Environmental Organic Chemistry

René P. Schwarzenbach, PhD, is a Professor em. of Environmental Chemistry at the Swiss Federal Institute of Technology (ETH) in Zurich, Switzerland. Philip M. Gschwend, PhD, is Full Professor of Civil and Environmental Engineering at the Massachusetts Institute of Technology in Cambridge, Massachusetts. Dieter M. Imboden, PhD, is a Professor em. of Environmental Physics at the Swiss Federal Institute of Technology (ETH) in Zurich, Switzerland.

• Preface xiiiAbout the Companion Website xvii1 General Topic and Overview 11.1 Introduction 21.2 Assessing Organic Chemicals in the Environment 41.3 What is This Book All About? 71.4 Bibliography 14Part I Background Knowledge 172 Background Knowledge on Organic Chemicals 192.1 The Makeup of Organic Compounds 202.2 Intermolecular Forces Between Uncharged Molecules 372.3 Questions and Problems 402.4 Bibliography 433 The Amazing World of Anthropogenic Organic Chemicals 453.1 Introduction 473.2 A Lasting Global Problem: Persistent Organic Pollutants (POPs) 473.3 Natural but Nevertheless Problematic: Petroleum Hydrocarbons 483.4 Notorious Air and Groundwater Pollutants: Organic Solvents 533.5 Safety First: Flame Retardants All Around Us 563.6 How to Make Materials “Repellent”: Polyfluorinated Chemicals (PFCs) 583.7 From Washing Machines to Surface Waters: Complexing Agents, Surfactants, Whitening Agents, and Corrosion Inhibitors 603.8 Health, Well-Being, and Water Pollution: Pharmaceuticals and Personal Care Products 633.9 Fighting Pests: Herbicides, Insecticides, and Fungicides 653.10 Our Companion Compounds: Representative Model Chemicals 693.11 Questions 723.12 Bibliography 734 Background Thermodynamics, Equilibrium Partitioning and Acidity Constants 814.1 Important Thermodynamic Functions 834.2 Using Thermodynamic Functions to Quantify Equilibrium Partitioning 894.3 Organic Acids and Bases I: Acidity Constant and Speciation in Natural Waters 984.4 Organic Acids and Bases II: Chemical Structure and Acidity Constant 1074.5 Questions and Problems 1164.6 Bibliography 1195 Earth Systems and ComPartments 1215.1 Introduction 1235.2 The Atmosphere 1255.3 Surface Waters and Sediments 1315.4 Soil and Groundwater 1485.5 Biota 1545.6 Questions 1555.7 Bibliography 1586 Environmental Systems: Physical Processes and Mathematical Modeling 1656.1 Systems and Models 1676.2 Box Models: A Concept for a Simple World 1746.3 When Space Matters: Transport Processes 1916.4 Models in Space and Time 1966.5 Questions and Problems 2036.6 Bibliography 211Part II Equilibrium Partitioning in Well-Defined Systems 2137 Partitioning Between Bulk Phases: General Aspects and Modeling Approaches 2157.1 Introduction 2167.2 Molecular Interactions Governing Bulk Phase Partitioning of Organic Chemicals 2177.3 Quantitative Approaches to Estimate Bulk Phase Partition Constants/Coefficients: Linear Free Energy Relationships (LFERs) 2257.4 Questions 2327.5 Bibliography 2348 Vapor Pressure (pi∗) 2378.1 Introduction and Theoretical Background 2388.2 Molecular Interactions Governing Vapor Pressure and Vapor Pressure Estimation Methods 2468.3 Questions and Problems 2538.4 Bibliography 2579 Solubility (Csatiw ) and Activity Coefficient (;;satiw) in Water; Air–Water Partition Constant (Kiaw) 2599.1 Introduction and Thermodynamic Considerations 2619.2 Molecular Interactions Governing the Aqueous Activity Coefficient and the Air–Water Partition Constant 2679.3 LFERs for Estimating Air–Water Partition Constants and Aqueous Activity Coefficients/Aqueous Solubilities 2709.4 Effect of Temperature, Dissolved Salts, and pH on the Aqueous Activity Coefficient/Aqueous Solubility and on the Air–Water Partition Constant 2729.5 Questions and Problems 2829.6 Bibliography 28510 Organic Liquid–Air and Organic Liquid–Water Partitioning 28910.1 Introduction 29110.2 Thermodynamic Considerations and Comparisons of Different Organic Solvents 29110.3 The Octanol–Water System: The Atom/Fragment Contribution Method for Estimation of the Octanol–Water PartitionConstant 29810.4 Partitioning Involving Organic Solvent–Water Mixtures 30110.5 Evaporation and Dissolution of Organic Compounds from Organic Liquid Mixtures–EquilibriumConsiderations 30710.6 Questions and Problems 31110.7 Bibliography 31711 Partitioning of Nonionic Organic Compounds Between Well-Defined Surfaces and Air or Water 32111.1 Introduction 32211.2 Adsorption from Air to Well-Defined Surfaces 32211.3 Adsorption from Water to Inorganic Surfaces 33511.4 Questions and Problems 34211.5 Bibliography 345Part III Equilibrium Partitioning in Environmental Systems 34912 General Introduction to Sorption Processes 35112.1 Introduction 35212.2 Sorption Isotherms and the Solid–Water Equilibrium Distribution Coefficient (Kid) 35412.3 Speciation (Sorbed versus Dissolved or Gaseous), Retardation, and Sedimentation 36012.4 Questions and Problems 36612.5 