ELEMENTS OF ENVIRONMENTAL CHEMISTRY A Note on the Cover The illustrations on the cover represent the four "elements" 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 (water) 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 Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by sales representatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You should consult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317)572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com 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.) Environmental chemistry I Raff, Jonathan D II Title TD193.H58 2012 577M4—dc23 2011046732 Printed in the United States of America 10 To Benjamin Atlee Hites Gavin James Mahoney Malte Thorben Raff CONTENTS Simple Tool Skills 1.1 Unit Conversions 1.2 Estimating 1.3 Ideal Gas Law 1.4 Stoichiometry 1.5 Problem Set 1 14 16 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 23 24 41 59 69 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 77 77 80 86 88 91 105 112 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 123 123 125 130 132 134 138 141 vii viii Contents 4.8 Global Warming Potentials 4.9 Concluding Remarks 4.10 Problem Set 142 144 146 Carbon Dioxide Equilibria 5.1 Pure Rain 5.2 Polluted Rain 5.3 Surface Water 5.4 Ocean Acidification 5.5 Problem Set 153 155 160 169 174 181 Pesticides, Mercury, and Lead 6.1 Pesticides 6.2 Mercury 6.3 Lead 6.4 Problem Set 189 191 210 213 217 Fates of Organic Compounds 7.1 Vapor Pressure 7.2 Water Solubility 7.3 Henry's Law Constant 7.4 Partition Coefficients 7.5 Lipophilicity 7.6 Bioaccumulation 7.7 Adsorption 7.8 Water-Air Transfer 7.9 Reactive Fates of Organics 7.10 Partitioning and Persistence 7.11 Problem Set 223 225 226 227 228 229 231 232 235 240 242 247 PCBs, Dioxins, and Flame Retardants 8.1 Polychlorinated Biphenyls (PCBs) 8.2 Polychlorinated Dibenzo-/?-dioxins and Dibenzofurans 8.3 Brominated Flame Retardants 8.4 Lessons Learned 259 259 277 297 304 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 M any chemistry and environmental science departments 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 background 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 environmental chemistry In fact, one could think of this book as providing the student with the essence of environmental chemistry and with a toolbox for solving problems These skills are transferable to other fields beyond 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 understand 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 problem, a strategy is developed, and the solution is provided 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 the student little good without actually doing the problems It is not sufficient for the student to say, "I could that problem if I really had to." The student must work out the problems 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 solutions are in a Solution Manual available from the authors Most of the problem sets include a problem that requires a bit more time and the application of simple computing; we have called these "Group Projects" to encourage students to work together on these problems They could be assigned to small groups of students or held back for the especially competent student As a stand-alone text, this book is suitable for a onesemester course (particularly if supplemented with a few lectures on the instructor's favorite environmental topics) aimed at upper-level undergraduate chemistry or chemical engineering majors or at first-year graduate students with only a modest physical science background Because of its tutorial nature, this book would also make a good self-study text for entry-level professionals A little calculus will help the reader follow the exposition in a few places, but it is hardly necessary 324 Elements of Environmental Chemistry Suffixes Functional Group -ol -ate -one -aldehyde or -al -ic acid II O