Holdings: Environmental chemistry

Environmental chemistry: fundamentals

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Bibliographic Details
Format:	Book
Language:	English
Published:	New York, NY Springer 2007
Subjects:	Environmental chemistry Ökologische Chemie
Online Access:	Inhaltstext Inhaltsverzeichnis
Physical Description:	XVIII, 334 S.
ISBN:	9780387314358 9780387260617

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adam_text	Contents Foreword .............................................................................................................. v Preface ................................................................................................................. vii Part 1 Introductory Concepts 1 Introduction to Environmental Chemistry ............................................................... 3 1.1 Chemistry of the Natural Processes in the Biosphere .............................................. 3 1.2 Chemistry Associated with Pollution Processes ..................................................... 4 1.3 Chemistry Applied to the Analysis of Pollutants and Natural Compounds .................... 6 1.4 Chemistry Applied to the Treatment and Remediation of Pollution ............................. 8 1.5 Green Chemistry .......................................................................................... 8 1.6 Importance of Environmental Chemistry ............................................................. 9 References and Further Reading ....................................................................... 10 2 Chemistry Fundamentals, Part A .......................................................................... 11 2.1 Chemical Equilibria ...................................................................................... 11 2.1.1 Equilibrium Values and Calculations ........................................................ 12 2.1.2 Exchange Reaction Equilibria: Systems of the Type МЦ/МЦ.,/ · · · ML/M ...... 12 2.2 Acid-Base Reactions ..................................................................................... 15 2.2.1 Acid-Base Characteristics of Common Chemical Species .............................. 15 2.2.2 Buffers ............................................................................................. 16 2.2.3 Acid/Base Character of Oxides ............................................................... 21 2.3 Redox Processes .......................................................................................... 23 2.3.1 Latimer Diagrams ............................................................................... 25 2.3.2 Frost Diagrams ................................................................................... 27 2.3.3 Nernst Equation .................................................................................. 27 2.3.4 Pourbaix Diagrams .............................................................................. 28 2.3.5 The p£ Scale ..................................................................................... 33 References and Further Reading ....................................................................... 41 3 Chemistry Fundamentals, Part В .......................................................................... 43 3.1 Complexes and Complex Formation .................................................................. 43 3.1.1 Definition and Generalities .................................................................... 43 Contents 3.1.2 Modification of Properties of Metal Ions .................................................... 43 3.1.3 Geometry of Metal Complexes ............................................................... 46 3.1.4 Inner and Outer Sphere Complexes .......................................................... 47 3.1.5 Mono and Polydentate Ligands. The HSAB Approach .................................. 48 3.1.6 The Chelate Effect ............................................................................... 48 3.1.7 Reactions of Complexes ........................................................................ 50 3.1.7.1 Ligand-Exchange Reactions ....................................................... 50 3.1.7.2 Electron-Exchange Reactions ..................................................... 50 3.2 Chemical Kinetics ........................................................................................ 51 3.2.1 Factors That Influence the Rate of a Mono Directional Reaction ...................... 52 3.2.1.1 Dependence of the Rate of Reaction on Concentrations: The Rate Law .. 53 3.2.1.2 The Rate Constant ................................................................... 54 3.2.2 Integrated Rate Equations ...................................................................... 54 3.2.2.1 Zeroth-Order Reactions ............................................................. 54 3.2.2.2 First-Order Reactions ............................................................... 54 3.2.2.3 Second-Order Reactions ............................................................ 55 3.2.2.4 Higher-Order Reactions ............................................................ 55 3.2.3 Complex Reactions .............................................................................. 55 3.2.3.1 Consecutive Reactions .............................................................. 56 3.2.3.2 Opposing (Reversible) Reactions ................................................. 56 3.2.3.3 Parallel Reactions .................................................................... 57 3.2.4 The Steady-State Approximation ............................................................. 57 3.2.5 Catalysis ........................................................................................... 57 3.2.6 Kinetics of Metal-Complex Dissociation ................................................... 58 3.3 Photochemical Processes ................................................................................ 59 3.3.1 Photochemical Processes After the Absorption of Light ................................. 59 3.3.2 BeeťsLaw ........................................................................................ 60 3.3.3 Homogeneous and Heterogeneous Processes .............................................. 61 3.4 Radiochemistry ............................................................................................ 