Description
Taylor & Francis Ltd Geochemistry Groundwater And Pollution 2Nd Edition 2005 by C.A.J. Appelo, Dieke Postma
Building on the success of its 1993 predecessor, this second edition of Geochemistry, Groundwater and Pollution has been thoroughly re-written, updated and extended to provide a complete and authoritative account of modern hydrogeochemistry.Offering a quantitative approach to the study of groundwater quality and the interaction of water, minerals, gases, pollutants and microbes, this book shows how physical and chemical theory can be applied to explain observed water qualities and variations over space and time. Integral to the presentation, geochemical modelling using PHREEQC code is demonstrated, with step-by-step instructions for calculating and simulating field and laboratory data. Numerous figures and tables illustrate the theory, while worked examples including calculations and theoretical explanations assist the reader in gaining a deeper understanding of the concepts involved. A crucial read for students of hydrogeology, geochemistry and civil engineering, professionals in the water sciences will also find inspiration in the practical examples and modeling templates. LIST OF EXAMPLES XIINOTATION XV1 INTRODUCTION TO GROUNDWATER GEOCHEMISTRY 11.1 Groundwater as drinking water 11.1.1 Standards for drinking water 11.2 Units of analysis 31.3 Groundwater quality 71.4 Sampling of groundwater 101.4.1 Depth integrated or depth specific sampling 101.4.2 Procedures for sampling of groundwater 121.5 Chemical analysis of groundwater 151.5.1 Field analyses and sample conservation 151.5.2 Accuracy of chemical analysis 17Problems 20References 212 FROM RAINWATER TO GROUNDWATER 232.1 The hydrological cycle 232.2 The composition of rainwater 262.2.1 Sources and transport of atmospheric pollutants 312.3 Stable isotopes in rain 312.3.1 Isotopic ratios and the < notation 322.3.2 The Rayleigh process 332.3.3 The isotopic composition of rain 372.4 Dry deposition and evapotranspiration 412.5 Mass balances and ecosystem dynamics 462.5.1 Water quality profiles in the unsaturated soil 492.6 Overall controls on water quality 51Problems 58References 593 FLOW AND TRANSPORT 633.1 Flow in the unsaturated zone 633.2 Flow in the saturated zone 643.2.1 Darcy's law 643.2.2 Flowlines in the subsoil 673.2.3 Effects of non-homogeneity 703.2.4 The aquifer as a chemical reactor 713.3 Dating of groundwater 723.4 Retardation 753.4.1 The retardation equation 763.4.2 Indifferent and broadening fronts 793.4.3 Sharpening fronts 823.4.4 Solid and solute concentrations 843.5 Diffusion 863.5.1 Diffusion coefficients 873.5.2 Diffusion as a random process 893.5.3 Diffusive transport 933.5.4 Isotope diffusion 963.6 Dispersion 993.6.1 Column breakthrough curves 1023.6.2 Dispersion coefficients and dispersivity 1053.6.3 Macrodispersivity 107Problems 113References 1154 MINERALS AND WATER 1194.1 Equilibria and the solubility of minerals 1194.2 Corrections for solubility calculations 1234.2.1 Concentration and activity 1234.2.2 Aqueous complexes 1274.2.3 Combined complexes and activity corrections 1284.2.4 Calculation of saturation states 1314.3 Mass action constants and thermodynamics 1324.3.1 The calculation of mass action constants 1324.3.2 Calculation of mass action constants at different temperature 1334.4 Equilibrium calculations with PHREEQC 1354.4.1 Speciation calculations using PHREEQC 1354.4.2 The PHREEQC database 1374.4.3 Mineral equilibration 1414.5 Solid solutions 1424.5.1 Basic theory 1424.5.2 The fractionation factor for solid solutions 1484.5.3 Kinetic effects on the fractionation factor 1494.6 Kinetics of geochemical processes 1524.6.1 Kinetics and equilibrium 1524.6.2 Chemical reactions and rates 1534.6.3 Temperature dependency of reaction rates 1594.6.4 Mechanisms of dissolution and crystallization 1604.6.5 Rate laws for mineral dissolution and precipitation 162Problems 169References 1715 CARBONATES AND CARBON DIOXIDE 1755.1 Carbonate minerals 1765.2 Dissolved carbonate equilibria 1785.2.1 The carbonic acid system 1795.2.2 Determining the carbonate speciation in groundwater 1835.3 Carbon dioxide in soils 1865.4 Calcite solubility and PCO2 1915.4.1 Calcite dissolution in systems open and closed for CO2 gas 1935.4.2 Two field examples 1955.5 Carbonate rock aquifers 1975.5.1 Dolomite and dedolomitization 2015.5.2 Pleistocene carbonate aquifers 2055.6 Kinetics of carbonate reactions 2105.6.1 Dissolution 2105.6.2 Precipitation 2175.7 Carbon isotopes 