ENVIRONMENTAL CHEMISTRY AND TOXICOLOGICAL. Fundamentals of. Sustainable Science. Stanley E. Manahan. Fourth Edition

Transcription

1 Fourth Edition Fundamentals of ENVIRONMENTAL AND TOXICOLOGICAL CHEMISTRY Sustainable Science Stanley E. Manahan /Os CRC Press VCJ*- J Taylor & Francis Group Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business

2 Contents Preface Author xxi xxiii Chapter 1 Environmental Chemistry and the Five Spheres of the Environment What Is Environmental Chemistry? Environmental Relationships in Environmental Chemistry Environmental Spheres and Biogeochemical Cycles Earth's Natural Capital Environmental Chemistry and Green Chemistry As We Enter into the Anthropocene 8 Questions and Problems 10 Literature Cited 11 Supplementary References 11 Chapter 2 Fundamentals of Biochemistry and Toxicological Chemistry Life Chemical Processes Biochemistry and the Cell Carbohydrates Proteins Lipids: Fats, Oils, and Hormones Nucleic Acids Enzymes Effects of Toxic Substances on Enzymes Biochemical Processes in Metabolism Energy-Yielding and Processing Processes Toxic Substances, Toxicology, and Toxicological Chemistry Exposure to Toxic Substances Distribution of Toxic Substances Dose-Response Relationship Toxicities Toxicological Chemistry Reactions of Toxicants and Protoxicants in Living Systems Kinetic Phase of Xenobiotic Metabolism Dynamic Phase of Toxicant Action Mutagenesis and Carcinogenesis Mutations from Chemical Exposure Carcinogenesis Developmental Effects and Teratogenesis Toxic Effects on the Immune System Damage to the Endocrine System Health Hazards of Toxic Substances Health Risk Assessment Structure-Activity Relationships in Toxicological Chemistry 36

3 vi Contents 2.19 Toxicological Chemistry and Ecotoxicology Effects of Toxicants on Ecosystems Biomarkers of Exposure to Toxic Substances Toxic Agents That May Be Used in Terrorist Attacks 38 Questions and Problems 39 Literature Cited 40 Supplementary References 40 Chapter 3 Environmental and Toxicological Chemistry of the Hydrosphere H20: Simple Formula, Remarkable Molecule Hydrosphere Occurrence of Water Standing Bodies of Water Flowing Water Sedimentation by Flowing Water Groundwater Water Supply and Availability Life and Its Influence on Environmental Chemistry in the Hydrosphere Aquatic Organisms and Chemical Transitions in the Hydrosphere Microbial Action on Organic Matter in the Hydrosphere Environmental Chemistry of the Hydrosphere Acid-Base Phenomena in the Hydrosphere Carbon Dioxide in Water Solubility and Phase Interactions Gas Solubilities Carbon Dioxide and Carbonate Species in Water Sediments Col loids in Water Oxidation Reduction pe and Toxicological Chemistry Metal Ions in Water Calcium and Hardness in Water Complexation and Speciation of Metals Toxicological Chemistry in the Hydrosphere Chemical Interactions with Organisms in the Hydrosphere Biodegradation in the Hydrosphere 70 Questions and Problems 72 Literature Cited 73 Supplementary References 73 Chapter 4 Pollution of the Hydrosphere Nature and Types of Water Pollutants Markers of Water Pollution Elemental Pollutants Heavy Metals Cadmium Lead Mercury 78

