Kevin Henke is a research scientist at the Centre for Applied Energy Research at the University of Kentucky. He has a M.S. and? Ph.D. in Geology from the University of North Dakota. His research includes investigating water and air quality issues related to coal combustion, studying the impact of mercury and other heavy metals on water quality, and investigating the leaching of inorganics from coal combustion by-products. He is also visiting Assistant Professor of Geology, Department of Geological Sciences, University of Kentucky, Lexington (1998, 2000-2002) and has taught geochemistry, mineralogy, teaching methods courses, and undergraduate introductory courses in environmental geology, natural resources and physical geology. Professor David A. Atwood, is based in the Chemistry Department of the University of Kentucky. He obtained his B.S. from the University of Alabama and his Ph.D. from the University of Texas in 1992. Research in the Atwood group is designed to address both fundamental and applied aspects of the main group metals. Professor Atwood's teaching includes courses in solid-state materials including biomineralization. Dr Lisa Blue is a graduate student based in the chemistry department of the University of Kentucky.

• List of contributors xvPreface xvii1. Introduction 1Kevin R. Henke1.1 Arsenic origin, chemistry, and use 11.2 Arsenic environmental impacts 21.3 Arsenic toxicity 31.4 Arsenic treatment and remediation 31.4.1 Introduction 31.4.2 Treatment and remediation of water 41.4.3 Treatment and remediation of solid wastes, soils, and sediments 41.4.4 Treatment of flue gases 5References 52. Arsenic Chemistry 9Kevin R. Henke and Aaron Hutchison2.1 Introduction 92.2 Atomic structure and isotopes of arsenic 92.3 Arsenic valence state and bonding 102.4 Chemistry of arsenic solids 132.4.1 Elemental arsenic 132.4.2 Common arsenic minerals and other solid arsenic compounds 152.4.3 Arsine and other volatile arsenic compounds 242.4.4 Organoarsenicals 242.5 Introduction to arsenic oxidation and reduction 262.5.1 Arsenic oxidation 262.5.2 Arsenic reduction 272.6 Introduction to arsenic methylation and demethylation 282.7 Arsenic in water 302.7.1 Introduction 302.7.2 Aqueous solubility of arsenic compounds and thermodynamics 312.7.3 Dissolved arsenic species 402.7.4 Dissociation of arsenious and arsenic acids 422.7.5 Eh-pH diagrams, and their limitations 452.7.6 Sorption, ion exchange, precipitation, and coprecipitation of arsenic in water 462.8 Chemistry of gaseous arsenic emissions 57References 593 Arsenic in Natural Environments 69Kevin R. Henke3.1 Introduction 693.2 Nucleosynthesis: the origin of arsenic 703.2.1 The Big Bang 703.2.2 Arsenic formation in stars 703.3 Arsenic in the universe as a whole 733.4 Arsenic chemistry of the solar system 733.4.1 Arsenic in the Sun, Moon, and planets 733.4.2 Arsenic in meteorites and tektites 743.5 Arsenic in the bulk Earth, crusts, and interior 773.5.1 Estimating arsenic concentrations of the bulk Earth and the Earth’s core and mantle 773.5.2 The core 783.5.3 The mantle 783.5.4 The Earth’s crusts 793.6 Arsenic in hydrothermal and geothermal fluids and their deposits 823.6.1 Introduction 823.6.2 Origins of hydrothermal fluids and their arsenic 833.6.3 Arsenic chemistry of hydrothermal fluids 853.6.4 Arsenic mineralogy of hydrothermal deposits 913.6.5 Surface and near-surface oxidation of hydrothermal arsenic 933.6.6 Arsenic chemistry in hot springs 943.6.7 Arsenic in geothermal power plant scales 953.6.8 Arsenic in volcanic gas emissions 963.6.9 Environmental impacts of arsenic in hydrothermal and geothermal fluids 963.7 Oxidation of arsenic-bearing sulfides in geologic materials and mining wastes 973.7.1 Oxidation of sulfide minerals 973.7.2 Factors influencing the oxidation of arsenic-bearing sulfide minerals 973.7.3 Environmental consequences of sulfide and arsenic oxidation 993.7.4 Oxidation chemistry of major arsenic-bearing sulfides 1023.8 Interactions between arsenic and natural organic matter (NOM) 1063.9 Sorption and coprecipitation of arsenic with iron and other (oxy)(hydr)oxides 1063.9.1 Introduction 1063.9.2 Iron, aluminum, and manganese (oxy)(hydr)oxides 1073.9.3 Sulfate (oxy)(hydr)oxides and related compounds 1083.10 Arsenate (inorganic As(V)) precipitation 1103.11 Reductive dissolution of iron and manganese (oxy)(hydr)oxides 1103.12 Arsenic and sulfide at < 50 ◦c 1143.13 Arsenic and its chemistry in mined materials 1153.13.1 Environmental issues with arsenic-bearing sulfide minerals in coal and ore deposits 1153.13.2 Behavior of arsenic within mining wastes 1153.13.3 Movement of arsenic from