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<p>Preface xiii</p> <p>About the Companion Website xvii</p> <p><b>1 General Topic and Overview 1</b></p> <p>1.1 Introduction 2</p> <p>1.2 Assessing Organic Chemicals in the Environment 4</p> <p>1.3 What is This Book All About? 7</p> <p>1.4 Bibliography 14</p> <p><b>Part I Background Knowledge 17</b></p> <p><b>2 Background Knowledge on Organic Chemicals 19</b></p> <p>2.1 The Makeup of Organic Compounds 20</p> <p>2.2 Intermolecular Forces Between Uncharged Molecules 37</p> <p>2.3 Questions and Problems 40</p> <p>2.4 Bibliography 43</p> <p><b>3 The Amazing World of Anthropogenic Organic Chemicals 45</b></p> <p>3.1 Introduction 47</p> <p>3.2 A Lasting Global Problem: Persistent Organic Pollutants (POPs) 47</p> <p>3.3 Natural but Nevertheless Problematic: Petroleum Hydrocarbons 48</p> <p>3.4 Notorious Air and Groundwater Pollutants: Organic Solvents 53</p> <p>3.5 Safety First: Flame Retardants All Around Us 56</p> <p>3.6 How to Make Materials “Repellent”: Polyfluorinated Chemicals (PFCs) 58</p> <p>3.7 From Washing Machines to Surface Waters: Complexing Agents, Surfactants, Whitening Agents, and Corrosion Inhibitors 60</p> <p>3.8 Health, Well-Being, and Water Pollution: Pharmaceuticals and Personal Care Products 63</p> <p>3.9 Fighting Pests: Herbicides, Insecticides, and Fungicides 65</p> <p>3.10 Our Companion Compounds: Representative Model Chemicals 69</p> <p>3.11 Questions 72</p> <p>3.12 Bibliography 73</p> <p><b>4 Background Thermodynamics, Equilibrium Partitioning and Acidity Constants 81</b></p> <p>4.1 Important Thermodynamic Functions 83</p> <p>4.2 Using Thermodynamic Functions to Quantify Equilibrium Partitioning 89</p> <p>4.3 Organic Acids and Bases I: Acidity Constant and Speciation in Natural Waters 98</p> <p>4.4 Organic Acids and Bases II: Chemical Structure and Acidity Constant 107</p> <p>4.5 Questions and Problems 116</p> <p>4.6 Bibliography 119</p> <p><b>5 Earth Systems and ComPartments 121</b></p> <p>5.1 Introduction 123</p> <p>5.2 The Atmosphere 125</p> <p>5.3 Surface Waters and Sediments 131</p> <p>5.4 Soil and Groundwater 148</p> <p>5.5 Biota 154</p> <p>5.6 Questions 155</p> <p>5.7 Bibliography 158</p> <p><b>6 Environmental Systems: Physical Processes and Mathematical Modeling 165</b></p> <p>6.1 Systems and Models 167</p> <p>6.2 Box Models: A Concept for a Simple World 174</p> <p>6.3 When Space Matters: Transport Processes 191</p> <p>6.4 Models in Space and Time 196</p> <p>6.5 Questions and Problems 203</p> <p>6.6 Bibliography 211</p> <p><b>Part II Equilibrium Partitioning in Well-Defined Systems 213</b></p> <p><b>7 Partitioning Between Bulk Phases: General Aspects and Modeling Approaches 215</b></p> <p>7.1 Introduction 216</p> <p>7.2 Molecular Interactions Governing Bulk Phase Partitioning of Organic Chemicals 217</p> <p>7.3 Quantitative Approaches to Estimate Bulk Phase Partition Constants/Coefficients: Linear Free Energy Relationships (LFERs) 225</p> <p>7.4 Questions 232</p> <p>7.5 Bibliography 234</p> <p><b>8 Vapor Pressure (<i>p_i</i></b><b>^∗) 237</b></p> <p>8.1 Introduction and Theoretical Background 238</p> <p>8.2 Molecular Interactions Governing Vapor Pressure and Vapor Pressure Estimation Methods 246</p> <p>8.3 Questions and Problems 253</p> <p>8.4 Bibliography 257</p> <p><b>9 Solubility (<i>C</i>^sat<i>_i</i>_w ) and Activity Coefficient (</b><b><i>𝜸</i>^sat<i>_i</i>_w ) in Water; Air–Water Partition Constant (<i>K_i</i>_aw) 259</b></p> <p>9.1 Introduction and Thermodynamic Considerations 261</p> <p>9.2 Molecular Interactions Governing the Aqueous Activity Coefficient and the Air–Water