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ENVIRONMENTAL CHEMISTRY

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ENVIRONMENTAL
CHEMISTRY
Fifth Edition

Colin Baird
University of Western Ontario

Michael Cann
University of Scranton

W. H. Freeman and Company • New York

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Executive Editor: Jessica Fiorillo
Development Editor: Brittany Murphy
Marketing Manager: Alicia Brady
Media and Supplements Editor: Dave Quinn
Senior Media Producer: Keri Fowler
Editorial Assistant: Nicholas Ciani
Senior Project Editor: Vivien Weiss
Photo Editor: Ted Szczepanski
Photo Researcher: Cecilia Varas
Art Director: Diana Blume
Illustrations: Macmillan Publishing Solutions
Senior Illustration Coordinator: Bill Page
Production Coordinator: Susan Wein
Composition: MPS Ltd.
Printing and Binding: RR Donnelley

Library of Congress Control Number: 2011945363

ISBN-13: 978-1-4292-7704-4
ISBN-10: 1-4292-7704-1

© 2012, 2008, 2005, 1999 by W. H. Freeman and Company
All rights reserved

Printed in the United States of America
First printing


W. H. Freeman and Company
41 Madison Avenue
New York, NY 10010
Houndmills, Basingstoke RG21 6XS, England
www.whfreeman.com

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Contents
Preface

xii

Introduction to Environmental Problems, Sustainability, and Green
Chemistry xix

PART I

Atmospheric Chemistry and Air Pollution

Chapter 1

Stratospheric Chemistry: The Ozone Layer

Introduction 3
The Physics, Chemistry, and Biology of UV 6

Activity 11
Stratospheric Chemistry: The Ozone Layer 13
Catalytic Processes of Ozone Destruction 20
Box 1-1 The Rates of Free-Radical Reactions 22
Box 1-2 Calculating the Rates of Reaction Steps 24
Box 1-3 The Steady-State Analysis of Atmospheric Reactions
Review Questions 33
Additional Problems 34

Chapter 2

The Ozone Holes

1

3

30

37

Introduction 37
The Ozone Hole and Mid-Latitude Ozone Depletion 37
The Chemistry of Ozone Depletion 40
Polar Ozone Holes 49
Activity 49
Box 2-1 The Chemistry Behind Mid-Latitude Decreases in Stratospheric
Ozone 52
The Chemicals That Cause Ozone Destruction 54
Green Chemistry: The Replacement of CFC and Hydrocarbon Blowing

Agents with Carbon Dioxide in Producing Foam Polystyrene 57
Green Chemistry: Harpin Technology—Eliciting Nature’s Own Defenses
Against Diseases 64
Review Questions 65
Green Chemistry Questions 66
Additional Problems 66

Chapter 3

The Chemistry of Ground-Level Air Pollution

Introduction 69
Box 3-1 The Interconversion of Gas Concentrations
Urban Ozone: The Photochemical Smog Process 76
Activity 81

69

71

v

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Contents


Improving Air Quality: Photochemical Smog 87
Green Chemistry: Strategies to Reduce VOCs Emanating from
Organic Solvents 101
Green Chemistry: A Nonvolatile, Reactive Coalescent for the
Reduction of VOCs in Latex Paints 101
Green Chemistry: The Replacement of Organic Solvents with
Supercritical and Liquid Carbon Dioxide; Development of Surfactants
for This Compound 103
Box 3-2 Supercritical Carbon Dioxide 104
Green Chemistry: Using Ionic Liquids to Replace Organic Solvents:
Cellulose, a Naturally Occurring Polymer Replacement for
Petroleum-Derived Polymers 105
Improving Air Quality: Sulfur-Based Emissions 109
Particulates in Air Pollution 118
Air Quality Indices and Size Characteristics for Particulate Matter 126
Box 3-3 The Distribution of Particle Sizes in an Urban Air Sample 129
Review Questions 131
Green Chemistry Questions 131
Additional Problems 132

Chapter 4 The Environmental and Health
Consequences of Polluted Air—Outdoors and Indoors 135
Introduction 135
Acid Rain 137
Activity 143
The Human Health Effects of Outdoor Air Pollutants
Indoor Air Pollution 152
Review Questions 161
Additional Problems 162


145

PART II

163

Chapter 5

Energy and Climate Change
The Greenhouse Effect

165

Introduction 165
The Mechanism of the Greenhouse Effect 166
Activity 169
Box 5-1 A Simple Model of the Greenhouse Effect 173
Molecular Vibrations: Energy Absorption by Greenhouse Gases 175
The Major Greenhouse Gases 177
Other Greenhouse Gases 187
Box 5-2 Determining the Emissions of “Old Carbon” Sources
of Methane 190
The Climate-Modifying Effects of Aerosols 197
Box 5-3 Cooling over China from Haze 202
Global Warming to Date 202

