Acknowledgements, xii About the Companion Website, xiii 1 BACKGROUND AND BASIC CHEMICAL PRINCIPLES: ELEMENTS, IONS, BONDING, REACTIONS, 1 1.1 An overview of environmental geochemistry - history, scope, questions, approaches, challenges for the future, 1 1.2 The naturally occurring elements - origins and abundances, 2 1.3 Atoms and isotopes: a brief review, 6 1.4 Measuring concentrations, 8 1.4.1 Mass-based concentrations, 8 1.4.
2 Molar concentrations, 9 1.4.3 Concentrations of gases, 10 1.4.4 Notes on precision and accuracy, significant figures and scientific notation, 10 1.5 Periodic table, 11 1.6 Ions, molecules, valence, bonding, chemical reactions, 14 1.6.
1 Ionic bond strength, 14 1.6.2 Covalent bonds, 16 1.6.3 Electronegativity, 17 1.6.4 Metallic bonds, hydrogen bonds and van der Waals forces, 18 1.7 Acid-base equilibria, pH, K values, 19 1.
8 Fundamentals of redox chemistry and chemical reactions, 21 1.9 Chemical reactions, 23 1.10 Equilibrium, thermodynamics and driving forces for reactions: systems, gibbs energies, enthalpy and heat capacity, entropy, volume, 23 1.10.1 Systems, species, phases and components, 24 1.10.2 First law of thermodynamics, 26 1.10.
3 Second law of thermodynamics, 27 1.10.4 Enthalpy, 27 1.10.5 Heat capacity, 29 1.10.6 Gibbs free energy, 30 1.10.
7 Gibbs free energy and the equilibrium constant, 31 1.11 Kinetics and reaction rates: distance from equilibrium, activation energy, metastability, 33 1.11.1 Reaction rate, reaction order, 34 1.11.2 Temperature and the Arrhenius equation, 36 Review questions, 37 References, 37 2 SURFICIAL AND ENVIRONMENTAL MINERALOGY, 39 2.1 Introduction to minerals and unit cells, 40 2.2 Ion coordination, Pauling''s rules and ionic substitution, 42 2.
2.1 Coordination and radius ratio, 42 2.2.2 Bond-strength considerations, 45 2.2.3 Pauling''s and Goldschmidt''s rules of ionic solids, 45 2.3 Silicates, 48 2.3.
1 Nesosilicates, 49 2.3.2 Inosilicates, 50 2.3.3 Phyllosilicates, 52 2.3.4 Tectosilicates, 58 2.4 Clay minerals (T-O minerals, T-O-T minerals, interstratified clays), 58 2.
4.1 Smectite, 59 2.4.2 Smectites with tetrahedrally derived layer charge, 60 2.4.3 Smectites with octahedrally derived layer charge, 60 2.4.4 Vermiculite, 62 2.
4.5 Illite, 62 2.4.6 Chlorite and Berthierine, 63 2.4.7 Kaolin (kaolinite and halloysite), 63 2.4.8 Interstratified clay minerals, 64 2.
4.9 Trace metals and metalloids in clay minerals, 64 2.5 Crystal chemistry of adsorption and cation exchange, 64 2.5.1 Cation exchange, 66 2.5.2 Double-layer complexes, 68 2.6 Low-temperature non-silicate minerals: carbonates, oxides and hydroxides, sulfides, sulfates, salts, 70 2.
6.1 Carbonates, 70 2.6.2 Oxides and hydroxides, 71 2.6.3 Sulfides and sulfates, 72 2.6.4 Halide and nitrate salts, 74 2.
7 Mineral growth and dissolution, 74 2.8 Biomineralization, 78 Review questions, 79 References, 80 3 ORGANIC COMPOUNDS IN THE ENVIRONMENT, 82 3.1 Introduction to organic chemistry: chains and rings, single, double, and triple bonds, functional groups, classes of organic compounds, organic nomenclature, 82 3.1.1 Definition of organic compounds, 82 3.1.2 Hybridization of carbon atoms in organic compounds, 83 3.1.
3 Alkanes, 84 3.1.4 Alkenes, 86 3.1.5 Functional groups, 86 3.1.6 Aromatic hydrocarbons and related compounds, 88 3.1.
7 Nitrogen, phosphorus and sulfur in organic compounds, 92 3.1.8 Pharmaceutical compounds, 93 3.2 Natural organic compounds at the earth surface, 94 3.2.1 Fossil fuels, 95 3.3 Fate and transport of organic pollutants, controls on bioavailability, behavior of DNAPLs and LNAPLs, biodegradation, remediation schemes, 96 3.3.
1 Solid-liquid-gas phase considerations, 96 3.3.2 Solubility considerations, 97 3.3.3 Interactions of organic compounds and organisms, 98 3.3.4 Adsorption of organic compounds, 99 3.3.
5 Non-aqueous phase liquids (NAPLs) in the environment, 103 3.3.6 Biodegradation, 104 3.3.7 Remediation, 105 3.4 Summary, 106 Questions, 106 References, 106 4 AQUEOUS SYSTEMS - CONTROLS ON WATER CHEMISTRY, 108 4.1 Introduction to the geochemistry of natural waters, 108 4.1.
1 Geochemistry and the hydrologic cycle, 108 4.2 The structure of water - geometry, polarity and consequences, 113 4.3 Dissolved versus particulate: examples of solutions and suspensions, 114 4.3.1 Dissolved vs. particulate vs. colloidal, 115 4.4 Speciation: simple ions, polyatomic ions and aqueous complexes, 116 4.
