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Textbook Ebook Green Chemistry An Inclusive Approach Bela Torok Editor All Chapter PDF
Textbook Ebook Green Chemistry An Inclusive Approach Bela Torok Editor All Chapter PDF
Edited by
BÉLA TÖRÖK
TIMOTHY DRANSFIELD
University of Massachusetts Boston, Boston, MA, United States
Elsevier
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ISBN: 978-0-12-809270-5
xi
xii LIST OF CONTRIBUTORS
The concept of this book was born in 2005 follow a textbook style, providing examples,
when we (along with Deyang Qu, who recommended reading, and problem sets.
wrote Chapter 3.23) taught Introduction to The third part of the work is designed for
Green Chemistry at UMass Boston. We team- researchers, as it contains in-depth reviews
taught the course because none of us indi- on selected topics. Our intention is that ed-
vidually had expertise in everything we ucators, after covering the fundamentals laid
wanted to cover. We were lucky to have down in the first part, may select some of the
faculty whose specialties included air pollu- specialized research chapters as case studies
tion, novel battery technologies, and green to further illustrate the state-of-the-art prac-
synthesis, but even with our combined tice of Green Chemistry. Although the book
backgrounds, we felt unprepared to show includes more topics than could be covered
the true breadth of the field of Green in a typical undergraduate or even graduate
Chemistry. We searched for a textbook to class, the variety of topics will provide op-
help us fill in the gaps, but we could not find portunity for the faculty instructors to select
one. We successfully ran the course using an topics they are comfortable covering and can
environmental chemistry textbook and a lot fit into their schedules.
of primary literature, but from the outset, we The centerpiece of the third part of the
realized that the course deserved a textbook book is Green Chemistry in practice. The
designed around it. topics included in this part focus on special
This, then, is the textbook we wish had areas of the field. Every chapter in this
been available to us. It is intended for a part provides an up-to-date reference sec-
broad audience, including industry and tion, together comprising thousands of
academia. It is aimed to be a contemporary original papers and review articles. We
and inclusive Green Chemistry text that can believe that by including experts in many of
be used in undergraduate and graduate ed- the fields discussed, the book provides the
ucation and as a resource for researchers. readers with “insider information”: the as-
The main goal of the work was to be as pects or challenges of a given field that the
broad as possible, including many aspects of specialists consider the most important and
Green Chemistry. The book includes three urgent. This way, we hope that the book
main parts. The first two parts are intended will serve as a primary resource for those
for those who teach Green Chemistry: it who are new to Green Chemistry or those
covers the basic definitions, environmental who intend to branch out and discover
chemistry, renewable energy, sustainable other topics that are related to their own
synthesis, fundamental chemical toxicology, research fields.
and the effect of environmental factors on We would like to thank our distinguished
our genetic information. These chapters colleagues and authors, experts in their fields,
xiii
xiv PREFACE
for contributing to this unique endeavor. Project Manager, for her enormous help and
We also thank Kathryn Morrissey and Laura continuous encouragements throughout the
Kelleher, who helped us through the proposal process.
phase of the book, and Anitha Sivaraj,
who handled the galley proofs. We are Béla Török and Timothy Dransfield
indebted to Emily Thomson, our Editorial Boston, May 1, 2017
C H A P T E R
1.1
Green Chemistry: Historical
Perspectives and Basic Concepts
Béla Török, Timothy Dransfield
University of Massachusetts Boston, Boston, MA, United States
Chemists and chemistry, in general, have made an enormous contribution to the history of
humankind. Beginning with the early alchemists, these contributions include several devel-
opments that changed the course of history for the better or, in some cases, for the worse.
Many of them may seem to be simple by today’s standards, but at the time, they were
groundbreaking discoveries and inventions. The fabrication of simple soaps made the forma-
tion of large cities possible by improving the personal hygiene. The production of dyes and
paints contributed significantly to fashion and art over the centuries. As the usefulness of
chemistry became clear, more people decided to pursue such endeavors, which brought
exponential growth in this field. As Dalton, Avogadro, and Lavoisier made their famous dis-
coveries, chemistry became viewed more and more as science than as black magic. With sig-
nificant developments in chemical theory came the increased pace of new applications that
inspired yet further progress. However, not every step along the way was problem free.
