Theoretical Background | p. 1 |
Equilibrium reactions | p. 1 |
Introduction | p. 1 |
Thermodynamic fundamentals | p. 5 |
Mass-action law | p. 5 |
Gibbs free energy | p. 7 |
Gibbs phase rule | p. 8 |
Activity | p. 8 |
Ionic strength | p. 10 |
Calculation of activity coefficient | p. 10 |
Theory of ion-association | p. 10 |
Theory of ion-interaction | p. 13 |
Comparison ion-association versus ion-interaction theory | p. 14 |
Interactions at the liquid-gaseous phase boundary | p. 17 |
Henry Law | p. 17 |
Interactions at the liquid-solid phase boundary | p. 19 |
Dissolution and precipitation | p. 19 |
Solubility-product | p. 19 |
Saturation index | p. 22 |
Limiting mineral phases | p. 22 |
Sorption | p. 25 |
Hydrophobic/hydrophilic substances | p. 25 |
Ion exchange | p. 25 |
Mathematical description of the sorption | p. 30 |
Interactions in the liquid phase | p. 35 |
Complexation | p. 35 |
Redox processes | p. 37 |
Measurement of the redox potential | p. 37 |
Calculation of the redox potential | p. 38 |
Presentation in predominance diagrams | p. 43 |
Redox buffer | p. 47 |
Significance of redox reactions | p. 47 |
Kinetics | p. 50 |
Kinetics of various chemical processes | p. 50 |
Half-life | p. 50 |
Kinetics of mineral dissolution | p. 51 |
Calculation of the reaction rate | p. 52 |
Subsequent reactions | p. 53 |
Parallel reactions | p. 54 |
Controlling factors on the reaction rate | p. 54 |
Empirical approaches for kinetically controlled reactions | p. 55 |
Reactive mass transport | p. 58 |
Introduction | p. 58 |
Flow models | p. 58 |
Transport models | p. 59 |
Definition | p. 59 |
Idealized transport conditions | p. 61 |
Real transport conditions | p. 61 |
Exchange within double-porosity aquifers | p. 62 |
Numerical methods of transport modeling | p. 63 |
Finite-difference/finite-element method | p. 65 |
Coupled methods | p. 66 |
Hydrogeochemical Modeling Programs | p. 69 |
General | p. 69 |
Geochemical algorithms | p. 69 |
Programs based on minimizing free energy | p. 71 |
Programs based on equilibrium constants | p. 72 |
Phreeqc | p. 72 |
EQ 3/6 | p. 74 |
Thermodynamic databases | p. 76 |
General | p. 76 |
Structure of thermodynamic databases | p. 78 |
Problems and sources of error in geochemical modeling | p. 81 |
Use of Phreeqc | p. 85 |
The structure of Phreeqc and its graphical user interfaces | p. 85 |
Input | p. 88 |
Database | p. 95 |
Output | p. 96 |
Grid | p. 97 |
Chart | p. 97 |
Introductory Examples for Phreeqc Modeling | p. 97 |
Equilibrium reactions | p. 97 |
Example 1a standard output - seawater analysis | p. 98 |
Example 1b equilibrium - solution of gypsum | p. 100 |
Example 1c equilibrium - solution of calcite with CO2 | p. 101 |
Example 1d: Modeling uncertainties - Ljungskile | p. 103 |
Introductory example for sorption | p. 107 |
Introductory examples for kinetics | p. 114 |
Defining reaction rates | p. 115 |
Basic within Phreeqc | p. 117 |
Introductory example for isotope fractionation | p. 122 |
Introductory example for reactive mass transport | p. 126 |
Simple 1D transport: Column experiment | p. 126 |
1D transport, dilution, and surface complexation in an abandoned uranium mine | p. 130 |
3D transport with Phast | p. 134 |
Exercises | p. 141 |
Equilibrium reactions | p. 143 |
Groundwater - Lithosphere | p. 143 |
Standard output well analysis | p. 143 |
Equilibrium reaction - solubility of gypsum | p. 144 |
Disequilibrium reaction - solubility of gypsum | p. 144 |
Temperature dependency of gypsum solubility in well water | p. 144 |
Temperature dependency of gypsum solubility in pure water | p. 144 |
Temperature-and P(CO2)-dependent calcite solubility | p. 144 |
Calcite precipitation and dolomite dissolution | p. 145 |
Calcite solubility in an open and a closed system | p. 145 |
Pyrite weathering | p. 145 |
Atmosphere - Groundwater - Lithosphere | p. 146 |
