Schweitzer Fachinformationen
Wenn es um professionelles Wissen geht, ist Schweitzer Fachinformationen wegweisend. Kunden aus Recht und Beratung sowie Unternehmen, öffentliche Verwaltungen und Bibliotheken erhalten komplette Lösungen zum Beschaffen, Verwalten und Nutzen von digitalen und gedruckten Medien.
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.
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
"Textbooks are outdated. Don't waste your time writing a textbook! Nowadays, teachers, students, and practitioners download whatever they need to know from the Internet. They don't depend on textbooks anymore."
These and other similarly "encouraging" statements were made by some dear colleagues three years ago, ten years after the 2nd edition and twenty years after the 1st edition of our textbook appeared, when we announced our plan to write a 3rd edition. However, numerous others also motivated us to sit down and reflect again about the broad, interdisciplinary field of environmental organic chemistry, which has excited us during our whole scientific careers. And they won! Here it is, the 3rd edition. Also, here is why we feel that textbooks are needed more than ever: in a time in which the number of scientific publications continue to explode, there is, from time to time, a need to assess in a more holistic way the state-of-the-art in a given field, and to summarize this state-of-the-art in a didactic form, so it can be used for educational purposes. In other words, between two physical or imaginary book covers, an attempt to define a given field and to give an account where this field stands. Of course, such an attempt represents only the biased, personal view of the book's authors, but this may be better than having no view at all.
What distinguishes the 3rd edition from the previous two editions? The first important message is: our main goal and approach is still the same. We want to provide an understanding of how molecular interactions and macroscopic transport phenomena determine the distribution in space and time of organic compounds released into natural and engineered environments. We hope to do this by teaching the reader to utilize the structure of a given chemical to deduce that chemical's physical chemical properties and intrinsic reactivities. Emphasis is placed on quantification of phase transfer, transformation, and transport processes at each level. By first considering each of the processes that act on organic chemicals one at a time, we try to build bits of knowledge and understanding that, combined in mathematical models, should enable the reader to assess organic compound behavior in the environment.
The second important message is: as was the case when going from the 1st to the 2nd edition, the new edition has undergone significant changes. Old chapters have been deleted, the remaining chapters have been substantially revised, and new chapters have been added. Another important goal was to diminish the total volume of the book. Of course, for all topics, we have tried hard to give an account of the state-of-the-art and to provide access to the pertinent literature. The most drastic change made was our decision to position an introduction of mathematical modeling in Part I (Chapter 6) among other introductory chapters and, in turn, to condense the chapters on transport and mixing, and on modeling of environmental systems.
However, this does not mean that the most important physical and mathematical modeling aspects have been lost. They are now just more focused and tailor-made to the needs of environmental chemists and environmental engineers. In addition to this main change, we have added four completely new chapters, which were neither present in the 1st nor 2nd edition, and which, in our opinion, can hardly be found anywhere else: (i) A look into the vast world of anthropogenic chemicals, illustrating the great innovations made by the chemical industry in customizing chemicals that fulfill important tasks in our daily lives, but also illustrating why many of them are of environmental concern (Chapter 3); (ii) A summary of the most important physical and chemical "properties" of environmental compartments including the atmosphere, surface waters, soils, and groundwater (Chapter 5); (iii) A quantitative treatment of aerosol-air partitioning of organic pollutants and the role of aerosols in determining their residence time in the stratosphere (Chapter 15); and (iv) An introduction to compound specific isotope analysis (CSIA) and its application to assess organic pollutant transformations in laboratory and field systems (Chapter 27).
Who should read and use this book, or at least keep it on their bookshelf? From our experience with the previous editions, and maybe still with a bit of wishful thinking, we are inclined to answer this question with "Everybody who has to deal with organic chemicals in the environment." More specifically,we believe that the theoretical explanations andmathematical relationships discussed are very useful for chemistry professors and students who want both fundamental explanations and concrete applications that students can use to remember those chemical principles. Likewise, we suggest that environmental and earth science professors as well as their students can utilize the chemical property information and quantitative descriptions of chemical cycling to think about how humans are playing an increasingly important role in changing the Earth system and how we may use specific chemicals as tracers of environmental processes. Further, we believe that civil and environmental engineering professors and students will benefit from detailed understanding of the fundamental phenomena supporting existing mitigation and remedial designs, and they should gain insights that allow them to invent the engineering approaches of the future. Environmental policy and management professors as well as students can also benefit by seeing our capabilities (and limitations) in estimating chemical exposures that result from our society's use of chemicals. Finally, chemists and chemical engineers in industry should be able to use this book's information to help make "green chemistry" decisions, whereas governmental regulators and environmental consultants can use the book in order to better assess the chemical uses they must permit and the problem sites theymust assess and manage.
