Chemistry of environmental systems

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Chemistry of Environmental Systems

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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

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This edition first published 2020
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Library of Congress Cataloging-in-Publication Data
Names: Gaffney, Jeffrey S., 1949- author. | Marley, Nancy A., 1948- author.
Title: Chemistry of environmental systems : fundamental principles and
analytical methods / Jeffrey S. Gaffney, Ph.D. (emeritus professor of
chemistry, University of Arkansas at Little Rock, Department of
Chemistry), Nancy A. Marley, Ph.D. (scientist, Argonne National
Laboratory, retired).
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. | Chemistry–Textbooks.
Classification: LCC TD193 (ebook) | LCC TD193 .G34 2019 (print) | DDC
577/.14–dc23
LC record available at />Cover Design: Wiley
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In memory of Dr. James N. Pitts, Jr., Dr. F. Sherwood Rowland, and Dr. Jack G. Calvert who
taught us about the importance of the fundamental principles of environmental chemistry

Dr. James N. Pitts, Jr. (January 10, 1921–June 19, 2014)

Dr. F. Sherwood Rowland (June 28, 1927–March 10, 2012)

Dr. Jack G. Calvert (May 9, 1923–June 1, 2016)

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vii

Contents
About the Authors xiii
Preface xv
Acknowledgments xix
Supplementary Material xxi
1

Introduction to Environmental Chemistry 1

1.1
1.2
1.3
1.4
1.5
1.6

What is Environmental Chemistry? 1
Anthropogenic Pollution 2
A Planet at Risk 4
Energy, Water, and Population Connections 6
The Need to Understand Environmental Problems 10
Atmosphere–Hydrosphere–Geosphere–Biosphere Linkages 13
References 16
Study Problems 16

2

Atmospheric Composition and Basic Physics 19

2.1
2.2
2.3
2.4
2.4.1
2.4.2
2.4.3
2.4.4

2.5

Evolution of the Atmosphere 19
Structure and Composition of the Modern Atmosphere 22
Atmospheric Circulation 27
Energy Balance 34
Milankovitch Cycles 35
Planetary Albedo 38
Greenhouse Gases 40
Aerosols 43
Global Climate Models 44
References 47
Study Problems 48

3

The Fundamentals of Photochemistry 51

3.1
3.2
3.3
3.3.1
3.3.2
3.4

Light and Photochemistry 51
The Laws of Photochemistry 57
Thermochemical and Photochemical Processes 59
Activation Energy 60
Kinetics 62

Photochemical Deactivation Processes 69
References 72

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Contents

Further Reading 72
Study Problems 72
4

Chemistry of the Stratosphere 75

4.1
4.2
4.3
4.3.1
4.3.2
4.3.3
4.4
4.4.1
4.4.2
4.4.3
4.4.4
4.5

Structure and Composition of the Stratosphere 75

The Ozone Layer 78
Ozone Formation in the Stratosphere 80
The Chapman Cycle 80
Term Symbols 81
The HOx and NOx Cycles 83
Ozone Depletion 85
Chlorofluorocarbons 85
The “Ozone Hole” 88
Altitude Dependence 90
Ozone-Depleting Substances 93
Summary 95
References 98
Further Reading 99
Study Problems 99

5

Chemistry of the Troposphere 103

5.1
5.2
5.3
5.3.1
5.3.2
5.4
5.4.1
5.4.2
5.4.3
5.4.4
5.5

5.6
5.7

Structure and Composition of the Troposphere 103
History of Smog 105
The Clean Air Act 110
Criteria Pollutants 110
Non-Criteria Pollutants 112
Formation of Ozone in the Troposphere 113
The Photostationary State 113
The Hydroxyl Radical 114
Hydroxyl Radical Abstraction Reactions 115
Hydroxyl Radical Addition Reactions 118
Nitrate Radical and Ozone 121
The Peroxyacyl Nitrates 122
Troposphere–Biosphere Interactions 124
References 127
Further Reading 128
Study Problems 128

6

Aerosols and Cloud Chemistry 133

6.1
6.2
6.2.1
6.2.2
6.2.3
6.2.4

6.3
6.4
6.5
6.6
6.7

Aerosol Size Distributions 133
Aerosol Sources and Sinks 136
Primary Aerosol Emissions 138
Secondary Aerosol Formation 140
Wet Deposition and Henry’s Law 143
Dry Deposition 145
Aerosol Lifetimes 148
Determination of Aerosol Sources 151
Aerosol Health Effects 156
Aerosol Visibility and Climate Effects 158
Aqueous Chemistry 164