4 Contents vii 4.4 Metalloids Organically Bound Metals Organotin Compounds Inorganic Species as Water Pollutants Cyanide Ammonia and Other Inorganic Water Pollutants Asbestos in Water Algal Nutrients and Eutrophication Acidity, Alkalinity, and Salinity Oxygen, Oxidants, and Reductants Organic Pollutants Sewage Soaps and Detergents Naturally Occurring Chlorinated and Brominated Compounds Microbial Toxins Pesticides in Water Natural Product Insecticides, Pyrethrins, and Pyrethroids DDT and Organochlorine Insecticides Organophosphate Insecticides Carbamates Fungicides Herbicides By-Products of Pesticide Manufacture Polychlorinated Biphenyls Emerging Water Pollutants, Pharmaceuticals, and Household Wastes Bactericides Estrogenic Substances in Wastewater Effluents Biorefractory Organic Pollutants Radionuclides in the Aquatic Environment Toxicological Chemistry and Water Pollution 110 Questions and Problems Ill Literature Cited 114 Supplementary References 114 Chapter 5 Sustaining the Hydrosphere More Important than Oil Greening of Water: Purification before and after Use Emerging Considerations in Water Treatment Municipal Water Treatment Contamination in Water Distribution Systems Treatment of Water for Industrial Use Wastewater Treatment Industrial Wastewater Treatment Removal of Solids Dissolved Air Flotation Removal of Calcium and Other Metals Removal of Iron and Manganese Removal of Heavy Metals Arsenic Removal 127

5 viii Contents 5.8 Removal of Dissolved Organics Removal of Herbicides Removal of Taste, Odor, and Color Photolysis Sonolysis Removal of Dissolved Inorganics Ion Exchange Phosphorus Removal Nitrogen Removal Membrane Processes and Reverse Osmosis for Water Purification Reverse Osmosis Electrodialysis Water Disinfection Pathogens Treated by Disinfection Disinfection Agents Disinfection with Chlorine and Chloramines Chlorine Dioxide Toxicities of Chlorine and Chlorine Dioxide Green Ozone for Water Disinfection Ozone Toxicity Miscellaneous Disinfection Agents Restoration of Wastewater Quality Primary Wastewater Treatment Secondary Waste Treatment by Biological Processes Tertiary Waste Treatment Physical-Chemical Treatment of Municipal Wastewater Natural Water Pu rification Processes Industrial Wastewater Treatment by Soil Sludges and Residues from Water Treatment Water, the Greenest Substance on Earth: Reuse and Recycling Water Conservation Rainwater Harvesting 149 Questions and Problems 149 Literature Cited 152 Supplementary References 152 Chapter 6 Environmental and Toxicological Chemistry of the Atmosphere Atmosphere: Air to Breathe and Much More Regions of the Atmosphere Atmospheric Composition Natural Capital of the Atmosphere Energy and Mass Transfer in the Atmosphere Meteorology, Weather, and Climate Global Weather Atmospheric Inversions and Atmospheric Chemical Phenomena Climate, Microclimate, and Microatmosphere Human Modifications of the Atmosphere Microclimate Effects of Urbanization on Microclimate Microatmosphere 167

6 Contents 6.9 Atmospheric Chemistry and Photochemical Reactions Atmospheric Ions and the Ionosphere Atmospheric Oxygen Toxicological Chemistry of Oxygen Atmospheric Nitrogen Atmospheric Water Atmospheric Particles Physical Behavior of Atmospheric Particles Atmospheric Chemical Reactions Involving Particles 176 Questions and Problems 177 Literature Cited 178 Supplementary References 179 Chapter 7 Pollution of the Atmosphere Pollution of the Atmosphere and Air Quality Pollutant Particles in the Atmosphere Physical and Chemical Processes for Particle Formation: Dispersion and Condensation Aerosols Chemical Processes for Inorganic Particle Formation Composition of Inorganic Particles Fly Ash Radioactivity in Atmospheric Particles Organic Pollutant Particles in the Atmosphere Effects of Atmospheric Pollutant Particles Health Effects and Toxicology of Particles Asian Brown Cloud: Climate and Health Effects Inorganic Gas Pollutants Nitrogen Oxide Air Pollutants Toxic Effects of Nitrogen Oxides Sulfur Dioxide Air Pollution Toxic Effects of Sulfur Dioxide Toxic Effects of Atmospheric Sulfuric Acid Acid-Base Reactions in the Atmosphere and Acid Rain Organic Air Pollutants Organics in the Atmosphere from Natural Sources Pollutant Hydrocarbons from the Anthrosphere Nonhydrocarbon Organics in the Atmosphere Organohalides Toxicological Chemistry of Organohalides Organosulfur Compounds Organonitrogen Compounds Toxicological Chemistry of Organonitrogen Compounds Photochemical Smog Harmful Effects of Smog Toxic Effects of Smog and Its Constituents to Humans Chlorofluorocarbons and Stratospheric Ozone Depletion Chlorofluorocarbons and Stratospheric Ozone Depletion Antarctic Ozone Hole Nobel Prize in Environmental Chemistry 209