Partition Constant 267</p> <p>9.3 LFERs for Estimating Air–Water Partition Constants and Aqueous Activity Coefficients/Aqueous Solubilities 270</p> <p>9.4 Effect of Temperature, Dissolved Salts, and pH on the Aqueous Activity Coefficient/Aqueous Solubility and on the Air–Water Partition Constant 272</p> <p>9.5 Questions and Problems 282</p> <p>9.6 Bibliography 285</p> <p><b>10 Organic Liquid–Air and Organic Liquid–Water Partitioning 289</b></p> <p>10.1 Introduction 291</p> <p>10.2 Thermodynamic Considerations and Comparisons of Different Organic Solvents 291</p> <p>10.3 The Octanol–Water System: The Atom/Fragment Contribution Method for Estimation of the Octanol–Water Partition</p> <p>Constant 298</p> <p>10.4 Partitioning Involving Organic Solvent–Water Mixtures 301</p> <p>10.5 Evaporation and Dissolution of Organic Compounds from Organic Liquid Mixtures–Equilibrium</p> <p>Considerations 307</p> <p>10.6 Questions and Problems 311</p> <p>10.7 Bibliography 317</p> <p><b>11 Partitioning of Nonionic Organic Compounds Between Well-Defined Surfaces and Air or Water 321</b></p> <p>11.1 Introduction 322</p> <p>11.2 Adsorption from Air to Well-Defined Surfaces 322</p> <p>11.3 Adsorption from Water to Inorganic Surfaces 335</p> <p>11.4 Questions and Problems 342</p> <p>11.5 Bibliography 345</p> <p><b>Part III Equilibrium Partitioning in Environmental Systems 349</b></p> <p><b>12 General Introduction to Sorption Processes 351</b></p> <p>12.1 Introduction 352</p> <p>12.2 Sorption Isotherms and the Solid–Water Equilibrium Distribution Coefficient (<i>K_i</i>_d) 354</p> <p>12.3 Speciation (Sorbed versus Dissolved or Gaseous), Retardation, and Sedimentation 360</p> <p>12.4 Questions and Problems 366</p> <p>12.5 Bibliography 368</p> <p><b>13 Sorption from Water to Natural Organic Matter (NOM) 369</b></p> <p>13.1 The Structural Diversity of Natural Organic Matter Present in Aquatic and Terrestrial Environments 371</p> <p>13.2 Quantifying Natural Organic Matter–Water Partitioning of Neutral Organic Compounds 376</p> <p>13.3 Sorption of Organic Acids and Bases to Natural Organic Matter 388</p> <p>13.4 Questions and Problems 392</p> <p>13.5 Bibliography 397</p> <p><b>14 Sorption of Ionic Organic Compounds to Charged Surfaces 405</b></p> <p>14.1 Introduction 407</p> <p>14.2 Cation and Anion Exchange Capacities of Solids in Water 408</p> <p>14.3 Ion Exchange: Nonspecific Adsorption of Ionized Organic Chemicals from Aqueous Solutions to Charged Surfaces 414</p> <p>14.4 Surface Complexation: Specific Bonding of Organic Compounds with Solid Phases in Water 426</p> <p>14.5 Questions and Problems 432</p> <p>14.6 Bibliography 436</p> <p><b>15 Aerosol–Air Partitioning: Dry andWet Deposition of Organic Pollutants 441</b></p> <p>15.1 Origins and Properties of Atmospheric Aerosols 442</p> <p>15.2 Assessing Aerosol–Air Partition Coefficients (<i>K_i</i>_PMa) 445</p> <p>15.3 Dry and Wet Deposition 453</p> <p>15.4 Questions and Problems 459</p> <p>15.5 Bibliography 464</p> <p><b>16 Equilibrium Partitioning From Water and Air to Biota 469</b></p> <p>16.1 Introduction 471</p> <p>16.2 Predicting Biota–Water and Biota–Air Equilibrium Partitioning 471</p> <p>16.3 Bioaccumulation and Biomagnification in Aquatic Systems 485</p> <p>16.4 Bioaccumulation and Biomagnification in Terrestrial Systems 498</p> <p>16.5 Baseline Toxicity (Narcosis) 503</p> <p>16.6 Questions and Problems 507</p> <p>16.7 Bibliography 514</p> <p><b>Part IV Mass Transfer Processes in Environmental Systems 523</b></p> <p><b>17 Random Motion, Molecular and Turbulent Diffusivity 525</b></p> <p>17.1 Random Motion 526</p> <p>17.2 Molecular