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References 165
Further Reading 166
Study Problems 166
7

Analytical Methods for Air Analysis 171

7.1
7.2
7.2.1

Sampling Methods 172
Gas Species Measurement Methods 175
The Oxidants: Ozone, Hydroxyl Radical, Peroxyacyl Nitrates, Peroxides, and
Peracids 175
The Oxides: Nitric Oxide, Nitrogen Dioxide, Nitric Acid, Carbon Monoxide, Carbon
Dioxide, Sulfur Dioxide, and Nitrous Oxide 186
Nitric Oxide, Nitrogen Dioxide, and Nitric Acid 186
Nitric Acid, Carbon Monoxide, Carbon Dioxide, Sulfur Dioxide, and Nitrous
Oxide 188
The Organics: Volatile Organic Hydrocarbons, Aldehydes, Ketones, and Halogenated
Hydrocarbons 191
Aerosols 195
Sample Collection 195
Aerosol Composition 196
Aerosol Optical Properties 199
Method Selection 201
The Importance of Baseline Measurements 204
References 207
Further Reading 207
Study Problems 208

7.2.2
7.2.2.1
7.2.2.2
7.2.3
7.3

7.3.1
7.3.2
7.4
7.5
7.6

8

8.1
8.2
8.3
8.4
8.4.1
8.4.2
8.5
8.5.1
8.5.2
8.5.3
8.5.4
8.6
8.6.1
8.6.2
8.7
8.8

213
The Unique Properties of Water 214
The Hydrological Cycle 216
Ocean Currents and Circulation 220
The Structure of Natural Aquatic Systems 224

The Oceans 224
Freshwater Systems 225
The Composition of Natural Aquatic Systems 228
Dissolved Oxygen 229
Nitrogen and Phosphorus 230
Sulfur 232
Carbon 233
Water Pollution 238
Point Sources 239
Nonpoint Sources 243
Contaminant Transformation 246
Contaminant Transport 252
References 257
Further Reading 258
Study Problems 258

Chemistry of Surface and Ground Waters

9

Analytical Methods for Water Analysis 263

9.1
9.2

Sampling Methods 263
Dissolved Species 266

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Contents

9.2.1
9.2.2
9.2.3
9.2.4
9.2.5
9.3
9.4

Electrochemical Methods 267
Spectroscopic Methods 272
Chromatographic Methods 286
Titration Methods 291
Radiochemical Methods 292
Particulates and Colloids 293
Contaminant Issues 297
References 299
Study Problems 300

10

Fossil and Biomass Fuels 305
Combustion Chemistry 305
Formation and Recovery of Fossil Fuels 308

The Formation of Fossil Fuels 309
Coal Mining 313
Oil and Gas Recovery 315
Fossil Fuel Use 319
Biomass Fuels 323
Biomass Fuel Production 324
Biomass Fuel Use 326
Impacts on Water Quality 330
Fossil Fuels 330
Biomass Fuels 335
Impacts on Air Quality 338
Fossil Fuels 338
Biomass Fuels 345
Gasoline Additives: Lessons Learned 347
References 349
Study Problems 350

10.1
10.2
10.2.1
10.2.2
10.2.3
10.3
10.4
10.4.1
10.4.2
10.5
10.5.1
10.5.2
10.6

10.6.1
10.6.2
10.7

11

Climate Change 355

11.1
11.2
11.2.1
11.2.2
11.2.3
11.3
11.4
11.5
11.6
11.7

Prehistoric Climates 358
Causes of Climate Change 360
Global Warming Potentials 362
Greenhouse Gas Sources and Sinks 363
Radiative Forcing 367
Climate Models 368
Predictions of Future Climate Change 370
Impacts from the Predicted Temperature Rise 373
Climate Effects on Air Quality and Health 377
Mitigation and Adaption Strategies 379
References 386

Study Problems 386

12

Nuclear Energy 391

12.1
12.2
12.3
12.4

Radioactivity 391
Radioactive Emissions and Decay Kinetics 394
Sources of Radioisotopes 399
Nuclear Fission 401

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12.5
12.6
12.6.1
12.6.2
12.6.3
12.6.4
12.7
12.8
12.9

Nuclear Weapons Testing and Fallout 403
Nuclear Power 407
Harnessing Nuclear Energy 407
Uranium Production 410
Nuclear Plant Designs 412
Nuclear Waste 414
Radioisotopes in the Environment 417
Radiation Exposure 421
Applications of Radioisotopes 424
References 428
Study Problems 429

