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Summary
Table of Contents
About the book series | p. vii |
Editorial board of the book series | p. ix |
Contributors | p. xvii |
Foreword | p. xix |
EditorsÆ preface | p. xxi |
About the editors | p. xxv |
Acknowledgements | p. xxvii |
Introduction to groundwater geochemistry and fundamentals of hydrogeochemical modeling | |
Hydrogeochemistry principles for geochemical modeling | p. 3 |
Sampling and analysis of water, solids and gases | p. 3 |
Measurement of field parameters | p. 5 |
Filtration and preservation of water samples | p. 7 |
Sampling of solid materials | p. 8 |
Sampling of gases | p. 9 |
Introduction to thermodynamics | p. 10 |
Chemical composition of precipitation | p. 15 |
Hydrochemical processes | p. 16 |
Introduction | p. 16 |
Oxidation-reduction reactions | p. 16 |
Organic matter decomposition, photosynthesis and aerobic respiration | p. 17 |
Nitrification and denitrification | p. 17 |
Sorption | p. 18 |
Kinetics | p. 22 |
Thermodynamics of gas and mineral solubility in the unsaturated-zone water | p. 27 |
Introduction | p. 27 |
Background | p. 27 |
Capillary water | p. 27 |
"Capillarizing" the water by the dryness of the soil atmosphere | p. 30 |
Capillarity and size of pores | p. 31 |
Capillary water: stable or metastable? | p. 32 |
Capillary thermodynamics | p. 33 |
Capillary solutions and the gas-solutions equilibria | p. 33 |
Solids in capillary situations | p. 34 |
Thermodynamic modeling of reactions in capillary systems | p. 34 |
Simplified modeling of salt solubility in capillary systems | p. 35 |
Illustrations in natural settings | p. 36 |
Capillarity and mineralogy of desert roses | p. 36 |
Capillarity and the dissolution of gases | p. 38 |
Hydrogeochemical modeling in the unsaturated zone | p. 39 |
Conclusions | p. 40 |
Governing equations and solution algorithms for geochemical modeling | p. 45 |
The formulation of reactions | p. 45 |
Species, reactions and stoichiometric coefficients | p. 45 |
Equilibrium reactions in terms of the stoichiometric matrix | p. 47 |
Primary and secondary species | p. 49 |
Components and component matrix | p. 52 |
Method 1 (aqueous components) | p. 53 |
Method 2 (eliminate constant activity species) | p. 57 |
Other methods | p. 57 |
Homogeneous reactions | p. 58 |
Speciation calculations | p. 59 |
Algorithm 1 | p. 60 |
Algorithm 2 | p. 61 |
Heterogeneous reactions | p. 63 |
Surface complexation reactions | p. 63 |
Cation exchange reactions | p. 68 |
Reactions with a solid phase | p. 71 |
Reactions with a gas phase | p. 71 |
Reaction paths | p. 73 |
Formulation of kinetic reactions | p. 76 |
Fluid flow, solute and heat transport equations | p. 83 |
Introduction | p. 83 |
Groundwater flow equations | p. 83 |
Single phase flow | p. 84 |
The conservation mass for the fluid | p. 84 |
The momentum mass balance equations for the fluid | p. 84 |
Flow equations | p. 87 |
Multiphase flow | p. 90 |
Multiphase system | p. 90 |
Transport of conservative solutes | p. 92 |
Advection, diffusion and dispersion | p. 92 |
Advection | p. 92 |
Diffusion | p. 93 |
Dispersion | p. 94 |
Transport equations of conservative solutes | p. 96 |
Heat transport equations | p. 97 |
Conduction and convection | p. 97 |
Heat conduction | p. 97 |
Heatconvection | p. 98 |
Heat transport in single fluid phase systems | p. 98 |
Heat transport in multiple fluid phases systems | p. 99 |
Reactive transport | p. 99 |
The need for reactive transport: calcite dissolution in the fresh-salt water mixing zone | p. 99 |
Mass balance equations | p. 102 |
Constant activity species | p. 106 |
Analytical solution for a binary system: equilibrium reaction rates | p. 108 |
Problem statement | p. 108 |
Methodology of solution | p. 109 |
An analytical solution: pulse injection in a binary system | p. 112 |
The effect of heterogeneity and non-local formulations | p. 115 |
The limitations of traditional formulations and the need for upscaling | p. 116 |
Solution of reactive transport in MRMT formulations | p. 119 |
Numerical solutions of reactive transport equations | p. 127 |
Introduction | p. 127 |
Methods for discretizing space and time | p. 127 |
Finite differences | p. 127 |
Fundamentals | p. 127 |
Application to conservative transport | p. 129 |
Finite elements | p. 131 |
Instability and numerical dispersion | p. 134 |
Methods for solving reactive transport equations | p. 135 |
Sequential Iteration Approach (SLA) | p. 136 |
Direct Substitution Approach (DSA) | p. 138 |
Comparison between SIA and DSA | p. 140 |
Elaboration of a geochemical model | p. 143 |
Introduction | p. 143 |
Model types and the most popular existing software packages | p. 143 |
Speciation-solubility models | p. 143 |
Reaction-path models | p. 145 |
Inverse (mass-balance) models | p. 145 |
Reactive transport models | p. 145 |
Data required for geochemical modeling | p. 145 |
Data for speciation-solubility models | p. 145 |
Data for reaction-path models | p. 147 |
Data for inverse (mass-balance) models | p. 147 |
Data for reactive transport models | p. 147 |
Schematization and choice of thermodynamic database | p. 147 |
Modeling and interpretation of its results | p. 149 |
Possible errors and misconceptions in model elaboration | p. 150 |
