McKay, Donald.

"Front matter" Multimedia Environmental Models Edited by Donald McKay Boca Raton: CRC Press LLC,2001

Multimedia Environmental Models

The Fugacity Approach Second Edition

Multimedia Environmental Models

The Fugacity Approach
Second Edition

Donald Mackay

LEWIS PUBLISHERS
Boca Raton London New York Washington, D.C.

Preface
This book is about the behavior of organic chemicals in our multimedia environment or biosphere of air, water, soil, and sediments, and the diversity of biota that reside in these media. It is a response to the concern that we have unwisely contaminated our environment with a large number of chemicals in the mistaken belief that the environments enormous capacity to dilute and degrade will reduce concentrations to negligible levels. We now know that the environment has only a nite capacity to dilute and degrade. Certain chemicals have persisted and accumulated to levels that have caused adverse effects on wildlife and even humans. Some chemicals have the potential to migrate from medium to medium, reaching unexpected destinations in unexpectedly high concentrations. We need to understand these processes, not only qualitatively in the form of assertions that DDT evaporates and bioaccumulates, but quantitatively as statements that DDT in a particular region evaporates at a rate of 100 kg per year and bioaccumulates from water at a concentration of 1 ng/L to sh at levels of 1 mg/g. We have learned that chemical behavior in the complex assembly of environmental media is not a random process like leaves blowing in the wind. The chemicals behave in accordance with the laws of nature, which dictate chemical partitioning and rates of transport and transformation. Most fundamentally, the chemicals are subject to the law of conservation of mass, i.e., a mass balance exists for the chemical that is a powerful constraint on quantities, concentrations, and uxes. By coupling the mass balance principle with expressions based on our understanding of the laws of nature, we can formulate a quantitative accounting of chemical inputs and outputs. This book is concerned with developing and applying these expressions in the form of mathematical statements or models of chemical fate. These accounts or models are invaluable summaries of chemical behavior. They can form the basis of remedial and proactive strategies. Such models can conrm (or deny) that we really understand chemical fate in the environment. Since many environmental calculations are complex and repetitive, they are particularly suitable for implementation on computers. Accordingly, for many of the calculations described in this book, computer programs are described and made available on the Internet with which a variety of chemicals can be readily assessed in a multitude of environmental situations. The models are formulated using the concept of fugacity, which was introduced by G.N. Lewis in 1901 as a criterion of equilibrium and has proved to be a very convenient and elegant method of calculating multimedia equilibrium partitioning. It has been widely and successfully used in chemical processing calculations. In this book, we exploit it as a convenient and elegant method of explaining and deducing the environmental fate of chemicals. Since publication of the rst edition of this book ten years ago, there has been increased acceptance of the benets of using fugacity to formulate models and interpret environmental fate. Multimedia fugacity models are now routinely used for evaluating chemicals before and after production. Much of the experience gained in these ten years is incorporated in this second edition. Mathematical simulations of chemical fate are now more accurate, compre-

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hensive, and reliable, and they have gained greater credibility as decision-support tools. No doubt this trend will continue, especially as young environmental scientists and engineers take over the reins of environmental science and continue to develop new fugacity models. This book has been written as a result of the author teaching graduate-level courses at the University of Toronto and Trent University. It is hoped that it will be suitable for other graduate courses and for practitioners of the environmental science of chemical fate in government, industry, and the private consulting sector. The simpler concepts are entirely appropriate for undergraduate courses, especially as a means of promoting sensitivity to the concept that chemicals, which provide modern society with so many benets, must also be more carefully managed from their cradle, in the chemical synthesis plant, to their grave of ultimate destruction. At the end of most chapters is a Concluding Example in which a student may be asked to apply the principles discussed in that chapter to one or more chemicals of their choice. Necessary data are given in Table 3.5 in Chapter 3. I have found this useful as a method of assigning different problems to a large number of students, while allowing them to explore the properties and fate of substances of particular interest to them. We no longer regard the environment as a convenient, low-cost dumping ground for unwanted chemicals. When we discharge chemicals into the environment, it must be with a full appreciation of their ultimate fate and possible effects. We must ensure that mistakes of the past with PCBs, mercury, and DDT are not repeated. This is best guaranteed by building up a quantitative understanding of chemical fate in our total multimedia environment, how chemicals will be transported and transformed, and where, and to what extent they may accumulate. It is hoped that this book is one step toward this goal and will be of interest and use to all those who value the environment and seek its more enlightened stewardship. Donald Mackay

