k k k Source: © Gettyimages k Chemistry of Environmental Systems Chemistry of Environmental Systems Fundamental Principles and Analytical Methods Jeffrey S. Gaffney University of Arkansas at Little Rock (retired) USA Nancy A. Marley Argonne National Laboratory (retired) USA This edition first published 2020 © 2020 John Wiley & Sons Ltd All rights reserved. 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 or otherwise, except as permitted by law.
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Library of Congress Cataloging-in-Publication Data Names: Gaffney, Jeffrey S. Title: Chemistry of environmental systems : fundamental principles and analytical methods / Jeffrey S. Gaffney, Ph. Description: First edition.
| Hoboken, NJ : Wiley, 2020. | Includes bibliographical references and index. | Identifiers: LCCN 2019014828 (print) | LCCN 2019017607 (ebook) | ISBN 9781119313632 (Adobe PDF) | ISBN 9781119313588 (ePub) | ISBN 9781119313403 (hardcover) Subjects: LCSH: Environmental chemistry–Textbooks. | Atmospheric chemistry–Textbooks.
Classification: LCC TD193 (ebook) | LCC TD193 .14–dc23 LC record available at https://lccn.gov/2019014828 Cover Design: Wiley Cover Image: © anucha sirivisansuwan/Getty Images Set in 10/12pt WarnockPro by SPi Global, Chennai, India 10 9 8 7 6 5 4 3 2 1 In memory of Dr. Sherwood Rowland, and Dr. Calvert who taught us about the importance of the fundamental principles of environmental chemistry Dr. Sherwood Rowland (June 28, 1927–March 10, 2012) Dr.
Calvert (May 9, 1923–June 1, 2016) vii Contents About the Authors xiii Preface xv Acknowledgments xix Supplementary Material xxi 1 Introduction to Environmental Chemistry 1 1.1 What is Environmental Chemistry? 1 1.3 A Planet at Risk 4 1.4 Energy, Water, and Population Connections 6 1.5 The Need to Understand Environmental Problems 10 1.6 Atmosphere–Hydrosphere–Geosphere–Biosphere Linkages 13 References 16 Study Problems 16 2 Atmospheric Composition and Basic Physics 19 2.1 Evolution of the Atmosphere 19 2.2 Structure and Composition of the Modern Atmosphere 22 2.5 Global Climate Models 44 References 47 Study Problems 48 3 The Fundamentals of Photochemistry 51 3.1 Light and Photochemistry 51 3.2 The Laws of Photochemistry 57 3.3 Thermochemical and Photochemical Processes 59 3.4 Photochemical Deactivation Processes 69 References 72 viii Contents Further Reading 72 Study Problems 72 4 Chemistry of the Stratosphere 75 4.1 Structure and Composition of the Stratosphere 75 4.2 The Ozone Layer 78 4.3 Ozone Formation in the Stratosphere 80 4.1 The Chapman Cycle 80 4.3 The HOx and NOx Cycles 83 4.2 The “Ozone Hole” 88 4.4 Ozone-Depleting Substances 93 4.5 Summary 95 References 98 Further Reading 99 Study Problems 99 5 Chemistry of the Troposphere 103 5.1 Structure and Composition of the Troposphere 103 5.2 History of Smog 105 5.3 The Clean Air Act 110 5.2 Non-Criteria Pollutants 112 5.4 Formation of Ozone in the Troposphere 113 5.1 The Photostationary State 113 5.2 The Hydroxyl Radical 114 5.3 Hydroxyl Radical Abstraction Reactions 115 5.4 Hydroxyl Radical Addition Reactions 118 5.5 Nitrate Radical and Ozone 121 5.6 The Peroxyacyl Nitrates 122 5.7 Troposphere–Biosphere Interactions 124 References 127 Further Reading 128 Study Problems 128 6 Aerosols and Cloud Chemistry 133 6.1 Aerosol Size Distributions 133 6.2 Aerosol Sources and Sinks 136 6.1 Primary Aerosol Emissions 138 6.2 Secondary Aerosol Formation 140 6.3 Wet Deposition and Henry’s Law 143 6.4 Determination of Aerosol Sources 151 6.5 Aerosol Health Effects 156 6.6 Aerosol Visibility and Climate Effects 158 6.7 Aqueous Chemistry 164 Contents ix References 165 Further Reading 166 Study Problems 166 7 Analytical Methods for Air Analysis 171 7.2 Gas Species Measurement Methods 175 7.1 The Oxidants: Ozone, Hydroxyl Radical, Peroxyacyl Nitrates, Peroxides, and Peracids 175 7.2 The Oxides: Nitric Oxide, Nitrogen Dioxide, Nitric Acid, Carbon Monoxide, Carbon Dioxide, Sulfur Dioxide, and Nitrous Oxide 186 7.1 Nitric Oxide, Nitrogen Dioxide, and Nitric Acid 186 7.2 Nitric Acid, Carbon Monoxide, Carbon Dioxide, Sulfur Dioxide, and Nitrous Oxide 188 7.3 The Organics: Volatile Organic Hydrocarbons, Aldehydes, Ketones, and Halogenated Hydrocarbons 191 7.4 Aerosol Optical Properties 199 7.6 The Importance of Baseline Measurements 204 References 207 Further Reading 207 Study Problems 208 8 Chemistry of Surface and Ground Waters 213 8.1 The Unique Properties of Water 214 8.2 The Hydrological Cycle 216 8.3 Ocean Currents and Circulation 220 8.4 The Structure of Natural Aquatic Systems 224 8.5 The Composition of Natural Aquatic Systems 228 8.2 Nitrogen and Phosphorus 230 8.8 Contaminant Transport 252 References 257 Further Reading 258 Study Problems 258 9 Analytical Methods for Water Analysis 263 9.2 Dissolved Species 266 x Contents 9.3 Particulates and Colloids 293 9.4 Contaminant Issues 297 References 299 Study Problems 300 10 Fossil and Biomass Fuels 305 10.2 Formation and Recovery of Fossil Fuels 308 10.1 The Formation of Fossil Fuels 309 10.3 Oil and Gas Recovery 