical expressions to calculate carbonate system parameters, answers to exercises and more.

Cover 1
Contents 10
Chapter 1. Equilibrium 16
1.1 The carbonate system 17
1.2 Alkalinity 42
1.3 pH scales 68
1.4 Partial pressure and fugacity 76
1.5 The Revelle factor 82
1.6 Worked out problems 89
Chapter 2. Kinetics 100
2.1 Basic concepts of kinetics 101
2.2 Temperature dependence of rate constants 106
2.3 Reactions and rate constants of the carbonate system 109
2.4 Approaching equilibrium: the carbonate system 126
2.5 Approaching isotopic equilibrium: 12C, 13C, and 14C 133
2.6 Diffusion and Reaction 138
2.7 Summary 154
Chapter 3. Stable Isotope Fractionation 156
3.1 Notation, abundances, standards 157
3.2 Carbon 182
3.3 Oxygen 200
3.4 Boron 230
3.5 Thermodynamic properties of isotopic substances 247
Appendix A: Equilibrium constants 266
A.1 CO2: Acidity constants K1* and K2* 268
A.2 Acidity constant of true carbonic acid 271
A.3 CO2 solubility in water (Henry's law) 271
A.4 Ion product of water: KW* 273
A.5 Bisulfate ion 274
A.6 Hydrogen fluoride 275
A.7 Boric acid 276
A.8 Phosphoric acid 278
A.9 Silicic acid 280
A.10 Solubility product of calcite and aragonite 281
A.11 Effect of pressure on equilibrium constants 282
A.12 Chemical composition of seawater 284
A.13 The equation of state of seawater 284
Appendix B: From two to six 286
Appendix C: Details and Calculations 294
C.1 Total alkalinity and charge balance 294
C.2 Saturation vapor pressure of water 296
C.3 The fugacity of a pure gas 297
C.4 Equilibrium at air-sea interface and chemical potential 299
C.5 Change CO2 concentration while keeping pH constant 300
C.6 The rate constant for the hydroxylation of CO2, k+4 302
C.7 A formula for the equilibration time of CO2 304
C.8 Kinetic rate laws of the carbonate system 305
C.9 Derivation of oxygen isotope partitioning 306
C.10 Mathematical derivation of the partition function ratio 312
Appendix D: Answers to Exercises 320
Appendix E: Notation and Symbols 324
References 328
Index 356

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