7 X Contents 7.10 Indoor Air Pollution and the Microatmosphere 209 Questions and Problems 210 Literature Cited 211 Supplementary References 212 Chapter 8 Sustaining the Atmosphere: Blue Skies for a Green Earth Preserving the Atmosphere Preservation of the Atmosphere's Natural Capital Greatest Threat: Global Climate Warming Increasing Temperature Passing the Tipping Points Loss of Ice Cover Glaciers and Water Supply Expansion of Subtropical Arid Regions and Drought Some Other Effects of Global Climate Change Dealing with Global Climate Change Mitigation and Minimization of Greenhouse Gas Emissions Less Carbon Dioxide from Internal Combusti on Engines Transportation Alternatives to the Internal Combustion Engine Heating and Cooling Carbon Capture Avoiding Fossil Fuels Avoiding Greenhouse Gases Other than Carbon Dioxide Economic and Political Measures Counteracting Measures Adaptation Heat Drought Water Banking Control of Particle Emissions Particle Removal by Sedimentation and Inertia Particle Filtration Scrubbers Electrostatic Precipitation Where Does It All Go? Control of Carbon Monoxide Emissions Control of Nitrogen Oxide Emissions Control of Sulfur Dioxide Emissions Control of Hydrocarbon Emissions and Photochemical Smog Compression-Fired Engines Catalytic Converters for Exhaust Gas Control Photochemical Smog and Vegetation Preventing Smog with Green Chemistry Biological Control of Air Pollution Bioreactors for Air Pollutant Removal Removing Air Pollution with Vegetation Controlling Acid Rain Dealing with Toxic and Other Adverse Effects of Acid Rain 238

8 Contents x' 8.11 Limiting Stratospheric Ozone Depletion 238 Questions and Problems 239 Literature Cited 241 Supplementary References 241 Chapter 9 Environmental and Toxicological Chemistry of the Geosphere Geosphere Geosphere Related to the Other Environmental Spheres Plate Tectonics Rock Cycle Chemical Composition of the Geosphere and Geochemistry Biological Aspects of Weathering Geosphere as a Source of Natural Capital Environmental Hazards of the Geosphere Volcanoes Toxicological and Public Health Aspects of Volcanoes Earthquakes Toxicological and Public Health Aspects of Earthquakes Surface Effects Radon, a Toxic Gas from the Geosphere Water in and on the Geosphere Geospheric 9.6 Anthrospheric Influences on the Geosphere 257 Water and Health Effects Geosphere as a Waste Repository 258 Questions and Problems 260 Literature Cited 261 Supplementary References 261 Chapter 10 Soil: A Critical Part of the Geosphere Have You Thanked a Clod Today? What Is Soil? Inorganic Solids in Soil Soil Organic Matter Water in Soil and the Soil Solution Chemical Exchange Processes in Soil Plant Nutrients and Fertilizers in Soil Soil and Plants Related to Wastes and Pollutants Soil Loss: Desertification and Deforestation Toxicological and Public Health Aspects of Soil Toxicological Aspects of Soil Herbicides Toxicological Considerations in Livestock Production 273 Questions and Problems 274 Literature Cited 275 Supplementary References 275 Chapter 11 Sustaining the Geosphere Managing the Geosphere for Sustainability Sustaining the Geosphere in the Face of Natural Hazards Vulnerable Coasts Threat of Rising Sea Levels 280