Several inventions that were made with the best intentions backfired and caused health or
environmental issues. The use of freons as inflammable carrier gases in all sorts of sprays
in the 1960se70s seemed to be perfect, until Rowland and Molina published their findings
on the terrible effect of these chemicals on the ozone layer that protects the earth from harm-
ful ultraviolet radiation. Antibiotics were hot commodities after World War II, until it was
found that bacteria can develop resistance toward these compounds making them more diffi-
cult to fight against. Plastics seemed like a blessing until it was found that their degradation
takes over a thousand years. Dichlorodiphenyltrichloroethane (DDT) appeared to be an effec-
tive agent to fight malaria-spreading mosquitos, until it was found in fish around Antarctica,
proving that it lingers for a long time. Contemporary pesticides can leach into natural waters
and cause gender change in frogs. Many drugs have unintended harmful side effects. The list
is long. What is common in all these cases is that a product was developed for a certain pur-
pose without a careful analysis of its broader impact on the ecosystem. All these disasters
initiated a different chemical thinking that now we call green chemistry.
Green Chemistry
http://dx.doi.org/10.1016/B978-0-12-809270-5.00001-7 3 Copyright © 2018 Elsevier Inc. All rights reserved.
4 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
Several tools and methods that are now considered as part of sustainable synthesis (e.g.,
catalysis) were developed much earlier than the formal green chemistry movement began.
It took concerted and conscious efforts to envision and design a framework that included
the earlier developments and initiated further progress in this field. The basic principle,
benign by design, emphasized that both the product and the process used to produce it should
conform to the basic rules of sustainability. In their seminal book in 1998, Anastas and
Warner established the major principles of green chemistry. Although since then several
“new principles” have been added to the list, the original list is still applicable.
1. INTRODUCTION
1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS 5
3. Less hazardous chemical syntheses: Wherever practicable, synthetic methods should be
designed to use and generate substances that possess little or no toxicity to human
health and the environment.
4. Designing safer chemicals: Chemical products should be designed to affect their desired
function while minimizing their toxicity.
5. Safer solvents and auxiliaries: The use of auxiliary substances (e.g., solvents, separation
agents, etc.) should be made unnecessary wherever possible and innocuous when
used.
6. Design for energy efficiency: Energy requirements of chemical processes should be recog-
nized for their environmental and economic impacts and should be minimized. If
possible, synthetic methods should be conducted at ambient temperature and pressure.
7. Use of renewable feedstocks: A raw material or feedstock should be renewable rather
than depleting whenever technically and economically practicable.
8. Reduce derivatives: Unnecessary derivatization (use of blocking groups, protection/
deprotection, temporary modification of physical/chemical processes) should be mini-
mized or avoided if possible, because such steps require additional reagents and can
generate waste.
9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents
10. Design for degradation: Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do not persist in
the environment.
11. Real-time analysis for pollution prevention: Analytical methodologies need to be further
developed to allow for real-time, in-process monitoring and control prior to the forma-
tion of hazardous substances.
12. Inherently safer chemistry for accident prevention: Substances and the form of a substance
used in a chemical process should be chosen to minimize the potential for chemical
accidents, including releases, explosions, and fires.
Since products that involve any chemistry during their preparation are all manufactured
by industry, the aforementioned list had to be amended to include specific issues that
chemical engineers face while transitioning a laboratory process to the industrial setting.
Hence, Anastas and Zimmerman developed a similar set of principles for engineering.
1. INTRODUCTION
6 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
1. INTRODUCTION
1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS 7
1. INTRODUCTION
8 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
SCHEME 1.1.2 Examples of chemical reactions producing toxic (red) and non-toxic (green) waste.
can be quantified by environmental friendliness metrics. These indicators include energy con-
sumption, carbon footprint and emission of other greenhouse gases, potential contributions
to ozone depletion or smog formation, amount of waste generation, and toxicity of the waste
generated. The application of EQ or LCA, however, requires extended analysis before a pro-
cess can be implemented, and this often contributes to the cost of a product. Nonetheless, as
highlighted by the original 12 principles, it is always better (and likely less expensive) to pre-
vent problems by a thorough analysis than to clean up after an environmental disaster.