61 3.4.1 Decay Kinetics ................................................................................... 62 3.4.2 Units of Radiation ............................................................................... 63 3.4.3 Detection Devices for Ionizing Radiations and Protection From Radiation .......... 64 3.4.3.1 Geiger Counter or Ionization in Gas-Filled Tubes ............................. 64 3.4.3.2 Scintillation Device .................................................................. 64 3.4.3.3 Photographic Films .................................................................. 64 3.4.3.4 Semiconductors ...................................................................... 64 3.4.3.5 Thermoluminescence ................................................................ 64 References and Further Reading ....................................................................... 64 Part 2 The Chemistry of Natural Environmental Processes 4 The Chemistry of Processes in the Atmosphere ........................................................ 69 4.1 Air ........................................................................................................... 69 4.2 How Did the Earth s Atmosphere Form? ............................................................. 70 4.3 Amounts of Constituents in the Atmosphere ........................................................ 71 4.4 Tropospheric Chemistry ................................................................................. 73 4.5 Physical Principles of the Greenhouse Effect ........................................................ 74 4.6 Stratospheric Chemistry ................................................................................. 75 4.7 Aerosols .................................................................................................... 76 Related Experiments in the Companion Book ....................................................... 76 Contents Additional Related Experiments/Activities .......................................................... 76 References and Further Reading ....................................................................... 77 The Chemistry of Processes in the Lithosphère ......................................................... 78 5.1 The Lithosphère and its Components ................................................................. 78 5.1.1 Structure of the Solid Earth .................................................................... 78 5.1.1.1 Core .................................................................................... 78 5.1.1.2 Mantle .................................................................................. 78 5.1.1.3 Crust .................................................................................... 78 5.1.2 Classification of Rocks ......................................................................... 79 5.1.2.1 Igneous Rocks ........................................................................ 79 5.1.2.2 Sedimentary Rocks .................................................................. 79 5.1.2.3 Metamorphic Rocks ................................................................. 80 5.1.2.4 Rock-Forming Minerals ............................................................ 80 5.2 Formation and Differentiation of Minerals and Ores ............................................... 80 5.3 Weathering ................................................................................................. 81 5.3.1 Physical Weathering ............................................................................ 81 5.3.2 Chemical Weathering ........................................................................... 82 5.3.2.1 Dissolution and Precipitation of Solids .......................................... 85 5.3.2.2 Dissolution of Natural Oxides ..................................................... 89 5.3.2.3 Stable and Metastable Solid Phases .............................................. 90 5.3.3 Biological Weathering .......................................................................... 92 5.4 Soil Characteristics ....................................................................................... 92 5.4.1 Soil Taxonomy ................................................................................... 93 5.4.2 Humic Substances (HS)........................................................................ 93 5.4.3 Decomposition of Organic Materials Adsorbed on Soil .................................. 93 Related Experiments in the Companion Book ....................................................... 93 Additional Related Experiments/Activities .......................................................... 94 References and Further Reading ....................................................................... 94 6 The Chemistry of Processes in the Hydrosphere ....................................................... 96 6.1 Natural Waters: Types and Composition .............................................................. 96 6.1.1 Processes That Affect Water Composition .................................................. 96 6.1.2 Rainwater ......................................................................................... 98 6.1.3 Surface Water .................................................................................... 99 6.1.3.1 Stream and River Water ............................................................. 101 6.1.3.2 Lake Water ............................................................................ 103 6.1.4 Groundwater ...................................................................................... 1 05 6.1.5 Seawater ........................................................................................... 106 6.1.6 Brackish/Saline Water .......................................................................... 107 6.2 Interactions of Water with Air and Sediments; Effects on 10 10 10 Aquatic Chemistry .................................................... 6.2.1 Gas Dissolution and Acidification of Natural Waters. 6.2.1.1 Henry s Law ...................... 6.2.1.2 Dissolved Oxygen in Water.... 6.2.1.3 Dissolution of CO2 in Water... 6.2.2 Interactions between Water and Sediments/Soil . 6.3 Physicochemical Processes in Aquatic Systems .......... 