mining wastes and into the environment 1163.14 Marine waters and sediments 1173.14.1 Inorganic arsenic in seawater 1173.14.2 Marine arsenic cycle 1203.14.3 Arsenic methylation in marine environments 1213.14.4 Arsenic in marine sediments 1213.15 Estuaries 1223.15.1 Arsenic in estuaries 1223.15.2 Seasonal effects on arsenic in estuaries 1253.15.3 Arsenic in pristine estuaries 1253.15.4 Arsenic in contaminated estuaries 1263.16 Rivers and other streams 1273.17 Lakes 1363.18 Wetlands 1453.19 Groundwater 1463.19.1 Subsurface water and groundwater 1463.19.2 Impacts of arsenic contamination in shallow (< 1 km deep) groundwaters 1483.19.3 ‘Dissolved’ and particulate arsenic in groundwater 1483.19.4 Arsenic mobility in groundwater 1483.19.5 Sources of arsenic contamination in groundwater 1493.19.6 Arsenic chemistry in groundwater 1613.20 Glacial ice and related sediments 1623.21 Arsenic in air and wind-blown sediments 1633.21.1 Arsenic emission sources 1633.21.2 Arsenic atmospheric chemistry 1653.21.3 Arsenic in precipitation 1663.21.4 Arsenic in atmospheric dust 1663.21.5 Arsenic in wind-blown sediment deposits (loess) 1683.21.6 Arsenic in soil and sediment gases 1683.22 Petroleum 1683.23 Soils 1693.23.1 Distinguishing between soils and sediments 1693.23.2 Arsenic chemistry in soils 1713.23.3 Soil porewater chemistry 1783.24 Sedimentary rocks 1783.24.1 Diagenesis and sedimentary rocks 1783.24.2 Coal 1803.24.3 Shales and oil shales 1903.24.4 Other sedimentary rocks 1953.25 Metamorphic rocks 196References 198Further reading 2354 Toxicology and Epidemiology of Arsenic and its Compounds 237Michael F. Hughes, David J. Thomas, and Elaina M. Kenyon4.1 Introduction 2374.2 Physical and chemical properties of arsenic 2384.3 Exposure to arsenic 2384.4 Arsenic disposition and biotransformation in mammals 2404.4.1 Introduction 2404.4.2 Respiratory deposition and absorption 2404.4.3 Gastrointestinal absorption 2414.4.4 Dermal absorption 2424.5 Systemic clearance of arsenic and binding to blood components 2434.6 Tissue distribution 2444.7 Placental transfer and distribution in the fetus 2464.8 Arsenic biotransformation 2474.8.1 Introduction 2474.8.2 Arsenic methylation in humans and other mammals 2484.8.3 Significance of arsenic methylation 2484.8.4 Molecular basis of the metabolism of inorganic arsenic 2484.8.5 Reconciling experimental data and the Challenger scheme 2514.9 Arsenic excretion 2524.10 Effects of arsenic exposure 2534.10.1 Acute exposure 2534.10.2 Chronic exposure 2544.11 Cardiovascular 2544.11.1 Introduction 2544.11.2 Peripheral vascular disease 2554.11.3 Ischemic heart disease 2554.11.4 Cerebrovascular disease 2554.11.5 Atherosclerosis 2554.11.6 Hypertension 2564.12 Endocrine 2564.13 Hepatic 2574.14 Neurological 2574.15 Skin 2574.16 Developmental 2584.17 Other organ systems 2584.18 Cancer 2594.18.1 Introduction 2594.18.2 Skin 2594.18.3 Lung 2604.18.4 Bladder 2604.19 Animal models for arsenic-induced cancer 2604.20 Mechanism of action 2614.20.1 Introduction 2614.20.2 Replacement of phosphate 2624.20.3 Enzyme inhibition 2624.20.4 Oxidative stress 2624.20.5 Genotoxicity 2634.20.6 Alteration of DNA repair 2634.20.7 Signal transduction 2634.20.8 Gene transcription 2634.20.9 DNA methylation 2644.20.10 Growth factors 2644.21 Regulation of arsenic 264References 2655 Arsenic in Human History and Modern Societies 277Kevin R. Henke and David A. Atwood5.1 Introduction 2775.2 Early recognition and uses of arsenic by humans 2785.3 Alchemy, development of methods to recover elemental arsenic, and the synthesis of arsenic compounds 2795.4 Applications with arsenic 2795.4.1 Medicinal applications: dangerous quackery and some important drugs 2795.4.2 Pesticides and agricultural applications 2805.4.3 Chemical weapons 2825.4.4 Embalming fluids 2825.4.5 Paints and dyes 2835.4.6 Wood treatment 2845.4.7 Semiconductors 2865.5 Increasing health, safety, and environmental concerns 2865.6 Arsenic in crime 2875.7 Poisoning controversies: Napoleon Bonaparte 2885.8 Arsenic in prospecting, mining, and markets 2895.8.1 Arsenic as a pathfinder element in prospecting 2895.8.2 Arsenic mining, production, and market trends 2905.9 Arsenic in coal and oil shale utilization and their by-products 2915.9.1 Coal cleaning and combustion 2915.9.2 Arsenic behavior during combustion 2915.9.3 Postcombustion flue gas treatment 2955.9.4 Arsenic chemistry in coal combustion byproducts 2955.9.5 Coal gasification 2965.9.6 Oil shale utilization 296References 2976 Major Occurrences of Elevated Arsenic in Groundwater and Other Natural Waters 303Abhijit Mukherjee, Alan E. Fryar, and Bethany M. O’Shea6.1 