Geochemical Modeling of Groundwater, Vadose and Geothermal Systems

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Format: Hardcover
Pub. Date: 2011-12-27
Publisher(s): CRC Press
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Summary

Geochemical modeling is an important tool for prognosis in both environmental studies and many tasks of subsurface and surface hydrology, mining geology, geothermics, hydrocarbon geology and the related engineering areas dealing with exploration and exploitation of natural resources. The modeling considers chemical and physical processes involving natural or anthropogenically produced chemical species within fluid liquid and gas phases, and interactions between these phases and solids (chemical reactions, sorption, ion exchange, decay, isotope fractionation etc.), which all may depend on temperature, pressure, ionic strength, etc. This book compiles and synthesizes the state-of-the-art of the principal fields of (hydro)geochemical modeling of low- and high-temperature subsurface systems such as groundwater, petroleum and geothermal systems and presents new and stimulating ideas of possible applications. It starts with an introduction to the basic principles of aqueous geochemistry and thermodynamics, it describes the construction of a conceptual hydrogeochemical model and defines the processes and model parameters relevant for individual field scenarios and modeling tasks. Then it discusses how a conceptual model is implemented into a mathematical/numerical model, and what field data and databases should be used. Limitations and problems of existing thermodynamic databases are discussed. The principle types of geochemical models (speciation, reaction-path or forward, inverse- and reactive-transport models) are described together with examples of the most common codes. Special emphasis is placed on case studies in different scientific areas and environmental settings, which focus on the practical aspects of modelling.