6.3.1 Chemical Processes in Aquatic Systems 6.3.1.1 Acid-Base Reactions. 13 14 15 15 16 Contents 6.3.1.2 Redox Reactions ..................................................................... 119 6.3.1.3 Complex Formation ................................................................. 122 6.3.1.4 Speciation ............................................................................. 122 6.3.1.5 Colloids: Properties, Types, Sources, and Formation ......................... 124 6.3.1.6 Photochemical Reactions ........................................................... 126 6.3.2 Natural Removal of Species from Aqueous Systems by Chemical and Physical Processes ......................................................................... 128 6.3.2.1 Sorption onto Colloidal, Suspended, or Settled Sediments .................. 128 6.3.2.2 Ion Exchange in Sediments and in Aqueous Colloidal and Suspended Matter .............................................................. 129 6.3.2.3 Precipitation Reactions and Co-precipitation ................................... 131 6.3.2.4 Solidification and Deposition Processes Due to Evaporation ........................................................................... 131 6.3.2.5 Colloidal and Sediment Transport into Surface Water ........................ 131 6.3.2.6 Volatilization of Organic and Inorganic Compounds .......................... 132 Related Experiments in the Companion Book ....................................................... 132 Additional Related Experiments/Activities .......................................................... 135 References and Further Reading ....................................................................... 135 Natural Biochemical Processes and Organisms in the Biosphere .................................. 137 7.1 Classification of Living Organisms .................................................................... 137 7.2 Nutritional Classification of Organisms .............................................................. 140 7.3 Basic Aspects of Ecology ............................................................................... 142 7.3.1 The Habitats of Life: Air, Land, and Water ................................................. 143 7.3.1.1 Atmosphere ........................................................................... 143 7.3.1.2 Land .................................................................................... 143 7.3.1.3 Water ................................................................................... 144 7.3.2 Trophic Levels ................................................................................... 145 7.3.3 Non-feeding Relations Among Species ..................................................... 146 7.3.4 Sustainability of Ecosystems .................................................................. 147 7.4 Biogeochemical Cycles .................................................................................. 148 7.4.1 Water Cycle ....................................................................................... 148 7.4.2 Hydrogen Cycle .................................................................................. 148 7.4.3 Carbon Cycle ..................................................................................... 149 7.4.4 Oxygen Cycle .................................................................................... 150 7.4.5 Nitrogen Cycle ................................................................................... 152 7.4.5.1 Fixation ................................................................................ 152 7.4.5.2 Ammonification ...................................................................... 153 7.4.5.3 Nitrification ........................................................................... 154 7.4.5.4 Nitrate Reduction and Denitrification ............................................ 154 7.4.6 Sulfur Cycle ...................................................................................... 155 7.4.6.1 Sulfur Mineralization ............................................................... 155 7.4.6.2 Oxidation of Sulfide and of Elemental Sulfur .................................. 156 7.4.6.3 Dissimilatory Sulfate or Sulfur Reduction ...................................... 157 7.4.6.4 Assimilatory Sulfate Reduction or Sulfur Immobilization ............................................................... 157 7.4.7 Phosphorus Cycle ............................................................................... 157 7.4.8 Iron Cycle ......................................................................................... 159 7.4.9 Interrelations Among Cycles .................................................................. 160 Contents Related Experiments in the Companion Book....................................................... 161 Additional Related Experiments/Activities .......................................................... 162 References and Further Reading ....................................................................... 162 Part 3 Effects, Treatment and Prevention of Pollution 8 Effects of Pollutants on the Chemistry of the Atmosphere, Hydrosphere, and Lithosphère ................................................................................................. 167 8.1 Importance of the Manufacture and Use of Chemical Substances ............................... 167 8.2 Sources of Chemical Substances as Contaminants and Pollutants ............................... 167 8.3 Transport, Mobility, and Partition of Pollutants ..................................................... 169 8.4 Air, Water, and Soil Pollution and Their Effects .................................................... 173 8.4.1 Effects of Pollutants on the Atmosphere .................................................... 173 8.4.1.1 Main Air Pollutants ................................................................ 173 8.4.1.2 Combustion Processes as the Main Air Pollution Source ................... 175 8.4.1.3 The Greenhouse Effect ............................................................ 176 8.4.1.4 Smog Formation .................................................................... 176 8.4.1.5 Stratospheric Ozone Destruction or the Ozone Hole ........................ 