Introduction 3036.2 Arsenic speciation and mobility in natural waters 3046.3 Immobilization of arsenic in hydrologic systems 3046.3.1 Precipitation, coprecipitation, and association with sulfides 3046.3.2 Arsenic sorption on metal (oxy)(hydr)oxides 3056.3.3 Arsenic sorption on clay minerals 3066.3.4 Carbonate interactions 3066.4 Mobilization of arsenic in water 3096.4.1 Competitive anion exchange 3096.4.2 Effect of natural organic matter (NOM) 3106.4.3 Effect of pH 3106.4.4 Redox-dependent mobilization 3116.4.5 Complex and colloid formation 3116.5 Natural occurrences of elevated arsenic around the world 3136.5.1 Introduction 3136.5.2 Bengal basin, India and Bangladesh 3176.5.3 Middle Ganges Plain, India 3246.5.4 Donargarh rift belt, Chattisgarh, central India 3266.5.5 Terai alluvial plain, Nepal 3266.5.6 Indus alluvial system, Pakistan 3276.5.7 Irrawaddy delta, Myanmar 3286.5.8 Mekong plain and delta, Cambodia, Vietnam, and Laos 3286.5.9 Red River delta, Vietnam 3316.5.10 Yellow River plains, Inner Mongolia, China 3326.5.11 Taiwan 3336.5.12 Coastal aquifers of Australia 3346.5.13 Sedimentary basins and basement complexes of West Africa 3346.5.14 Western USA 3356.5.15 New England, USA 3366.5.16 Northern Chile 3376.5.17 Chaco and Pampa plains of Argentina 338References 3397 Waste Treatment and Remediation Technologies for Arsenic 351Kevin R. Henke7.1 Introduction 3517.2 Treatment technologies for arsenic in water 3527.2.1 Introduction 3527.2.2 Preoxidation of As(III) in water 3537.2.3 Sorption and ion-exchange technologies 3577.2.4 Precipitation/coprecipitation 3907.2.5 Permeable reactive barriers 3947.2.6 Filtration, membranes, and other separation technologies 3957.2.7 Biological treatment and bioremediation 3987.2.8 Natural remediation 4017.3 Treatment technologies for arsenic in solids 4017.3.1 Introduction 4017.3.2 Review of various treatment technologies for arsenic in inorganic solids 4027.3.3 Review of various treatment technologies for chromated copper arsenate  (CCA)-treated wood 4107.4 Treatment technologies for arsenic in gases 414References 415Appendices A Common Physical and Chemical Constants and Conversions for Units of Measure 431B Glossary of Terms 437B. 1 Introduction 437B. 2 Glossary 437References 472C Arsenic Thermodynamic Data 475C. 1 Introduction 475C. 2 Modeling applications with thermodynamic data 493C. 3 Thermodynamic data 493References 493D Locations of Significant Arsenic Contamination 495References 524E Regulation of Arsenic: A Brief Survey and Bibliography 545E. 1 Introduction 545E. 2 Regulation of arsenic in water 545E.2. 1 Drinking water 546E. 2 Arsenic standards of natural surface waters and groundwaters 549E. 3 Regulation of arsenic in solid and liquid wastes 549E.3. 1 Bangladesh 549E.3. 2 European Union (EU) 550E. 3 Japan 550E.3. 4 Norway 550E.3. 5 Taiwan 550E.3. 6 United States of America 550E. 4 Sediment and soil guidelines and standards for arsenic 553E.4. 1 Introduction 553E.4. 2 Australia 553E.4. 3 Canada 553E. 4 European Union 554E.4. 5 Italy 554E.4. 6 Japan 554E.4. 7 Korea (South) 554E.4. 8 Thailand 554E.4. 9 United States of America 554E. 5 Regulation of arsenic in food and drugs 555E.5. 1 Australia and New Zealand 555E.5. 2 Canada 555E.5. 3 United States of America 555E. 6 Regulation of arsenic in air 556E.6. 1 European Union 556E.6. 2 United States of America 556References 556Index 559

Kevin Henke is a research scientist at the Centre for Applied Energy Research at the University of Kentucky. He has a M.S. and? Ph.D. in Geology from the University of North Dakota. His research includes investigating water and air quality issues related to coal combustion, studying the impact of mercury and other heavy metals on water quality, and investigating the leaching of inorganics from coal combustion by-products. He is also visiting Assistant Professor of Geology, Department of Geological Sciences, University of Kentucky, Lexington (1998, 2000-2002) and has taught geochemistry, mineralogy, teaching methods courses, and undergraduate introductory courses in environmental geology, natural resources and physical geology. Professor David A. Atwood, is based in the Chemistry Department of the University of Kentucky. He obtained his B.S. from the University of Alabama and his Ph.D. from the University of Texas in 1992. Research in the Atwood group is designed to address both fundamental and applied aspects of the main group metals. Professor Atwood's teaching includes courses in solid-state materials including biomineralization. Dr Lisa Blue is a graduate student based in the chemistry department of the University of Kentucky.