5 Controls on the solubility of inorganic elements and ions, 117 4.5.1 The ratio of ionic charge: ionic radius and its effect on solubility, 119 4.5.2 Reduction-oxidation reactions, 120 4.5.3 Half-cell reactions, 120 4.5.
4 Redox reactions in the environment, 122 4.5.5 pH and acid-base consideration, 123 4.5.6 Ligands and elemental mobility, 124 4.6 Ion activities, ionic strength, TDS, 125 4.6.1 Ion activity product, 126 4.
6.2 Ionic strength, 126 4.6.3 Total dissolved solids, 126 4.7 Solubility products, saturation, 127 4.8 Co-precipitation, 128 4.9 Behavior of selected elements in aqueous systems, 129 4.9.
1 Examples of heavy metals and metalloids, 129 4.9.2 Eh-pH diagrams, 132 4.9.3 Silicon in solutions, 136 4.10 Effect of adsorption and ion exchange on water chemistry, 137 4.10.1 Ionic potential, hydration radius and adsorption, 138 4.
10.2 Law of mass action and adsorption, 138 4.10.3 Adsorption edges, 140 4.10.4 Adsorption isotherms, 142 4.11 Other graphical representations of aqueous systems: piper and stiff diagrams, 143 4.12 Summary, 146 Questions, 147 References, 147 5 CARBONATE GEOCHEMISTRY AND THE CARBON CYCLE, 149 5.
1 Carbonate geochemistry: inorganic carbon in the atmosphere and hydrosphere, 149 5.1.1 Atmospheric CO2, carbonate species and the pH of rain, 150 5.1.2 Speciation in the carbonate system as a function of pH, 151 5.1.3 Alkalinity, 152 5.1.
4 Carbonate solubility and saturation, 155 5.1.5 The effect of CO2 partial pressure on stability of carbonate minerals, 157 5.1.6 The effect of mineral composition on stability of carbonate minerals, 157 5.2 The carbon cycle, 158 5.2.1 Oxidation states of carbon, 158 5.
2.2 Global-scale reservoirs and fluxes of carbon, 159 5.2.3 Fixation of carbon into the crust, 161 5.2.4 Rates of flux to and from the crust, 164 5.2.5 The ocean reservoir, 166 5.
2.6 Fixation of C into oceans, 166 5.2.7 Long-term viability of oceans as C sink, 168 5.2.8 The atmospheric reservoir, 171 5.2.9 Sequestration, 174 Questions, 175 References, 176 6 BIOGEOCHEMICAL CYCLES - N, P, S, 177 6.
1 The nitrogen cycle, 180 6.1.1 Nitrogen valence, nitrogen species, 181 6.1.2 Processes operating within the nitrogen cycle, 182 6.1.3 Global scale reservoirs and fluxes of nitrogen, 184 6.1.
4 Human perturbation of the nitrogen cycle and resulting environmental impacts, 186 6.2 The phosphorus cycle, 190 6.2.1 P cycling in soils, 191 6.2.2 The global phosphorus cycle, 193 6.2.3 Phosphorus and eutrophication, 194 6.
3 Comparison of N and P, 195 6.4 The sulfur cycle, 196 6.4.1 Sulfur valence, sulfur species, 196 6.4.2 The global S cycle, 197 6.4.3 The marine S cycle, 198 6.
4.4 Soils and biota, 200 6.4.5 Atmosphere, 200 6.4.6 River flux, 201 6.5 Integrating the C, N, P and S cycles, 202 Questions, 203 References, 203 7 THE GLOBAL ATMOSPHERE: COMPOSITION, EVOLUTION AND ANTHROPOGENIC CHANGE, 206 7.1 Atmospheric structure, circulation and composition, 206 7.
1.1 Structure and layering of the atmosphere, 207 7.1.2 Geological record of atmospheric composition, 208 7.1.3 Climate proxies, 209 7.1.4 Orbital control on C, 210 7.
1.5 Composition of the current atmosphere, 213 7.1.6 Air circulation, 214 7.2 Evaporation, distillation, CO2 dissolution and the composition of natural precipitation, 218 7.3 The electromagnetic spectrum, greenhouse gases and climate, 219 7.3.1 Electromagnetic spectrum, 219 7.
3.2 Re-radiation from earth surface, 219 7.3.3 Greenhouse effect and heat trapping, 222 7.4 Greenhouse gases: structures, sources, sinks and effects on climate, 223 7.4.1 Molecular structures and vibrations of greenhouse gases, 223 7.4.
2 Greenhouse gases, radiative forcing, GWPs, 224 7.4.3 Global warming, 227 Questions, 228 References, 228 8 URBAN AND REGIONAL AIR POLLUTION, 230 8.1 Oxygen and its impact on atmospheric chemistry, 231 8.2 Free radicals, 232 8.3 Sulfur dioxide, 234 8.4 Nitrogen oxides, 237 8.5 Carbon monoxide, 238 8.
6 Particulate matter, 240 8.7 Lead (Pb), 242 8.8 Hydrocarbons and air quality: tropospheric ozone and photochemical smog, 242 8.9 Stratospheric ozone chemistry, 245 8.10 Sulfur and nitrogen gases and acid deposition, 249 8.11 Trace elements in atmospheric deposition: organochlorine pesticides, mercur.