177 8.4.1.6 Acid Rain ............................................................................ 178 8.4.1.7 Indoor Pollution .................................................................... 179 8.4.2 Effects of Pollutants on the Hydrosphere ................................................... 180 8.4.2.1 Oxygen-Demanding Materials ................................................... 180 8.4.2.2 Nutrients ............................................................................. 182 8.4.2.3 Pathogenic Organisms ............................................................. 183 8.4.2.4 Suspended Solids ................................................................... 183 8.4.2.5 Oil and Grease Spills .............................................................. 184 8.4.2.6 Metallic and Metalloid Compounds ............................................ 185 8.4.2.7 Radionuclides ....................................................................... 185 8.4.2.8 Detergents (Surfactants) and Nutrient Enrichment ........................... 185 8.4.2.9 Salts ................................................................................... 186 8.4.2.10 Heat ................................................................................... 186 8.4.2.11 Other Contributions ................................................................ 187 8.4.2.12 Groundwater Pollution ............................................................ 187 8.4.2.13 Surface Waters ...................................................................... 187 8.4.3 Effects of Pollutants on the Lithosphère .................................................... 187 8.4.3.1 Transformation of Pollutants in Soils ........................................... 187 8.4.3.2 Transport, Mobility, and Partitioning of Pollutants in Soils ................ 188 8.4.3.3 Agriculture and the Chemistry of Soils ........................................ 188 8.4.3.4 Metals and Mining Processes .................................................... 189 8.4.3.5 Other Wastes and Pollutants in Soil ............................................. 190 Related Experiments in the Companion Book ....................................................... 190 Additional Related Experiments/Activities .......................................................... 191 References and Further Reading ....................................................................... 196 9 Effects of Pollutants on the Biosphere: Biodegradability, Toxicity, and Risks .................. 198 9.1 Types of Pollutants According to Their Capacity to Undergo Biotransformation ............ 198 9.1.1 Biodegradable Substances and Biodegradation Processes ............................... 198 9.1.2 Biotic Transformation Reactions ............................................................. 199 9.1.3 Recalcitrance and Recalcitrant Compounds ................................................ 204 xv¡ Contents 9.2 Hazardous and Non-hazardous Substances or Pollutants .......................................... 207 9.2.1 Classification of Hazardous Substances ..................................................... 208 9.2.2 Toxicity and Related Definitions .............................................................. 208 9.2.3 Factors That Affect the Toxicity of Chemical Substances ............................... 208 9.3 Human Health Risk Assessment ....................................................................... 220 9.3.1 Hazard Identification ............................................................................ 221 9.3.2 Dose-Response Assessment ................................................................... 222 9.3.2.1 Non-carcinogenic Risk Assessment ............................................ 223 9.3.2.2 Cancer Risk Assessment .......................................................... 224 9.3.3 Exposure Assessment ........................................................................... 226 9.3.4 Risk Characterization ........................................................................... 226 9.3.5 Risk Management ............................................................................... 227 9.4 Ecotoxicology ............................................................................................. 228 9.4.1 Methods of Ecotoxicology ..................................................................... 229 9.4.1.1 Toxic Endpoints.................................................................... 230 9.4.1.2 Bioassays ............................................................................ 230 9.4.2 Ecotoxicity Determination ................................................................ 231 9.4.2.1 Short-Time Toxicity Tests .................................................... 231 9.4.2.2 Long-Term Toxicity Tests .................................................... 231 9.4.3 Bioconcentration, Bioaccumulation, and Biomagnification ........................ 232 9.4.4 Biomarkers and Bioindicators ............................................................ 233 9.4.5 In Situ Monitoring .......................................................................... 233 9.4.6 Ecological Risk Assessment .............................................................. 234 9.4.6.1 Characterization of the Baseline Ecology and Identification of Potential Receptor Populations .......................................... 234 9.4.6.2 Ecological Toxicity Assessment ............................................ 234 9.4.6.3 Evaluation of Potential Exposures .......................................... 234 9.4.6.4 Risk Characterization ......................................................... 234 9.4.7 Risk Assessment ............................................................................ 234 Related Experiments in the Companion Book .................................................... 235 Additional Related Experiments/Activities ....................................................... 236 References and Further Reading .................................................................... 236 10 Physicochemical and Physical Treatment of Pollutants and Wastes ............................. 237 10.1 Physicochemical Processes .......................................................................... 237 10.1.1 Redox Processes ............................................................................ 