Environmental Chemistry Book

Foreword     v
Preface     vii
Introductory Concepts
Introduction to Environmental Chemistry     3
Chemistry of the Natural Processes in the Biosphere     3
Chemistry Associated with Pollution Processes     4
Chemistry Applied to the Analysis of Pollutants and Natural Compounds     6
Chemistry Applied to the Treatment and Remediation of Pollution     8
Green Chemistry     8
Importance of Environmental Chemistry     9
References and Further Reading     10
Chemistry Fundamentals, Part A     11
Chemical Equilibria     11
Equilibrium Values and Calculations     12
Exchange Reaction Equilibria: Systems of the Type ML[subscript n]/ML[subscript n-1]/...ML/M     12
Acid-Base Reactions     15
Acid-Base Characteristics of Common Chemical Species     15
Buffers     16
Acid/Base Character of Oxides     21
Redox Processes     23
Latimer Diagrams     25
Frost Diagrams     27
Nernst Equation     27
Pourbaix Diagrams     28
The pE Scale     33
References and Further Reading     41
Chemistry Fundamentals, PartB     43
Complexes and Complex Formation     43
Definition and Generalities     43
Modification of Properties of Metal Ions     43
Geometry of Metal Complexes     46
Inner and Outer Sphere Complexes     47
Mono and Polydentate Ligands. The HSAB Approach     48
The Chelate Effect     48
Reactions of Complexes     50
Ligand-Exchange Reactions     50
Electron-Exchange Reactions     50
Chemical Kinetics     51
Factors That Influence the Rate of a Mono Directional Reaction     52
Dependence of the Rate of Reaction on Concentrations: The Rate Law     53
The Rate Constant     54
Integrated Rate Equations     54
Zeroth-Order Reactions     54
First-Order Reactions     54
Second-Order Reactions     55
Higher-Order Reactions     55
Complex Reactions     55
Consecutive Reactions     56
Opposing (Reversible) Reactions     56
Parallel Reactions     57
The Steady-State Approximation     57
Catalysis     57
Kinetics of Metal-Complex Dissociation     58
Photochemical Processes     59
Photochemical Processes After the Absorption of Light     59
Beer's Law     60
Homogeneous and Heterogeneous Processes     61
Radiochemistry     61
Decay Kinetics     62
Units of Radiation     63
Detection Devices for Ionizing Radiations and Protection From Radiation     64
Geiger Counter or Ionization in Gas-Filled Tubes     64
Scintillation Device     64
Photographic Films     64
Semiconductors     64
Thermoluminescence     64
References and Further Reading     64
The Chemistry of Natural Environmental Processes
The Chemistry of Processes in the Atmosphere     69
Air     69
How Did the Earth's Atmosphere Form?     70
Amounts of Constituents in the Atmosphere     71
Tropospheric Chemistry     73
Physical Principles of the Greenhouse Effect     74
Stratospheric Chemistry     75
Aerosols     76
Related Experiments in the Companion Book     76
Additional Related Experiments/Activities     76
References and Further Reading     77
The Chemistry of Processes in the Lithosphere      78
The Lithosphere and its Components     78
Structure of the Solid Earth     78
Core     78
Mantle     78
Crust     78
Classification of Rocks     79
Igneous Rocks     79
Sedimentary Rocks     79
Metamorphic Rocks     80
Rock-Forming Minerals     80
Formation and Differentiation of Minerals and Ores     80
Weathering     81
Physical Weathering     81
Chemical Weathering     82
Dissolution and Precipitation of Solids     85
Dissolution of Natural Oxides     89
Stable and Metastable Solid Phases     90
Biological Weathering     92
Soil Characteristics     92
Soil Taxonomy     93
Humic Substances (HS)     93
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
The Chemistry of Processes in the Hydrosphere     96
Natural Waters: Types and Composition     96
Processes That Affect Water Composition      96
Rainwater     98
Surface Water     99
Stream and River Water     101
Lake Water     103
Groundwater     105
Seawater     106
Brackish/Saline Water     107
Interactions of Water with Air and Sediments; Effects on Aquatic Chemistry     110
Gas Dissolution and Acidification of Natural Waters     110
Henry's Law     110
Dissolved Oxygen in Water     111
Dissolution of CO[subscript 2] in Water     113
Interactions between Water and Sediments/Soil     114
Physicochemical Processes in Aquatic Systems     115
