Includes a large number of questions and problems allowing teachers to explore the depth of understanding of t
Table of Contents
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 (𝜸satiw ) 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