Diffusion 534</p> <p>17.3 Other Random Transport Processes in the Environment 545</p> <p>17.4 Questions and Problems 550</p> <p>17.5 Bibliography 557</p> <p><b>18 Transport at Boundaries 559</b></p> <p>18.1 The Role of Boundaries in the Environment 560</p> <p>18.2 Bottleneck Boundaries 562</p> <p>18.3 Wall Boundaries 567</p> <p>18.4 Hybrid Boundaries 572</p> <p>18.5 Questions and Problems 577</p> <p>18.6 Bibliography 580</p> <p><b>19 Air–Water Exchange 581</b></p> <p>19.1 The Air–Water Interface 583</p> <p>19.2 Air–Water Exchange Models 585</p> <p>19.3 Measurement of Air–Water Exchange Velocities 592</p> <p>19.4 Air–Water Exchange in Flowing Waters 599</p> <p>19.5 Questions and Problems 604</p> <p>19.6 Bibliography 613</p> <p><b>20 Interfaces Involving Solids 617</b></p> <p>20.1 The Sediment–Water Interface 618</p> <p>20.2 Transport in Unsaturated Soil 626</p> <p>20.3 Questions and Problems 630</p> <p>20.4 Bibliography 634</p> <p><b>Part V Transformation Processes 635</b></p> <p><b>21 Background Knowledge on Transformation Reactions of Organic Pollutants 637</b></p> <p>21.1 Identifying Reactive Sites Within Organic Molecules 638</p> <p>21.2 Thermodynamics of Transformation Reactions 643</p> <p>21.3 Kinetics of Transformation Reactions 650</p> <p>21.4 Questions and Problems 657</p> <p>21.5 Bibliography 661</p> <p><b>22 Hydrolysis And ReactionsWith Other Nucleophiles 663</b></p> <p>22.1 Nucleophilic Substitution and Elimination Reactions Involving Primarily Saturated Carbon Atoms 665</p> <p>22.2 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives 680</p> <p>22.3 Enzyme-Catalyzed Hydrolysis Reactions: Hydrolases 695</p> <p>22.4 Questions and Problems 701</p> <p>22.5 Bibliography 710</p> <p><b>23 Redox Reactions 715</b></p> <p>23.1 Introduction 716</p> <p>23.2 Evaluating the Thermodynamics of Redox Reactions 719</p> <p>23.3 Examples of Chemical Redox Reactions in Natural Systems 730</p> <p>23.4 Examples of Enzyme-Catalyzed Redox Reactions 747</p> <p>23.5 Questions and Problems 756</p> <p>23.6 Bibliography 765</p> <p><b>24 Direct Photolysis in Aquatic Systems 773</b></p> <p>24.1 Introduction 775</p> <p>24.2 Some Basic Principles of Photochemistry 776</p> <p>24.3 Light Absorption by Organic Compounds in Natural Waters 788</p> <p>24.4 Quantum Yield and Rate of Direct Photolysis 800</p> <p>24.5 Effects of Solid Sorbents (Particles, Soil Surfaces, Ice) on Direct Photolysis 803</p> <p>24.6 Questions and Problems 804</p> <p>24.7 Bibliography 811</p> <p><b>25 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere 815</b></p> <p>25.1 Introduction 816</p> <p>25.2 Indirect Photolysis in Surface Waters 817</p> <p>25.3 Indirect Photolysis in the Atmosphere (Troposphere): Reaction with Hydroxyl Radical (HO^∙) 829</p> <p>25.4 Questions and Problems 833</p> <p>25.5 Bibliography 838</p> <p><b>26 Biotransformations 845</b></p> <p>26.1 Introduction 847</p> <p>26.2 Some Important Concepts about Microorganisms Relevant to Biotransformations 848</p> <p>26.3 Initial Biotransformation Strategies 858</p> <p>26.4 Rates of Biotransformations 864</p> <p>26.5 Questions and Problems 882</p> <p>26.6 Bibliography 889</p> <p><b>27 Assessing Transformation Processes Using Compound-Specific Isotope Analysis (CSIA) 897</b></p> <p>27.1 Introduction, Methodology, and Theoretical Background 898</p> <p>27.2 Using CSIA for Assessing Organic Compound Transformations in Laboratory and Field Systems 914</p> <p>27.3 Questions and Problems 930</p> <p>27.4 Bibliography 936</p> <p><b>Part VI Putting Everything Together 945</b></p> <p><b>28 Exposure Assessment of Organic Pollutants Using Simple Modeling Approaches 947</b></p> <p>28.1 One-Box Model: The Universal Tool for Process Integration 948</p> <p>28.2 Assessing Equilibrium Partitioning in Simple Multimedia Systems 952</p> <p>28.3 Simple Dynamic Systems 956</p> <p>28.4 Systems Driven by Advection 960</p> <p>28.5 Bibliography 974</p> <p>Appendix 977</p> <p>Index 995</p>