• List of contributors xvPreface xvii1. Introduction 1Kevin R. Henke1.1 Arsenic origin, chemistry, and use 11.2 Arsenic environmental impacts 21.3 Arsenic toxicity 31.4 Arsenic treatment and remediation 31.4.1 Introduction 31.4.2 Treatment and remediation of water 41.4.3 Treatment and remediation of solid wastes, soils, and sediments 41.4.4 Treatment of flue gases 5References 52. Arsenic Chemistry 9Kevin R. Henke and Aaron Hutchison2.1 Introduction 92.2 Atomic structure and isotopes of arsenic 92.3 Arsenic valence state and bonding 102.4 Chemistry of arsenic solids 132.4.1 Elemental arsenic 132.4.2 Common arsenic minerals and other solid arsenic compounds 152.4.3 Arsine and other volatile arsenic compounds 242.4.4 Organoarsenicals 242.5 Introduction to arsenic oxidation and reduction 262.5.1 Arsenic oxidation 262.5.2 Arsenic reduction 272.6 Introduction to arsenic methylation and demethylation 282.7 Arsenic in water 302.7.1 Introduction 302.7.2 Aqueous solubility of arsenic compounds and thermodynamics 312.7.3 Dissolved arsenic species 402.7.4 Dissociation of arsenious and arsenic acids 422.7.5 Eh-pH diagrams, and their limitations 452.7.6 Sorption, ion exchange, precipitation, and coprecipitation of arsenic in water 462.8 Chemistry of gaseous arsenic emissions 57References 593 Arsenic in Natural Environments 69Kevin R. Henke3.1 Introduction 693.2 Nucleosynthesis: the origin of arsenic 703.2.1 The Big Bang 703.2.2 Arsenic formation in stars 703.3 Arsenic in the universe as a whole 733.4 Arsenic chemistry of the solar system 733.4.1 Arsenic in the Sun, Moon, and planets 733.4.2 Arsenic in meteorites and tektites 743.5 Arsenic in the bulk Earth, crusts, and interior 773.5.1 Estimating arsenic concentrations of the bulk Earth and the Earth’s core and mantle 773.5.2 The core 783.5.3 The mantle 783.5.4 The Earth’s crusts 793.6 Arsenic in hydrothermal and geothermal fluids and their deposits 823.6.1 Introduction 823.6.2 Origins of hydrothermal fluids and their arsenic 833.6.3 Arsenic chemistry of hydrothermal fluids 853.6.4 Arsenic mineralogy of hydrothermal deposits 913.6.5 Surface and near-surface oxidation of hydrothermal arsenic 933.6.6 Arsenic chemistry in hot springs 943.6.7 Arsenic in geothermal power plant scales 953.6.8 Arsenic in volcanic gas emissions 963.6.9 Environmental impacts of arsenic in hydrothermal and geothermal fluids 963.7 Oxidation of arsenic-bearing sulfides in geologic materials and mining wastes 973.7.1 Oxidation of sulfide minerals 973.7.2 Factors influencing the oxidation of arsenic-bearing sulfide minerals 973.7.3 Environmental consequences of sulfide and arsenic oxidation 993.7.4 Oxidation chemistry of major arsenic-bearing sulfides 1023.8 Interactions between arsenic and natural organic matter (NOM) 1063.9 Sorption and coprecipitation of arsenic with iron and other (oxy)(hydr)oxides 1063.9.1 Introduction 1063.9.2 Iron, aluminum, and manganese (oxy)(hydr)oxides 1073.9.3 Sulfate (oxy)(hydr)oxides and related compounds 1083.10 Arsenate (inorganic As(V)) precipitation 1103.11 Reductive dissolution of iron and manganese (oxy)(hydr)oxides 1103.12 Arsenic and sulfide at < 50 ◦c 1143.13 Arsenic and its chemistry in mined materials 1153.13.1 Environmental issues with arsenic-bearing sulfide minerals in coal and ore deposits 1153.13.2 Behavior of arsenic within mining wastes 1153.13.3 Movement of arsenic from mining wastes and into the environment 1163.14 Marine waters and sediments 1173.14.1 Inorganic arsenic in seawater 1173.14.2 Marine arsenic cycle 1203.14.3 Arsenic methylation in marine environments 1213.14.4 Arsenic in marine sediments 1213.15 Estuaries 1223.15.1 Arsenic in estuaries 1223.15.2 Seasonal effects on arsenic in estuaries 1253.15.3 Arsenic in pristine estuaries 1253.15.4 Arsenic in contaminated estuaries 1263.16 Rivers and other streams 1273.17 Lakes 1363.18 Wetlands 1453.19 Groundwater 1463.19.1 Subsurface water and groundwater 1463.19.2 Impacts of arsenic contamination in shallow (< 1 km deep) groundwaters 1483.19.3 ‘Dissolved’ and particulate arsenic in groundwater 1483.19.4 Arsenic mobility in groundwater 1483.19.5 Sources of arsenic contamination in groundwater 1493.19.6 Arsenic chemistry in groundwater 1613.20 Glacial ice and related sediments 1623.21 Arsenic in air and wind-blown sediments 1633.21.1 Arsenic emission sources 1633.21.2 Arsenic atmospheric chemistry 1653.21.3 Arsenic in precipitation 1663.21.4 Arsenic in atmospheric dust 1663.21.5 Arsenic in wind-blown sediment deposits (loess) 1683.21.6 Arsenic in soil and sediment gases 1683.22 Petroleum 1683.23 Soils 1693.23.1 Distinguishing between soils and sediments 1693.23.2 Arsenic chemistry in soils 1713.23.3 Soil porewater chemistry 1783.24 Sedimentary rocks 1783.24.1 Diagenesis and sedimentary rocks 1783.24.2 Coal 1803.24.3 