Principles of Environmental Geochemistry

Description

Many geochemists focus on natural systems with less emphasis on the human impact on those systems. Environmental chemists frequently approach their subject with less consideration of the historical record than geoscientists. The field of environmental geochemistry combines these approaches to address questions about the natural environment and anthropogenic effects on it. Eby provides students with a solid foundation in basic aqueous geochemistry before discussing the important role carbon compounds, isotopes, and minerals play in environmental issues. He then guides students through how these concepts apply to problems facing our atmosphere, continental lands, and oceans. Rather than broadly discussing a variety of environmental problems, the author focuses on principles throughout the text, leading students to understand processes and how knowledge of those processes can be applied to environmental problem solving. A wide variety of case studies and quantitative problems accompany each chapter, giving each instructor the flexibility to tailor the material to his/her course. Many problems have no single correct answer, illustrating the analytical nature of solving real-world environmental problems. Not-for-sale instructor's resource materials available online to college and university faculty only; contact publisher directly. Cover Contents Preface Chapter 1: Basic Principles The Atom The Bohr Atom Beyond the Bohr Atom - Quantum Mechanics Ionization and Valences Spectra and Elemental Analysis The Nucelus Chemical Bonding Atomic and Molecular Weights Measurement of Concentration Types of Chemical Reactions Determining and Balancing a Chemical Equation Gases Structure and Properties of Water Box Models and Geochemical Cycles Questions and Problems Chapter 2: Equilibrium Thermodynamics and Kinetics The Laws of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Equilibrium Thermodynamics Free Energy Chemical Potential Activity and Fugacity The Equilibrium Constant Henry's Law Free Energies at Temperatures Other than 25°C Le Chatelier's Principle Changes in Concentration Changes in Pressure Changes in Temperature Calculation of Activity-Coefficient Debye-Hückel Model Truesdell-Jones Model Pitzer Model Why Do We Care about Activity-Coefficient Modelss? Calculation of Activity Coefficients for Uncharged Species Activity of Water Aqueous Complexes Measurement of Disequilbrium Kinetics Order of Reactions The Arrhenius Equation Nucleation Dissolution and Growth Water-Chemistry Computer Models Case Studies Questions and Problems Chapter 3: Acid-Base Equilibria Definition of Acids and Bases Acids Bases The Dissociation of Water and pH pH of Natural Waters Strong Acids Weak Acids Acetic Acid Carbonic Acid Silicic Acid Carbonic Acid-Carbonate System Salts of Weak Acids and Strong Bases Strong Bases Amphoteric Hydroxides Acidity and Alkalinity Acidity and Alkalinity Titrations Buffers Buffering Index for H2O Buffering Index for a Weak Monoprotic Acid Buffering Index for a Weak Polyprotic Acids Mineral-Water Reactions Buffering Index for the Calcite-Carbonic Acid System Buffering Index for the Water-Silicate Mineral Systems Buffering Capacities of Natural Waters Mineral Reactivity Acid-Base Equilibria Case Studies Questions and Problems Chapter 4: Oxidation-Reduction Reactions Basic Principles Electrochemical Cells Electromotive Series Electromotive Force Balancing Oxidation-Reduction Equations The Nernst Equation and Eh Oxidation-Reduction Reactions and pe Oxidation-Reduction Diagrams Stability of Water Constructing Eh-pH Diagrams The Iron Eh-pH Diagram The Nitrogen Eh-pH Diagram The Role of Microorganisms in Oxidation-Reduction Reactions Microorganisms and Energy Pathways Examples of Oxidation-Reduction Reactions Mediated by Microorganisms Oxidation-Reduction