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Environmental Organic Chemistry, 3rd Edition

ISBN: 978-1-118-76723-8
1026 pages
November 2016, ©2017
Environmental Organic Chemistry, 3rd Edition (1118767233) cover image

Description

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
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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 (Csat iw) and Activity Coefficient (γ 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

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