Chemical Processes in Aquatic Systems     115
Acid-Base Reactions     116
Redox Reactions     119
Complex Formation     122
Speciation     122
Colloids: Properties, Types, Sources, and Formation     124
Photochemical Reactions     126
Natural Removal of Species from Aqueous Systems by Chemical and Physical Processes     128
Sorption onto Colloidal, Suspended, or Settled Sediments     128
Ion Exchange in Sediments and in Aqueous Colloidal and Suspended Matter     129
Precipitation Reactions and Co-precipitation     131
Solidification and Deposition Processes Due to Evaporation     131
Colloidal and Sediment Transport into Surface Water     131
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
Classification of Living Organisms     137
Nutritional Classification of Organisms     140
Basic Aspects of Ecology     142
The Habitats of Life: Air, Land, and Water     143
Atmosphere     143
Land     143
Water     144
Trophic Levels     145
Non-feeding Relations Among Species     146
Sustainability of Ecosystems     147
Biogeochemical Cycles     148
Water Cycle     148
Hydrogen Cycle     148
Carbon Cycle     149
Oxygen Cycle     150
Nitrogen Cycle     152
Fixation     152
Ammonification     153
Nitrification     154
Nitrate Reduction and Denitrification     154
Sulfur Cycle     155
Sulfur Mineralization     155
Oxidation of Sulfide and of Elemental Sulfur     156
Dissimilatory Sulfate or Sulfur Reduction     157
Assimilatory Sulfate Reduction or Sulfur Immobilization     157
Phosphorus Cycle     157
Iron Cycle     159
Interrelations Among Cycles     160
Related Experiments in the Companion Book     161
Additional Related Experiments/Activities     162
References and Further Reading     162
Effects, Treatment and Prevention of Pollution
Effects of Pollutants on the Chemistry of the Atmosphere, Hydrosphere, and Lithosphere     167
Importance of the Manufacture and Use of Chemical Substances     167
Sources of Chemical Substances as Contaminants and Pollutants     167
Transport, Mobility, and Partition of Pollutants     169
Air, Water, and Soil Pollution and Their Effects     173
Effects of Pollutants on the Atmosphere     173
Main Air Pollutants     173
Combustion Processes as the Main Air Pollution Source     175
The Greenhouse Effect     176
Smog Formation     176
Stratospheric Ozone Destruction or the Ozone Hole      177
Acid Rain     178
Indoor Pollution     179
Effects of Pollutants on the Hydrosphere     180
Oxygen-Demanding Materials     180
Nutrients     182
Pathogenic Organisms     183
Suspended Solids     183
Oil and Grease Spills     184
Metallic and Metalloid Compounds     185
Radionuclides     185
Detergents (Surfactants) and Nutrient Enrichment     185
Salts     186
Heat     186
Other Contributions     187
Groundwater Pollution     187
Surface Waters     187
Effects of Pollutants on the Lithosphere     187
Transformation of Pollutants in Soils     187
Transport, Mobility, and Partitioning of Pollutants in Soils     188
Agriculture and the Chemistry of Soils     188
Metals and Mining Processes     189
Other Wastes and Pollutants in Soil     190
Related Experiments in the Companion Book     190
Additional Related Experiments/Activities     191
References and Further Reading     196
Effects of Pollutants on the Biosphere: Biodegradability, Toxicity, and Risks      198
Types of Pollutants According to Their Capacity to Undergo Biotransformation     198
Biodegradable Substances and Biodegradation Processes     198
Biotic Transformation Reactions     199
Recalcitrance and Recalcitrant Compounds     204
Hazardous and Non-hazardous Substances or Pollutants     207
Classification of Hazardous Substances     208
Toxicity and Related Definitions     208
Factors That Affect the Toxicity of Chemical Substances     208
Human Health Risk Assessment     220
Hazard Identification     221
Dose-Response Assessment     222
Non-carcinogenic Risk Assessment     223
Cancer Risk Assessment     224
Exposure Assessment     226
Risk Characterization     226
Risk Management     227
Ecotoxicology     228
Methods of Ecotoxicology     229
Toxic Endpoints     230
Bioassays     230
Ecotoxicity Determination     231
Short-Time Toxicity Tests     231
Long-Term Toxicity Tests     231
Bioconcentration, Bioaccumulation, and Biomagnification     232