Processes in Natural Systems Redox Buffering Classification of Oxidation-Reduction Environments Oxidative and Reductive Capacity Oxidation-Reduction Ladders The Redox Interface Questions and Problems Chapter 5: Carbon Chemistry Basic Structures and Naming of Organic Compounds Formulas Isomers Hydrocarbons Naming and Types of Hydrocarbon Compounds Alkanes Alkenes and Alkynes Cyclic Hydrocarbons Aromatic (Aryl) Hydrocarbons Polycyclic Aromatic Hydrocarbons (PAH) Functional Groups Organohalide Compounds Organooxygen Compounds Organonitrogen Compounds Organsulfer Compounds Organophosphorus Compounds Esters Polymers Carbon Compounds in the Environment Natural Sources Anthropogenic Sources Humic Substances Soil and Marine Organic Matter Soil Organic Matter Marine Organic Matter Fossil Fuels Coals Petroleum Natural Carbon Inputs to Surface and Ground Waters Anthropogenic Carbon Inputs to Surface and Ground Waters Organic Carbon Pesticides Dioxins, PCBs, and Dibenzofurans (DFs) PAHs NAPLs Geochemical and Biochemical Processes That Control the Concentration or Oganic Chemicals in Water Sorption/Partition Precipitation Volatilization Oxidation-Reduction Biolgical Processes Degradation Half-life Questions and Problems Chapter 6: Isotopes Radioactive Isotopes Basic Principles Radioactive Decay and Growth Measurement of Radioactivity Radioactive Isotopes Used in Environmental Studies Tritium Dating Carbon-14 Dating U-series Disequilibrium Methods of Dating ²³⁰Th Dating of Marine Sediments ²³⁰Th/²³²Th Dating of Marine Sediments ²³⁰Th/²³¹Pa Dating of Marine Sediments Activity and Sedimentation-Rate Relationships ²³⁰Th/²³⁴U Dating of Calcium Carbonate Who Do We Want to Date Marine Sediments and Carbonate Minerals? ²¹⁰Pb Dating Radiogenic Isotopic Tracers Rb-Sr System Th-U-Pb Isotopic Systems Stable Isotopes Basic Principles Stable Isotope Fractionation Fractionation Factor The ẟ (Delta) Notation Oxygen and Hydrogen Isotopes in Water Factors Affecting the Isotopic Composition of Water Climate Change Carbon DIC in Aqueous Systems Sources in Methane DOC in Aqueous Systems Tracers in Food Chains Nitrogen Nitrates in Surface and Ground Waters NH₄⁺ and NO₃⁻ in Rain Sulfur Mixing Binary Isotopic Mixing Multi-End-Member Mixing of Chemical Species Paleothermometry Questions and Problems Chapter 7: Environmental Mineralogy Basic Mineralogy Definition of a Mineral Types of Minerals Crystal Chemistry Types of Bonding Coordination Numbers Ionic Substitutions X-ray Crystallography Basic Silicate Structures Clay Minerals Clay Mineral Structures 1:1 Clays 2:1 Clays Ion-Exchange Properties-Origin Suface Charge Surface Area Ion-Exchange Properties - Determination Batch Method Adsorption Isotherms Column Test Method Zeolites The Asbestos Minerals Crystal Structures of Asbestos Minerals Types of Asbestos and Their Uses Health Effects of Asbestos Exposure Dissolution of Fibers Chemistry of Exposed Fiber Surface Surface Charge Biological Interactions Determining the Effect of Asbestos Exposure Crystalline and Amorphous Silica Dissolution of Silica Minerals Health Effects of Silica Exposure Mineral-Microorganism Interactions Questions and Problems Chapter 8: The Atmospheric Environment Properties of the Earth's Atmosphere Structure and Composition of the Atmosphere Solar and Terrestrial Radiation Atmospheric Circulation Temperature and Water Vapor Variations Air Pollution Types of Air Pollutants Aerosols Smogs Greenhouse Gases and Climate Change Greenhouse Gases Carbon Dioxide (CO₂) Methane (CH₄) Nitrous Oxide (N₂O) Climate Change and the Geologic Record Ice Cores Sediment Record Ozone Stratospheric Ozone Ozone-Destroying Reactions Kinetic Considerations The Antartic Ozone Hole Tropospheric Ozone Radon Rainwater Chemistry Ionic Species Gaseous Species National Atmospheric Deposition Program (NADP) pH of Rainwater and Acid Rain Chemistry and