To meet the needs of this very diverse audience, we have tried wherever possible to present the various topics in a way to make this book useful for beginners as well as for people with more expertise. We have also incorporated a large number of references throughout the text to help those who want to follow particular topics further. Finally, by including numerous problems, we want to motivate students as well as practitioners to attempt to arrive at quantitative answers for particular cases of interest to them. For all problems, solutions are made available electronically through a web site provided by the publisher-some of them to everybody but all of them to teachers, practitioners, and others with special permission. The possibility of making materials available electronically has allowed us to turn most of the illustrative examples of the 2nd edition into problems, thus making the main text more readable. It also allows us to provide the appendices, in particular the large Appendix Containing properties of numerous diverse chemicals, solely in electronic form.
In conclusion, this book is 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 practical hazard and risk assessment of organic chemicals in the environment. We hope that with this 3rd edition, we can continue to make a useful contribution to the education of environmental scientists and engineers and, thus, to better protection of our environment.
Acknowledgments. Those who have ever written a textbook know that the authors are not the only ones who play an important role in the realization of the final product. In this particular case, one person made all the difference: Jeanne Tomaszewski, who we appointed as editor and general manager for this textbook. Jeanne has not only turned our "Swiss-English" into a language that can be understood by any Englishspeaking person, she has also been a relentless critic of how we present things, and she has helped us in literature searches and in the compilation of data. Last but not least, she has managed the entire process of readying the manuscript for the publisher. THANK YOU Jeanne; without you, there would most likely not be a 3rd edition of Environmental Organic Chemistry.
Many thanks to those who helped us with the numerous figures and structures in the book: above all,Werner Angst and Martin Hoffmann, but also Lauren McLean, Konstanze Schiessel, and Thierry Sollberger. Thanks as well to our professional colleagues who lent a keen eye to make sure some of our chapters are at their scientific best: Kathrin Fenner (Chapter 3), Kai-Uwe Goss (Chapter 7), Satoshi Endo (Chapters 7-10), Hans Peter Arp (Chapter 15), Beate Escher (Chapter 16), Kristopher McNeill (Chapters 24 and 25), Fatima Hussain and Allison Perrotta (Chapter 26), and Martin Elsner, Thomas Hofstetter, Elisabeth Janssen, and Michael Sander (Chapter 27).
We are also indebted to the Swiss Federal Institute of Technology in Zurich (ETH-Zurich) for significant financial support. Finally, we thank our wives Theres Schwarzenbach, Colleen Cavanaugh, and Sibyl Imboden for their continuous support during the many years of our professional lives.
René P. Schwarzenbach Zürich, Switzerland
Philip M. Gschwend Cambridge,...
Dateiformat: ePUBKopierschutz: Adobe-DRM (Digital Rights Management)
Systemvoraussetzungen:
Das Dateiformat ePUB ist sehr gut für Romane und Sachbücher geeignet – also für „fließenden” Text ohne komplexes Layout. Bei E-Readern oder Smartphones passt sich der Zeilen- und Seitenumbruch automatisch den kleinen Displays an. Mit Adobe-DRM wird hier ein „harter” Kopierschutz verwendet. Wenn die notwendigen Voraussetzungen nicht vorliegen, können Sie das E-Book leider nicht öffnen. Daher müssen Sie bereits vor dem Download Ihre Lese-Hardware vorbereiten.Bitte beachten Sie: Wir empfehlen Ihnen unbedingt nach Installation der Lese-Software diese mit Ihrer persönlichen Adobe-ID zu autorisieren!
Weitere Informationen finden Sie in unserer E-Book Hilfe.