237 10.1.1.1 Chemical Oxidation and Incineration ...................................... 238 10.1.1.2 Advanced Oxidation Processes (AOP) .................................... 249 10.1.1.3 Chemical Reduction ........................................................... 253 10.1.2 Precipitation/Immobilization, Acid-Base/Hydrolysis, and Ion-Exchange Processes ................................................................... 255 10.1.2.1 Chemical Precipitation/Metal Immobilization ........................... 255 10.1.2.2 Acid-Base/Hydrolysis Processes ........................................... 256 10.1.2.3 Ion Exchange ................................................................... 256 10.1.3 Complexation Processes ................................................................... 258 10.1.3.1 Gaseous Pollutants ............................................................ 258 10.1.3.2 Aqueous Pollutants ............................................................ 258 10.1.3.3 Soil Pollutants .................................................................. 259 10.1.4 Electrochemical Processes ................................................................ 260 10.1.4.1 Direct and Indirect Processes ................................................ 260 Contents xvii 10.1.4.2 Electrochemical Processes Based on Ion Exchange............................................................... 261 10.1.4.3 Electrochemical Treatment of Gases....................................... 261 10.1.4.4 Electrokinetic Treatment of Soils ........................................... 262 10.1.4.5 Electrochemical Production of Water Disinfectants ..................... 263 10.1.4.6 Hybrid Processes that Involve an Electrochemical Step for the Treatment of Aqueous Wastes ............................................... 263 10.1.5 Other Chemical Processes ................................................................. 264 10.1.5.1 Selective Dissolution in CO2 ................................................ 264 10.1.5.2 Extraction with Other Liquefied Gases .................................... 264 10.1.5.3 Extraction with Liquid Solvents (Liquid-Liquid Extraction) ......... 264 10.1.5.4 Catalytic Hydrodechlorination .............................................. 264 10.2 Physical Processes ..................................................................................... 264 10.2.1 Adsorption Processes ...................................................................... 264 10.2.2 Incorporation of Pollutants into Solid Materials ...................................... 265 10.2.2.1 Clay Incorporation ............................................................ 265 10.2.2.2 Supersoaker Materials ........................................................ 265 10.2.2.3 Vitrification ..................................................................... 265 10.2.3 Radiation-Based Processes ................................................................ 265 10.2.3.1 Microwave Energy ............................................................ 265 10.2.3.2 Electron Beams ................................................................ 266 10.2.3.3 Ultrasound ...................................................................... 266 10.2.3.4 Photochemical Methods ...................................................... 266 10.2.4 Methods Based on Magnetic Fields ..................................................... 266 10.2.4.1 Magnetic Treatment ........................................................... 266 10.2.4.2 Magnetic Particles ............................................................. 266 10.2.5 Filtration Methods .......................................................................... 267 10.2.6 Evaporation .................................................................................. 268 10.2.7 Air/Steam Stripping ........................................................................ 268 10.3 Combined Treatments ................................................................................. 268 Related Experiments in the Companion Book .................................................... 269 Additional Related Experiments/Activities ....................................................... 272 References and Further Reading .................................................................... 272 11 Biological Treatment of Pollutants and Wastes ....................................................... 276 11.1 Removal of Pollutants from Wastewater ........................................................... 276 11.1.1 Preliminary Treatment ..................................................................... 276 11.1.2 Primary Treatment .......................................................................... 276 11.1.3 Secondary Treatment ....................................................................... 277 11.1.3.1 Aerobic Processes ............................................................. 277 11.1.3.2 Anaerobic Treatment of Wastewater ....................................... 281 11.1.3.3 Biological Nutrient Removal ................................................ 283 11.1.4 Tertiary Treatment .......................................................................... 287 11.1.5 Chemical and Physical Disinfection ..................................................... 288 11.2 Sludge Treatment Options ............................................................................ 288 11.2.1 Anaerobic Digestion of Sludge ........................................................... 289 11.2.2 Composting .................................................................................. 289 11.2.3 Pasteurization and Drying ................................................................. 289 11.2.4 Lime Stabilization .......................................................................... 289 11.3 Wastewater Reuse ...................................................................................... 290 xviii Contents 11.4 Biological Treatment of Soil and Groundwater .................................................. 290 11.4.1 In Situ Bioremediation ..................................................................... 291 11.4.2 Treatment of Excavated Soils ............................................................. 