Shales and oil shales 1903.24.4 Other sedimentary rocks 1953.25 Metamorphic rocks 196References 198Further reading 2354 Toxicology and Epidemiology of Arsenic and its Compounds 237Michael F. Hughes, David J. Thomas, and Elaina M. Kenyon4.1 Introduction 2374.2 Physical and chemical properties of arsenic 2384.3 Exposure to arsenic 2384.4 Arsenic disposition and biotransformation in mammals 2404.4.1 Introduction 2404.4.2 Respiratory deposition and absorption 2404.4.3 Gastrointestinal absorption 2414.4.4 Dermal absorption 2424.5 Systemic clearance of arsenic and binding to blood components 2434.6 Tissue distribution 2444.7 Placental transfer and distribution in the fetus 2464.8 Arsenic biotransformation 2474.8.1 Introduction 2474.8.2 Arsenic methylation in humans and other mammals 2484.8.3 Significance of arsenic methylation 2484.8.4 Molecular basis of the metabolism of inorganic arsenic 2484.8.5 Reconciling experimental data and the Challenger scheme 2514.9 Arsenic excretion 2524.10 Effects of arsenic exposure 2534.10.1 Acute exposure 2534.10.2 Chronic exposure 2544.11 Cardiovascular 2544.11.1 Introduction 2544.11.2 Peripheral vascular disease 2554.11.3 Ischemic heart disease 2554.11.4 Cerebrovascular disease 2554.11.5 Atherosclerosis 2554.11.6 Hypertension 2564.12 Endocrine 2564.13 Hepatic 2574.14 Neurological 2574.15 Skin 2574.16 Developmental 2584.17 Other organ systems 2584.18 Cancer 2594.18.1 Introduction 2594.18.2 Skin 2594.18.3 Lung 2604.18.4 Bladder 2604.19 Animal models for arsenic-induced cancer 2604.20 Mechanism of action 2614.20.1 Introduction 2614.20.2 Replacement of phosphate 2624.20.3 Enzyme inhibition 2624.20.4 Oxidative stress 2624.20.5 Genotoxicity 2634.20.6 Alteration of DNA repair 2634.20.7 Signal transduction 2634.20.8 Gene transcription 2634.20.9 DNA methylation 2644.20.10 Growth factors 2644.21 Regulation of arsenic 264References 2655 Arsenic in Human History and Modern Societies 277Kevin R. Henke and David A. Atwood5.1 Introduction 2775.2 Early recognition and uses of arsenic by humans 2785.3 Alchemy, development of methods to recover elemental arsenic, and the synthesis of arsenic compounds 2795.4 Applications with arsenic 2795.4.1 Medicinal applications: dangerous quackery and some important drugs 2795.4.2 Pesticides and agricultural applications 2805.4.3 Chemical weapons 2825.4.4 Embalming fluids 2825.4.5 Paints and dyes 2835.4.6 Wood treatment 2845.4.7 Semiconductors 2865.5 Increasing health, safety, and environmental concerns 2865.6 Arsenic in crime 2875.7 Poisoning controversies: Napoleon Bonaparte 2885.8 Arsenic in prospecting, mining, and markets 2895.8.1 Arsenic as a pathfinder element in prospecting 2895.8.2 Arsenic mining, production, and market trends 2905.9 Arsenic in coal and oil shale utilization and their by-products 2915.9.1 Coal cleaning and combustion 2915.9.2 Arsenic behavior during combustion 2915.9.3 Postcombustion flue gas treatment 2955.9.4 Arsenic chemistry in coal combustion byproducts 2955.9.5 Coal gasification 2965.9.6 Oil shale utilization 296References 2976 Major Occurrences of Elevated Arsenic in Groundwater and Other Natural Waters 303Abhijit Mukherjee, Alan E. Fryar, and Bethany M. O’Shea6.1 Introduction 3036.2 Arsenic speciation and mobility in natural waters 3046.3 Immobilization of arsenic in hydrologic systems 3046.3.1 Precipitation, coprecipitation, and association with sulfides 3046.3.2 Arsenic sorption on metal (oxy)(hydr)oxides 3056.3.3 Arsenic sorption on clay minerals 3066.3.4 Carbonate interactions 3066.4 Mobilization of arsenic in water 3096.4.1 Competitive anion exchange 3096.4.2 Effect of natural organic matter (NOM) 3106.4.3 Effect of pH 3106.4.4 Redox-dependent mobilization 3116.4.5 Complex and colloid formation 3116.5 Natural occurrences of elevated arsenic around the world 3136.5.1 Introduction 3136.5.2 Bengal basin, India and Bangladesh 3176.5.3 Middle Ganges Plain, India 3246.5.4 Donargarh rift belt, Chattisgarh, central India 3266.5.5 Terai alluvial plain, Nepal 3266.5.6 Indus alluvial system, Pakistan 3276.5.7 Irrawaddy delta, Myanmar 3286.5.8 Mekong plain and delta, Cambodia, Vietnam, and Laos 3286.5.9 Red River delta, Vietnam 3316.5.10 Yellow River plains, Inner Mongolia, China 3326.5.11 Taiwan 3336.5.12 Coastal aquifers of Australia 3346.5.13 Sedimentary basins and basement complexes of West Africa 3346.5.14 Western USA 3356.5.15 New England, USA 3366.5.16 Northern Chile 3376.5.17 Chaco and Pampa plains of Argentina 338References 3397 Waste Treatment and Remediation Technologies for Arsenic 351Kevin R. Henke7.1 Introduction 3517.2 Treatment technologies for arsenic in water 3527.2.1 Introduction 3527.2.2 Preoxidation of As(III) in water 3537.2.3 Sorption and ion-exchange technologies 3577.2.4 Precipitation/coprecipitation 3907.2.5 Permeable