ENVIRONMENTAL

ORGANIC CHEMISTRY

Second Edition

ENVIRONMENTAL ORGANIC CHEMISTRY

Second Edition

Rene P. Schwarzenbach Philip M. Gschwend Dieter M. Imboden

@WI LEY-INTERSCI ENCE A JOHN WILEY & SONS, INC., PUBLICATION

This text is printed on acid-free paper. @

Copyright 0 2003 by John Wiley & Sons, Inc. All rights reserved

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Printed in the United States of America

10 9 8 7 6 5 4 3

V

CONTENTS

Preface xi

PART I Introduction

1 General Topic and Overview

1.1 Introduction / 4 1.2

1.3

Assessing Organic Chemicals in the Environment: The Needs and the Tasks / 6 What Is This Book All About? / 8

2 An Introduction to Environmental Organic Chemicals

2.1 Introduction / 14 2.2 2.3

2.4

The Makeup of Organic Compounds / 14 Classification, Nomenclature, and Examples of Environmental Organic Chemicals / 3 1 Questions and Problems / 5 1

PART I1 Equilibrium Partitioning Between Gaseous, Liquid, and Solid Phases

3

13

55

3 Partitioning: Molecular Interactions and Thermodynamics 57

3.1 Introduction / 59 3.2

3.3

3.4

3.5

Molecular Interactions Determining the Partitioning of Organic Compounds Between Different Phases / 59 Using Thermodynamic Functions to Quantify Molecular Energies / 73 Using Thermodynaimc Functions to Quantify Equilibrium Partitioning / 84 Using Partition Constants/Coefficients to Assess the Equilibrium Distribution of Neutral Organic Compounds in Multiphase Systems / 93 Questions and Problems / 95 3.6

vi

4 Vapor Pressure

4.1 Introduction / 98 4.2 Theoretical Background / 98 4.3 4.4

4.5

Molecular Interactions Governing Vapor Pressure / 110 Availability of Experimental Vapor Pressure Data and Estimation Methods / 11 8 Questions and Problems / 126

97

5 Activity Coefficient and Solubility in Water 133

5.1 Introduction / 135 5.2 Thermodynamic Considerations / 135 5.3

5.4

5.5

5.6

Molecular Interpretation of the Excess Free Energy of Organic Compounds in Aqueous Solutions / 142 Effect of Temperature and Solution Composition on Aqueous Solubility and Activity Coefficient / 154 Availability of Experimental Data; Methods for Estimation of Aqueous Activity Coefficient and Aqueous Solubility / 172 Questions and Problems / 175

6 Air-Organic Solvent and Air-Water Partitioning

6.1 Introduction / 182 6.2 Thermodynamic Considerations / 183 6.3 6.4 Air-Water Partitioning / 197 6.5

Air-Organic Solvent Partitioning / 185

Questions and Problems / 208

181

7 Organic Liquid-Water Partitioning 213

7.1 Introduction / 214 7.2 Thermodynamic Considerations / 214 7.3 7.4 7.5

7.6

Comparison of Different Organic Solvent-Water Systems / 2 16 The n-Octanol-Water Partition Constant / 223 Dissolution of Organic Compounds in Water from Organic Liquid Mixtures-Equilibrium Considerations (Advanced Topic) / 235 Questions and Problems / 239

8 Organic Acids and Bases: Acidity Constant and Partitioning Behavior

8.1 Introduction / 246 8.2 Thermodynamic Considerations / 246 8.3 Chemical Structure and Acidity Constant / 256

245

vii

8.4 Availability of Experimental Data; Methods for Estimation ofAcidity Constants 1261

8.5 Aqueous Solubility and Partitioning Behavior of Organic Acids and Bases 1268

8.6 Questions and Problems 1272

9 Sorption I: General Introduction and Sorption Processes Involving Organic Matter

9.1 Introduction I 277 9.2 Sorption Isotherms, Solid-Water Distribution

9.3

9.4

9.5

9.6

Coefficients (Kid), and the Fraction Dissolved V;,,,) / 280 Sorption of Neutral Organic Compounds from Water to Solid-Phase Organic Matter (POM) / 29 1 Sorption of Neutral Compounds to "Dissolved" Organic Matter (DOM) I 3 14 Sorption of Organic Acids and Bases to Natural Organic Matter (NOM) I 32 1 Questions and Problems / 326