It is not within the scope of this text to provide a comprehensive examination of environ-
mental chemistry. Indeed, many fine textbooks exist on that subject, and our goal is not to
reduplicate such works. Rather, the goal of the various environmental chemistry chapters in
this text is to put into context the impact of human society on the natural world. While the
precise placement of the dividing line between green chemistry and environmental chem-
istry can be debated, it is clear that the entire purpose of green chemistry is to minimize
that impact. This is most evident in principles 1 and 10: waste prevention and the design
of chemicals such that they degrade harmlessly in the environment. Obviously, then, the
practice of green chemistry requires an understanding of those degradation pathways
and an understanding of what happens to the waste and by-products when they are
emitted. Although various textbooks exist that provide greener pathways for industrial
synthesis, for example, there is an alarming shortage of texts that train green chemists to
think about the chemistry of their products in the wild. With this work, we hope to begin
to bridge that gap.
1. INTRODUCTION
1.1.3 GREEN CHEMISTRY AND THE ENVIRONMENT 9
It may come as a surprise to some readers that society has long been aware of the impacts
of science and industry on the environment. The Mishnah laws of first- and second-century
Israel specified that threshing floors, leather tanneries, and lime kilns be removed 50 cubits
from the city to reduce exposure to airborne pollutants, and that flax stems be soaked at least
4e5 m from any vegetable fields to prevent water pollution from affecting the neighbor’s
food crops. The impetus for the construction of the Roman aqueducts was to transport clean
drinking water, as the Tiber had become so fouled with human waste. English laws attemp-
ted to curb pollution from the burning of coal as early as 1273, but the wave of the Industrial
Revolution overwhelmed those early efforts.
Even if we as a species were unaware of our effect on the environment, there has been
pollution as long as there has been civilization. There is evidence in ice core data that the
expansion of agriculture by the Romans and the cultivation of rice by the Han dynasty in
China, both in 1st century BCE, led to measurable increases in global methane concentrations.
Looking even further into the past, there is clear evidence of heavy metal pollution of soil and
water arising from metallurgy as long ago as 1500 BCE and continuing for nearly 2000 years.
Indeed, significant levels of these pollutants measured in modern lakes may in fact be
sourced to ancient industry rather than to more modern endeavors.
Ancient impacts aside, it is clear that since the Industrial Revolution the scale and the char-
acter of the pollution has fundamentally changed. Perhaps we can date this to 17th century
England, when John Evelyn wrote of the damage caused by London’s coal smoke in his
pamphlet, Fumifugium, although even this document refers to the history of England’s prob-
lems with coal dating back to the middle ages. Perhaps it dates to the cholera outbreaks
around the world in the 19th century, caused by contaminated drinking water in the growing
cities; or perhaps the burning of the Cuyahoga River, most notably in 1952, a result of the
accumulation of oil slicks on its surface; or the smog incidents of the mid-20th century in Lon-
don, and Pennsylvania and Belgium, in which thousands of people died; or the widespread
use of DDT after World War II, now found in animal tissue samples from the most remote
locations on Earth; or the tragedy of Love Canal, where people living in houses built on a
landfill were exposed to toxic waste as the containers leeched into the soil; or the 1984 Union
Carbide disaster in Bhopal, India, where 4000 people died from exposure to methyl isocya-
nate; or the photochemical smog in Los Angeles during the 1980s, or that of Mexico City,
Delhi, and Beijing today; or Three Mile Island, Chernobyl, and Fukushima, reminding us
that the wonders of the nuclear age bring with them new dangers. It is true that human sci-
ence and technology have combined to produce a society that is awe inspiring. However, it is
also true that this society has wreaked havoc on our natural environment.