reactive barriers 3947.2.6 Filtration, membranes, and other separation technologies 3957.2.7 Biological treatment and bioremediation 3987.2.8 Natural remediation 4017.3 Treatment technologies for arsenic in solids 4017.3.1 Introduction 4017.3.2 Review of various treatment technologies for arsenic in inorganic solids 4027.3.3 Review of various treatment technologies for chromated copper arsenate  (CCA)-treated wood 4107.4 Treatment technologies for arsenic in gases 414References 415Appendices A Common Physical and Chemical Constants and Conversions for Units of Measure 431B Glossary of Terms 437B. 1 Introduction 437B. 2 Glossary 437References 472C Arsenic Thermodynamic Data 475C. 1 Introduction 475C. 2 Modeling applications with thermodynamic data 493C. 3 Thermodynamic data 493References 493D Locations of Significant Arsenic Contamination 495References 524E Regulation of Arsenic: A Brief Survey and Bibliography 545E. 1 Introduction 545E. 2 Regulation of arsenic in water 545E.2. 1 Drinking water 546E. 2 Arsenic standards of natural surface waters and groundwaters 549E. 3 Regulation of arsenic in solid and liquid wastes 549E.3. 1 Bangladesh 549E.3. 2 European Union (EU) 550E. 3 Japan 550E.3. 4 Norway 550E.3. 5 Taiwan 550E.3. 6 United States of America 550E. 4 Sediment and soil guidelines and standards for arsenic 553E.4. 1 Introduction 553E.4. 2 Australia 553E.4. 3 Canada 553E. 4 European Union 554E.4. 5 Italy 554E.4. 6 Japan 554E.4. 7 Korea (South) 554E.4. 8 Thailand 554E.4. 9 United States of America 554E. 5 Regulation of arsenic in food and drugs 555E.5. 1 Australia and New Zealand 555E.5. 2 Canada 555E.5. 3 United States of America 555E. 6 Regulation of arsenic in air 556E.6. 1 European Union 556E.6. 2 United States of America 556References 556Index 559

Kevin Henke is a research scientist at the Centre for Applied Energy Research at the University of Kentucky. He has a M.S. and? Ph.D. in Geology from the University of North Dakota. His research includes investigating water and air quality issues related to coal combustion, studying the impact of mercury and other heavy metals on water quality, and investigating the leaching of inorganics from coal combustion by-products. He is also visiting Assistant Professor of Geology, Department of Geological Sciences, University of Kentucky, Lexington (1998, 2000-2002) and has taught geochemistry, mineralogy, teaching methods courses, and undergraduate introductory courses in environmental geology, natural resources and physical geology. Professor David A. Atwood, is based in the Chemistry Department of the University of Kentucky. He obtained his B.S. from the University of Alabama and his Ph.D. from the University of Texas in 1992. Research in the Atwood group is designed to address both fundamental and applied aspects of the main group metals. Professor Atwood's teaching includes courses in solid-state materials including biomineralization. Dr Lisa Blue is a graduate student based in the chemistry department of the University of Kentucky.

• List of contributors xvPreface xvii1. Introduction 1Kevin R. Henke1.1 Arsenic origin, chemistry, and use 11.2 Arsenic environmental impacts 21.3 Arsenic toxicity 31.4 Arsenic treatment and remediation 31.4.1 Introduction 31.4.2 Treatment and remediation of water 41.4.3 Treatment and remediation of solid wastes, soils, and sediments 41.4.4 Treatment of flue gases 5References 52. Arsenic Chemistry 9Kevin R. Henke and Aaron Hutchison2.1 Introduction 92.2 Atomic structure and isotopes of arsenic 92.3 Arsenic valence state and bonding 102.4 Chemistry of arsenic solids 132.4.1 Elemental arsenic 132.4.2 Common arsenic minerals and other solid arsenic compounds 152.4.3 Arsine and other volatile arsenic compounds 242.4.4 Organoarsenicals 242.5 Introduction to arsenic oxidation and reduction 262.5.1 Arsenic oxidation 262.5.2 Arsenic reduction 272.6 Introduction to arsenic methylation and demethylation 282.7 Arsenic in water 302.7.1 Introduction 302.7.2 Aqueous solubility of arsenic compounds and thermodynamics 312.7.3 Dissolved arsenic species 402.7.4 Dissociation of arsenious and arsenic acids 422.7.5 Eh-pH diagrams, and their limitations 452.7.6 Sorption, ion exchange, precipitation, and coprecipitation of arsenic in water 462.8 Chemistry of gaseous arsenic emissions 57References 593 Arsenic in Natural Environments 69Kevin R. Henke3.1 Introduction 693.2 Nucleosynthesis: the origin of arsenic 703.2.1 The Big Bang 703.2.2 Arsenic formation in stars 703.3 Arsenic in the universe as a whole 733.4 Arsenic chemistry of the solar system 733.4.1 Arsenic in the Sun, Moon, and planets 733.4.2 Arsenic in meteorites and tektites 743.5 Arsenic in the bulk Earth, crusts, and interior 773.5.1 Estimating arsenic concentrations of the bulk Earth and the Earth’s core and