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 (Csat iw) and Activity Coefficient (gamma sat iw ) 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 and Wet 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 Reactions With 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