According to most geology textbooks, the most recent geological epoch began nearly
12,000 years ago with the dawn of the Holocene. However, the conversation in recent years
has recognized the shift in mankind’s ability to harm our planet on a global scale. In 2000,
Nobel laureate Paul Crutzen argued for the use of the term Anthropocene, referencing that
our current period is defined by our species more than by any other characteristic. Crutzen
did not coin the phrasedit had been used by Soviet scientists as early as the 1960s, and
perhaps even predates them. However, the dawn of the 21st century was also the dawn of
widespread acceptance of the harsh realities of global warming and its associated climate
1. INTRODUCTION
10 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
changes. Already the pH of the oceans is dropping, leading to the distinct possibility of mass
extinction of life in the sea. The ongoing “Holocene extinction” is removing up to 140,000 spe-
cies from our planet each year, a rate that rivals that of the extinction that took the dinosaurs.
Left unchecked, the modern tail of the Industrial Revolution threatens all life on the planet.
Often doomsayers will claim that we are on the verge of destroying the planet itself. This is
presumably hyperboledthe planet has seen mass extinction before, and will again. However,
the same cannot be said of the human race.
To be clear, the authors do not believe that we are witnessing the end of human civiliza-
tion. Because one way or another, our destruction of the environment will be checked. At
some point, the financial arguments against change will fall by the wayside as the need for
change becomes more urgent. Whether driven by government intervention or an industrial
recognition of the bottom line, at some point the solutions to these problems will become
financially competitive with the cost of doing nothing. It falls to practitioners of green chem-
istry to provide the solutions at a cost that obtains that result as soon as possible.
Environmental regulatory agencies are part of life in most countries. They provide guid-
ance for new developments and oversight for existing industrial technologies as well as com-
mon aspects of life, from the disposal of restaurant waste to application of cosmetics. Since
the detailed discussion of environmental law and regulatory agencies is far beyond the scope
of this introductory chapter, here we describe several of most visible regulatory agencies that
are charged with managing the environmental issues in the largest economies.
1. INTRODUCTION
1.1.4 REGULATORY AGENCIES 11
single most successful international agreement to date.” This is in marked contrast to the inter-
national community’s much slower and more contested response to global warming. The most
important and well-known treaties to combat climate change are the Kyoto Protocol (1997) and
the Paris Agreement (2015). The Kyoto Protocol described the commitment of the participating
countries to reduce the emission of greenhouse gases. The Paris Agreement, the result of the UN
Framework Convention on Climate Change, while aiming for a similar goal, made recommenda-
tions on how much to limit the annual temperature increase of the planet. As of today, 131
(out of 197) parties have ratified the Paris Agreement.
This leads us to mention the weaknesses of some of the UN-facilitated agreements. Given
the nature of the UN, these treaties are negotiated by the governments of the participating
countries. However, once the agreement is signed, the law-making bodies of the nations
have to ratify it; thus the countries essentially commit themselves by their own laws to up-
hold the agreement. That has been so far the Achilles’ heel of many such agreements: several
countries ratified it, whereas many others did not. The reasons for not ratifying vary from
country to country and depend on economic development, energy/fuel production and
use, and many other socioeconomic factors. Unfortunately, many of these agreements are
purely political and do not include the development of actual technologies as a response
to global warming.
1. INTRODUCTION
12 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
agency; however, in many states, there are separate entities to deal with separate issues
(water, agriculture, etc.).
The National Oceanic and Atmospheric Administration (NOAA) (part of the Department of
Commerce) also concerns itself with environmental issues. It grew out of some of the oldest
government branches dedicated to the environment, including the United States Coast and
Geodetic Survey, which was first established in 1807 by Thomas Jefferson. In 1970, President
Nixon created NOAA from several other agencies, including the Weather Bureau (1870) and
the Bureau of Commercial Fisheries (1871). Its current substructure includes the National
Weather Service, the National Ocean Service, and the Environmental Satellite, Data and In-
formation Service, among others. Through these divisions it contributes by observing and
communicating data related to global warming and atmospheric and water pollution. Similar
to the EPA, the NOAA has facilities that conduct active research on the environment.