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

<p><b>A Completely Revised and Updated Edition of the Authorative Text in Environmental Organic Chemistry</b></p><p><i>Environmental Organic Chemistry, Third Edition</i> focuses on the molecular processes and macroscopic transport phenomena that determine the spatiotemporal distributions of organic chemicals released into the environment; this knowledge is then applied to quantitatively assess the fates of those chemicals in natural and engineered systems.</p><p>Long established as the discipline’s authoritative text, the third edition of <i>Environmental Organic Chemistry</i> significantly revises, regroups, and expands the contents of its predecessor along with a complete account of the state of the art of the field. By explaining in a pedagogical way how to relate the structure of a given chemical to its physical chemical properties and intrinsic reactivities, by providing the necessary background knowledge on the chemistry and physics of microscopic and macroscopic environmental systems, and by introducing simple modeling approaches, the reader is able to quantify phase transfers, transformations, and transport processes at each level. Compared to the 2nd edition, the 3rd edition provides a more holistic and teachable description of partitioning and transformation processes, as well as a more focused and tailor-made presentation of physical and mathematical modeling aspects. Divided into six main parts, <i>Environmental Organic Chemistry, Third Edition</i> features:</p><ul> <li>Pertinent background knowledge on the make-up and on the use of anthropogenic organic chemicals, on the thermodynamics and kinetics of partitioning and transformation processes, on the molecular interactions governing partitioning processes, on the chemical and physical characteristics of environmental systems, and on simple modeling approaches used to quantitatively assess organic chemicals</li><li>A quantitative treatment of equilibrium partitioning of organic chemicals in well-defined as well as in environmental systems including air—water partitioning, sorption from air or water to organic and inorganic sorbents, and bioaccumulation in aquatic and terrestrial systems</li><li>A quantitative treatment of transport processes across interfaces and its application to atmosphere—surface water, atmosphere—soil, and sediment bed—water exchanges.</li><li>A quantitative treatment of chemical, photochemical, and microbiological transformation processes including a new chapter on the use of compound-specific isotope analysis to assess transformation reactions in laboratory and field systems</li><li>Case studies illustrating how to put everything together using simple modeling approaches</li></ul><p>Intended as a comprehensive text for (introductory) courses in environmental organic chemistry at the graduate level, as well as an important source of information for risk assessment of organic chemicals and for solving practical problems at contaminated sites, <i>Environmental Organic Chemistry, Third Edition</i> continues to make a significant contribution to the education of environmental scientists and engineers and, thus, to a better protection of our environment.</p>

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