mantle 773.5.2 The core 783.5.3 The mantle 783.5.4 The Earth’s crusts 793.6 Arsenic in hydrothermal and geothermal fluids and their deposits 823.6.1 Introduction 823.6.2 Origins of hydrothermal fluids and their arsenic 833.6.3 Arsenic chemistry of hydrothermal fluids 853.6.4 Arsenic mineralogy of hydrothermal deposits 913.6.5 Surface and near-surface oxidation of hydrothermal arsenic 933.6.6 Arsenic chemistry in hot springs 943.6.7 Arsenic in geothermal power plant scales 953.6.8 Arsenic in volcanic gas emissions 963.6.9 Environmental impacts of arsenic in hydrothermal and geothermal fluids 963.7 Oxidation of arsenic-bearing sulfides in geologic materials and mining wastes 973.7.1 Oxidation of sulfide minerals 973.7.2 Factors influencing the oxidation of arsenic-bearing sulfide minerals 973.7.3 Environmental consequences of sulfide and arsenic oxidation 993.7.4 Oxidation chemistry of major arsenic-bearing sulfides 1023.8 Interactions between arsenic and natural organic matter (NOM) 1063.9 Sorption and coprecipitation of arsenic with iron and other (oxy)(hydr)oxides 1063.9.1 Introduction 1063.9.2 Iron, aluminum, and manganese (oxy)(hydr)oxides 1073.9.3 Sulfate (oxy)(hydr)oxides and related compounds 1083.10 Arsenate (inorganic As(V)) precipitation 1103.11 Reductive dissolution of iron and manganese (oxy)(hydr)oxides 1103.12 Arsenic and sulfide at < 50 ◦c 1143.13 Arsenic and its chemistry in mined materials 1153.13.1 Environmental issues with arsenic-bearing sulfide minerals in coal and ore deposits 1153.13.2 Behavior of arsenic within mining wastes 1153.13.3 Movement of arsenic from mining wastes and into the environment 1163.14 Marine waters and sediments 1173.14.1 Inorganic arsenic in seawater 1173.14.2 Marine arsenic cycle 1203.14.3 Arsenic methylation in marine environments 1213.14.4 Arsenic in marine sediments 1213.15 Estuaries 1223.15.1 Arsenic in estuaries 1223.15.2 Seasonal effects on arsenic in estuaries 1253.15.3 Arsenic in pristine estuaries 1253.15.4 Arsenic in contaminated estuaries 1263.16 Rivers and other streams 1273.17 Lakes 1363.18 Wetlands 1453.19 Groundwater 1463.19.1 Subsurface water and groundwater 1463.19.2 Impacts of arsenic contamination in shallow (< 1 km deep) groundwaters 1483.19.3 ‘Dissolved’ and particulate arsenic in groundwater 1483.19.4 Arsenic mobility in groundwater 1483.19.5 Sources of arsenic contamination in groundwater 1493.19.6 Arsenic chemistry in groundwater 1613.20 Glacial ice and related sediments 1623.21 Arsenic in air and wind-blown sediments 1633.21.1 Arsenic emission sources 1633.21.2 Arsenic atmospheric chemistry 1653.21.3 Arsenic in precipitation 1663.21.4 Arsenic in atmospheric dust 1663.21.5 Arsenic in wind-blown sediment deposits (loess) 1683.21.6 Arsenic in soil and sediment gases 1683.22 Petroleum 1683.23 Soils 1693.23.1 Distinguishing between soils and sediments 1693.23.2 Arsenic chemistry in soils 1713.23.3 Soil porewater chemistry 1783.24 Sedimentary rocks 1783.24.1 Diagenesis and sedimentary rocks 1783.24.2 Coal 1803.24.3 Shales and oil shales 1903.24.4 Other sedimentary rocks 1953.25 Metamorphic rocks 196References 198Further reading 2354 Toxicology and Epidemiology of Arsenic and its Compounds 237Michael F. Hughes, David J. Thomas, and Elaina M. Kenyon4.1 Introduction 2374.2 Physical and chemical properties of arsenic 2384.3 Exposure to arsenic 2384.4 Arsenic disposition and biotransformation in mammals 2404.4.1 Introduction 2404.4.2 Respiratory deposition and absorption 2404.4.3 Gastrointestinal absorption 2414.4.4 Dermal absorption 2424.5 Systemic clearance of arsenic and binding to blood components 2434.6 Tissue distribution 2444.7 Placental transfer and distribution in the fetus 2464.8 Arsenic biotransformation 2474.8.1 Introduction 2474.8.2 Arsenic methylation in humans and other mammals 2484.8.3 Significance of arsenic methylation 2484.8.4 Molecular basis of the metabolism of inorganic arsenic 2484.8.5 Reconciling experimental data and the Challenger scheme 2514.9 Arsenic excretion 2524.10 Effects of arsenic exposure 2534.10.1 Acute exposure 2534.10.2 Chronic exposure 2544.11 Cardiovascular 2544.11.1 Introduction 2544.11.2 Peripheral vascular disease 2554.11.3 Ischemic heart disease 2554.11.4 Cerebrovascular disease 2554.11.5 Atherosclerosis 2554.11.6 Hypertension 2564.12 Endocrine 2564.13 Hepatic 2574.14 Neurological 2574.15 Skin 2574.16 Developmental 2584.17 Other organ systems 2584.18 Cancer 2594.18.1 Introduction 2594.18.2 Skin 2594.18.3 Lung 2604.18.4 Bladder 2604.19 Animal models for arsenic-induced cancer 2604.20 Mechanism of action 2614.20.1 Introduction 2614.20.2 Replacement of phosphate 2624.20.3 Enzyme inhibition 2624.20.4 Oxidative stress 2624.20.5 Genotoxicity 2634.20.6 Alteration of DNA repair 2634.20.7 Signal transduction 2634.20.8 Gene transcription 