275

10 Sorption 11: Partitioning to Living Media - Bioaccumulation and Baseline Toxicity 331

10.1 Introduction 1333 10.2 Partitioning to Defined Biomedia 1335 10.3 Bioaccumulation in Aquatic Systems I 349 10.4 Bioaccumulation in Terrestrial Systems / 36 I 10.5 Biomagnification 1366 10.6 Baseline Toxicity (Narcosis) / 374 10.7 Questions and Problems I 381

11 Sorption 111: Sorption Processes Involving Inorganic Surfaces

11.1 Introduction I 389 11.2 Adsorption of Nonionic Organic Compounds to

Inorganic Surfaces from Air I 39 1 11.3 Sorption of Nonionic Organic Compounds to Inorganic

Surfaces in Water 1408 11.4 Adsorption of Ionized Organic Compounds from

Aqueous Solutions to Charged Mineral Surfaces / 417 11.5 Surface Reactions of Organic Compounds (Advanced Topic) I 441 11.6 Questions and Problems I 448

387

viii

Part I11 Transformation Processes 459

12 Thermodynamics and Kinetics of Transformation Reactions 461

12.1 Introduction / 462 12.2 Thermodynamics of Transformation Reactions / 463 12.3 Kinetic Aspects of Transformation Reactions / 468 12.4 Well-Mixed Reactor or One-Box Model / 482 12.5 Questions and Problems / 486

13 Chemical Transformations I: Hydrolysis and Reactions Involving Other Nucleophilic Species

13.1 Introduction, Overview / 49 1 1 3.2 Nucleophilic Substitution and Elimination

at Saturated Carbon Atoms / 495 13.3 Hydrolytic Reactions of Carboxylic and

Carbonic Acid Derivatives / 5 13 13.4 Hydrolytic Reactions of Phosphoric and Thiophosphoric

Acid Esters / 536 13.5 Effects of Dissolved Metal Species and of Mineral Oxide

Surfaces on Hydrolytic Reactions (Advanced Topic) / 540 13.6 Questions and Problems / 546

14 Chemical Transformations 11: Redox Reactions

14.1 Introduction, Overview / 556 14.2 Thermodynamic Considerations of Redox Reactions / 559 14.3 Reaction Pathways and Kinetics of Redox Reactions / 580 14.4 Questions and Problems / 602

15 Direct Photolysis

15.1 Introduction / 6 13 15.2 Some Basic Principles of Photochemistry / 6 14 15.3 Light Absorption by Organic Chemicals in Natural Waters / 627 15.4 Quantum Yield and Rate of Direct Photolysis / 641 15.5 Effects of Solid Sorbents (Particles, Soil Surfaces) on

Direct Photolysis / 649 15.6 Questions and Problems / 650

16 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere

16.1 Introduction / 656 16.2 Indirect Photolysis in Surface Waters / 658

489

555

611

655

ix

16.3 Indirect Photolysis in the Atmosphere (Troposphere)- Reactions with Hydroxyl Radical (HO') / 672

16.4 Questions and Problems I 683

17 Biological Transformations

17.1 Introduction / 689 17.2 Some Important Concepts about Microorganisms 1694 17.3 Biochemical Strategies of Microbial Organic Chemists / 702 17.4 Rates of Biotransformations: Uptake / 734 17.5 Rates of Biotransformations: Microbial Growth / 739 17.6 Rates of Biotransformations: Enzymes / 750 17.7 Questions and Problems I767

PART IV Modeling Tools: Transport and Reaction

687

775

18 Transport by Random Motion 777

18.1 Introduction: Advection and Diffusion / 779 18.2 Random Motion I 780 18.3 Random Motion at the Molecular Level:

Molecular Diffusion Coefficients / 798 18.4 Diffusion in Porous Media / 8 15 18.5 Other Random Transport Processes in the Environment / 825 18.6 Questions and Problems / 828