292 11.4.2.1 Composting ..................................................................... 292 11.4.2.2 Slurry Reactors ................................................................. 292 11.4.3 Treatment Strategies for Aquifers ........................................................ 292 11.4.3.1 Physical Containment ......................................................... 292 11.4.3.2 In Situ Biorestoration ......................................................... 292 11.4.3.3 Above-Ground Bioreactors (Pump-and-Treat Technology) ........... 293 11.4.4 Marine OU Spills ............................................................................ 293 11.5 Biological Treatment of Volatile Compounds .................................................... 294 Related Experiments in the Companion Book .................................................... 295 Additional Related Experiments/Activities ....................................................... 295 References and Further Reading .................................................................... 295 12 The Minimization and Prevention of Pollution; Green Chemistry ............................... 296 12.1 Industrial Ecology ..................................................................................... 296 12.2 Life-Cycle Assessment ............................................................................... 296 12.3 Green Chemistry ....................................................................................... 297 12.3.1 Prevent Waste Production ................................................................. 297 12.3.2 Design Effective, Non-toxic Products ................................................... 298 12.3.3 Design Good Syntheses .................................................................... 298 12.3.4 Use Alternative Feedstock/Starting Materials ........................................ 299 12.3.5 Minimize Waste Using Catalytic Reactions ............................................ 302 12.3.6 Avoid Temporary Modifications ......................................................... 304 12.3.7 Maximize the Use of Starting Materials ................................................ 305 12.3.8 Minimize the Use of Auxiliary Chemicals ............................................. 307 12.3.8.1 Ionic Liquids (Љѕ) ......................................................... 307 12.3.8.2 Fluorous Compounds and Solvents ..................................... 312 12.3.8.3 Supercritical Fluids ........................................................ 313 12.3.8.4 Solventless Reactions ...................................................... 314 12.3.8.5 Aqueous Systems ........................................................... 315 12.3.8.6 Biosolvents .................................................................. 316 12.3.9 Energy Requirements ..................................................................... 316 12.3.9.1 Microwave Radiation ...................................................... 317 12.3.9.2 Green Photochemistry ..................................................... 317 12.3.10 Design Benign Products .................................................................. 318 12.3.10.1 Synthetic Biodegradable Polymers ...................................... 318 12.3.10.2 Starch-Based Biodegradable Plastics ................................... 319 12.3.11 Optimize Monitoring and Control ...................................................... 319 12.3.12 Minimize the Potential for Accidents .................................................. 320 Related Experiments in the Companion Book .................................................... 320 Additional Related Experiments/Activities ....................................................... 320 References and Further Reading .................................................................... 322 Index .................................................................................................................... 325
adam_txt	Contents Foreword . v Preface . vii Part 1 Introductory Concepts 1 Introduction to Environmental Chemistry . 3 1.1 Chemistry of the Natural Processes in the Biosphere . 3 1.2 Chemistry Associated with Pollution Processes . 4 1.3 Chemistry Applied to the Analysis of Pollutants and Natural Compounds . 6 1.4 Chemistry Applied to the Treatment and Remediation of Pollution . 8 1.5 Green Chemistry . 8 1.6 Importance of Environmental Chemistry . 9 References and Further Reading . 10 2 Chemistry Fundamentals, Part A . 11 2.1 Chemical Equilibria . 11 2.1.1 Equilibrium Values and Calculations . 12 2.1.2 Exchange Reaction Equilibria: Systems of the Type МЦ/МЦ.,/ · · · ML/M . 12 2.2 Acid-Base Reactions . 15 2.2.1 Acid-Base Characteristics of Common Chemical Species . 15 2.2.2 Buffers . 16 2.2.3 Acid/Base Character of Oxides . 21 2.3 Redox Processes . 23 2.3.1 Latimer Diagrams . 25 2.3.2 Frost Diagrams . 27 2.3.3 Nernst Equation . 27 2.3.4 Pourbaix Diagrams . 28 2.3.5 The p£ Scale . 33 References and Further Reading . 41 3 Chemistry Fundamentals, Part В . 43 3.1 Complexes and Complex Formation . 43 3.1.1 Definition and Generalities . 43 Contents 3.1.2 Modification of Properties of Metal Ions . 43 3.1.3 Geometry of Metal Complexes . 46 3.1.4 Inner and Outer Sphere Complexes . 47 3.1.5 Mono and Polydentate Ligands. The HSAB Approach . 48 3.1.6 The Chelate Effect . 48 3.1.7 Reactions of Complexes . 50 3.1.7.1 Ligand-Exchange Reactions . 50 3.1.7.2 Electron-Exchange Reactions . 50 3.2 Chemical Kinetics . 51 3.2.1 Factors That Influence the Rate of a Mono Directional Reaction . 52 3.2.1.1 Dependence of the Rate of Reaction on Concentrations: The Rate Law . 53 3.2.1.2 The Rate Constant . 54 3.2.2 Integrated Rate Equations . 54 3.2.2.1 Zeroth-Order Reactions . 54 3.2.2.2 First-Order Reactions . 54 3.2.2.3 Second-Order Reactions . 55 3.2.2.4 Higher-Order Reactions . 55 3.2.3 Complex Reactions . 55 3.2.3.1 Consecutive Reactions . 56 3.2.3.2 Opposing (Reversible) Reactions . 56 3.2.3.3 Parallel Reactions . 57 3.2.4 The Steady-State Approximation . 57 3.2.5 Catalysis . 57 3.2.6 Kinetics of Metal-Complex Dissociation . 58 3.3 Photochemical Processes . 59 3.3.1 Photochemical Processes After the Absorption of Light . 59 3.3.2 BeeťsLaw . 60 3.3.3 Homogeneous and Heterogeneous Processes . 