Environmental Organic Chemistry

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

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 Vapor Pressure (pi∗) 237

8.1 Introduction and Theoretical Background 238

8.2 Molecular Interactions Governing Vapor Pressure and Vapor Pressure Estimation Methods 246

8.3 Questions and Problems 253

8.4 Bibliography 257

9 Solubility (Csatiw ) and Activity Coefficient (;;satiw) in Water; Air–Water Partition Constant (Kiaw) 259

9.1 Introduction and Thermodynamic Considerations 261

9.2 Molecular Interactions Governing the Aqueous Activity Coefficient and the Air–Water Partition Constant 267

9.3 LFERs for Estimating Air–Water Partition Constants and Aqueous Activity Coefficients/Aqueous Solubilities 270

9.4 Effect of Temperature, Dissolved Salts, and pH on the Aqueous Activity Coefficient/Aqueous Solubility and on the Air–Water Partition Constant 272

9.5 Questions and Problems 282

9.6 Bibliography 285

10 Organic Liquid–Air and Organic Liquid–Water Partitioning 289

10.1 Introduction 291

10.2 Thermodynamic Considerations and Comparisons of Different Organic Solvents 291

10.3 The Octanol–Water System: The Atom/Fragment Contribution Method for Estimation of the Octanol–Water Partition

Constant 298

10.4 Partitioning Involving Organic Solvent–Water Mixtures 301

10.5 Evaporation and Dissolution of Organic Compounds from Organic Liquid Mixtures–Equilibrium

Considerations 307

10.6 Questions and Problems 311

10.7 Bibliography 317

11 Partitioning of Nonionic Organic Compounds Between Well-Defined Surfaces and Air or Water 321

11.1 Introduction 322

11.2 Adsorption from Air to Well-Defined Surfaces 322

11.3 Adsorption from Water to Inorganic Surfaces 335

11.4 Questions and Problems 342

11.5 Bibliography 345

Part III Equilibrium Partitioning in Environmental Systems 349

12 General Introduction to Sorption Processes 351

12.1 Introduction 352

12.2 Sorption Isotherms and the Solid–Water Equilibrium Distribution Coefficient (Kid) 354

12.3 Speciation (Sorbed versus Dissolved or Gaseous), Retardation, and Sedimentation 360

12.4 Questions and Problems 366

12.5 Bibliography 368

13 Sorption from Water to Natural Organic Matter (NOM) 369

13.1 The Structural Diversity of Natural Organic Matter Present in Aquatic and Terrestrial Environments 371

13.2 Quantifying Natural Organic Matter–Water Partitioning of Neutral Organic Compounds 376

13.3 Sorption of Organic Acids and Bases to Natural Organic Matter 388

13.4 Questions and Problems 392

13.5 Bibliography 397

14 Sorption of Ionic Organic Compounds to Charged Surfaces 405

14.1 Introduction 407

14.2 Cation and Anion Exchange Capacities of Solids in Water 408

14.3 Ion Exchange: Nonspecific Adsorption of Ionized Organic Chemicals from Aqueous Solutions to Charged Surfaces 414

14.4 Surface Complexation: Specific Bonding of Organic Compounds with Solid Phases in Water 426

14.5 Questions and Problems 432

14.6 Bibliography 436

15 Aerosol–Air Partitioning: Dry andWet Deposition of Organic Pollutants 441

15.1 Origins and Properties of Atmospheric Aerosols 442

15.2 Assessing Aerosol–Air Partition Coefficients (KiPMa) 445

15.3 Dry and Wet Deposition 453

15.4 Questions and Problems 459

15.5 Bibliography 464

16 Equilibrium Partitioning From Water and Air to Biota 469

16.1 Introduction 471

16.2 Predicting Biota–Water and Biota–Air Equilibrium Partitioning 471

16.3 Bioaccumulation and Biomagnification in Aquatic Systems 485

16.4 Bioaccumulation and Biomagnification in Terrestrial Systems 498

16.5 Baseline Toxicity (Narcosis) 503

16.6 Questions and Problems 507

16.7 Bibliography 514

Part IV Mass Transfer Processes in Environmental Systems 523