19 Transport Through Boundaries

19.1 The Role of Boundaries in the Environment / 835 19.2 Bottleneck Boundaries / 839 19.3 Wall Boundaries 1848 19.4 Diffusive Boundaries / 866 19.5 Spherical Boundaries (Advanced Topic) / 871 19.6 Questions and Problems / 883

20 Air-Water Exchange

20.1 Introduction / 889 20.2 Measurement of Air-Water Transfer Velocities I 896 20.3 Air-Water Exchange Models 1906 20.4 Air-Water Exchange in Flowing Waters I 92 1 20.5 Influence of Surface Films and Chemical Reactions

on Air-Water Exchange (Advanced Topic) / 929 20.6 Questions and Problems 1939

833

887

X

21 BoxModels

21.1 Principles of Modeling / 947 21.2 One-Box Models / 955 21.3 Two-Box Models / 982 2 1.4 Dynamic Properties of Linear Multidimensional Models

(Advanced Topic) / 991 2 1.5 Questions and Problems / 1000

945

22 Models in Space and Time 1005

22.1 One-Dimensional Diffusion /Advection / Reaction Models / 1006 22.2 Turbulent Diffusion / 1019 22.3 Horizontal Diffusion: Two-Dimensional Mixing / 1030 22.4 Dispersion (Advanced Topic) / 1038 22.5 Questions and Problems / 1044

Part V Environmental Systems and Case Studies 1049

23 Ponds, Lakes, and Oceans 1051

23.1 Linear One-Box Models of Lakes, Ponds, and Oceans / 1054 23.2 The Role of Particles and the Sediment-Water Interface / 1059 23.3 Two-Box Models of Lakes / 1075 23.4 One-Dimensional Continuous Lake Models (Advanced Topic) / 1082 23.5 Questions and Problems / 1093

24 Rivers 1101

24.1 Transport and Reaction in Rivers / 1 102 24.2 Turbulent Mixing and Dispersion in Rivers / 1120 24.3 A Linear TransportReaction Model for Rivers / 11 30 24.4 Questions and Problems / 1141

25 Groundwater 1147

25.1 Groundwater Hydraulics / 1148 25.2 Time-Dependent Input into an Aquifer (Advanced Topic) / 1160 25.3 Sorption and Transformations / 1170 25.4 Questions and Problems / 1179

Appendix 1185

Bibliography 1213

Index (Subject Index, Compound Index, List of Illustrative Examples) 1255

xi

PREFACE

“Don’t worry, we will never do it again!” This is the promise we sincerely made almost 10 years ago to our families, friends, and colleagues after having survived together the writing of the first edition of our textbook Environmental Organic Chemistry, and made once more after finishing the companion Problems Book two years later. But keeping such promises and keeping up with this rapidly expanding, exciting field of environmental sciences seem to be two things that are mutually exclusive. Hence, with fading memories of what it was really like, and flattered by the success of the first edition of our textbook, we decided to take on the challenge again; maybe at first not realizing that we have grown older and, as a consequence, that our professional lives have become much more diverse and busy than they used to be. Furthermore, what began as a minor revision and updating of the first edition soon developed its own dynamics, completely overturned old chapters and created new ones. During this process it became clear to us that the integration of the Problems Book with its two additional system chapters on rivers and groundwater into the main book would shift the gravity of the new edition to- ward the system approach, however, not at the expense of the fundamental chemical principles, but by adding more physics and mathematical modeling. This is now the product of four years of struggling with an immense amount of recent literature, as well as of continuously suffering from being on the horns of a dilemma; that is, the attempt to provide a fundamental text combining background theory, illustrative examples, and questions and problems, and, at the same time, to give a state-of-the- art account of a rather broad and interdisciplinary field. However, it would be com- pletely wrong to view the writing of this second edition solely as an ordeal; on the contrary, particularly the many exciting discussions with numerous students and colleagues have been very rewarding and most enjoyable. We hope that some of this joy will also be felt by our readers.

