Elements of Environmental Chemistry Second Edition
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Elements of Environmental Chemistry Second Edition


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ELEMENTS OF 
ENVIRONMENTAL 
CHEMISTRY 
A Note on the Cover 
The illustrations on the cover represent the four "ele-
ments" in an environmental chemist's periodic table: 
air, earth, fire, and water. The images were taken by J. 
D. Raff and show clouds over the Pacific Ocean (air), a 
mesa near Capitol Reef National Park, Utah (earth), 
wildfire smoke obscuring the sun (fire), and ripples in 
the Pacific Ocean near Monterey Bay, California (wa-
ter). This bit of whimsy was suggested by a Sidney 
Harris cartoon appearing in his book What's So Funny 
About Science? (William Kaufmann, Los Altos, CA. 
1977). A full periodic table is given in Appendix C. 
ELEMENTS OF 
ENVIRONMENTAL 
CHEMISTRY 
Second Edition 
Ronald A. Hites 
Jonathan D. Raff 
School of Public and Environmental Affairs 
Indiana University 
WILEY 
A JOHN WILEY & SONS, INC., PUBLICATION 
Copyright © 2012 by John Wiley & Sons, Inc. All rights reserved 
Published by John Wiley & Sons, Inc., Hoboken, New Jersey 
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Library of Congress Cataloging-in-Publication Data: 
Hites, R. A. 
Elements of environmental chemistry / Ronald A. Hites and Jonathan D. 
Raff.\u20142nd ed. 
p. cm. 
Includes index. 
ISBN 978-1-118-04155-0 (pbk.) 
1. Environmental chemistry. I. Raff, Jonathan D. II. Title. 
TD193.H58 2012 
577M4\u2014dc23 2011046732 
Printed in the United States of America. 
10 9 8 7 6 5 4 3 2 1 
To 
Benjamin Atlee Hites 
Gavin James Mahoney 
Malte Thorben Raff 
CONTENTS 
1. Simple Tool Skills 
1.1. Unit Conversions 
1.2. Estimating 
1.3. Ideal Gas Law 
1.4. Stoichiometry 
1.5. Problem Set 
2. Mass Balance and Kinetics 
2.1. Steady-State Mass Balance 
2.2. Non-Steady-State Mass Balance 
2.3. Chemical Kinetics 
2.4. Problem Set 
3. Atmospheric Chemistry 
3.1. Atmospheric Structure 
3.2. Light and Photochemistry 
3.3. Atmospheric Oxidants 
3.4. Kinetics of Atmospheric Reactions 
3.5. Stratospheric Ozone 
3.6. Smog 
3.7. Problem Set 
4. Climate Change 
4.1. Historical Perspective 
4.2. Blackbody Radiation and Earth's 
Temperature 
4.3. Absorption of Infrared Radiation 
4.4. Greenhouse Effect 
4.5. Earth's Radiative Balance 
4.6. Aerosols and Clouds 
4.7. Radiative Forcing 
1 
1 
5 
9 
14 
16 
23 
24 
41 
59 
69 
77 
77 
80 
86 
88 
91 
105 
112 
123 
123 
125 
130 
132 
134 
138 
141 
vii
viii Contents 
4.8. Global Warming Potentials 142 
4.9. Concluding Remarks 144 
4.10. Problem Set 146 
5. Carbon Dioxide Equilibria 153 
5.1. Pure Rain 155 
5.2. Polluted Rain 160 
5.3. Surface Water 169 
5.4. Ocean Acidification 174 
5.5. Problem Set 181 
6. Pesticides, Mercury, and Lead 189 
6.1. Pesticides 191 
6.2. Mercury 210 
6.3. Lead 213 
6.4. Problem Set 217 
7. Fates of Organic Compounds 223 
7.1. Vapor Pressure 225 
7.2. Water Solubility 226 
7.3. Henry's Law Constant 227 
7.4. Partition Coefficients 228 
7.5. Lipophilicity 229 
7.6. Bioaccumulation 231 
7.7. Adsorption 232 
7.8. Water-Air Transfer 235 
7.9. Reactive Fates of Organics 240 
7.10. Partitioning and Persistence 242 
7.11. Problem Set 247 
8. PCBs, Dioxins, and Flame Retardants 259 
8.1. Polychlorinated Biphenyls (PCBs) 259 
8.2. Polychlorinated Dibenzo-/?-dioxins and 
Dibenzofurans 277 
8.3. Brominated Flame Retardants 297 
8.4. Lessons Learned 304 
Contents ix 
A. Primer on Organic Structures and Names 307 
B. Answers to the Problem Sets 325 
C. Periodic Table of the Elements 328 
Index 331 
PREFACE 
Many chemistry and environmental science de-partments now feature a course on environmental 
chemistry, and several textbooks support these courses. 
The coverage and quality of these textbooks varies - in 
some cases dramatically. Although it is obviously a 
matter of opinion (depending on the instructor's back-
ground and skills), it seems to us that a good textbook 
should be quantitative and should develop students' 
skills with numerous real-world problems. 
This book aims at a quantitative approach to environ-
mental chemistry. In fact, one could think of this book 
as providing the student with the essence of environ-
mental chemistry and with a toolbox for solving prob-
lems. These skills are transferable to other fields be-
yond environmental chemistry. With effort, this book 
will allow students to understand problem-solving 
methods in the context of environmental chemistry and 
provide basic concepts of environmental chemistry such 
that these problem-solving skills can be used to under-
stand even more complex environmental challenges. 
This is a relatively short book. Its goal is to be tutorial 
and informal; thus, the text features many quantitative 
story problems (indicated by bold font). For each prob-
lem, a strategy is developed, and the solution is provid-
ed. Although short, this book is not intended to be read 
quickly. It is an interactive textbook, and it is intended 
XÍ 
xi¡ Preface 
to be read with a pencil in hand so that the reader can 
follow the problem statement, the strategy for solving 
the problem, and the calculations used in arriving at an 
answer. "Reading" this book will do the student little 
good without actually doing the problems. It is not suf-
ficient for the student to say, "I could do that problem if 
I really had to." The student must work out the prob-
lems if he or she is going to learn this material. 
In addition to the problems in the text, each chapter 
ends with a problem set. Besides reinforcing concepts 
introduced in the chapter, we have tried to incorporate 
issues from the scientific literature and from the "real 
world" in these problem-set questions. The answers to 
these questions are at the back of the book, and full so-
lutions