2001 CRC Press LLC

Acknowledgments
It is a pleasure to acknowledge the contribution of many colleagues. Much of the credit for the approaches devised in this book is due to the pioneering work by George Baughman, who saw most clearly the evolution of multimedia environmental modeling as a coherent and structured branch of environmental science amid the often frightening complexity of the environment and the formidable number of chemicals with which it is contaminated. Brock Neely, Russ Christman, and Don Crosby were instrumental in encouraging me to apply the fugacity concept to environmental calculations. I am indebted to my former colleagues at the University of Toronto, especially Wan Ying Shiu and Sally Paterson, whose collaboration has been crucial in developing the fugacity approach. I am grateful to my more recent colleagues at Trent University, and our industrial and government partners who have made the Canadian Environmental Modelling Centre a successful focus for the development, validation, and dissemination of mass balance models. This second edition was written in part when on research leave at the Department of Environmental Toxicology at U.C. Davis, where Marion Miller, Don Crosby, and their colleagues were characteristically generous and supportive. At Trent, I was greatly assisted by David Woodne, Rajesh Seth, Merike Perem, Lynne Milford, Angela McLeod, Adrienne Holstead, Todd Gouin, Alison Fraser, Ian Cousins, Tom Cahill, Jenn Brimecombe, and Andreas Beyer. I am particularly grateful to Steve Sharpe for the gures, to Matt MacLeod and Christopher Warren for their critical review and comments, and to Eva Webster for her outstanding scientic and editorial contributions. Without the support and diligent typing of my wife, Ness, this book would not have been possible. Thank you. I dedicate this book to Ness, Neil, Ian, Julia, and Gwen, and especially to Beth, who was born as this edition neared completion. I hope it will help to ensure that her life is spent in a cleaner, more healthful environment.

2001 CRC Press LLC

Contents
Chapter 1 Introduction Chapter 2 Some Basic Concepts 2.1 Introduction 2.2 Units 2.3 The Environment as Compartments 2.4 Mass Balances 2.5 Eulerian and Lagrangian Coordinate Systems 2.6 Steady State and Equilibrium 2.7 Diffusive and Nondiffusive Environmental Transport Processes 2.8 Residence Times and Persistence 2.9 Real and Evaluative Environments 2.10 Summary Chapter 3 Environmental Chemicals and Their Properties 3.1 Introduction and Data Sources 3.2 Identifying Priority Chemicals 3.3 Key Chemical Properties and Classes 3.4 Concluding Example Chapter 4 The Nature of Environmental Media 4.1 Introduction 4.2 The Atmosphere 4.3 The Hydrosphere or Water 4.4 Bottom Sediments 4.5 Soils 4.6 Summary 4.7 Concluding Example Chapter 5 Phase Equilibrium 5.1 Introduction 5.2 Properties of Pure Substances 5.3 Properties of Solutes in Solution 5.4 Partition Coefficients 5.5 Environmental Partition Coefficients and Z Values 5.6 Multimedia Partitioning Calculations 5.7 Level I Calculations 5.8 Concluding Examples Chapter 6 Advection and Reactions 6.1 Introduction

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6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9

Advection Degrading Reactions Combined Advection and Reaction Unsteady-State Calculations The Nature of Environmental Reactions Level II Computer Calculations Summary Concluding Example

Chapter 7 Intermedia Transport 7.1 Introduction 7.2 Diffusive and Nondiffusive Processes 7.3 Molecular Diffusion within a Phase 7.4 Turbulent or Eddy Diffusion within a Phase 7.5 Unsteady-State Diffusion 7.6 Diffusion in Porous Media 7.7 Diffusion between Phases: The Two-Resistance Concept 7.8 Measuring Transport D Values 7.9 Combining Series and Parallel D Values 7.10 Level III Calculations 7.11 Level IV Calculations 7.12 Concluding Examples Chapter 8 Applications of Fugacity Models 8.1 Introduction, Scope, and Strategies 8.2 Level I, II, and III Models 8.3 An Air-Water Exchange Model 8.4 A Surface Soil Model 8.5 A Sediment-Water Exchange Model 8.6 QWASI Model of Chemical Fate in a Lake 8.7 QWASI Model of Chemical Fate in Rivers 8.8 QWASI Multi-segment Models 8.9 A Fish Bioaccumulation Model 8.10 Sewage Treatment Plants 8.11 Indoor Air Models 8.12 Uptake by Plants 8.13 Pharmacokinetic Models 8.14 Human Exposure to Chemicals 8.15 The PBTLRT Attributes 8.16 Global Models 8.17 Closure Appendix Fugacity Forms References and Bibliography

2001 CRC Press LLC