61 3.4 Radiochemistry . 61 3.4.1 Decay Kinetics . 62 3.4.2 Units of Radiation . 63 3.4.3 Detection Devices for Ionizing Radiations and Protection From Radiation . 64 3.4.3.1 Geiger Counter or Ionization in Gas-Filled Tubes . 64 3.4.3.2 Scintillation Device . 64 3.4.3.3 Photographic Films . 64 3.4.3.4 Semiconductors . 64 3.4.3.5 Thermoluminescence . 64 References and Further Reading . 64 Part 2 The Chemistry of Natural Environmental Processes 4 The Chemistry of Processes in the Atmosphere . 69 4.1 Air . 69 4.2 How Did the Earth"s Atmosphere Form? . 70 4.3 Amounts of Constituents in the Atmosphere . 71 4.4 Tropospheric Chemistry . 73 4.5 Physical Principles of the Greenhouse Effect . 74 4.6 Stratospheric Chemistry . 75 4.7 Aerosols . 76 Related Experiments in the Companion Book . 76 Contents Additional Related Experiments/Activities . 76 References and Further Reading . 77 The Chemistry of Processes in the Lithosphère . 78 5.1 The Lithosphère and its Components . 78 5.1.1 Structure of the Solid Earth . 78 5.1.1.1 Core . 78 5.1.1.2 Mantle . 78 5.1.1.3 Crust . 78 5.1.2 Classification of Rocks . 79 5.1.2.1 Igneous Rocks . 79 5.1.2.2 Sedimentary Rocks . 79 5.1.2.3 Metamorphic Rocks . 80 5.1.2.4 Rock-Forming Minerals . 80 5.2 Formation and Differentiation of Minerals and Ores . 80 5.3 Weathering . 81 5.3.1 Physical Weathering . 81 5.3.2 Chemical Weathering . 82 5.3.2.1 Dissolution and Precipitation of Solids . 85 5.3.2.2 Dissolution of Natural Oxides . 89 5.3.2.3 Stable and Metastable Solid Phases . 90 5.3.3 Biological Weathering . 92 5.4 Soil Characteristics . 92 5.4.1 Soil Taxonomy . 93 5.4.2 Humic Substances (HS). 93 5.4.3 Decomposition of Organic Materials Adsorbed on Soil . 93 Related Experiments in the Companion Book . 93 Additional Related Experiments/Activities . 94 References and Further Reading . 94 6 The Chemistry of Processes in the Hydrosphere . 96 6.1 Natural Waters: Types and Composition . 96 6.1.1 Processes That Affect Water Composition . 96 6.1.2 Rainwater . 98 6.1.3 Surface Water . 99 6.1.3.1 Stream and River Water . 101 6.1.3.2 Lake Water . 103 6.1.4 Groundwater . 1 05 6.1.5 Seawater . 106 6.1.6 Brackish/Saline Water . 107 6.2 Interactions of Water with Air and Sediments; Effects on 10 10 10 Aquatic Chemistry . 6.2.1 Gas Dissolution and Acidification of Natural Waters. 6.2.1.1 Henry's Law . 6.2.1.2 Dissolved Oxygen in Water. 6.2.1.3 Dissolution of CO2 in Water. 6.2.2 Interactions between Water and Sediments/Soil . 6.3 Physicochemical Processes in Aquatic Systems . 6.3.1 Chemical Processes in Aquatic Systems 6.3.1.1 Acid-Base Reactions. 13 14 15 15 16 Contents 6.3.1.2 Redox Reactions . 119 6.3.1.3 Complex Formation . 122 6.3.1.4 Speciation . 122 6.3.1.5 Colloids: Properties, Types, Sources, and Formation . 124 6.3.1.6 Photochemical Reactions . 126 6.3.2 Natural Removal of Species from Aqueous Systems by Chemical and Physical Processes . 128 6.3.2.1 Sorption onto Colloidal, Suspended, or Settled Sediments . 128 6.3.2.2 Ion Exchange in Sediments and in Aqueous Colloidal and Suspended Matter . 129 6.3.2.3 Precipitation Reactions and Co-precipitation . 131 6.3.2.4 Solidification and Deposition Processes Due to Evaporation . 131 6.3.2.5 Colloidal and Sediment Transport into Surface Water . 131 6.3.2.6 Volatilization of Organic and Inorganic Compounds . 132 Related Experiments in the Companion Book . 132 Additional Related Experiments/Activities . 135 References and Further Reading . 135 Natural Biochemical Processes and Organisms in the Biosphere . 137 7.1 Classification of Living Organisms . 137 7.2 Nutritional Classification of Organisms . 140 7.3 Basic Aspects of Ecology . 142 7.3.1 The Habitats of Life: Air, Land, and Water . 143 7.3.1.1 Atmosphere . 143 7.3.1.2 Land . 143 7.3.1.3 Water . 144 7.3.2 Trophic Levels . 145 7.3.3 Non-feeding Relations Among Species . 146 7.3.4 Sustainability of Ecosystems . 147 7.4 Biogeochemical Cycles . 148 7.4.1 Water Cycle . 148 7.4.2 Hydrogen Cycle . 148 7.4.3 Carbon Cycle . 149 7.4.4 Oxygen Cycle . 150 7.4.5 Nitrogen Cycle . 152 7.4.5.1 Fixation . 152 7.4.5.2 Ammonification . 153 7.4.5.3 Nitrification . 154 7.4.5.4 Nitrate Reduction and Denitrification . 154 7.4.6 Sulfur Cycle . 155 7.4.6.1 Sulfur Mineralization . 155 7.4.6.2 Oxidation of Sulfide and of Elemental Sulfur . 156 7.4.6.3 Dissimilatory Sulfate or Sulfur Reduction . 157 7.4.6.4 Assimilatory Sulfate Reduction or Sulfur Immobilization . 157 7.4.7 Phosphorus Cycle . 157 7.4.8 Iron Cycle . 159 7.4.9 Interrelations Among Cycles . 160 Contents Related Experiments in the Companion Book. 161 Additional Related Experiments/Activities . 162 References and Further Reading . 162 Part 3 Effects, Treatment and Prevention of Pollution 8 Effects of Pollutants on the Chemistry of the Atmosphere, Hydrosphere, and Lithosphère . 167 8.1 Importance of the Manufacture and Use of Chemical Substances . 167 8.2 Sources of Chemical Substances as Contaminants and Pollutants . 167 8.3 Transport, Mobility, and Partition of Pollutants . 169 8.4 Air, Water, and Soil Pollution and Their Effects . 173 8.4.1 Effects of Pollutants on the Atmosphere . 173 8.4.1.1 Main Air Pollutants . 173 8.4.1.2 Combustion Processes as the Main Air Pollution Source . 175 8.4.1.3 The Greenhouse Effect . 176 8.4.1.4 Smog Formation . 176 8.4.1.5 Stratospheric Ozone Destruction or the Ozone Hole . 177 8.4.1.6 Acid Rain . 178 8.4.1.7 Indoor Pollution . 179 8.4.2 Effects of Pollutants on the Hydrosphere . 180 8.4.2.1 Oxygen-Demanding Materials . 180 8.4.2.2 Nutrients . 182 8.4.2.3 Pathogenic Organisms . 183 8.4.2.4 Suspended Solids . 183 8.4.2.5 Oil and Grease Spills . 184 8.4.2.6 Metallic and Metalloid Compounds . 185 8.4.2.7 Radionuclides . 185 8.4.2.8 Detergents (Surfactants) and Nutrient Enrichment . 185 8.4.2.9 Salts . 186 8.4.2.10 Heat . 186 8.4.2.11 Other Contributions . 187 8.4.2.12 Groundwater Pollution . 187 8.4.2.13 Surface Waters . 187 8.4.3 Effects of Pollutants on the Lithosphère . 187 8.4.3.1 Transformation of Pollutants in Soils . 187 8.4.3.2 Transport, Mobility, and Partitioning of Pollutants in Soils . 188 8.4.3.3 Agriculture and the Chemistry of Soils . 188 8.4.3.4 Metals and Mining Processes . 189 8.4.3.5 Other Wastes and Pollutants in Soil . 190 Related Experiments in the Companion Book . 190 Additional Related Experiments/Activities . 191 References and Further Reading . 