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Contents

vii

Geoengineering Earth’s Climate to Combat Global Warming 210
Atmospheric Residence Time Analysis 216
Review Questions 219
Additional Problems 220

Chapter 6 Energy Use, Fossil Fuels, CO2 Emissions,
and Global Climate Change 223
Introduction 223
Global Energy Usage 224
Fossil Fuels 230
Box 6-1 Shale Gas 233
Box 6-2 Petroleum Refining: Fractional Distillation 237
Box 6-3 The Deepwater Horizon Oil Spill Disaster 242
Green Chemistry: Polylactic Acid—The Production of Biodegradable
Polymers from Renewable Resources; Reducing the Need for Petroleum
and the Impact on the Environment 249
Sequestration of CO2 252
The Storage of Carbon Dioxide 257
Activity 264
Other Schemes to Reduce Greenhouse Gases 264
Box 6-4 Removing CO2 from the Atmosphere: Direct
Air Capture 265
Carbon Dioxide Emissions in the Future 267
Activity 268

The Extent and Potential Consequences of Future Global
Warming 276
Review Questions 288
Green Chemistry Questions 289
Additional Problems 290

Chapter 7

Biofuels and Other Alternative Fuels

291

Introduction 291
Biomass and Biofuels: Issues 292
Ethanol 295
Biodiesel from Plant Oils and from Algae 303
Activity 310
Green Chemistry: Bio-based Liquid Fuels and Chemicals 310
Green Chemistry: Recycling Carbon Dioxide—A Feedstock for the
Production of Chemicals and Liquid Fuels 311
Thermochemical Production of Fuels, Including Methanol 313
Hydrogen—Fuel of the Future? 320
Review Questions 334
Green Chemistry Questions 335
Additional Problems 336

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Contents

Chapter 8 Renewable Energy Technologies: Hydroelectric,
Wind, Solar, Geothermal, and Marine Energy and
Their Storage 337
Introduction 337
Hydroelectric Power 338
Wind Energy 340
Marine Energy: Wave and Tidal Power 348
Geothermal Energy 349
Direct Solar Energy 354
The Storage of Renewable Energy—Electricity and Heat
Activity 371
Review Questions 371
Additional Problems 372

Chapter 9

369

Radioactivity, Radon, and Nuclear Energy 373

Introduction 373
Radioactivity and Radon Gas 374
Box 9-1 Steady-State Analysis of the Radioactive Decay
Series 379
Nuclear Energy 383

Environmental Problems of Uranium Fuel 390
Box 9-2 Radioactive Contamination by Plutonium Production
Accidents and the Future of Nuclear Power 398
Nuclear Fusion 402
Review Questions 405
Additional Problems 406

PART III Water Chemistry and Water Pollution
Chapter 10 The Chemistry of Natural Waters

395

407

409

Introduction 409
Oxidation–Reduction Chemistry in Natural Waters 413
Green Chemistry: Enzymatic Preparation of Cotton Textiles 418
Acid–Base and Solubility Chemistry in Natural Waters:
The Carbonate System 430
Box 10-1 Derivation of the Equations for Species Diagram
Curves 432
The CO2–Carbonate System 432
Box 10-2 Solubility of CaCO3 in Buffered Solutions 437
Ion Concentrations in Natural Waters and Drinking Water 442
Activity 445
Review Questions 451
Green Chemistry Questions 452
Additional Problems 452


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Contents

Chapter 11 The Pollution and Purification of Water

455

Introduction 455
Water Disinfection 456
Box 11-1 Activated Carbon 457
Box 11-2 The Desalination of Salty Water 463
Box 11-3 The Mechanism of Chloroform Production in
Drinking Water 470
Groundwater: Its Supply, Chemical Contamination, and Remediation
Activity 491
The Chemical Contamination and Treatment of Wastewater and
Sewage 498
Box 11-4 Time Dependence of Concentrations in the Two-Step
Oxidation of Ammonia 502
Green Chemistry: Sodium Iminodisuccinate, a Biodegradable
Chelating Agent 505
Modern Wastewater and Air Purification Techniques 510
Review Questions 515
Green Chemistry Questions 516
Additional Problems 516


Chapter 12 Toxic Heavy Metals

ix

478

519

Introduction 519
Mercury 521
Activity 531
Lead 537
Green Chemistry: Replacement of Lead in Electrodeposition
Coatings 543
Activity 551
Cadmium 552
Arsenic 555
Box 12-1 Organotin Compounds 558
Chromium 566
Green Chemistry: Removing the Arsenic and Chromium from
Pressure-Treated Wood 568
Review Questions 570
Green Chemistry Questions 571
Additional Problems 571