9 xii Contents 11.3 Sustainable Development on the Geosphere's Surface Site Evaluation Kinds of Structures on the Geosphere Digging in the Dirt Subsurface Excavations Green Underground Storage Salt Dome Storage Extraction of Materials from Earth Environmental Effects of Mining and Mineral Extraction Sustainable Utilization of Geospheric Mineral Resources Metals Nonmetal Mineral Resources How Long Will Essential Minerals Last? Green Sources of Minerals Exploitation of Lower Grade Ores Mining the Ocean Floors Waste Mining Recycling Toxicological Implications of Mineral Mining and Processing Pneumoconiosis from Exposure to Mineral Dust Heavy Metal Poisoning Sustaining the Geosphere to Manage Water China's Three Gorges Dam Project Water Pollution and the Geosphere Waste Disposal and the Geosphere Municipal Refuse Hazardous Waste Disposal Derelict Lands and Brownfields Land Restoration from the Fukushima Daiichi Nuclear Accident Sustaining Soil Biochar for Soil Conservation and Enrichment Reversing Desertification Reforestation Water and Soil Conservation 305 Questions and Problems 306 Literature Cited 307 Supplementary References 307 Chapter 12 Environmental and Toxicological Chemistry of the Biosphere Life and the Biosphere Biosphere in Stabilizing the Earth System: Gaia Hypothesis Organisms and Sustainable Science and Technology Life Systems Biosphere/Atmosphere Interface and the Crucial Importance of Climate Metabolism and Control in Organisms Enzymes in Metabolism Nutrients Control in Organisms 315

10 Contents xiii 12.5 Reproduction arid Inherited Traits Stability and Equilibrium of the Biosphere Biomes in Unexpected Places Response of Life Systems to Stress Relationships among Organisms Populations DNA and the Human Genome Biological Interaction with Environmental Chemicals Biodegradation Effects of the Anthrosphere on the Biosphere Beneficial Effects of Humans on the Biosphere 322 Questions and Problems 323 Literature Cited 324 Supplementary References 324 Chapter 13 Sustaining the Biosphere and Its Natural Capital Keeping 13.2 Natural Capital of the Biosphere 325 Life Alive Types of Biomaterials from the Biosphere Biorefineries Using the Biosphere through Agriculture Genome Sequencing and Green Chemistry Genetic Engineering Recombinant DNA and Genetic Engineering Major Transgenic Crops and Their Characteristics Crops versus Pests Future Crops Role of Human Activities in Preserving and Enhancing the Biosphere Artificial Habitats and Habitat Restoration Preserving the Biosphere by Preserving the Atmosphere Preserving the Biosphere by Preserving the Hydrosphere Preserving the Biosphere by Preserving the Geosphere Constructing the Geosphere to Support the Biosphere: What the Ancient Incas Knew 340 Questions and Problems 340 Literature Cited 341 Supplementary References 342 Chapter 14 Environmental and Toxicological Chemistry of the Anthrosphere Anthrosphere Crucial Anthrospheric Infrastructure Sociosphere Industrial Ecology and Industrial Ecosystems Kalundborg Industrial Ecosystem Metabolic Processes in Industrial Ecosystems Attributes of Successful Industrial Ecosystems Diversity Life Cycles in Industrial Ecosystems Product Stewardship 354

11 xiv Contents 14.5 Kinds of Products Environmental Impacts of the Anthrosphere Impact of Agricultural Production Design of Industrial Ecosystems to Minimize Impact Green Chemistry and the Anthrosphere Presidential Green Chemistry Challenge Awards Predicting and Reducing Hazards with Green Chemistry Atom Economy and the E Factor in Green Chemistry Yield and Atom Economy Nature of Wastes Catalysts and Catalysis in Green Chemistry Biocatalysis with Enzymes Immobilized Enzyme Catalysts Reduction in Synthesis Steps with Enzyme Catalysts Enzyme Catalysts and Chirality Energizing Chemical Reactions and Process Intensification Process Intensification and Increased Safety with Smaller Size Solvents and Alternate Reaction Media Water Solvent Carbon Dioxide Solvent Ionic Liquid Solvents Feedstocks and Reagents Feedstocks Reagents Reagents for Oxidation and Reduction Electrons as Reagents for Oxidation and Reduction Anthrosphere and Occupational Health Role of Green Chemistry in Occupational Health 377 Questions and Problems 377 Literature Cited 379 Supplementary References 379 Chapter 15 Anthrosphere, Pollution, and Wastes Wastes from the Anthrosphere History of Hazardous Substances Pesticide Burial Grounds Legislation Classification of Hazardous Substances and Wastes Characteristics and Listed Wastes Hazardous Wastes and Air and Water Pollution Control Sources of Wastes Types of Hazardous Wastes Hazardous Waste Generators Flammable and Combustible Substances Combustion of Finely Divided Particles Oxidizers Spontaneous Ignition Toxic Products of Combustion 389