315 10.3 Fossil Fuel Use 319 10.1 Biomass Fuel Production 324 10.2 Biomass Fuel Use 326 10.5 Impacts on Water Quality 330 10.6 Impacts on Air Quality 338 10.7 Gasoline Additives: Lessons Learned 347 References 349 Study Problems 350 11 Climate Change 355 11.2 Causes of Climate Change 360 11.1 Global Warming Potentials 362 11.2 Greenhouse Gas Sources and Sinks 363 11.4 Predictions of Future Climate Change 370 11.5 Impacts from the Predicted Temperature Rise 373 11.6 Climate Effects on Air Quality and Health 377 11.7 Mitigation and Adaption Strategies 379 References 386 Study Problems 386 12 Nuclear Energy 391 12.2 Radioactive Emissions and Decay Kinetics 394 12.3 Sources of Radioisotopes 399 12.4 Nuclear Fission 401 Contents xi 12.5 Nuclear Weapons Testing and Fallout 403 12.1 Harnessing Nuclear Energy 407 12.3 Nuclear Plant Designs 412 12.7 Radioisotopes in the Environment 417 12.9 Applications of Radioisotopes 424 References 428 Study Problems 429 13 Future Energy Sources and Sustainability 433 13.1 The Need for Non-Fossil Energy Sources 434 13.2 Alternative Energy Sources 437 13.4 Long-Term Planning 455 References 460 Study Problems 461 Appendix A Answers to Study Problems 465 Appendix B List of U. EPA Hazardous Air Pollutants – Air Toxics 503 Appendix C Henry’s Law Constants (Hx ) for Selected Inorganic and Organic Compounds 509 Appendix D Organic Water Pollutants, their Chemical Structures, Sources, and Concentration Limits in U. Drinking Water 519 Appendix E Chemicals Used in the Hydraulic Fracturing of Oil Shales for Natural Gas Extraction 527 Glossary 529 Index 541 xiii About the Authors Dr. Gaffney obtained his undergraduate and graduate training in physical organic chemistry from the University of California at Riverside, under the guidance of Dr.
He was a nationally and internationally known Senior Chemist at three of the U. Department of Energy (DOE) National Labs (Brookhaven, Los Alamos, and Argonne) for 31 years before coming to the University of Arkansas at Little Rock (UALR) in 2006 as Chair and Tenured Professor of Chemistry. On July 1, 2016 Dr. Gaffney retired as Emeritus Profes- sor of Chemistry at UALR.
Gaffney has published over 200 peer-reviewed papers, 25 book chapters, and edited two American Chemical Society symposium book volumes. His research spans a wide range of chemistry in all of the basic areas, and he is internationally known for his work in air and water chemistry and global change research. Gaffney has taught undergrad- uate and graduate courses in general chemistry, organic chemistry, environmental chemistry, and the history of chemistry. He developed a one-semester course for senior undergraduates and graduate chemistry students entitled “Environmental Chemistry,” that he has taught for eight years.
This course combines the chemistry of the atmosphere, hydrosphere, geosphere, and biosphere – and the interactions between each of these areas – which is needed to success- fully understand the chemistry of the environment as a whole system. Marley obtained her B. in Chemistry from Jacksonville University and her Ph. in Analytical Chemistry and Optical Spectroscopy from Florida State University under the direction of Dr.
degree and doctoral degree, Dr. Mar- ley was District Chemist for the Department of Environmental Quality in Florida and also the Lead Chemist for the Childhood Lead Poisoning Program for the Florida Department of Health and Rehabilitative Services. She was a postdoctoral researcher at Los Alamos National Labora- tory before joining Argonne National Laboratory, where she worked for 18 years. After retiring from Argonne National Laboratory, she joined the University of Arkansas at Little Rock as an Associate Research Professor.
Currently a retired scientist/scholar, she has published over 140 peer-reviewed papers, 14 book chapters, and edited two American Chemical Society sympo- sium book volumes. Her research has focused on the applications of laser Raman, infrared, and UV–visible–near IR spectroscopy to problems in environmental chemistry and geochemistry. She has also developed a number of analytical methods using chemiluminescent reactions and fast gas chromatography in collaboration with Dr. Gaffney and Dr.
Marley worked closely as co-principal investigators with the geo- chemistry/environmental chemistry/atmospheric science staff at both Los Alamos National Laboratory and Argonne National Laboratory. They also collaborated with geoscientists at the University of Chicago and the University of Illinois at Chicago on projects ranging from atmospheric chemistry to climate change, aqueous transport of radionuclides, and instrument development. xv Preface Chemistry of Environmental Systems is written with the overall concept of teaching the subject in a manner that develops a proactive science, learning from our past experiences and using the knowledge obtained from these experiences to prevent future environmental impacts. This is differentiated from the reactive science that environmental chemistry has been in the past.