PART IV Toxic Organic Compounds
Chapter 13 Pesticides

573


575

Introduction 575
Activity 579
DDT 580

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x

Contents

The Accumulation of Organochlorines in Biological Systems 584
Principles of Toxicology 589
Organophosphate and Carbamate Insecticides 597
Activity 599
Activity 601
Natural and Green Insecticides, and Integrated Pest Management 601
Green Chemistry: Insecticides That Target Only Certain Insects 603
Green Chemistry: A New Method for Controlling Termites 604
Green Chemistry: Spinetoram, an Improvement on a Green
Pesticide 605
Herbicides 607
Box 13-1 Genetically Engineered Plants 611
Final Thoughts on Pesticides 616
Box 13-2 The Environmental Distribution of Pollutants 617

Review Questions 620
Green Chemistry Questions 621
Additional Problems 621

Chapter 14 Dioxins, Furans, and PCBs

623

Introduction 623
Dioxins 623
Box 14-1 Deducing the Probable Chlorophenolic Origins of a Dioxin 628
PCBs 631
Box 14-2 Predicting the Furans That Will Form from a Given PCB 638
Other Sources of Dioxins and Furans 641
Green Chemistry: H2O2, an Environmentally Benign Bleaching Agent
for the Production of Paper 643
The Health Effects of Dioxins, Furans, and PCBs 646
Review Questions 659
Green Chemistry Questions 660
Additional Problems 660

Chapter 15 Other Toxic Organic Compounds
of Environmental Concern 663
Introduction 663
Polynuclear Aromatic Hydrocarbons (PAHs) 664
Box 15-1 More on the Mechanism of PAH Carcinogenesis
Environmental Estrogens 672
Box 15-2 Bisphenol-A 675
The Long-Range Transport of Atmospheric Pollutants 683
Fire Retardants 686

Perfluorinated Sulfonates and Related Compounds 692
Review Questions 694
Additional Problems 694

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Contents

PART V Environment and the Solid State
Chapter 16 Wastes, Soils, and Sediments

xi

695

697

Introduction 697
Domestic and Commercial Garbage: Its Disposal and Minimization
The Recycling of Household and Commercial Waste 705
Green Chemistry: Development of Bio-based Toners 710
Activity 715
Green Chemistry: Development of Recyclable Carpeting 717
Soils and Sediments 719
Hazardous Wastes 742

Review Questions 750
Green Chemistry Questions 751
Additional Problems 752

PART VI Advanced Atmospheric Chemistry

698

753

Chapter 17 The Detailed Free-Radical Chemistry
of the Atmosphere 755
Introduction 755
Box 17-1 Lewis Structures of Simple Free Radicals
Tropospheric Chemistry 757
Systematics of Stratospheric Chemistry 772
Review Questions 775
Additional Problems 776

756

Appendix Oxidation Numbers and Redox Equation
Balancing Reviewed AP-1
Answers to Selected Odd-Numbered Problems AN-1
Index I-1

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Preface
To the Student
There are many definitions of environmental chemistry. To some, it is solely
the chemistry of Earth’s natural processes in air, water, and soil. More commonly, as in this book, it is concerned principally with the chemical aspects
of problems that humankind have created in the natural environment.
Part  of this infringement on the natural chemistry of our planet has been a
result of the activities of our everyday lives. In addition, chemists, through the
products that they create and the processes by which they make these products,
have also had a significant impact on the chemistry of the environment.
Chemistry has played a major role in the advancement of society and in
making our lives longer, healthier, more comfortable, and more enjoyable.
The effects of human-made chemicals are ubiquitous and in many instances
quite positive. Without chemistry there would be no pharmaceutical drugs,
no computers, no automobiles, no TVs, no DVDs, no lights, no synthetic
fibers. However, along with all the positive advances that result from chemistry, copious amounts of toxic and corrosive chemicals have been produced
and dispersed into the environment. Historically, chemists as a whole have
not always paid enough attention to the environmental consequences of
their activities.
But it is not just the chemical industry, or even industry as a whole, that
has emitted substances into the air, water, and soil that are troublesome. The
fantastic increase in population and affluence since the Industrial Revolution
has overloaded our atmosphere with carbon dioxide and toxic air pollutants,
our waters with sewage, and our soil with garbage. We are exceeding the
planet’s natural capacity to cope with waste, and in many cases, we do not
know the consequences of these actions. As a character in Margaret
Atwood’s novel Oryx and Crake (McClelland and Stewart, 2003) stated,
“The whole world is now one vast uncontrolled experiment.”
During your journey through the chapters in this text, you will see that
scientists do have a good handle on many environmental chemistry problems and have suggested ways—although sometimes very expensive ones—