12 Contents xv 15.5 Reactive Substances Chemical Structure and Reactivity Corrosive Substances Sulfuric Acid Toxic Substances Physical Forms and Segregation of Wastes Environmental Chemistry of Hazardous Wastes Transport, Effects, and Fates of Hazardous Wastes Physical Properties of Wastes Chemical Factors Environmental Effects of Hazardous Wastes Fates of Hazardous Wastes Hazardous Wastes and the Anthrosphere Hazardous Wastes in the Geosphere Hazardous Wastes in the Hydrosphere Hazardous Wastes in the Atmosphere Hazardous Wastes in the Biosphere Microbial Metabolism in Waste Degradation Hazardous Substances and Environmental Health and Safety 405 Questions and Problems 405 Literature Cited 407 Supplementary References 407 Chapter 16 Industrial Ecology and Green Chemistry for Sustainable Management of the Anthrosphere Managing the Anthrosphere for Sustainability Feeding the Anthrosphere Utilization of Feedstocks Key Feedstock: Abundant Elemental Hydrogen from Sustainable Sources Feedstocks from the Geosphere Occupational and Public Health Aspects of Mining Toxic Hazards of Cyanide in Gold Recovery Biological Feedstocks Monosaccharide Feedstocks: Glucose and Fructose Hydrocarbons and Similar Materials from Sugars Cellulose Feedstocks from Cellulose Wastes Lignin Biosynthesis of Chemicals Fermentation and Industrial Microbiology Metabolic Engineering and Chemical Biosynthesis Production of Materials by Plants Direct Biosynthesis of Polymers Biorefineries and Biomass Utilization Green Chemistry and Industrial Ecology in Waste Management Recycling Waste Oil Utilization and Recovery Waste Solvent Recovery and Recycling Recovery of Water from Wastewater 432

13 (Vi Contents Hazardous Waste Treatment Processes Methods of Physical Treatment Chemical Treatment Electrolysis Hydrolysis Chemical Extraction and Leaching Ion Exchange Photolytic Reactions Thermal Treatment Methods Incineration Effectiveness of Incineration Hazardous Waste Fuel Biodegradation of Hazardous Wastes Oxic and Anoxic Waste Biodegradation Land Treatment and Composting Preparation of Wastes for Disposal Ultimate Disposal of Wastes Leachate and Gas Emissions In Situ Treatment of Disposed Hazardous Wastes Treatment In Situ Questions and Problems Literature Cited Supplementary References Chapter 17 Sustainable Energy: The Key to Everything Energy Problem 17.2 Nature of Energy Sustainable Energy: Away from the Sun and Back Again The Brief Era of Fossil Fuels Back to the Sun 17.4 Sources of Energy Used in the Anthrosphere: Present and Future 17.5 Energy Devices and Conversions Fuel Cells Green Technology and Energy Conversion Efficiency Energy Conservation and Renewable Energy Sources Petroleum Hydrocarbons and Natural Gas Liquids Heavy Oil Shale Oil Natural Gas Liquids Natural Gas Coal Coal Conversion Carbon Sequestration for Fossil Fuel Utilization Great Plains Synfuels Plant: Industrial Ecology in Practice to Produce Energy and Chemicals Nuclear Energy Thorium-Fueled Reactors Nuclear Fusion Geothermal Energy

