vi
Contents
2.3.8 Calcium ........................................................................................................... 66
2.3.9 Potassium ........................................................................................................ 66
2.3.10 Sodium ............................................................................................................ 66
2.4 Composition and Stoichiometry of Average Seawater .......................................... 66
2.5 Methods of Determining Salinity ............................................................................ 69
2.6 Causes of the Major Components Not Being Conservative .................................. 69
2.6.1 Estuaries .......................................................................................................... 69
2.6.2 Evaporation in Isolated Basins ..................................................................... 78
2.6.3 Admixture with Brines ................................................................................. 81
2.6.4 Precipitation and Dissolution ....................................................................... 81
2.6.5 Submarine Volcanism ................................................................................... 81
2.6.6 Exchange between Atmosphere and Sea ................................................... 82
2.6.7 Anoxic Basins .................................................................................................84
2.6.8 Freezing ...........................................................................................................84
2.6.9 Interstitial Waters ...........................................................................................84
2.7 Isotopic Variations ......................................................................................................85
2.7.1 Hydrogen and Oxygen ..................................................................................85
2.7.2 Deuterium ....................................................................................................... 86
2.7.3 Oxygen-18 ........................................................................................................ 86
2.7.4 Isotopes of Sulfur ........................................................................................... 87
References and Further Reading ......................................................................................... 87
3. Minor Elements in Seawater .............................................................................................. 91
3.1 Classification of Elements .......................................................................................... 91
3.1.1 d 0 Cations ........................................................................................................ 91
3.1.2 d 10 Cations ....................................................................................................... 92
3.1.3 Transition Metals between d 0 and d 10 ......................................................... 97
3.2 Residence Times .......................................................................................................... 98
3.3 Distribution of Trace Elements in the Oceans ...................................................... 102
3.4 Biological Interactions .............................................................................................. 109
3.5 Geochemical Balance of Elements .......................................................................... 113
References and Further Reading ....................................................................................... 127
4. Ionic Interactions ................................................................................................................ 129
4.1 Introduction ............................................................................................................... 129
4.2 Water, the Unique Solvent ........................................................................................ 130
4.3 Review of the Structure of Water ............................................................................ 134
4.3.1 Uniformist (Average) Models ..................................................................... 135
4.3.2 Mixture Models ............................................................................................ 135
4.3.2.1 Ice- Like Models ............................................................................ 136
4.3.2.2 Cluster Theories............................................................................ 137
4.3.2.3 Clathrate Cage Models ................................................................ 138
4.3.2.4 Significant Structure Theory and Eucken’s Polymer Model ... 139
4.4 Ion–Water Interactions ............................................................................................. 141
4.4.1 Electrostriction ............................................................................................. 145
4.4.2 Proton Structure in Aqueous Solutions .................................................... 152
4.5 Ion–Ion Interactions .................................................................................................. 153
4.5.1 Ion- Pairing Model ........................................................................................ 161
4.5.2 Specific Interaction Model .......................................................................... 166
Contents
2.3.8 Calcium ........................................................................................................... 66
2.3.9 Potassium ........................................................................................................ 66
2.3.10 Sodium ............................................................................................................ 66
2.4 Composition and Stoichiometry of Average Seawater .......................................... 66
2.5 Methods of Determining Salinity ............................................................................ 69
2.6 Causes of the Major Components Not Being Conservative .................................. 69
2.6.1 Estuaries .......................................................................................................... 69
2.6.2 Evaporation in Isolated Basins ..................................................................... 78
2.6.3 Admixture with Brines ................................................................................. 81
2.6.4 Precipitation and Dissolution ....................................................................... 81
2.6.5 Submarine Volcanism ................................................................................... 81
2.6.6 Exchange between Atmosphere and Sea ................................................... 82
2.6.7 Anoxic Basins .................................................................................................84
2.6.8 Freezing ...........................................................................................................84
2.6.9 Interstitial Waters ...........................................................................................84
2.7 Isotopic Variations ......................................................................................................85
2.7.1 Hydrogen and Oxygen ..................................................................................85
2.7.2 Deuterium ....................................................................................................... 86
2.7.3 Oxygen-18 ........................................................................................................ 86
2.7.4 Isotopes of Sulfur ........................................................................................... 87
References and Further Reading ......................................................................................... 87
3. Minor Elements in Seawater .............................................................................................. 91
3.1 Classification of Elements .......................................................................................... 91
3.1.1 d 0 Cations ........................................................................................................ 91
3.1.2 d 10 Cations ....................................................................................................... 92
3.1.3 Transition Metals between d 0 and d 10 ......................................................... 97
3.2 Residence Times .......................................................................................................... 98
3.3 Distribution of Trace Elements in the Oceans ...................................................... 102
3.4 Biological Interactions .............................................................................................. 109
3.5 Geochemical Balance of Elements .......................................................................... 113
References and Further Reading ....................................................................................... 127
4. Ionic Interactions ................................................................................................................ 129
4.1 Introduction ............................................................................................................... 129
4.2 Water, the Unique Solvent ........................................................................................ 130
4.3 Review of the Structure of Water ............................................................................ 134
4.3.1 Uniformist (Average) Models ..................................................................... 135
4.3.2 Mixture Models ............................................................................................ 135
4.3.2.1 Ice- Like Models ............................................................................ 136
4.3.2.2 Cluster Theories............................................................................ 137
4.3.2.3 Clathrate Cage Models ................................................................ 138
4.3.2.4 Significant Structure Theory and Eucken’s Polymer Model ... 139
4.4 Ion–Water Interactions ............................................................................................. 141
4.4.1 Electrostriction ............................................................................................. 145
4.4.2 Proton Structure in Aqueous Solutions .................................................... 152
4.5 Ion–Ion Interactions .................................................................................................. 153
4.5.1 Ion- Pairing Model ........................................................................................ 161
4.5.2 Specific Interaction Model .......................................................................... 166