to keep us from inheriting the whirlwind of uncontrolled experiments on
the planet. Chemists have also become more aware of the contributions of
their own profession and industry in creating pollution and have created the
concept of green chemistry to help minimize their environmental footprint in
the future.
To illustrate these efforts, case studies of their initiatives have been included in the text. However, as a prelude to these studies, the Introduction
discusses something of the history of environmental regulations—especially
in the United States—and the principles, as well as an illustrative application, of the green chemistry movement that has developed. As concerns over
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Preface

xiii

such issues as food, water, energy, climate change, and waste production escalate, the concept of sustainability is rapidly moving from the wings to center
stage on the world agenda. Sustainability is introduced in the following
Introduction section and issues related to sustainability are blended throughout
the text.
Although the science underlying environmental problems is often maddeningly complex, the central aspects of it can usually be understood and
appreciated with only introductory chemistry as background preparation.
However, students who have not had some introduction to organic chemistry are encouraged to work through the Background Organic Chemistry section in the online Appendix, particularly before tackling Chapters 13 to 15.
Furthermore, the listing of general chemistry concepts that will be used in
each chapter should assist in identifying topics from the earlier course material that would be worth reviewing.

To the Instructor

Environmental Chemistry, Fifth Edition, has been revised, updated, and expanded in line with comments and suggestions made by a variety of users
and reviewers of the fourth edition. Since some instructors prefer to cover
chapters in an order different from ours, each chapter’s opening outline lists
previously introduced concepts that will be used again, which should facilitate reordering. Furthermore, we have divided the material into smaller
subsections and numbered them. The Detailed Chemistry of the Atmosphere
chapter has been repositioned to the end of the book since many instructors
do not teach from it, although in a course, it can readily follow Chapter 3.
In addition, following discussions with our reviewers, in Chapter 13 we have
deleted some of the descriptive information about pesticides that are no
longer in use.
We have expanded the coverage of topics related to climate change,
especially the generation of sustainable, renewable energy—which is now
covered in two chapters, the first on biofuels and other alternative fuels, and
the second on solar energy. As a consequence, this edition could be used as
the text for a number of types of courses in addition to Environmental
Chemistry. For example, a one-semester Energy and the Environment course
might use Chapters 3 through 9. Instructors who do not cover policy implications of energy and climate change topics could skip the first and last parts
of Chapter 6.
As in previous editions, the background required to solve both in-text
and end-of-chapter problems is either developed in the text or would have
been covered previously in a general chemistry course—as listed for each
chapter at its beginning. Where appropriate, hints are given to start students
on the solution. The Solutions Manual to the text includes worked solutions
to most problems (other than Review Questions, which are designed to
direct students back to descriptive material within each chapter).

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xiv

Preface

New to This Edition
Our philosophy in revising the textbook this time has been to make it more
user-friendly (both for instructors and for students) as well as to bring it upto-date. Furthermore, we have expanded the coverage of energy production
(especially for biofuels), the generation and disposal of CO2, and innovative
ways to combat climate change.

New Features
• Green text—to emphasize the most important statements, definitions,
and conclusions.
• Greater use of bullets and tables—to cover points most readily covered
in a list or sequence.
• Subsection numbering—to allow instructors to assign material to be covered
or skipped more easily and students to find particular topics more easily.
• Breaking the text into smaller subsections and shorter paragraphs—to
promote student understanding and allow maximum instructor flexibility.
• More schematic diagrams—to promote student comprehension of the
more complicated chemistry and appeal to a variety of learning styles.
• An Activity has been inserted into many chapters—these Web- or
library-based miniprojects could be assigned to individual students or to a
group to report on.
• Marginal notes—to supplement the main text with additional interesting
material and to indicate which Review Questions are relevant to the material
at hand.
• More hints and background—added to the more difficult in-text Problems
and Additional Problems.

• Parts III and IV have been interchanged—so that water chemistry
appears earlier in the book, as preferred by many instructors.
• Detailed mathematical material has been repositioned—toward the end
of the chapter in many cases, so instructors have flexibility in coverage.
• Increased international coverage—to give all students a better perspective
on environmental problems and solutions around the world. For example, there
is increased coverage of gaseous and particulate air pollution and CO2 emissions
and air quality standards in developed as well as developing countries.
• An Appendix has been added—to review the balancing of redox equations
and assignment of oxidation numbers (states).
• Organic Chemistry Appendix has been moved—to the textbook’s Web site
at www.whfreeman.com/envchem5e.