Advances in geochemical modeling for geothermal applications | p. 153 |
Introduction | p. 153 |
Development of geothermal reservoir tools | p. 153 |
Types of geochemical models for geothermal systems | p. 155 |
Requirements for geochemical simulations of geothermal reservoirs | p. 156 |
Popular computer software for geothermal system modeling | p. 156 |
Flow and geochemical model calibration | p. 159 |
Selection of recent applications (2000-2010)ùCase studies | p. 160 |
General applications | p. 160 |
Conceptual reservoir models | p. 160 |
Lumped parameter models | p. 164 |
Advanced numerical modeling | p. 165 |
Reservoir design and magnitudeùReconstruction of reservoir parameters | p. 165 |
Origin of acidity for reservoir fluids | p. 165 |
Mineral-fluid equilibria | p. 165 |
Fluid reinjectionùScaling effects | p. 165 |
Hot-Dry Rock (HDR) systems (Soultz-sous-Forêts, France) | p. 168 |
CO2 injection into geothermal reservoirs | p. 169 |
ConclusionsùFuture challenges | p. 170 |
Cases studies | |
Integrating field observations and inverse and forward modeling: application at a site with acidic, heavy-metal-contaminated groundwater | p. 181 |
Introduction | p. 181 |
Geochemical modeling: computer codes, theory and assumptions | p. 182 |
Inverse geochemical modeling | p. 182 |
Principles, codes and theory | p. 182 |
Assumptions used in inverse modeling | p. 183 |
Forward geochemical modeling | p. 186 |
Principles and codes | p. 186 |
The Pinal Creek basin site: brief description | p. 188 |
Geology | p. 189 |
Hydrology and groundwater flow | p. 190 |
Inverse geochemical modeling at the Pinal Creek site | p. 190 |
Examination of end-member waters and their conservative constituents | p. 191 |
The thermodynamic state of the end-member waters | p. 192 |
NETPATH inverse modeling: simulation results | p. 194 |
Inverse geochemical modeling with PHREEQC | p. 200 |
Reactive-transport modeling at the Pinal Creek site | p. 203 |
Summary of previous reactive-transport modeling | p. 205 |
A reactive-transport sensitivity analysis on the movement of pH and pe-controlling mineral fronts | p. 206 |
A simple model for advective transport of a reactive front: the MnO2 dissolution front | p. 206 |
Determination of the initial MnO2,5 and carbonate mineral concentrations | p. 207 |
Setup of the 1-D reactive-transport simulations | p. 209 |
Simulation results: movement of the Fe(II)-rich waters and of the MnO2 dissolution front | p. 211 |
Simulation results: evolution of the low-pH waters | p. 212 |
The effect of the initial carbonate to initial MnO2 ratio on the evolution of the low-pH waters | p. 213 |
Influence of the aluminum mineral allowed to precipitate on the evolution of the low-pH waters | p. 215 |
Effects of the irreversible dissolution of Ca and Mg silicates on the evolution of low-pH Fe(II)-rich waters | p. 217 |
The effect of not allowing rhodochrosite precipitation | p. 218 |
The CO2 open system simulations | p. 218 |
The effect of longitudinal dispersion | p. 219 |
The influence of cation exchange and surface-complexation sorption processes | p. 220 |
Other minor effects on the evolution of the low-pH waters | p. 221 |
Comparison of the reactive transport simulation result with observations at the Pinal Creek site | p. 221 |
Conclusions | p. 224 |
The Senior Author's fifteen year perspective on the Glynn and Brown (1996) paper | p. 226 |
Models and measurements of porosity and permeability evolution in a sandstone formation | p. 235 |
Introduction | p. 235 |
Porosity measurements in mineralized rock | p. 236 |
Theory and numerical modeling of porosity evolution | p. 238 |
Conceptual model of the porous medium | p. 238 |
Reaction kinetics | p. 240 |
Reactive transport equations | p. 243 |
Numerical solution and model optimization | p. 244 |
Comparison between numerical models and measurements | p. 245 |
Implications for bulk reaction rates | p. 247 |
Implications for permeability evolution in aquifers | p. 248 |
Concluding remarks | p. 249 |
Geochemical modeling of water chemistry evolution in the Guarani Aquifer System in São Paulo, Brazil | p. 253 |
Modeling of reactive transport at a site contaminated by petroleum hydrocarbons at Hnevice, Czech Republic | p. 259 |
Site characterization and conceptual model | p. 259 |
Speciation and inverse geochemical modeling | p. 261 |
Modeling of reactive transport | p. 263 |
Numerical modeling for preliminary assessment of natural remediation of phosphorus in variably saturated soil in a peri-urban settlement in Kampala, Uganda | p. 267 |
Introduction | p. 267 |
Setting | p. 267 |
Numerical model | p. 269 |
Flow model | p. 269 |
Solute model | p. 274 |
Soil phosphorus sorption | p. 274 |
Solute transport model | p. 275 |
Simulations | p. 276 |
Results and discussion | p. 277 |
Field measurements | p. 277 |
Pollution and remediation simulation scenarios | p. 278 |
Sensitivity analyses | p. 279 |
Impact of change of sorption coefficients (KL and Kplin) on pollution time | p. 279 |
Impact of change of the pore size distribution values on pollution time | p. 279 |
Impact of change of the air entry values on pollution time | p. 281 |
Conclusions | p. 281 |
Subject index | p. 287 |
Book series page | p. 305 |
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