2185.7.1 Carbon-13 trends in aquifers 2215.7.2 14C and groundwater age 2265.7.3 Retardation by sorption and stagnant zone diffusion 228Problems 232References 2366 ION EXCHANGE 2416.1 Cation exchange at the salt/fresh water interface 2426.2 Adsorbents in soils and aquifers 2476.2.1 Clay minerals 2486.3 Exchange equations 2516.3.1 Values for exchange coefficients 2546.3.2 Calculation of exchanger composition 2556.3.3 Calculation of exchanger composition with PHREEQC 2576.3.4 Determination of exchangeable cations 2606.4 Chromatography of cation exchange 2626.4.1 Field examples of freshening 2636.4.2 Salinity effects on cation exchange 2686.4.3 Quality patterns with salinization 2716.4.4 Fronts and chromatographic sequences 2726.4.5 Modeling chromatographic sequences with PHREEQC 2756.5 Physical non-equilibrium 2836.5.1 Modeling stagnant zones 2856.6 The Gouy-Chapman theory of the double layer 2886.6.1 Numerical integration of the double layer equations 2936.6.2 Practical aspects of double layer theory 2966.7 Irrigation water quality 299Problems 303References 3067 SORPTION OF TRACE METALS 3117.1 The origin and occurrence of heavy metals in groundwater 3117.2 Sorption isotherms and distribution coefficients 3157.2.1 Distribution coefficients from ion exchange 3187.3 Variable charge surfaces 3227.3.1 Titration curves with suspended oxide particles 3227.3.2 Surface charge and point of zero charge, PZC 3247.3.3 Sorption edges 3287.3.4 Sorption, absorption, and coprecipitation 3337.4 Surface complexation 3347.4.1 Surface complexation models 3387.4.2 The ferrihydrite (Fe(OH)3) database 3407.4.3 Diffuse double layer concentrations in surface complexation models 3437.5 Complexation to humic acids 3447.5.1 The ion association model 3467.5.2 Tipping and Hurley's discrete site model "WHAM" 3487.5.3 Distribution models 3547.5.4 Humic acids as carriers of trace elements 3567.6 Kinetics of surface complexation 3587.6.1 Extrapolation of adsorption kinetics for other metal ions 3637.7 Field applications 363Problems 367References 3698 SILICATE WEATHERING 3758.1 Weathering processes 3758.2 The stability of weathering products 3808.3 Incongruent dissolution of primary silicates 3838.4 The mass balance approach to weathering 3898.5 Kinetics of silicate weathering 3958.6 Field weathering rates 4008.7 Acid groundwater 4048.7.1 Buffering processes in aquifers 405Problems 410References 4129 REDOX PROCESSES 4159.1 Basic theory 4159.1.1 The significance of redox measurements 4209.1.2 Redox reactions and the pe concept 4229.2 Redox diagrams 4239.2.1 Stability of water 4249.2.2 The stability of dissolved species and gases: Arsenic 4259.2.3 The stability of minerals in redox diagrams 4329.3 Sequences of redox reactions and redox zoning 4389.3.1 Decomposition of organic matter 4429.4 Oxygen consumption 4469.4.1 Pyrite oxidation 4509.4.2 Kinetics of pyrite oxidation 4509.4.3 Oxygen transport and pyrite oxidation 4539.5 Nitrate reduction 4589.5.1 Nitrate reduction by organic matter oxidation 4599.5.2 Nitrate reduction by pyrite and ferrous iron 4629.6 Iron reduction and sources of iron in groundwater 4659.6.1 Iron in aquifer sediments 4659.6.2 Reductive dissolution of iron oxides 4669.7 Sulfate reduction and iron sulfide formation 4729.7.1 The formation of iron sulfides 4769.8 The formation of methane 477Problems 479References 48010 POLLUTION BY ORGANIC CHEMICALS 48910.1 Gas-water exchange 48910.1.1 Evaporation of a pure organic liquid 49410.2 Transport of pure organic liquids through soil 49610.3 Sorption of organic chemicals 49910.3.1 Sorption of charged organic molecules 50410.3.2 Sorption in stagnant zones 50610.3.3 Release from stagnant zones and blobs 51010.4 Transformation reactions of organic chemicals 51610.4.1 Monod biotransformation kinetics 51810.5 Kinetic complexation of heavy metals on organics 529Problems 535References 53711 NUMERICAL MODELING 54111.1 Numerical modeling of transport 54311.1.1 Only diffusion 54311.1.2 Advection and diffusion/dispersion 55011.1.3 Non-linear reactions 55811.2 Examples of hydrogeochemical transport modeling 56011.2.1 Tritium-Helium age dating 56111.2.2 Toluene degradation in an aquifer 56511.2.3 Remediation of a BTEX polluted site 56811.2.4 Acid drainage from a Uranium mine 57011.2.5 In-situ iron removal from groundwater 57911.2.6 Arsenic in Bangladesh groundwater 58511.2.7 Fractionation of isotopes 590References 595APPENDIX A: HYDROGEOCHEMICAL MODELING WITH PHREEQC 599APPENDIX B: ANSWERS TO PROBLEMS 617INDEX 635show more