Environmental Organic Chemistry
3. Auflage Dezember 2016
1024 Seiten, Softcover
Lehrbuch
ISBN:
978-1-118-76723-8
John Wiley & Sons
Weitere Versionen
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 (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
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