13

Future Energy Sources and Sustainability 433
The Need for Non-Fossil Energy Sources 434
Alternative Energy Sources 437
Wind Power 438
Hydropower 442
Geothermal Energy 444
Solar Power 445
Biomass 449
Hydrogen 450
Sustainability 452
Long-Term Planning 455
References 460
Study Problems 461

13.1

13.2
13.2.1
13.2.2
13.2.3
13.2.4
13.2.5
13.2.6
13.3
13.4

Appendix A Answers to Study Problems 465
Appendix B List of U.S. 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.S. Drinking Water 519
Appendix E

Chemicals Used in the Hydraulic Fracturing of Oil Shales for Natural
Gas Extraction 527

Glossary

529

Index 541

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xiii

About the Authors
Dr. Jeffrey S. Gaffney obtained his undergraduate and graduate training in physical organic
chemistry from the University of California at Riverside, under the guidance of Dr. James N.
Pitts, Jr. He was a nationally and internationally known Senior Chemist at three of the U.S.
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 Professor of Chemistry at UALR. Dr. 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. Dr. Gaffney has taught undergraduate 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 successfully understand the chemistry of the environment as a whole system.
Dr. Nancy A. Marley obtained her B.S. in Chemistry from Jacksonville University and her
Ph.D. in Analytical Chemistry and Optical Spectroscopy from Florida State University under
the direction of Dr. Thomas J. Vickers. Between her B.S. degree and doctoral degree, Dr. Marley 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 Laboratory 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 symposium 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.
Both Dr. Gaffney and Dr. Marley worked closely as co-principal investigators with the geochemistry/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.

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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.
Thus, environmental chemistry as a subject is not simply the measurement of pollution species
in the various environmental phases, but is the understanding of the chemical processes in the
natural environment and how these natural chemical processes react when perturbed by either
acute or chronic additions of chemical compounds into the whole Earth system.
This book addresses the development of the chemistry of environmental systems as it has
changed over the past 50 years. Chemistry of Environmental Systems evolved from a senior-level
undergraduate/lower-level graduate course in Environmental Chemistry taught by one of the
authors (JSG) at the University of Arkansas at Little Rock. This course used two textbooks as
resources: Chemistry of the Upper and Lower Atmosphere, by Dr. Barbara Finlayson-Pitts and

Dr. James N. Pitts, Jr. and the Second Edition of Chemistry of the Environment, by Dr. Ronald
A. Bailey, Dr. Herbert M. Clark, Dr. James P. Ferris, Dr. Sonja Krause, and Dr. Robert L. Strong.
Both of these texts have influenced the writing of this book and while Chemistry of the Upper
and Lower Atmosphere details atmospheric chemistry as it was known at the date of publication (2000), Chemistry of the Environment covers the subject with a more holistic approach,
including the environmental problems of the atmosphere, hydrosphere, and geosphere that
were clearly identified by the year of publication (2002). While teaching the Environmental
Chemistry course, it became increasingly apparent that the impacts of pollution on the chemistry of the environment are global in nature, even though they were originally thought to be
local issues. Also, environmental chemical reactions are not restricted to one specific environmental phase. For example, the fundamental reaction mechanisms that are important in
gas-phase chemistry of the troposphere and stratosphere are, in many cases, also important
mechanisms for aqueous and surface phase reactions.
Major environmental problems, such as urban air pollution, stratospheric ozone depletion,
acid rain, and catastrophic releases of pollutants like oil spills, have been well known for
decades, if not centuries. The potential impacts of climate change have now brought even more
attention to the fact that these environmental problems are not standalone one-time events,
but will continue to be major issues as we move forward in the Anthropocene. The impacts of
the ever-growing human population on the environment are real and require that we address
these issues in a more fundamental way, focusing on the principles of environmental chemistry. This approach is very important in training future scientists in all disciplines to begin to
develop critical thinking skills in order to avoid future major environmental impacts and to
move toward a sustainable global environment. Indeed, fully understanding environmental
impacts requires that students and future environmental researchers have a solid background