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xv

New Green Chemistry Cases
• A Nonvolatile, Reactive Coalescent for the Reduction of VOCs in
Latex Paints
• Development of Bio-Based Toners
• Recycling Carbon Dioxide: A Feedstock for the Production of
Chemicals and Liquid Fuels
• Bio-Based Liquid Fuels and Chemicals
• Spinetoram, an Improvement on a Green Pesticide


New Material on Climate Change and CO2
Substantial sections on the following topics have been added:
• Geoengineering the Climate (by chemical and physical means)
• Energy and CO2 Intensity Parameters and Predicted Global Trends
• Carbon Capture and Storage (CCS)—The Sequestration of CO2
• Shale-Gas Production and the Alberta Oil Sands
• The Deepwater Horizon Disaster
• Biodiesel Production from Algae and Other Sources
• Renewable Energy (Solar, Wind) Storage by Chemical Means
• Dye-Sensitized Solar Cells
• The Fukushima Nuclear Accident, and the Storage of Spent
Nuclear Fuel
Significant additions have also been made on many other topics, including:
• A new box reviewing the calculation of reaction rates
• Smoke from wood stoves and new technology for developing countries
• Removing CO2 from ambient air
• Biodegradable plastics
• The alternative theory to LRTAP
• E-waste and its disposal and recycling
Updates have been made throughout the book, especially concerning:
• Melanoma rates and UV-A protection in sunscreens
• The polar ozone holes and ODS concentration declines
• Smog, SO2 emission rates, and air-quality standards around the world

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Preface

• Catalytic converters for diesel-powered vehicles
• Particulate pollution and the atmospheric brown cloud
• Sea-level rises and the melting of glaciers
• Point-of-use water disinfection
• Desalination box—expanded to incorporate recent advances and news
• Increased and updated coverage on by-products of chlorination,
including in swimming pools
• Material on arsenic in drinking water updated and expanded in
geographic scope
• Origin of lead in drinking water from transit pipes
• New information concerning the effect of lead on children’s health
• New fire retardants

Supplements
The book companion Web site at www.whfreeman.com/envchem5e offers
Case Studies that let students explore current environmental controversies
and a Background Organic Chemistry section that provides a necessary introduction for those students who have not taken organic chemistry. Here,
instructors can also access PowerPoint slides of all art, tables, and graphs
from the text.
The Solutions Manual (1-4641-0646-0) includes worked solutions to almost
all problems (other than Review Questions, which are designed to direct students back to the appropriate material within each chapter).

To All Readers of the Text
The authors are happy to receive comments and suggestions about the content of this book from instructors and students. Please contact Colin Baird at
and Michael Cann at


Acknowledgments
The authors wish to express their gratitude and appreciation to a number of
people who in various ways have contributed to this fifth edition:
To the students and instructors who have used previous editions of the
text, and via their reviews and e-mails have pointed out subsections and
problems that needed clarifying or extending.

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xvii

To W. H. Freeman Executive Editor for the third, fourth, and fifth editions, Jessica Fiorillo; Senior Project Editor Vivien Weiss; and Development
Editor Brittany Murphy—for their encouragement, ideas, insightful suggestions, patience, and organizational abilities. To Margaret Comaskey for her
careful copyediting and suggestions again in this edition, to Cecilia Varas
for finding the photographs and for obtaining permissions for figures and
photographs, to Diana Blume for design, and to Susan Wein for coordinating production.
Colin Baird wishes to express his thanks . . .
To his colleagues at the University of Western Ontario and elsewhere
who made valuable suggestions and supplied information and answered queries on various subjects: Myra Gordon, Ron Martin, Martin Stillman, Garth
Kidd, Duncan Hunter, Roland Haines, Edgar Warnhoff, Marguerite Kane,
Currie Palmer, Rob Lipson, Dave Shoesmith, Felix Lee, Peter Guthrie, Geoff
Rayner-Canham, and Chris Willis.
To his daughter, Jenny, and his granddaughters, Olivia and Sophie, for
whom and for others of their generations this subject really matters.
Mike Cann wishes to express his thanks . . .