Table of Contents

About the book seriesp. vii
Editorial board of the book seriesp. ix
Contributorsp. xvii
Forewordp. xix
EditorsÆ prefacep. xxi
About the editorsp. xxv
Acknowledgementsp. xxvii
Introduction to groundwater geochemistry and fundamentals of hydrogeochemical modeling
Hydrogeochemistry principles for geochemical modelingp. 3
Sampling and analysis of water, solids and gasesp. 3
Measurement of field parametersp. 5
Filtration and preservation of water samplesp. 7
Sampling of solid materialsp. 8
Sampling of gasesp. 9
Introduction to thermodynamicsp. 10
Chemical composition of precipitationp. 15
Hydrochemical processesp. 16
Introductionp. 16
Oxidation-reduction reactionsp. 16
Organic matter decomposition, photosynthesis and aerobic respirationp. 17
Nitrification and denitrificationp. 17
Sorptionp. 18
Kineticsp. 22
Thermodynamics of gas and mineral solubility in the unsaturated-zone waterp. 27
Introductionp. 27
Backgroundp. 27
Capillary waterp. 27
"Capillarizing" the water by the dryness of the soil atmospherep. 30
Capillarity and size of poresp. 31
Capillary water: stable or metastable?p. 32
Capillary thermodynamicsp. 33
Capillary solutions and the gas-solutions equilibriap. 33
Solids in capillary situationsp. 34
Thermodynamic modeling of reactions in capillary systemsp. 34
Simplified modeling of salt solubility in capillary systemsp. 35
Illustrations in natural settingsp. 36
Capillarity and mineralogy of desert rosesp. 36
Capillarity and the dissolution of gasesp. 38
Hydrogeochemical modeling in the unsaturated zonep. 39
Conclusionsp. 40
Governing equations and solution algorithms for geochemical modelingp. 45
The formulation of reactionsp. 45
Species, reactions and stoichiometric coefficientsp. 45
Equilibrium reactions in terms of the stoichiometric matrixp. 47
Primary and secondary speciesp. 49
Components and component matrixp. 52
Method 1 (aqueous components)p. 53
Method 2 (eliminate constant activity species)p. 57
Other methodsp. 57
Homogeneous reactionsp. 58
Speciation calculationsp. 59
Algorithm 1p. 60
Algorithm 2p. 61
Heterogeneous reactionsp. 63
Surface complexation reactionsp. 63
Cation exchange reactionsp. 68
Reactions with a solid phasep. 71
Reactions with a gas phasep. 71
Reaction pathsp. 73
Formulation of kinetic reactionsp. 76
Fluid flow, solute and heat transport equationsp. 83
Introductionp. 83
Groundwater flow equationsp. 83
Single phase flowp. 84
The conservation mass for the fluidp. 84
The momentum mass balance equations for the fluidp. 84
Flow equationsp. 87
Multiphase flowp. 90
Multiphase systemp. 90
Transport of conservative solutesp. 92
Advection, diffusion and dispersionp. 92
Advectionp. 92
Diffusionp. 93
Dispersionp. 94
Transport equations of conservative solutesp. 96
Heat transport equationsp. 97
Conduction and convectionp. 97
Heat conductionp. 97
Heatconvectionp. 98
Heat transport in single fluid phase systemsp. 98
Heat transport in multiple fluid phases systemsp. 99
Reactive transportp. 99
The need for reactive transport: calcite dissolution in the fresh-salt water mixing zonep. 99
Mass balance equationsp. 102
Constant activity speciesp. 106
Analytical solution for a binary system: equilibrium reaction ratesp. 108
Problem statementp. 108
Methodology of solutionp. 109
An analytical solution: pulse injection in a binary systemp. 112
The effect of heterogeneity and non-local formulationsp. 115
The limitations of traditional formulations and the need for upscalingp. 116
Solution of reactive transport in MRMT formulationsp. 119
Numerical solutions of reactive transport equationsp. 127
Introductionp. 127
Methods for discretizing space and timep. 127
Finite differencesp. 127
Fundamentalsp. 127
Application to conservative transportp. 129
Finite elementsp. 131
Instability and numerical dispersionp. 134
Methods for solving reactive transport equationsp. 135
Sequential Iteration Approach (SLA)p. 136
Direct Substitution Approach (DSA)p. 138
Comparison between SIA and DSAp. 140
Elaboration of a geochemical modelp. 143
Introductionp. 143
Model types and the most popular existing software packagesp. 143
Speciation-solubility modelsp. 143
Reaction-path modelsp. 145
Inverse (mass-balance) modelsp. 145
Reactive transport modelsp. 145
Data required for geochemical modelingp. 145
Data for speciation-solubility modelsp. 145
Data for reaction-path modelsp. 147
Data for inverse (mass-balance) modelsp. 147
Data for reactive transport modelsp. 147
Schematization and choice of thermodynamic databasep. 147
Modeling and interpretation of its resultsp. 149
Possible errors and misconceptions in model elaborationp. 150
Advances in geochemical modeling for geothermal applicationsp. 153
Introductionp. 153
Development of geothermal reservoir toolsp. 153
Types of geochemical models for geothermal systemsp. 155
Requirements for geochemical simulations of geothermal reservoirsp. 156
Popular computer software for geothermal system modelingp. 156
Flow and geochemical model calibrationp. 159
Selection of recent applications (2000-2010)ùCase studiesp. 160
General applicationsp. 160
Conceptual reservoir modelsp. 160
Lumped parameter modelsp. 164
Advanced numerical modelingp. 165
Reservoir design and magnitudeùReconstruction of reservoir parametersp. 165
Origin of acidity for reservoir fluidsp. 165
Mineral-fluid equilibriap. 165
Fluid reinjectionùScaling effectsp. 165
Hot-Dry Rock (HDR) systems (Soultz-sous-Forêts, France)p. 168
CO2 injection into geothermal reservoirsp. 169
ConclusionsùFuture challengesp. 170
Cases studies
Integrating field observations and inverse and forward modeling: application at a site with acidic, heavy-metal-contaminated groundwaterp. 181
Introductionp. 181
Geochemical modeling: computer codes, theory and assumptionsp. 182
Inverse geochemical modelingp. 182
Principles, codes and theoryp. 182
Assumptions used in inverse modelingp. 183
Forward geochemical modelingp. 186
Principles and codesp. 186
The Pinal Creek basin site: brief descriptionp. 188
Geologyp. 189
Hydrology and groundwater flowp. 190
Inverse geochemical modeling at the Pinal Creek sitep. 190
Examination of end-member waters and their conservative constituentsp. 191
The thermodynamic state of the end-member watersp. 192
NETPATH inverse modeling: simulation resultsp. 194
Inverse geochemical modeling with PHREEQCp. 200
Reactive-transport modeling at the Pinal Creek sitep. 203
Summary of previous reactive-transport modelingp. 205
A reactive-transport sensitivity analysis on the movement of pH and pe-controlling mineral frontsp. 206
A simple model for advective transport of a reactive front: the MnO2 dissolution frontp. 206
Determination of the initial MnO2,5 and carbonate mineral concentrationsp. 207
Setup of the 1-D reactive-transport simulationsp. 209
Simulation results: movement of the Fe(II)-rich waters and of the MnO2 dissolution frontp. 211
Simulation results: evolution of the low-pH watersp. 212
The effect of the initial carbonate to initial MnO2 ratio on the evolution of the low-pH watersp. 213
Influence of the aluminum mineral allowed to precipitate on the evolution of the low-pH watersp. 215
Effects of the irreversible dissolution of Ca and Mg silicates on the evolution of low-pH Fe(II)-rich watersp. 217
The effect of not allowing rhodochrosite precipitationp. 218
The CO2 open system simulationsp. 218
The effect of longitudinal dispersionp. 219
The influence of cation exchange and surface-complexation sorption processesp. 220
Other minor effects on the evolution of the low-pH watersp. 221
Comparison of the reactive transport simulation result with observations at the Pinal Creek sitep. 221
Conclusionsp. 224
The Senior Author's fifteen year perspective on the Glynn and Brown (1996) paperp. 226
Models and measurements of porosity and permeability evolution in a sandstone formationp. 235
Introductionp. 235
Porosity measurements in mineralized rockp. 236
Theory and numerical modeling of porosity evolutionp. 238
Conceptual model of the porous mediump. 238
Reaction kineticsp. 240
Reactive transport equationsp. 243
Numerical solution and model optimizationp. 244
Comparison between numerical models and measurementsp. 245
Implications for bulk reaction ratesp. 247
Implications for permeability evolution in aquifersp. 248
Concluding remarksp. 249
Geochemical modeling of water chemistry evolution in the Guarani Aquifer System in São Paulo, Brazilp. 253
Modeling of reactive transport at a site contaminated by petroleum hydrocarbons at Hnevice, Czech Republicp. 259
Site characterization and conceptual modelp. 259
Speciation and inverse geochemical modelingp. 261
Modeling of reactive transportp. 263
Numerical modeling for preliminary assessment of natural remediation of phosphorus in variably saturated soil in a peri-urban settlement in Kampala, Ugandap. 267
Introductionp. 267
Settingp. 267
Numerical modelp. 269
Flow modelp. 269
Solute modelp. 274
Soil phosphorus sorptionp. 274
Solute transport modelp. 275
Simulationsp. 276
Results and discussionp. 277
Field measurementsp. 277
Pollution and remediation simulation scenariosp. 278
Sensitivity analysesp. 279
Impact of change of sorption coefficients (KL and Kplin) on pollution timep. 279
Impact of change of the pore size distribution values on pollution timep. 279
Impact of change of the air entry values on pollution timep. 281
Conclusionsp. 281
Subject indexp. 287
Book series pagep. 305
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