Precipitation under the influence of soil CO2 | p. 146 |
Buffering systems in the soil | p. 147 |
Mineral precipitates at hot sulfur springs | p. 147 |
Formation of stalactites in karst caves | p. 148 |
Evaporation | p. 149 |
Groundwater | p. 150 |
The pE-pH diagram for the system iron | p. 150 |
The Fe pE-p-H diagram considering carbon and sulfur | p. 152 |
The pH dependency of uranium species | p. 152 |
Origin of groundwater | p. 153 |
Pumping of fossil groundwater in arid regions | p. 155 |
Salt water/fresh water interface | p. 156 |
Anthropogenic use of groundwater | p. 157 |
Sampling: Ca titration with Edta | p. 157 |
Carbonic acid aggressiveness | p. 157 |
Water treatment by aeration - well water | p. 158 |
Water treatment by areation - sulfur spring | p. 158 |
Mixing of waters | p. 159 |
Rehabilitation of groundwater | p. 159 |
Reduction of nitrate with methanol | p. 159 |
Fe(0) barriers | p. 160 |
Increase in pH through a calcite barrier | p. 160 |
Reaction kientics | p. 160 |
Pyrite weathering | p. 160 |
Quartz-feldspar-dissolution | p. 161 |
Degradation of organic matter within the aquifer on reduction of redox-sensitive elements (Fe, As, U, Cu, Mn, S) | p. 162 |
Degradation of tritium in the unsaturated zone | p. 163 |
Reactive transport | p. 166 |
Lysimeter | p. 166 |
Karst spring discharge | p. 167 |
Karstification (corrosion along a karst fracture) | p. 168 |
The pH increase of an acid mine water | p. 169 |
In-situ leaching | p. 170 |
3D Transport - Uranium and arsenic contamination plume | p. 171 |
Solutions | p. 173 |
Equilibrium reactions | p. 173 |
Groundwater - Lithosphere | p. 173 |
Standard output well analysis | p. 173 |
Equilibrium reaction - solubility of gypsum | p. 175 |
Disequilibrium reaction - solubility of gypsum | p. 175 |
Temperature dependency of gypsum solubility in well water | p. 176 |
Temperature dependency of gypsum solubility in pure water | p. 177 |
Temperature- and P(CO2)-dependent calcite solubility | p. 177 |
Calcite precipitation and dolomite dissolution | p. 178 |
Comparison of the calcite solubility in an open and a closed system | p. 179 |
Pyrite weathering | p. 179 |
Atmosphere - Groundwater - Lithosphere | p. 181 |
Precipitation under the influence of soil CO2 | p. 181 |
Buffering systems in the soil | p. 181 |
Mineral precipitations at hot sulfur springs | p. 182 |
Formation of stalactites in karst caves | p. 183 |
Evaporation | p. 183 |
Groundwater | p. 184 |
The pE-pH diagram for the system iron | p. 184 |
The Fe pE-pH diagram considering carbon and sulfur | p. 186 |
The pH dependency of uranium species | p. 187 |
Origin of groundwater | p. 188 |
Pumping of fossil groundwater in arid regions | p. 188 |
Salt water/fresh water interface | p. 189 |
Anthropogenic use of groundwater | p. 190 |
Sampling: Ca titration with Edta | p. 190 |
Carbonic acid aggressiveness | p. 191 |
Water treatment by aeration - well water | p. 191 |
Water treatment by aeration - sulfur spring | p. 191 |
Mixing of waters | p. 193 |
Rehabilitation of groundwater | p. 194 |
Reduction of nitrate with methanol | p. 194 |
Fe(0) barriers | p. 195 |
Increase in pH through a calcite barrier | p. 196 |
Reaction kinetics | p. 197 |
Pyrite weathering | p. 197 |
Quartz-feldspar-dissolution | p. 199 |
Degradation of organic matter within the aquifer on reduction of redox-sensitive elements (Fe, As, U, Cu, Mn, S) | p. 201 |
Degradation of tritium in the unsaturated zone | p. 203 |
Reactive transport | p. 205 |
Lysimeter | p. 205 |
Karst spring discharge | p. 205 |
Karstification (corrosion along a karst fracture) | p. 207 |
The pH increase of an acid mine water | p. 208 |
In-situ leaching | p. 210 |
3D Transport - Uranium and arsenic contamination plume | p. 212 |
References | p. 215 |
Index | p. 221 |
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