Sources of Atmospheric Particulates (Aerosols) Types of Particulates Mineral Dust Sea Salt Sulfates Carbonaceous Particles Removal of Particulates from the Atmosphere Dry Deposition Wet Deposition Particulate Sampling Air Mass Trajectories Source Identification and Apportionment Enrichment Factor Elemental Signatures Molecular Signatures Isotopic Signatures - Pb Isotopic Signatures - C Temporal Variations in Particulate Compositions Questions and Problems Chapter 9: The Continental Environment The Hydrologic Cycle Weathering Dissolution and Precipitation of Silica Dissolution and Precipitation of Aluminum and Iron Hydroxides Stability Diagrams Geochemistry of Surfaces and Ground Waters Variations in River and Groundwater Graphical Representations of Water Chemistry Hydrofacies Rivers Groundwaters Lakes Structure and Mixing of Lake Waters Lake (Box) Models pH of Surface and Ground Waters Carbonic Acid Systems Water - Mineral Interactions Adsorption - Desorption Processes Adsorption of Metal Cations Colloids Isotherms and Partitioning of Species Ion Exchange Adsorption and Contaminant Transport Complex Formation and Chelation Metals Metal Cycles Natural Anthropogenic Acid Drainage Heavy Metals Transition metals, Zn, Cd, and Pb Selective Extraction Arsenic and Selenium Mercury Metal Variations in Space and Time Metal Contamination of Soils and Sediments Radioactive Isotopes and Radioactive Waste Disposal Nuclear Fuel Cycle Nuclear Fission Mobility and Sequestering of Radioactive Isotopes in the Surface Environment The Okli Fossil Fission Reactors Nonmetals Carbon Halogens Fluorine Cl⁻ and Br⁻ Nitrogen Phosphorus Sulfur Questions and Problems Chapter 10: The Marine Environment Physical Aspects of the Open Ocean Vertical Structure of the Ocean Ocean Circulation Surface Currents Upwelling and Downwelling Thermohaline Circulation Constancy of Composition and Salinity Chemical Composition of the Open Ocean Residence Time of Seawater Species The Global Chemical Cycle for Seawater Species Processes Controlling Seawater Composition Biological Controls on Seawater Composition Seawater - Sediment Interactions Seawater - Basalt Interactions Summary of Processes Controlling Seawater Composition Seawater Chemistry Seawater Alkalinity and Dissolved Inorganic Carbon (DIC) Seawater pH Speciation and Stoichiometric Equilibrium Constants Seawater Buffers and Buffering Capacity Inorganic and Organic Ligands in Seawater Inorganic Ligands Organic Ligands Trace Metals in Marine Colloids Trace Metals in Seawater Sources of Trace Metals Removal of Trace Metals from the Ocean Types of Metal Distributions Conservative-Type Distributions Nutrient-Type Distributions Surface-Water Enrichments Mid-Depth Maxima and Minima Determination of Scavenging Rates Sediment Traps Radioactivity Measurements Geochemistry of Marine Sediments Distribution of Deep-Sea Sediments Siliceous Sediments Calcareous Sediments Authigenesis in Marine Sediments Age of Seafloor Sediments Methane Hydrates The Marginal Marine Environment Estuaries Water Circulation in Semi-Isolated Basins Evaporation Greater than Precipitation Precipitation Greater than Evaporation Flushing Time Water Column Chemistry Equilbrium Constants Adsorption-Desportion Redox Reactions Suspended Particulate matter (SPM) Pore Water Chemistry Release of Metals to Pore Waters and the Water Column Transport of Metals in Pore Waters Removal of Metals from Pore Waters Sediment Chemistry Sediment Age and Accumulation Rate Redox Indicators Metal Indicators Bioindicators Organic Contaminants Questions and Problems References Appendix I: Electronic Structure and Valences of the Elements Appendix II: Standard State Thermodynamic Data Appendix III: Ionic Radii in A for Different Charges and Coordination Numbers Appendix IV: Piper Diagram for Water Chemistry Problems Answers to Selected Problems Index Credits