What is this book all about? Everything you ever needed to know for assessing the environmental behavior of organic chemicals and more? Not quite, but we hope a

xii

great deal of it, and certainly more than in the first edition. As in the first edition, our major goal is to provide an understanding of how molecular interactions and macro- scopic 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 intrinsic physical properties and reactivities. Emphasis is placed on guantzjtcation 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 understandings that later in the book are combined in mathematical models to assess organic compound behavior in the environment.

Who should read and use this book, or at least keep it on their bookshelf? From our experience with the first edition, and maybe still with a little bit of wishful thinking, we are inclined to answer this question with “Everybody who has to deal with organic pollutants in the environment”. More specifically, we believe that the theoretical ex- planations and mathematical relationships discussed are very useful for chemistry professors and students who want both fundamental explanations and concrete applications that the students can use to remember those chemical principles. Like- wise, we suggest that environmental and earth science professors and 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. Environmentalpolicy and management professors and students should also bene- fit 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, and governmental regulators and environmental consultants should use the book to be better able to analyze the problem sites they must assess and manage.

To meet the needs of this very diverse audience, we have tried, wherever possible, to divide the various chapters or topics into more elementary and more advanced parts, hoping to make this book useful for beginners as well as for people with more exper- tise. At many points, we have tried to explain concepts from the very beginning level (e.g., chemical potential) so that individuals who do not recall (or never had) their basic chemistry can still develop insights into and understand the origin and limits of modeling calculations and correlation equations. We have also incorporated numerous references throughout the text to help people who want to follow particular topics further. Finally, by including many illustrative examples, we have attempted to show environmental practitioners how to arrive at quantitative results for particu- lar cases of interest to them. Hence, this book should serve as a text for introductory courses in environmental organic chemistry, as well as a source of information for hazard and risk assessment of organic chemicals in the environment. We hope that

xiii

with this textbook, we can make a contribution to the education of environmental scientists and engineers and, thus, to a better protection of our environment.

Acknowledgments. Those who have ever written textbooks know that the authors are not the only ones who play an important role in the realization of the final product. Without the help of many of our co-workers, colleagues and students, it would have taken another millennium to finish this book. We thank all of them, but above all BCatrice Schwertfeger who, together with Lilo Schwarz and CCcile Haussener produced the entire camera-ready manuscript. Furthermore, we acknow- ledge Toni Bernet for his professional help with the final layout, and Sabine Koch for helping in assembling the reference list. We are especially grateful to Dieter Diem for reviewing the whole manuscript and, particularly, for producing the compound and subject indices. Another key role was played by Werner Angst who drew most of the more complicated structures and reaction schemes, and who helped with the compound index and with thousands of small details. Further- more, we are particularly indepted to Kai-Uwe Goss, whose significant input into Part I1 of the book and whose review of several other chapters are especially acknowledged. Many important comments and criticisms were made by other colleagues and students including Andreas Kappler and Torsten Schmidt who reviewed Parts I to 111, Mike McLachlan (Part II), Stefan Haderlein (Chapters 9 to ll), Beate Escher and Zach Schreiber (Chapter lO), Lynn Roberts (Chapters 13 and 14), Martin Elsner, Luc Zwank and Paul Tratnyek (Chapter 14), Andrea Ciani and Silvio Canonica (Chapters 15 and 16), Werner Angst, Colleen Cavanaugh, Hans Peter Kohler, Rainer Meckenstock and Alexander Zehnder (Chapter 17), and Frank Peeters (Part IV). We are also deeply indepted to the Swiss Federal Institute of Environmental Sciences and Technology (EAWAG) and the Swiss Federal Institute of Technology in Zurich (ETHZ) for significant financial support, which made it possible to produce a low-cost textbook. Finally with no further promises but with some guilty feelings, we thank our families for their patience and support, particularly our wives Theres Schwarzenbach, Colleen Cavanaugh, and Sibyl Imboden who will hopefully still recognize their husbands after what again must have seemed an endless preoccupation with THE NEW BOOK!

RenC P. Schwarzenbach Dubendorf and Zurich, Switzerland

Philip M. Gschwend Cambridge, Massachussetts, USA

Dieter M. Imboden Zurich, Switzerland