Preface ...................................................... xiii
Chapter 1 Components of Soil and Rock—Solution Systems ......... 1
1.1 Solid: Soil and Rock ....................................... 1
1.1.1 Mineral and Chemical Composition of Rocks and
Soils ............................................... 2
1.1.1.1 Silicates .................................. 3
1.1.1.2 Oxides ..................................... 9
1.1.1.3 Other Minerals ............................ 10
1.1.2 Organic Matter in Soil ............................. 11
1.1.3 Particle and Pore Sizes, External and Internal
Surfaces ........................................... 13
1.2 Liquid: Soil and Groundwater Solutions .................... 15
1.2.1 Compositions of Natural Water ...................... 15
1.2.2 Parameters Affecting Chemical Speciation ........... 15
1.2.3 Dissolution and Precipitation of Solids ............ 22
1.2.4 Properties of Very Dilute Solutions ................ 27
1.3 Interface of Rock/Soil—Aqueous Solutions .................. 29
1.3.1 The Structure of the Interface ..................... 30
1.3.2 Characterization of the Interface of Geological
System/Groundwater ................................. 33
1.3.2.1 Characterization of External Surfaces ..... 33
1.3.2.2 Characterization of Internal Surfaces ..... 39
1.3.3 Interfacial Processes Related to External and
Internal Surfaces .................................. 40
1.3.3.1 Adsorption ................................ 40
1.3.3.2 Ion Exchange .............................. 41
1.3.3.3 Precipitation ............................. 44
1.3.3.4 Evaluation and Separation of Interfacial
Processes ................................. 45
1.3.4 Quantitative Treatment of Interfacial Processes .... 45
1.3.4.1 Adsorption Isotherms ...................... 45
1.3.4.2 Treatment of Ion-Exchange Processes ....... 51
1.3.4.3 Treatment of Simultaneous Ion-Exchange
and Adsorption Processes .................. 63
1.3.4.4 Treatment of Heterogeneous Isotope
Exchange .................................. 64
1.3.5 Catalytic Effects of Clays ......................... 64
1.3.6 Kinetics of Interfacial Processes in Rocks and
Soils .............................................. 66
1.3.6.1 Steps in Interfacial Reactions ............ 67
1.3.6.2 Migration of Water-Soluble Substances in
Rocks and Soils ........................... 70
References ..................................................... 75
Chapter 2 Interfacial Processes in Geological Systems
Studies on Montmorillonite Model Substance .......... 83
2.1 Use of Montmorillonite as a Model Substance: The
Important Interfacial Processes on Montmorillonite ........ 84
2.1.1 Crystal Structure and Layer Charge of
Montmorillonite .................................... 84
2.1.2 Clay-Water Interactions ............................ 86
2.1.3 Edge Charges of Montmorillonite .................... 88
2.1.4 Montmorillonite as a Model Substance ............... 89
2.2 Cation Exchange: Outer-Sphere Complexation ................ 90
2.3 Synthesis and Characterization of Cation-Exchanged
Montmorillonites .......................................... 94
2.4 Surface Acid-Base Properties of Montmorillonite ........... 98
2.4.1 Formation of Edge Sites on Montmorillonite ......... 98
2.4.2 Effect of Permanent Charge on the Study of Edge
Charges ............................................ 99
2.4.3 Acid-Base Properties of Cation-Exchanged
Montmorillonites .................................. 100
2.5 Ion Adsorption on the External Surfaces .................. 104
2.5.1 Some Examples of Ion Sorption Processes on
Montmorillonite ................................... 105
2.5.1.1 Sorption of Zinc Ion on
Montmorillonite .......................... 105
2.5.1.2 Sorption of Manganese Ion on
Montmorillonite .......................... 106
2.5.1.3 Sorption of Palladium Ion on
Montmorillonite .......................... 106
2.5.1.4 Sorption of Lead Ions on
Montmorillonite .......................... 108
2.6 Separation of Interfacial Processes of Montmorillonite ... 109
2.7 Role of Hydrogen Ions in the Interfacial and
Dissolution Processes of Montmorillonite ................. 112
2.7.1 Effect of Hydrogen Ion on Cation-Exchange
Processes ......................................... 112
2.7.2 Acidic Destruction of Montmorillonite ............. 117
2.8 Effect of Complexation Agents ............................ 118
2.8.1 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite System ......................... 122
2.8.2 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite/Manganese(II) Ion System ....... 126
2.8.3 Effect of Stability Constants on the Cation
Composition of the Interlayer Space ............... 129
2.8.4 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite/Lead(II) Ion System ............ 130
2.9 Sorption of Organic Matter on Minerals ................... 133
2.9.1 Sorption of EDTA on Montmorillonite ............... 133
2.9.2 Sorption of Valine on Montmorillonite ............. 134
2.10 Transformations Initiated by Interfacial Processes
of Montmorillonite ....................................... 139
2.10.1 Oxidation of Mn(II) Ion and Formation of a
Nanolayer in the Interlayer Space of
Montmorillonite ................................... 140
2.10.2 Formation of an Iron(III) Oxyhydroxide Nanolayer
in the Interlayer Space of Montmorillonite ........ 143
2.10.3 Reduction of Ions ................................. 147
2.10.3.1 Reduction of Silver and Palladium Ion .... 147
2.10.3.2 Reduction of Fe(III) Ions ................ 149
2.10.4 Heterogeneous Nucleation on Edge Sites:
Formation of Lead Oxide Fine Particles on the
Edges of Montmorillonite .......................... 150
References .................................................... 160
Chapter 3 Interfacial Reactions at Rock and Soil
Interfaces ......................................... 169
3.1 Relationship between Interfacial Properties and
Geological Origin of Bentonite Clay ...................... 169
3.1.1 Geological and Mineral Characteristics of
Sajóbábony Bentonites ............................. 170
3.1.2 Interfacial Properties of Bentonite Samples from
Sajóbábony (HU) ................................... 173
3.1.3 Relations of Geological Origin and Interfacial
Properties ........................................ 177
3.1.4 Applications of Bentonites of Different
Interfacial Properties ............................ 178
3.2 Migration of Water-Soluble Substances in Rocks ........... 179
3.2.1 Sorption and Migration of Carrier-Free
Radioactive Isotopes in Rocks ..................... 179
3.2.1.1 A Model Predicting Migration Rate on
the Basis of Mineral Composition ......... 179
3.2.1.2 The Application of the Linear Model for
the Sorption of Cs-137 and Sr-85 Ions .... 182
3.2.2 Effect of Sorption on the Migration of Ions in
Bentonite ......................................... 189
3.2.3 Effect of Precipitation in Migration .............. 193
3.3 Interfacial Acid-Base Properties of Soils ................ 194
3.4 Sorption of Cyanide Anion on Soil and Sediment ........... 198
References .................................................... 205
Chapter 4 Experimental Methods in Studying Interfacial
Processes of Rocks and Soils ....................... 207
4.1 Analysis of the Solid Phase .............................. 207
4.1.1 Methods of Chemical Analyses ...................... 207
4.1.2 Study of Mineral Composition ...................... 209
4.1.3 Study of Morphology ............................... 210
4.1.4 Study of Soil Organic Matter ...................... 211
4.2 Analysis of the Liquid Phase ............................. 212
4.3 Study of Interfaces ...................................... 213
References .................................................... 218
Index ......................................................... 221
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