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Preface

in all areas of chemistry and are trained to be able to ask the right questions of engineers,
biologists, and ecologists, to aid in providing the answers to important questions of energy

and technology development in the years to come. These scientists will also need to be able to
effectively communicate their findings to public policy makers and leaders to insure that we,
as a global community, make the best decisions regarding chemical and energy use to insure
that our air and water quality is maintained and to prepare to adapt to the potential impacts
of our changing climate and weather patterns, induced by anthropogenic emissions from an
increasing world population.
This book is intended not only for use as a textbook, but also as a reference guide to provide a
solid background in environmental chemistry and the basic mechanisms involved in the various
phases of the environment, which are in constant equilibrium. Some key references used in this
text are pre-2000 and are typically not accessed by current scientists, who rely on the Internet as
their major source of information. Following in the tradition of the influential environmental
texts noted earlier, units of measurement that are still commonly used in the environmental
chemistry literature are used in this text but they are defined in terms of the accepted SI units
to assist the reader in connecting current and past work in environmental chemistry with the
most ease. The organization of the book first addresses the chemistry and radiative balance of
the atmosphere associated with climate change and air quality. It then continues into the areas
of aqueous and heterogeneous chemistry. The linkages between these areas and the biosphere
are stressed to indicate the important concept that environmental impacts, in many cases, can
be amplified by biospheric or geospheric feedbacks. Key concepts that are fundamental to many
areas of chemistry – such as the basic principles and laws of photochemistry, thermodynamics,
and kinetics – are reviewed, along with principles of organic and nuclear chemistry related
to energy use. Analytical methods that are commonly used in environmental chemistry for
both air and water analyses are also included so that the reader will appreciate the relationship
between the fundamental principles of chemistry and the methods used to perform analyses
on key environmental species.
Throughout the chapters, brief histories of the subject areas are presented to give the reader
a perspective of the developing awareness of some environmental problems that we have come
to understand today. In many cases these problems actually arose from perceived solutions of
another problem. A classic example of this is the development of chlorofluorocarbons (CFCs)
as the working fluids in refrigeration by Thomas Midgley. Seen as a major safety improvement

over ammonia and butane as working fluids, the potential impacts of CFCs on the protective
ozone layer in the stratosphere were not considered until almost 40 years later. The recognition
and evaluation of the impacts of the CFCs led to a Nobel Prize in Chemistry to Rowland, Molina,
and Crutzen in 1995, as well as to a major change in the global use of chlorinated chemicals (the
Montreal Protocol of 1992). These and other examples are used to emphasize a basic principle
of environmental chemistry, which is the analysis of “cradle to grave” impacts of chemicals on
the environment in order to develop safer chemical products and processes for tomorrow’s
sustainable economies.
During seven years of teaching a senior undergraduate and first-year graduate one-semester
course entitled “Environmental Chemistry,” Dr. Gaffney compiled student responses to the
material presented in the course. Working with Dr. Marley, they determined that there was a
real need for an environmental chemistry textbook that taught a proactive approach to environmental problems, stressed the fundamental principles of chemistry necessary to their understanding, and also included information about the analytical methods used in environmental
measurements. This recognition has led to the joint effort by Dr. Gaffney and Dr. Marley to produce Chemistry of Environmental Systems: Fundamental Principles and Analytical Methods.

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Preface

While this text is not meant to be an extensive review of the literature, it is aimed at covering the key aspects and mechanisms of the currently identified environmental issues, which
can be used to address both current and future environmental problems in a routine manner.
Key fundamental properties of chemical compounds, such as their solubilities and volatilities,
along with basic chemical reaction mechanisms, are reviewed and stressed. It is hoped that this
textbook will encourage future environmental chemists to learn from past mistakes and use
our current knowledge of the fundamental chemistry and physics of molecules and atoms to
minimize future environmental impacts. Indeed, future environmental chemists will need to
work together with engineers and biotechnologists to develop a safe, sustainable methodology
for the global community. As part of that approach, study problems are provided at the end of
each chapter, with answers provided in Appendix A. These can be used as class assignments or
as individual exercises to reinforce the reader’s comprehension of the material.

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Acknowledgments
Chemistry of Environmental Systems was conceived from a one-semester course that
Dr. Gaffney developed and taught during his tenure as Chair and Professor of Chemistry
at the University of Arkansas at Little Rock. During the evolution of this course, it was
clear that available textbooks in this area were either outdated or did not cover the breadth
of the chemistry encountered in environmental chemistry. While writing this textbook, a
number of questions arose concerning how best to present the material in the context of the
various chemical disciplines that are fundamental to environmental chemistry (i.e. analytical,
biochemical, inorganic, organic, and physical chemistry). The authors wish to acknowledge all
of the faculty members in the Department of Chemistry at the College of Arts, Letters, and
Science, University of Arkansas at Little Rock for their assistance and helpful discussions in
the various chemical disciplines that helped make this a better book. We also wish to thank the
upper-level undergraduate and graduate students who took CHEM 4352/5352 Environmental
Chemistry over the years for their useful feedback and encouragement, which ultimately
affirmed that we were on the right track with Chemistry of Environmental Systems.

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Supplementary Material
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