17 Random Motion, Molecular and Turbulent Diffusivity 525

17.1 Random Motion 526

17.2 Molecular Diffusion 534

17.3 Other Random Transport Processes in the Environment 545

17.4 Questions and Problems 550

17.5 Bibliography 557

18 Transport at Boundaries 559

18.1 The Role of Boundaries in the Environment 560

18.2 Bottleneck Boundaries 562

18.3 Wall Boundaries 567

18.4 Hybrid Boundaries 572

18.5 Questions and Problems 577

18.6 Bibliography 580

19 Air–Water Exchange 581

19.1 The Air–Water Interface 583

19.2 Air–Water Exchange Models 585

19.3 Measurement of Air–Water Exchange Velocities 592

19.4 Air–Water Exchange in Flowing Waters 599

19.5 Questions and Problems 604

19.6 Bibliography 613

20 Interfaces Involving Solids 617

20.1 The Sediment–Water Interface 618

20.2 Transport in Unsaturated Soil 626

20.3 Questions and Problems 630

20.4 Bibliography 634

Part V Transformation Processes 635

21 Background Knowledge on Transformation Reactions of Organic Pollutants 637

21.1 Identifying Reactive Sites Within Organic Molecules 638

21.2 Thermodynamics of Transformation Reactions 643

21.3 Kinetics of Transformation Reactions 650

21.4 Questions and Problems 657

21.5 Bibliography 661

22 Hydrolysis And ReactionsWith Other Nucleophiles 663

22.1 Nucleophilic Substitution and Elimination Reactions Involving Primarily Saturated Carbon Atoms 665

22.2 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives 680

22.3 Enzyme-Catalyzed Hydrolysis Reactions: Hydrolases 695

22.4 Questions and Problems 701

22.5 Bibliography 710

23 Redox Reactions 715

23.1 Introduction 716

23.2 Evaluating the Thermodynamics of Redox Reactions 719

23.3 Examples of Chemical Redox Reactions in Natural Systems 730

23.4 Examples of Enzyme-Catalyzed Redox Reactions 747

23.5 Questions and Problems 756

23.6 Bibliography 765

24 Direct Photolysis in Aquatic Systems 773

24.1 Introduction 775

24.2 Some Basic Principles of Photochemistry 776

24.3 Light Absorption by Organic Compounds in Natural Waters 788

24.4 Quantum Yield and Rate of Direct Photolysis 800

24.5 Effects of Solid Sorbents (Particles, Soil Surfaces, Ice) on Direct Photolysis 803

24.6 Questions and Problems 804

24.7 Bibliography 811

25 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere 815

25.1 Introduction 816

25.2 Indirect Photolysis in Surface Waters 817

25.3 Indirect Photolysis in the Atmosphere (Troposphere): Reaction with Hydroxyl Radical (HO∙) 829

25.4 Questions and Problems 833

25.5 Bibliography 838

26 Biotransformations 845

26.1 Introduction 847

26.2 Some Important Concepts about Microorganisms Relevant to Biotransformations 848

26.3 Initial Biotransformation Strategies 858

26.4 Rates of Biotransformations 864

26.5 Questions and Problems 882

26.6 Bibliography 889

27 Assessing Transformation Processes Using Compound-Specific Isotope Analysis (CSIA) 897

27.1 Introduction, Methodology, and Theoretical Background 898

27.2 Using CSIA for Assessing Organic Compound Transformations in Laboratory and Field Systems 914

27.3 Questions and Problems 930

27.4 Bibliography 936

Part VI Putting Everything Together 945

28 Exposure Assessment of Organic Pollutants Using Simple Modeling Approaches 947

28.1 One-Box Model: The Universal Tool for Process Integration 948

28.2 Assessing Equilibrium Partitioning in Simple Multimedia Systems 952

28.3 Simple Dynamic Systems 956

28.4 Systems Driven by Advection 960

28.5 Bibliography 974

Appendix 977

Index 995

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 air—water 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 atmosphere—surface water, atmosphere—soil, and sediment bed—water 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.