2634.20.9 DNA methylation 2644.20.10 Growth factors 2644.21 Regulation of arsenic 264References 2655 Arsenic in Human History and Modern Societies 277Kevin R. Henke and David A. Atwood5.1 Introduction 2775.2 Early recognition and uses of arsenic by humans 2785.3 Alchemy, development of methods to recover elemental arsenic, and the synthesis of arsenic compounds 2795.4 Applications with arsenic 2795.4.1 Medicinal applications: dangerous quackery and some important drugs 2795.4.2 Pesticides and agricultural applications 2805.4.3 Chemical weapons 2825.4.4 Embalming fluids 2825.4.5 Paints and dyes 2835.4.6 Wood treatment 2845.4.7 Semiconductors 2865.5 Increasing health, safety, and environmental concerns 2865.6 Arsenic in crime 2875.7 Poisoning controversies: Napoleon Bonaparte 2885.8 Arsenic in prospecting, mining, and markets 2895.8.1 Arsenic as a pathfinder element in prospecting 2895.8.2 Arsenic mining, production, and market trends 2905.9 Arsenic in coal and oil shale utilization and their by-products 2915.9.1 Coal cleaning and combustion 2915.9.2 Arsenic behavior during combustion 2915.9.3 Postcombustion flue gas treatment 2955.9.4 Arsenic chemistry in coal combustion byproducts 2955.9.5 Coal gasification 2965.9.6 Oil shale utilization 296References 2976 Major Occurrences of Elevated Arsenic in Groundwater and Other Natural Waters 303Abhijit Mukherjee, Alan E. Fryar, and Bethany M. O’Shea6.1 Introduction 3036.2 Arsenic speciation and mobility in natural waters 3046.3 Immobilization of arsenic in hydrologic systems 3046.3.1 Precipitation, coprecipitation, and association with sulfides 3046.3.2 Arsenic sorption on metal (oxy)(hydr)oxides 3056.3.3 Arsenic sorption on clay minerals 3066.3.4 Carbonate interactions 3066.4 Mobilization of arsenic in water 3096.4.1 Competitive anion exchange 3096.4.2 Effect of natural organic matter (NOM) 3106.4.3 Effect of pH 3106.4.4 Redox-dependent mobilization 3116.4.5 Complex and colloid formation 3116.5 Natural occurrences of elevated arsenic around the world 3136.5.1 Introduction 3136.5.2 Bengal basin, India and Bangladesh 3176.5.3 Middle Ganges Plain, India 3246.5.4 Donargarh rift belt, Chattisgarh, central India 3266.5.5 Terai alluvial plain, Nepal 3266.5.6 Indus alluvial system, Pakistan 3276.5.7 Irrawaddy delta, Myanmar 3286.5.8 Mekong plain and delta, Cambodia, Vietnam, and Laos 3286.5.9 Red River delta, Vietnam 3316.5.10 Yellow River plains, Inner Mongolia, China 3326.5.11 Taiwan 3336.5.12 Coastal aquifers of Australia 3346.5.13 Sedimentary basins and basement complexes of West Africa 3346.5.14 Western USA 3356.5.15 New England, USA 3366.5.16 Northern Chile 3376.5.17 Chaco and Pampa plains of Argentina 338References 3397 Waste Treatment and Remediation Technologies for Arsenic 351Kevin R. Henke7.1 Introduction 3517.2 Treatment technologies for arsenic in water 3527.2.1 Introduction 3527.2.2 Preoxidation of As(III) in water 3537.2.3 Sorption and ion-exchange technologies 3577.2.4 Precipitation/coprecipitation 3907.2.5 Permeable reactive barriers 3947.2.6 Filtration, membranes, and other separation technologies 3957.2.7 Biological treatment and bioremediation 3987.2.8 Natural remediation 4017.3 Treatment technologies for arsenic in solids 4017.3.1 Introduction 4017.3.2 Review of various treatment technologies for arsenic in inorganic solids 4027.3.3 Review of various treatment technologies for chromated copper arsenate  (CCA)-treated wood 4107.4 Treatment technologies for arsenic in gases 414References 415Appendices A Common Physical and Chemical Constants and Conversions for Units of Measure 431B Glossary of Terms 437B. 1 Introduction 437B. 2 Glossary 437References 472C Arsenic Thermodynamic Data 475C. 1 Introduction 475C. 2 Modeling applications with thermodynamic data 493C. 3 Thermodynamic data 493References 493D Locations of Significant Arsenic Contamination 495References 524E Regulation of Arsenic: A Brief Survey and Bibliography 545E. 1 Introduction 545E. 2 Regulation of arsenic in water 545E.2. 1 Drinking water 546E. 2 Arsenic standards of natural surface waters and groundwaters 549E. 3 Regulation of arsenic in solid and liquid wastes 549E.3. 1 Bangladesh 549E.3. 2 European Union (EU) 550E. 3 Japan 550E.3. 4 Norway 550E.3. 5 Taiwan 550E.3. 6 United States of America 550E. 4 Sediment and soil guidelines and standards for arsenic 553E.4. 1 Introduction 553E.4. 2 Australia 553E.4. 3 Canada 553E. 4 European Union 554E.4. 5 Italy 554E.4. 6 Japan 554E.4. 7 Korea (South) 554E.4. 8 Thailand 554E.4. 9 United States of America 554E. 5 Regulation of arsenic in food and drugs 555E.5. 1 Australia and New Zealand 555E.5. 2 Canada 555E.5. 3 United States of America 555E. 6 Regulation of arsenic in air 556E.6. 1 European Union 556E.6. 2 United States of America 556References 556Index 559