Biomarkers and Bioindicators     233
In Situ Monitoring     233
Ecological Risk Assessment     234
Characterization of the Baseline Ecology and Identification of Potential Receptor Populations     234
Ecological Toxicity Assessment     234
Evaluation of Potential Exposures     234
Risk Characterization     234
Risk Assessment     234
Related Experiments in the Companion Book     235
Additional Related Experiments/Activities     236
References and Further Reading     236
Physicochemical and Physical Treatment of Pollutants and Wastes     237
Physicochemical Processes     237
Redox Processes     237
Chemical Oxidation and Incineration     238
Advanced Oxidation Processes (AOP)     249
Chemical Reduction     253
Precipitation/Immobilization, Acid-Base/Hydrolysis, and Ion-Exchange Processes     255
Chemical Precipitation/Metal Immobilization     255
Acid-Base/Hydrolysis Processes     256
Ion Exchange     256
Complexation Processes     258
Gaseous Pollutants     258
Aqueous Pollutants     258
Soil Pollutants     259
Electrochemical Processes     260
Direct and Indirect Processes     260
Electrochemical Processes Based on Ion Exchange     261
Electrochemical Treatment of Gases     261
Electrokinetic Treatment of Soils     262
Electrochemical Production of Water Disinfectants     263
Hybrid Processes that Involve an Electrochemical Step for the Treatment of Aqueous Wastes     263
Other Chemical Processes     264
Selective Dissolution in CO[subscript 2]     264
Extraction with Other Liquefied Gases     264
Extraction with Liquid Solvents (Liquid-Liquid Extraction)     264
Catalytic Hydrodechlorination     264
Physical Processes     264
Adsorption Processes     264
Incorporation of Pollutants into Solid Materials     265
Clay Incorporation     265
Supersoaker Materials     265
Vitrification     265
Radiation-Based Processes     265
Microwave Energy     265
Electron Beams     266
Ultrasound     266
Photochemical Methods     266
Methods Based on Magnetic Fields     266
Magnetic Treatment     266
Magnetic Particles     266
Filtration Methods      267
Evaporation     268
Air/Steam Stripping     268
Combined Treatments     268
Related Experiments in the Companion Book     269
Additional Related Experiments/Activities     272
References and Further Reading     272
Biological Treatment of Pollutants and Wastes     276
Removal of Pollutants from Wastewater     276
Preliminary Treatment     276
Primary Treatment     276
Secondary Treatment     277
Aerobic Processes     277
Anaerobic Treatment of Wastewater     281
Biological Nutrient Removal     283
Tertiary Treatment     287
Chemical and Physical Disinfection     288
Sludge Treatment Options     288
Anaerobic Digestion of Sludge     289
Composting     289
Pasteurization and Drying     289
Lime Stabilization     289
Wastewater Reuse     290
Biological Treatment of Soil and Groundwater     290
In Situ Bioremediation     291
Treatment of Excavated Soils     292
Composting     292
Slurry Reactors     292
Treatment Strategies for Aquifers      292
Physical Containment     292
In Situ Biorestoration     292
Above-Ground Bioreactors (Pump-and-Treat Technology)     293
Marine Oil Spills     293
Biological Treatment of Volatile Compounds     294
Related Experiments in the Companion Book     295
Additional Related Experiments/Activities     295
References and Further Reading     295
The Minimization and Prevention of Pollution; Green Chemistry     296
Industrial Ecology     296
Life-Cycle Assessment     296
Green Chemistry     297
Prevent Waste Production     297
Design Effective, Non-toxic Products     298
Design Good Syntheses     298
Use Alternative Feedstock/ Starting Materials     299
Minimize Waste Using Catalytic Reactions     302
Avoid Temporary Modifications     304
Maximize the Use of Starting Materials     305
Minimize the Use of Auxiliary Chemicals     307
Ionic Liquids (ILs)     307
Fluorous Compounds and Solvents     312
Supercritical Fluids     313
Solventless Reactions     314
Aqueous Systems     315
Biosolvents      316
Energy Requirements     316
Microwave Radiation     317
Green Photochemistry     317
Design Benign Products     318
Synthetic Biodegradable Polymers     318
Starch-Based Biodegradable Plastics     319
Optimize Monitoring and Control     319
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