14 Contents xvii Sun: An Ideal, Renewable Energy Source Solar Photovoltaic Energy Systems Artificial Photosynthesis for Capturing Solar Energy Energy from Earth's Two Great Fluids in Motion Surprising Success of Wind Power Energy from Moving Water Energy from Moving Water without Dams Biomass Energy: An Overview of Biofuels and Their Resources Processing of Biofuel to More Compact Forms Decarbonization with Biomass Utilization Conversion of Biomass to Other Fuels EthanolFuel Biodiesel Fuel Fuel from Algae Unrealized Potential of Lignocellulose Fuels Chemical Conversion of Biomass to Synthetic Fuels Biogas Biorefineries and Systems of Industrial Ecology for Utilizing Biomass System of Industrial Ecology for Methane Production from Renewable Sources Hydrogen as a Means to Store and Utilize Energy Combined Power Cycles Environmental Health Aspects of Energy Production and Utilization Coal Petroleum and Natural Gas Nuclear Energy 501 Questions and Problems 502 Literature Cited 504 Supplementary References 505 Chapter 18 Analytical Chemistry and Industrial Hygiene Analytical Chemistry Industrial Hygiene and Analytical Chemistry What Is Industrial Hygiene? Laws and Regulations Pertaining to Occupational Safety and Health Categories of Workplace Hazards Chemical Hazards Exposure Limits Workplace Sampling and Personal Monitoring Chemical Analysis Process Major Categories of Chemical Analysis Error and Treatment of Data Gravimetric Analysis Volumetric Analysis: Titration Spectrophotometric Methods of Analysis 516

15 xviii Contents Absorption Spectrophotometry Atomic Absorption and Emission Analyses Atomic Emission Techniques Electrochemical Methods of Analysis Chromatography High-Performance Liquid Chromatography Ion Chromatography Chromatography-Based Methods of Analysis for Water Pollutants Mass Spectrometry Automated Analyses Immunoassay Screening Total Organic Carbon in Water Measurement of Radioactivity in Water Analysis of Wastes and Solids Toxicity Characteristic Leaching Procedure Atmospheric Monitoring Methods for Sampling and Analyzing Atmospheric Pollutants Determination of Atmospheric Sulfur Dioxide by the West-Gaeke Method Atmospheric Particulate Matter Nitrogen Oxides in the Atmosphere Determination of Atmospheric Oxidants Atmospheric Carbon Monoxide by Infrared Absorption Determination of Hydrocarbons and Organics in the Atmosphere Direct Spectrophotometric Analysis of Gaseous Air Pollutants Analysis of Biological Materials and Xenobiotics Indicators of Exposure to Xenobiotics Immunological Methods of Xenobiotics Analysis 534 Questions and Problems 534 Literature Cited 535 Supplementary References 536 Chapter 19 Fundamentals of Chemistry Science of Matter States of Matter Gases and the Gas Laws Elements Subatomic Particles and Atoms Atom Nucleus and Electron Cloud Isotopes Important Elements Periodic Table Electrons in Atoms Lewis Structures and Symbols of Atoms Metals, Nonmetals, and Metalloids 546

16 Contents XIX 19.3 Chemical Bonding Chemical Compounds Molecular Structure Summary of Chemical Compounds and the Ionic Bond Molecular Mass Mole and Molar Mass Oxidation State Chemical Reactions and Equations Reaction Rates Solutions Solution Concentration Water as a Solvent Solutions of Acids, Bases, and Salts Concentration of H+ Ion and ph Metal Ions Dissolved in Water Complex Ions Dissolved in Water Colloidal Suspensions Solution Equilibria Distribution between Phases 556 Questions and Problems 556 Literature Cited 559 Supplementary References 559 Chapter 20 Organic Chemistry Organic Chemistry Molecular Geometry in Organic Chemistry Chirality and the Shapes of Organic Molecules Hydrocarbons Alkanes Alkenes Aromatic Hydrocarbons Using Lines to Show Structural Formulas Functional Groups Organooxygen Compounds Organonitrogen Compounds Organohalide Compounds Organosulfur and Organophosphorus Compounds Giant Molecules from Small Organic Molecules 572 Questions and Problems 574 Supplementary References 576 Index 577