Examines in a pedagogical way all pertinent molecular and macroscopic processes that govern the distribution and fate of organic chemicals in the environment and provides simple modeling tools to quantitatively describe these processes and their interplay in a given environmental system

* Treats fundamental aspects of chemistry, physics, and mathematical modeling as applied to environmentally relevant problems, and gives a state of the art account of the field

* Teaches the reader how to relate the structure of a given chemical to its physical chemical properties and intrinsic reactivities

* Provides a holistic and teachable treatment of phase partitioning and transformation processes, as well as a more focused and tailor-made presentation of physical, mathematical, and modeling aspects that apply to environmental situations of concern

* Includes a large number of questions and problems allowing teachers to explore the depth of understanding of their students or allowing individuals who use the book for self-study to check their progress

* Provides a companion website, which includes solutions for all problems as well as a large compilation of physical constants and compound properties

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.

A Completely Revised and Updated Edition of the Authorative Text in Environmental Organic Chemistry

Environmental Organic Chemistry, Third Edition 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.

Long established as the discipline's authoritative text, the third edition of Environmental Organic Chemistry 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, Environmental Organic Chemistry, Third Edition features:

• 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
• A quantitative treatment of equilibrium partitioning of organic chemicals in well-defined as well as in environmental systems including airwater partitioning, sorption from air or water to organic and inorganic sorbents, and bioaccumulation in aquatic and terrestrial systems
• A quantitative treatment of transport processes across interfaces and its application to atmospheresurface water, atmospheresoil, and sediment bedwater exchanges.
• 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
• Case studies illustrating how to put everything together using simple modeling approaches

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, Environmental Organic Chemistry, Third Edition continues to make a significant contribution to the education of environmental scientists and engineers and, thus, to a better protection of our environment.

Preface xiii

About the Companion Website xvii

1 General Topic and Overview 1

1.1 Introduction 2

1.2 Assessing Organic Chemicals in the Environment 4

1.3 What is This Book All About? 7

1.4 Bibliography 14

Part I Background Knowledge 17

2 Background Knowledge on Organic Chemicals 19

2.1 The Makeup of Organic Compounds 20

2.2 Intermolecular Forces Between Uncharged Molecules 37

2.3 Questions and Problems 40

2.4 Bibliography 43

3 The Amazing World of Anthropogenic Organic Chemicals 45

3.1 Introduction 47

3.2 A Lasting Global Problem: Persistent Organic Pollutants (POPs) 47

3.3 Natural but Nevertheless Problematic: Petroleum Hydrocarbons 48

3.4 Notorious Air and Groundwater Pollutants: Organic Solvents 53

3.5 Safety First: Flame Retardants All Around Us 56

3.6 How to Make Materials Repellent: Polyfluorinated Chemicals (PFCs) 58

3.7 From Washing Machines to Surface Waters: Complexing Agents, Surfactants, Whitening Agents, and Corrosion Inhibitors 60

3.8 Health, Well-Being, and Water Pollution: Pharmaceuticals and Personal Care Products 63

3.9 Fighting Pests: Herbicides, Insecticides, and Fungicides 65

3.10 Our Companion Compounds: Representative Model Chemicals 69

3.11 Questions 72

3.12 Bibliography 73

4 Background Thermodynamics, Equilibrium Partitioning and Acidity Constants 81

4.1 Important Thermodynamic Functions 83

4.2 Using Thermodynamic Functions to Quantify Equilibrium Partitioning 89

4.3 Organic Acids and Bases I: Acidity Constant and Speciation in Natural Waters 98

4.4 Organic Acids and Bases II: Chemical Structure and Acidity Constant 107

4.5 Questions and Problems 116

4.6 Bibliography 119

5 Earth Systems and ComPartments 121

5.1 Introduction 123

5.2 The Atmosphere 125

5.3 Surface Waters and Sediments 131

5.4 Soil and Groundwater 148

5.5 Biota 154

5.6 Questions 155

5.7 Bibliography 158

6 Environmental Systems: Physical Processes and Mathematical Modeling 165

6.1 Systems and Models 167

6.2 Box Models: A Concept for a Simple World 174

6.3 When Space Matters: Transport Processes 191

6.4 Models in Space and Time 196

6.5 Questions and Problems 203

6.6 Bibliography 211

Part II Equilibrium Partitioning in Well-Defined Systems 213

7 Partitioning Between Bulk Phases: General Aspects and Modeling Approaches 215

7.1 Introduction 216

7.2 Molecular Interactions Governing Bulk Phase Partitioning of Organic Chemicals 217

7.3 Quantitative Approaches to Estimate Bulk Phase Partition Constants/Coefficients: Linear Free Energy Relationships (LFERs) 225

7.4 Questions 232

7.5 Bibliography 234

8 V…