To his students (especially Marc Connelly and Tom Umile) and fellow
faculty at the University of Scranton, who have made valuable suggestions
and contributions to his understanding of green chemistry and environmental chemistry.
To Joe Breen, who was one of the pioneers of green chemistry and one
of the founders of the Green Chemistry Institute.
To Paul Anastas and Tracy Williamson (both of the U.S. Environmental Protection Agency), whose boundless energy and enthusiasm for green
chemistry are contagious.
To his loving wife, Cynthia, who has graciously and enthusiastically endured countless discussions of green chemistry and environmental chemistry.
To his children, Holly and Geoffrey, and his grandchildren, McKenna,
Alexia, Alan Joshua, Samantha, and Arik, who, along with future generations, will reap the rewards of sustainable chemistry.
Both authors wish to express thanks to the reviewers of the fourth edition, as well as draft versions of sections of the fifth edition of the text, for
their helpful comments and suggestions:
Samuel Melaku Abegaz, Columbus State University
John J. Bang, North Carolina Central University
James Boulter, University of Wisconsin–Eau Claire

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George P. Cobb, Texas Tech University
David B. Ford, University of Tampa
Chaoyang Jiang, University of South Dakota

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xviii

Preface

Joseph P. Kakareka, Florida Gulf Coast University

Michael E. Ketterer, Northern Arizona University
Cielito DeRamos King, Bridgewater State University
Rachael A. Kipp, Suffolk University
Min Li, California University of Pennsylvania
Kerry MacFarland, Averett University
Matthew G. Marmorino, Indiana University–
South Bend
Robert Milofsky, Fort Lewis College

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Jim Phillips, University of Wisconsin–Eau Claire
Ramin Radfar, Wofford College
A. Lynn Roberts, Johns Hopkins University
Kathryn Rowberg, Purdue University–Hammond
John Shapley, University of Illinois
Joshua Wang, Delaware State University
Darcey Wayment, Nicholls State University
Chunlong (“Carl”) Zhang, University of
Houston–Clear Lake

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Introduction to Environmental
Problems, Sustainability, and
Green Chemistry
In this book you will study the chemistry of the air, water, and soil, as well as
the effects of anthropogenic activities on the chemistry of the Earth. In addition, you will learn about sustainability and green chemistry, which aims to
design technologies that lessen the ecological footprint of our activities.


If mankind is to survive,
we shall require a
substantially new
manner of thinking.
Albert Einstein

Environmental chemistry deals with the reactions, fates, movements,
and sources of chemicals in the air, water, and soil. In the absence of humans,
the discussion would be limited to naturally occurring chemicals and processes. Today, with the burgeoning population of the Earth, coupled with
continually advancing technology, human activities have an ever-increasing
influence on the chemistry of the environment. The earliest humans, and
even those living little more than a century ago, must have thought of the
Earth as so vast that human activity could scarcely have any more than local
effects on the soil, water, and air. Today we realize that our activities can
have not only local and regional, but also global, consequences.
The quotation from Einstein that begins this section was in reference to
the dawn of the nuclear age and the concomitant threat of nuclear war.
Today, Einstein’s words are just as appropriate from the perspective that the
effects upon the Earth of our current consumption of resources and accompanying production of waste cannot be sustained. The environmental impact (I)
of humans may be thought of as a function of population (P), affluence (A),
and technology (T).
IϭPϫAϫT
The last 100 years have been witness to rapid growth in all of these areas,
leading to the “perfect environmental storm.” It took until 1800 for the
human population of the Earth to reach 1 billion. Since that time there has
been a seven-fold increase in population, with projections of 9 billion people
by 2050. By the end of today, there will be an additional 200,000 people on
this planet to feed, clothe, and shelter. Although many people still live in
abject poverty, in terms of sheer numbers, never have so many lived so well.

xix

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xx

Introduction to Environmental Problems, Sustainability, and Green Chemistry

China and India, the world’s two most populous countries with one-third of
the world’s population, have recently had unprecedented economic growth,
as evidenced by their GDP growth rate of about 10% for several years. This
has lifted many of their people out of poverty and elevated their lifestyles.
Unfortunately, their model for rising affluence is the same consumption/
waste paradigm common in the West. The accompanying consumption of
both renewable and nonrenewable resources and the production of pollution
are simply not sustainable for so many across the globe.
Fueled by human ingenuity and innovation, the last 100 years have also
witnessed more technological advances than all of preceding human history.
Remarkable discoveries include humans walking on the moon over 40 years ago,
drugs and medical advances that have helped to increase our life expectancy in
the United States from 47 years in 1900 to 79 years today, electronic devices that
were not even imaginable a century ago, agricultural advances that allow us to
feed 7 billion people, transportation that allows us to eat dinner in New York and
breakfast the following morning in London, and the discovery of DNA and the
human genome project that have unlocked many of the secrets of life. However,
most of these technological advances have been made with little attention to
their local, regional, and even global environmental consequences. This combination of exponential population growth, dramatic rise in affluence, and unprecedented technological advancement has left a legacy of toxic waste dumps,

