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.—2nd 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—dc23 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