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9780444505798

CO2 in Seawater : Equilibrium, Kinetics, Isotopes

by ;
  • ISBN13:

    9780444505798

  • ISBN10:

    0444505792

  • Edition: 2nd
  • Format: Hardcover
  • Copyright: 2001-10-01
  • Publisher: Elsevier Science Serials
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Summary

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, p H 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.

Table of Contents

Equilibrium
1(84)
The carbonate system
2(25)
Effect of temperature, salinity, and pressure
9(2)
Ionic strength and activity coefficient
11(5)
Thermodynamic, hybrid, and stoichiometric equilibrium constants
16(2)
Effect of ionic strength on pK* values
18(1)
Effect of chemical composition on pK* values
19(1)
The choice of equilibrium constants
19(3)
CaCO3 solubility and the saturation state of seawater
22(5)
Alkalinity
27(26)
A shortcut to alkalinity
28(2)
Carbonate alkalinity
30(6)
Dickson's definition of alkalinity
36(5)
Total alkalinity and charge balance
41(4)
The charge balance in natural seawater
45(3)
Conservation of total alkalinity
48(2)
Total alkalinity in the ocean
50(3)
pH scales
53(8)
Conversion between pH scales
57(2)
Conversion of acidity constants
59(2)
Partial pressure and fugacity
61(6)
Mole fraction and partial pressure
61(3)
Fugacity
64(3)
The Revelle factor
67(7)
Titration of a weak acid by a strong base: pH-buffering
68(2)
CO2-buffering
70(4)
Worked out problems
74(11)
Formation of CaCO3 leads to higher CO2 levels
74(2)
The Revelle factor as a function of rain ratio
76(4)
Equilibration time for air-sea gas exchange
80(1)
Glacial to interglacial changes in CO2
81(2)
Future CO2 emissions and change in pH
83(2)
Kinetics
85(56)
Basic concepts of kinetics
86(5)
Temperature dependence of rate constants
91(3)
Reactions and rate constants of the carbonate system
94(17)
The hydration of carbon dioxide
95(3)
Temperature dependence of the rate constants k±1 and k±4
98(3)
Rate constants of the diffusion-controlled reactions
101(3)
Protolysis and hydrolysis
104(2)
Kinetics of the boric acid-borate equilibrium
106(2)
Summary
108(3)
Approaching equilibrium: the carbonate system
111(7)
Equilibration time for CO2
111(3)
The complete chemical system
114(4)
Approaching isotopic equilibrium: 12C, 13C, and 14C
118(5)
Diffusion and Reaction
123(16)
Diffusion-reaction equations
129(10)
Summary
139(2)
Stable Isotope Fractionation
141(110)
Notation, abundances, standards
142(25)
Notation
144(3)
Isotopic fractionation: Beans and peas
147(2)
Isotope effects and isotope fractionation in nature
149(8)
Natural abundances and standards
157(3)
Mass-balance calculations
160(1)
Rayleigh process
161(4)
Rayleigh process: Uptake of silicon
165(2)
Carbon
167(18)
Natural variations
168(2)
Equilibrium 13C fractionation in the carbonate system
170(5)
Temperature dependence of fractionation factors
175(2)
Fractionation between CaCO3 and HCO-3
177(3)
Carbon isotope partitioning as a function of pH
180(2)
Kinetic 13C fractionation in the carbonate system
182(3)
Oxygen
185(30)
Natural variations
186(2)
The Dole effect
188(3)
Paleotemperature scale
191(7)
Temperature dependence of 18O fractionation between H2O, CO2, and CaCO3
198(2)
Equilibrium 18O fractionation in the carbonate system
200(5)
Time required for oxygen isotope equilibration
205(3)
The effect of pH on foraminiferal oxygen isotopes
208(3)
The effect of pH on synthetic carbonates
211(4)
Boron
215(17)
Natural variations
215(3)
Boron isotope partitioning
218(6)
Boron in calcium carbonate
224(3)
Boron abundances in calcium carbonate
227(3)
Boron coordination
230(2)
Thermodynamic properties of isotopic substances
232(19)
Physical background
233(3)
Oxygen isotope equilibrium: CO2(g) and H2O(1) at 25C
236(7)
Carbon isotope equilibrium: CO23 and CO2(g)
243(8)
A Equilibrium constants 251(20)
A.1 CO2: Acidity constants K1 and K2
253(3)
A.2 Acidity constant of truce carbonic acid
256(1)
A.3 CO2 solubility in water (Henry's law)
256(2)
A.4 Ion product of water: KW
258(1)
A.5 Bisulfate ion
259(1)
A.6 Hydrogen fluoride
260(1)
A.7 Boric acid
261(2)
A.8 Phosphoric acid
263(2)
A.9 Silicic acid
265(1)
A.10 Solubility product of calcite and aragonite
266(1)
A.11 Effect of pressure on equilibrium constants
267(2)
A.12 Chemical composition of seawater
269(1)
A.13 The equation of state of seawater
269(2)
B From two to six 271(8)
C Details and Calculations 279(26)
C.1 Total alkalinity and charge balance
279(2)
C.2 Saturation vapor pressure of water
281(1)
C.3 The fugacity of a pure gas
282(2)
C.4 Equilibrium at air-sea interface and chemical potential
284(1)
C.5 Change CO2 concentration while keeping pH constant
285(2)
C.6 The rate constant for the hydroxylation of CO2, k+4
287(2)
C.7 A formula for the equilibration time of CO2
289(1)
C.8 Kinetic rate laws of the carbonate system
290(1)
C.9 Derivation of oxygen isotope partitioning
291(6)
C.10 Mathematical derivation of the partition function ratio
297(8)
D Answers to Exercises 305(4)
E Notation and Symbols 309(4)
References 313(28)
Index 341

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