denuded landscapes, daunting climate change, spent natural resources, and accelerated extinction of species. Never has a group of living organisms had such a
far-reaching and significant impact on the environment of the Earth.
There are now many indications that we have exceeded the carrying
capacity of the Earth—that is, the ability of the planet to convert our wastes
back into resources (often called nature’s interest) as fast as we consume its
natural resources and produce waste. Some say that we are living beyond the
“interest” that nature provides us and dipping into nature’s capital. In short,
many of our activities are not sustainable.
As we write these introductory remarks, we are reminded of the environmental consequences of human activities that impact the areas where we live
and beyond. Colin spends his summers on a small island just off the north
Atlantic coast in Nova Scotia, while Mike spends a few weeks each winter on
the west coast of southern Florida, a few kilometers from the Gulf of Mexico.
Although these locations are a great distance apart, if predictions are correct,
both may be permanently submerged by the end of this century as a result of
rising sea levels brought about by enhanced global warming (see Chapters 6
and 7). The public footbridge that links Colin’s island to the mainland is
treated with creosote, and the local residents no longer harvest mussels from
the beds below for fear they may be contaminated with PAHs (Chapter 15).
Colin’s well on this island was tested for arsenic, a common pollutant in that
area of abandoned gold mines (Chapter 12). To the north, the once robust
cod fishing industry of Newfoundland has collapsed due to overfishing.
Mike lives in northeastern Pennsylvania on a lake where the wood in his
dock is preserved with the heavy metals arsenic, chromium, and copper

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(Chapter 12). Within a short distance are two landfills (Chapter 16), which
take in an excess of 8,000 tonnes of garbage per day (from municipalities as
far as 150 kilometers away), as well as two Superfund Sites (Chapter 16) and
a nuclear power plant that generates plutonium and other radioactive wastes
for which there is no working disposal plan in the United States (Chapter 9).
Furthermore, within the last couple of years, natural gas wells have sprung up
like weeds as drillers use a hydraulic fracturing process (fracking) (Chapter 6)
that may leave a legacy of contaminated groundwater (Chapter 11) in many
states in the United States.
Colin’s home in London, Ontario, is within an hour’s drive of Lake Erie,
famous for nearly having “died” of phosphate pollution (Chapter 11), and
nuclear power plants on Lake Huron. Nearby farmers grow corn to supply to
a new factory that produces ethanol for use as an alternative fuel (Chapter 7),
and in Ottawa, a Canadian company has built the first demonstration plant
to convert the cellulose from agricultural residue into ethanol (Chapter 7).
On sunny days we both apply extra sunscreen because of the thinning of
the ozone layer (Chapters 1 and 2) and suffer the effects on our eyes and
lungs of ozone-polluted ground-level air each summer (Chapters 3 and 4).
Three of the best salmon rivers in North America in Nova Scotia must be
stocked each season because the salmon no longer migrate up the acidified
waters. Many of the lakes and streams of the beautiful Adirondack region of
upstate New York are a deceptively beautifully crystal clear, only because they
are virtually devoid of plant and animal life, again because of acidified waters
(Chapter 4).
Environmental issues like these probably have parallels that exist where
you live, and learning more about them may convince you that environmental chemistry is not just a topic of academic interest, but one that touches your
life every day in very practical ways. Many of these environmental threats are

a consequence of anthropogenic activities over the last 50 to 100 years.
In 1983 the United Nations charged a special commission with developing
a plan for long-term sustainable development. In 1987 the report titled “Our
Common Future” was issued. In this report (more commonly known as the The
Brundtland Report), the following definition of sustainable development is found:
Sustainable development is development that meets the needs of the
present without compromising the ability of future generations to meet
their own needs.

Although there are many definitions of sustainable development (or sustainability), this is the most widely used. The three intersecting areas of sustainability are
focused on society, the economy, and the environment. Together they are
known as the triple bottom line. In all three areas, consumption (particularly of
natural resources) and the concomitant production of waste are central issues.
The concept of an “ecological footprint” is an attempt to measure the
amount of biologically productive space that is needed to support a particular
human lifestyle. Currently there are about 4.5 acres of biologically productive
space for each person on the Earth. This land provides us with the resources that