Bibliography 36813 Sorption from Water to Natural Organic Matter (NOM) 36913.1 The Structural Diversity of Natural Organic Matter Present in Aquatic and Terrestrial Environments 37113.2 Quantifying Natural Organic Matter–Water Partitioning of Neutral Organic Compounds 37613.3 Sorption of Organic Acids and Bases to Natural Organic Matter 38813.4 Questions and Problems 39213.5 Bibliography 39714 Sorption of Ionic Organic Compounds to Charged Surfaces 40514.1 Introduction 40714.2 Cation and Anion Exchange Capacities of Solids in Water 40814.3 Ion Exchange: Nonspecific Adsorption of Ionized Organic Chemicals from Aqueous Solutions to Charged Surfaces 41414.4 Surface Complexation: Specific Bonding of Organic Compounds with Solid Phases in Water 42614.5 Questions and Problems 43214.6 Bibliography 43615 Aerosol–Air Partitioning: Dry andWet Deposition of Organic Pollutants 44115.1 Origins and Properties of Atmospheric Aerosols 44215.2 Assessing Aerosol–Air Partition Coefficients (KiPMa) 44515.3 Dry and Wet Deposition 45315.4 Questions and Problems 45915.5 Bibliography 46416 Equilibrium Partitioning From Water and Air to Biota 46916.1 Introduction 47116.2 Predicting Biota–Water and Biota–Air Equilibrium Partitioning 47116.3 Bioaccumulation and Biomagnification in Aquatic Systems 48516.4 Bioaccumulation and Biomagnification in Terrestrial Systems 49816.5 Baseline Toxicity (Narcosis) 50316.6 Questions and Problems 50716.7 Bibliography 514Part IV Mass Transfer Processes in Environmental Systems 52317 Random Motion, Molecular and Turbulent Diffusivity 52517.1 Random Motion 52617.2 Molecular Diffusion 53417.3 Other Random Transport Processes in the Environment 54517.4 Questions and Problems 55017.5 Bibliography 55718 Transport at Boundaries 55918.1 The Role of Boundaries in the Environment 56018.2 Bottleneck Boundaries 56218.3 Wall Boundaries 56718.4 Hybrid Boundaries 57218.5 Questions and Problems 57718.6 Bibliography 58019 Air–Water Exchange 58119.1 The Air–Water Interface 58319.2 Air–Water Exchange Models 58519.3 Measurement of Air–Water Exchange Velocities 59219.4 Air–Water Exchange in Flowing Waters 59919.5 Questions and Problems 60419.6 Bibliography 61320 Interfaces Involving Solids 61720.1 The Sediment–Water Interface 61820.2 Transport in Unsaturated Soil 62620.3 Questions and Problems 63020.4 Bibliography 634Part V Transformation Processes 63521 Background Knowledge on Transformation Reactions of Organic Pollutants 63721.1 Identifying Reactive Sites Within Organic Molecules 63821.2 Thermodynamics of Transformation Reactions 64321.3 Kinetics of Transformation Reactions 65021.4 Questions and Problems 65721.5 Bibliography 66122 Hydrolysis And ReactionsWith Other Nucleophiles 66322.1 Nucleophilic Substitution and Elimination Reactions Involving Primarily Saturated Carbon Atoms 66522.2 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives 68022.3 Enzyme-Catalyzed Hydrolysis Reactions: Hydrolases 69522.4 Questions and Problems 70122.5 Bibliography 71023 Redox Reactions 71523.1 Introduction 71623.2 Evaluating the Thermodynamics of Redox Reactions 71923.3 Examples of Chemical Redox Reactions in Natural Systems 73023.4 Examples of Enzyme-Catalyzed Redox Reactions 74723.5 Questions and Problems 75623.6 Bibliography 76524 Direct Photolysis in Aquatic Systems 77324.1 Introduction 77524.2 Some Basic Principles of Photochemistry 77624.3 Light Absorption by Organic Compounds in Natural Waters 78824.4 Quantum Yield and Rate of Direct Photolysis 80024.5 Effects of Solid Sorbents (Particles, Soil Surfaces, Ice) on Direct Photolysis 80324.6 Questions and Problems 80424.7 Bibliography 81125 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere 81525.1 Introduction 81625.2 Indirect Photolysis in Surface Waters 81725.3 Indirect Photolysis in the Atmosphere (Troposphere): Reaction with Hydroxyl Radical (HO∙) 82925.4 Questions and Problems 83325.5 Bibliography 83826 Biotransformations 84526.1 Introduction 84726.2 Some Important Concepts about Microorganisms Relevant to Biotransformations 84826.3 Initial Biotransformation Strategies 85826.4 Rates of Biotransformations 86426.5 Questions and Problems 88226.6 Bibliography 88927 Assessing Transformation Processes Using Compound-Specific Isotope Analysis (CSIA) 89727.1 Introduction, Methodology, and Theoretical Background 89827.2 Using CSIA for Assessing Organic Compound Transformations in Laboratory and Field Systems 91427.3 Questions and Problems 93027.4 Bibliography 936Part VI Putting Everything Together 94528 Exposure Assessment of Organic Pollutants Using Simple Modeling Approaches 94728.1 One-Box Model: The Universal Tool for Process Integration 94828.2 Assessing Equilibrium Partitioning in Simple Multimedia Systems 95228.3 Simple Dynamic Systems 95628.4 Systems Driven by Advection 96028.5 Bibliography 974Appendix 977Index 995

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