196 9 Effects of Pollutants on the Biosphere: Biodegradability, Toxicity, and Risks . 198 9.1 Types of Pollutants According to Their Capacity to Undergo Biotransformation . 198 9.1.1 Biodegradable Substances and Biodegradation Processes . 198 9.1.2 Biotic Transformation Reactions . 199 9.1.3 Recalcitrance and Recalcitrant Compounds . 204 xv¡ Contents 9.2 Hazardous and Non-hazardous Substances or Pollutants . 207 9.2.1 Classification of Hazardous Substances . 208 9.2.2 Toxicity and Related Definitions . 208 9.2.3 Factors That Affect the Toxicity of Chemical Substances . 208 9.3 Human Health Risk Assessment . 220 9.3.1 Hazard Identification . 221 9.3.2 Dose-Response Assessment . 222 9.3.2.1 Non-carcinogenic Risk Assessment . 223 9.3.2.2 Cancer Risk Assessment . 224 9.3.3 Exposure Assessment . 226 9.3.4 Risk Characterization . 226 9.3.5 Risk Management . 227 9.4 Ecotoxicology . 228 9.4.1 Methods of Ecotoxicology . 229 9.4.1.1 Toxic Endpoints. 230 9.4.1.2 Bioassays . 230 9.4.2 Ecotoxicity Determination . 231 9.4.2.1 Short-Time Toxicity Tests . 231 9.4.2.2 Long-Term Toxicity Tests . 231 9.4.3 Bioconcentration, Bioaccumulation, and Biomagnification . 232 9.4.4 Biomarkers and Bioindicators . 233 9.4.5 In Situ Monitoring . 233 9.4.6 Ecological Risk Assessment . 234 9.4.6.1 Characterization of the Baseline Ecology and Identification of Potential Receptor Populations . 234 9.4.6.2 Ecological Toxicity Assessment . 234 9.4.6.3 Evaluation of Potential Exposures . 234 9.4.6.4 Risk Characterization . 234 9.4.7 Risk Assessment . 234 Related Experiments in the Companion Book . 235 Additional Related Experiments/Activities . 236 References and Further Reading . 236 10 Physicochemical and Physical Treatment of Pollutants and Wastes . 237 10.1 Physicochemical Processes . 237 10.1.1 Redox Processes . 237 10.1.1.1 Chemical Oxidation and Incineration . 238 10.1.1.2 Advanced Oxidation Processes (AOP) . 249 10.1.1.3 Chemical Reduction . 253 10.1.2 Precipitation/Immobilization, Acid-Base/Hydrolysis, and Ion-Exchange Processes . 255 10.1.2.1 Chemical Precipitation/Metal Immobilization . 255 10.1.2.2 Acid-Base/Hydrolysis Processes . 256 10.1.2.3 Ion Exchange . 256 10.1.3 Complexation Processes . 258 10.1.3.1 Gaseous Pollutants . 258 10.1.3.2 Aqueous Pollutants . 258 10.1.3.3 Soil Pollutants . 259 10.1.4 Electrochemical Processes . 260 10.1.4.1 Direct and Indirect Processes . 260 Contents xvii 10.1.4.2 Electrochemical Processes Based on Ion Exchange. 261 10.1.4.3 Electrochemical Treatment of Gases. 261 10.1.4.4 Electrokinetic Treatment of Soils . 262 10.1.4.5 Electrochemical Production of Water Disinfectants . 263 10.1.4.6 Hybrid Processes that Involve an Electrochemical Step for the Treatment of Aqueous Wastes . 263 10.1.5 Other Chemical Processes . 264 10.1.5.1 Selective Dissolution in CO2 . 264 10.1.5.2 Extraction with Other Liquefied Gases . 264 10.1.5.3 Extraction with Liquid Solvents (Liquid-Liquid Extraction) . 264 10.1.5.4 Catalytic Hydrodechlorination . 264 10.2 Physical Processes . 264 10.2.1 Adsorption Processes . 264 10.2.2 Incorporation of Pollutants into Solid Materials . 265 10.2.2.1 Clay Incorporation . 265 10.2.2.2 Supersoaker Materials . 265 10.2.2.3 Vitrification . 265 10.2.3 Radiation-Based Processes . 265 10.2.3.1 Microwave Energy . 265 10.2.3.2 Electron Beams . 266 10.2.3.3 Ultrasound . 266 10.2.3.4 Photochemical Methods . 266 10.2.4 Methods Based on Magnetic Fields . 266 10.2.4.1 Magnetic Treatment . 266 10.2.4.2 Magnetic Particles . 266 10.2.5 Filtration Methods . 267 10.2.6 Evaporation . 268 10.2.7 Air/Steam Stripping . 268 10.3 Combined Treatments . 268 Related Experiments in the Companion Book . 269 Additional Related Experiments/Activities . 272 References and Further Reading . 272 11 Biological Treatment of Pollutants and Wastes . 276 11.1 Removal of Pollutants from Wastewater . 276 11.1.1 Preliminary Treatment . 276 11.1.2 Primary Treatment . 276 11.1.3 Secondary Treatment . 277 11.1.3.1 Aerobic Processes . 277 11.1.3.2 Anaerobic Treatment of Wastewater . 281 11.1.3.3 Biological Nutrient Removal . 283 11.1.4 Tertiary Treatment . 287 11.1.5 Chemical and Physical Disinfection . 288 11.2 Sludge Treatment Options . 288 11.2.1 Anaerobic Digestion of Sludge . 289 11.2.2 Composting . 289 11.2.3 Pasteurization and Drying . 289 11.2.4 Lime Stabilization . 289 11.3 Wastewater Reuse . 290 xviii Contents 11.4 Biological Treatment of Soil and Groundwater . 290 11.4.1 In Situ Bioremediation . 291 11.4.2 Treatment of Excavated Soils . 292 11.4.2.1 Composting . 292 11.4.2.2 Slurry Reactors . 292 11.4.3 Treatment Strategies for Aquifers . 292 11.4.3.1 Physical Containment . 292 11.4.3.2 In Situ Biorestoration . 292 11.4.3.3 Above-Ground Bioreactors (Pump-and-Treat Technology) . 293 11.4.4 Marine OU Spills . 293 11.5 Biological Treatment of Volatile Compounds . 294 Related Experiments in the Companion Book . 295 Additional Related Experiments/Activities . 295 References and Further Reading . 295 12 The Minimization and Prevention of Pollution; Green Chemistry . 296 12.1 Industrial Ecology . 296 12.2 Life-Cycle Assessment . 296 12.3 Green Chemistry . 297 12.3.1 Prevent Waste Production . 297 12.3.2 Design Effective, Non-toxic Products . 298 12.3.3 Design Good Syntheses . 298 12.3.4 Use Alternative Feedstock/Starting Materials . 299 12.3.5 Minimize Waste Using Catalytic Reactions . 302 12.3.6 Avoid Temporary Modifications . 304 12.3.7 Maximize the Use of Starting Materials . 305 12.3.8 Minimize the Use of Auxiliary Chemicals . 307 12.3.8.1 Ionic Liquids (Љѕ) . 307 12.3.8.2 Fluorous Compounds and Solvents . 312 12.3.8.3 Supercritical Fluids . 313 12.3.8.4 Solventless Reactions . 314 12.3.8.5 Aqueous Systems . 315 12.3.8.6 Biosolvents . 316 12.3.9 Energy Requirements . 316 12.3.9.1 Microwave Radiation . 317 12.3.9.2 Green Photochemistry . 317 12.3.10 Design Benign Products . 318 12.3.10.1 Synthetic Biodegradable Polymers . 318 12.3.10.2 Starch-Based Biodegradable Plastics . 319 12.3.11 Optimize Monitoring and Control . 319 12.3.12 Minimize the Potential for Accidents . 320 Related Experiments in the Companion Book . 320 Additional Related Experiments/Activities . 320 References and Further Reading . 322 Index . 325
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title	Environmental chemistry fundamentals
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