Hydrogeochemistry Fundamentals and Advances, Mass Transfer and Mass Transport

Viatcheslav V. Tikhomirov, PhD, is a professor, engineer, and researcher in the science of groundwater and its practical applications. An associate professor in the Department of Hydrology at the St. Petersburg State University in Russia, he has taught hydrogeochemistry for many years and has over 150 publications to his credit.

• Abstract xiPreface xiiiSpontaneous Processes and Mineral Equilibrium xv1 Chemical Reactions 11.1 Real Water Solution 21.1.1 Properties of Water Solution 31.1.2 Composition of Water Solution 71.1.3 Structure of the Water Solution 131.1.4 Basis Components of a Solution 181.2 Spontaneous Processes 211.2.1 Energy of Spontaneous Processes 251.2.2 Direction of the Spontaneous Processes 271.2.3 Chemical Potential 281.2.4 Thermodynamical Concentration 321.2.4.1 Activities in Ideal Solutions 331.2.4.2 Activities in Real Solutions 371.3 Chemical Reactions 481.3.1 Restrictions of Spontaneous Reactions 491.3.2 Law of Mass Action 521.3.3 Equilibrium Constants of Reactions 551.3.4 Direction of Reactions 611.3.5 Reaction Rate 651.3.5.1 Elementary Reactions 661.3.5.2 Complex Reactions 721.3.6 Dependent and Independent Reactions 772 Hydrogeochemical Processes 812.1 Homogenous Processes 822.1.1 Electron Exchange 822.1.1.1 The Mechanism of Redox Processes 842.1.1.2 Oxidation Potential 882.1.1.3 Determination of Oxidation Potential 912.1.1.4 Oxygen Fugacity 972.1.2 Proton Exchange 982.1.2.1 Mechanism of Acid-based Reactions 992.1.2.2 Hydrogen Parameter 1002.1.2.3 Buffer Systems 1032.1.2.4 Determination of Solution’s pH 1052.1.3 Complexation 1072.1.3.1 Mechanism of Complexation 1082.1.3.2 Stability of Complex Formations 1152.1.3.3 Complexation Function 1192.1.4 Real Composition of Water 1252.1.4.1 Rates of Homogenous Processes 1262.1.4.2 Ionic Equilibrium in the Solution 1272.1.4.3 Models of Water Solution’s Composition 1302.2 Heterogeneous Processes 1342.2.1 Phase Rules 1362.2.2 Mass Transfer by Mineral Components 1402.2.2.1 Mineral-salt Complex of Rocks 1422.2.2.2 Adsorption and Desorption 1462.2.2.3 Ion Exchange 1612.2.2.4 Surface Complexation 1872.2.2.5 Adsorption and Desorption Rate 2012.2.2.6 Dissolution and Minerogenesis 2072.2.3 Mass Transfer of Nonpolar Components 3042.2.3.1 Mass Transfer with Underground Gas 3122.2.3.2 Mass Transfer with Nonpolar Substances 3252.2.3.3 Distribution of Nonpolar Components 3412.2.4 Equilibrium of Heterogeneous Processes 3432.3 Bio-geochemical Processes 3472.3.1 Biogeochemical Cycle 3482.3.2 Niches of the Detrital Trophic Chain 3542.3.3 Biodegradation of Organic Matter 3702.2.3.1 Reactions of Biodegradation 3722.3.3.2 Digestion 3772.3.4 Rates of Biochemical Processes 3832.3.5 Redox Geochemical Zoning 3922.4 Isotopic Processes 3992.4.1 Radioactive Decay 4002.4.1.1 Primordial Radionuclides 4002.4.1.2 Cosmogenic Radionuclides 4032.4.2 Balanced Fractionating 4072.4.3 Isotopic Mixing 4142.4.4 Ground Water Chronometry 4163 Migration of Elements 4213.1 Migration forms 4223.1.1 Subsurface Transporters 4233.1.2 Aquaphiles 4263.1.2.1 Estimates of Migration Capability 4273.1.2.2 Properties of Aquaphilic Migration Forms 4513.1.3 Organophiles 4803.1.3.1 Amphiphilic Organophiles 4813.1.3.2 Nonpolar Organophiles 4863.1.4 Gasophiles 4873.2 Mixing and Mass Transport 4943.2.1 Hydrodynamic Dispersion 4963.2.1.1 Diffusion Mixing 4963.2.1.2 Advective Mixing 5023.2.1.3 Dynamic Dispersivity and Methods of its Determination 5053.2.2 Advection-dispersion Mass Transport 5103.2.2.1 Equation of Advection-dispersion Mass Transport 5113.2.2.2 Analytical Solution of Mass Transport Equations 5134 Hydrogeochemical Forecasting 5414.1 Methods of Forecasting 5414.2 Model Forecasting Method 5454.2.1 Problem Identification 5474.2.2 Construction of Mathematical Models 5484.2.2.1 Types of Hydrogeochemical Models 5504.2.2.2 Selection of a Computation Process 5594.2.2.3 Input Data 5654.2.2.4 Selection of the Program Software 5694.2.3 Reliability of Model Forecasting Results 570Symbols 581References 593Normative Publications 608Appendices 609I Thermodynamic Properties of Mineral Forms of Migration 609II The Partition Coefficients of the Gas Components 609III Physical and Chemical Properties of Organic Compounds 609APPENDIX I Thermodynamic Properties of Mineral Forms of Migration 611A. Cation Generating Elements 611B. Complex Generating Elements 627C. Ligand Generating Elements 668D. Salt and Minerals 677APPENDIX II The Partition Coefficients of the Gas Components 685А. Underground Gases of Methane Composition 685B. Underground Gases of Nitrogen Composition 695C. Underground Gases of Carbon dioxide Composition 697APPENDIX III Physical and Chemical Properties of Organic Compounds. 698A. Physical and Chemical Properties of Organic Carbon Compounds 698B. Physical and Chemical Properties of Pesticides 709Index 715