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we need to support our lifestyles and to receive the waste that we generate and
convert it back into resources. If the entire population of 7 billion people lived
like Colin and Mike, rather typical North Americans, the total ecological footprint would require more than four planet Earths. Obviously, everyone on the

planet can’t live in as large and as inefficient a house, drive as many kilometers
in such an inefficient vehicle, consume as much food (in particular, meat) and
energy, create as much waste, etc., as those living in developed countries.
As developing countries such as China and India (with a combined total
of over 2 billion people and two of the fastest growing economies in the
world) expand economically, they look to the lifestyles of the 1 billion people on the planet that live in developed countries. Factor in the expected
increase in global population to 9 billion by 2050 and clearly this is not sustainable development. The people of the world (including and in particular
those in developed countries) must strive to develop a lifestyle that is sustainable. This does not necessarily mean a lower standard of living for those
in the developed world, but it does mean finding ways (more efficient technologies along with conservation) to reduce our consumption of natural resources and the concomitant production of waste.
There is now a widespread movement toward the growth and implementation of sustainable, or green, technologies. These technologies seek to reduce energy and resource consumption, use and expand renewable resources,
and reduce the production of waste. In chemistry, these developments are
known as green chemistry, which we will describe later in this introduction and
will see as a theme throughout this text.
Our ecological footprint in many cases is not limited to our backyard.
As mentioned above, the consequences of our activities may be regional
and even global. As we will see in Chapter 4, the burning of coal to produce electricity in the midwestern United States produces acid rain that
falls in Ontario; in turn, emissions from Ontario are responsible for producing much of the acid rain in northern New York State. Rising global temperatures (Chapters 5 and 6), due in part to the burning of fossil fuels, have
significant adverse impacts on those who use little, if any, fossil fuels.
One of these groups is the Inuit, who inhabit the northern reaches of
Canada, Russia, Greenland, and Alaska. These people depend on hunting
and fishing for sustenance. Ironically, the northern latitudes of the planet
have experienced some of the most significant temperature rises due to global
warming—warming that has resulted in major changes in the surrounding
flora and fauna and that has significantly altered the Inuits’ way of life. The
atmosphere of our planet is a commons, or perhaps more appropriately described as an open resource. We all use and benefit from this commons, but
no one is directly responsible for it. Its use as a dumping ground for pollutants
often affects more than those who are doing the dumping, a concept known
as the tragedy of the commons.
What we perceive as normal is primarily what we encounter in our everyday lives. But of course, things change, sometimes in seconds or over millennia.


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To the untrained “eye,” most environmental changes are not that noticeable.
But what we now think of as normal may not have been so 100 years ago or
even 50 years ago. In the 1600s, English fishermen were quoted as saying the
cod off Newfoundland were “so thick by the shore that we hardly have been
able to row a boat through them.” In 1951 factory fishing began, and in a mere
50 years the cod industry off Newfoundland, the area’s main economic activity,
was dead, leading not only to environmental but to economic disaster. To today’s Newfoundland teenagers this is the norm, although to their parents and
grandparents this is far from what they grew up with. This is an example of
shifting baselines, as well as another example of the tragedy of the commons.
The melting ice sheets and loss of habitat for caribou that the Inuit are
experiencing is also an example of shifting baselines.
The triple bottom line, ecological footprint, the tragedy of the commons, and shifting baselines are all examples of concepts that are commonly
used in discussing sustainability. We will encounter these and other sustainability concepts throughout this book. We suggest that you make a list of
these concepts (Table 0-1) and as you read the text keep a record of where
and in what context these are encountered.
TABLE 0-1

Sustainability Concepts

Triple Bottom Line (TBL): Although corporations have traditionally been solely focused on the
economic (prosperity) bottom line, many (in this age of a greater corporate social responsibility)

are adopting a wider corporate strategy that also includes the social (equality) and environmental
(quality) bottom lines. This is also called people, profits, and planet.
Tragedy of the Commons: In 1968, biologist Garrett Hardin put forth the argument that a common
(open) resource (e.g., water, air, land) used by rational individuals for their own good will result in
decimation of that resource.
Systems Thinking: Requires one to understand an entire system and how aspects of the system are
interconnected. This understanding will allow one to realize that introducing change may have
unintended consequences far beyond the original intent of the change. This is particularly true of
environmental systems and is a major theme of this book.
Life-Cycle Assessment (LCA): Provides an inventory of materials and energy (inputs) that are
consumed and the waste and emissions produced during the entire life cycle of a product, from
acquiring the materials (e.g., mining) needed to produce the product to disposing of the product;
i.e., from cradle to grave or better yet, cradle to cradle. After identification of the inputs and releases
at each step of the LC, an analysis of the impact on the environment (in some cases, both social and
economic impacts) can determine the steps that can be taken to minimize inputs and releases,
and thus the impact on the environment.
Cradle-to-Cradle: At the end of a product’s life cycle, rather than being disposed of (as in cradleto-grave), the spent product becomes the material to produce another product, thus mimicking the
regenerative approach of nature.
(continued on p. xxiv)

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