1.1.4.4 Canada
The Environment and Climate Change Canada is the major government agency that reg-
ulates and enforces environmental protection in Canada. It was established in 1971 by the
Department of Environment Act to assess, monitor, and protect the environment, including
providing basic weather and meteorological services to the citizens of Canada. The agency’s
responsibilities are those of a typical environmental agency: making environmental deci-
sions/regulations based on available evidence, especially with regard to pollution prevention
and the like. In addition to its support to policy making, the agency is a supporter of a broad
variety of environment-related research through many funding initiatives. Just as in the
United States, the Canadian Provinces have their own environmental agencies.
1.1.4.6 Russia
The Ministry of Natural Resources and the Environment (MNRE) is the main policy-making
and enforcing body in Russia. Russia has had some sort of natural resources governmental
1. INTRODUCTION
1.1.4 REGULATORY AGENCIES 13
unit since the 18th century. The MNRE was created in 2008 by merging the former Ministry of
Environment and Ministry of Natural Resources (both founded in 1996, after the collapse of
the Soviet Union). It has several agencies such as the Federal Service for the Supervision
of Natural Resources, the Service for Hydrometeorology and Environmental Monitoring,
and separate agencies for subsoil, water, and forestry management.
1.1.4.7 China
Immediately after the Stockholm Declaration, China created its Environmental Protection
Leadership Group (1974) and environmental protection became a state policy in 1983 with the
Environmental Protection Commission. After several upgrades and name changes, the cur-
rent Ministry of Environmental Protection (MEP) was established in 2008. China, the most
populous country in the world, has seen an unprecedented industrial growth and urbaniza-
tion since the 1980s, which has brought with it significant environmental problems, including
water and air pollution. The major mandates of the MEP include the design, organization,
and implementation of national policies, programs, and plans for environmental protection,
policy making, and regulations and leading the response to major environmental problems.
In addition, it carries out environmental protection science and technological activities
including the organization of projects on engineering, and facilitates the development of envi-
ronmental technology management systems as well as conducts and organizes environ-
mental education.
1.1.4.8 India
India, as the second most populous country in the world, with rapidly growing industrial
activity has its fair share of environmental problems. In addition to industrial accidents, wa-
ter shortages, soil problems (e.g., exhaustion, erosion), deforestation, and, especially in the
major metropolitan areas, air and water pollution affect many areas in the country. To
address these problems, the Central Pollution Control Board (founded in 1974) created the
National Air Quality Monitoring Program. Due to the inspirational power of the Stockholm
Declaration, in 1972, the National Council for Environmental Policy and Planning within the
Department of Science and Technology was established to protect the environment. This
council later became the Ministry of Environment and Forest, which is India’s most important
governmental agency for environmental protection. The Environment Protection Act of 1986
is one of the major early milestones in its actions. The current legislative framework includes
climate change, deforestation management, coastal regulations zones, and pollution control,
among many other tasks.
1.1.4.9 Japan
Many countries started seriously considering environmental protection only after the
Stockholm Declaration (1972), whereas Japan was among the first countries to enact environ-
mental regulations after four major pollution outbreaks occurred in the country in the
1950se60s. In 1958, a water quality conservation law was passed, which was followed in
1. INTRODUCTION
14 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
1962 by a smoke and soot emission control law. In 1971, the first Environmental Agency
was established in Japan. Currently, the Ministry of the Environment is the branch of the
Government of Japan that is responsible for activities related to the environment. This agency
has broad responsibilities, as it is involved in policy making concerning waste management
and recycling, pollution control, nature conservation, wildlife protection, air quality and
transportation, as well as health and chemicals, and is also charged with the care of Japan’s
national parks.
1.1.4.10 Australia
The Department of Environment and Energy (DEE) is the major government agency in
Australia in charge of environmental protection. It designs and implements government pol-
icies and programs to protect and conserve the environment, water, and heritage, and pro-
motes climate action. DEE deals with a broad array of activities, such as far-reaching
environmental protection of Australian air, land, and water; managing the national parks;
conducting research on environmental problems; as well as acting as a funding agency for
environmental research. Similar to the United States and Canada, the Australian states also
have their own individual environmental agencies.
The nature and scope of the field of chemistry has changed dramatically since the days of
the alchemists. Chemistry impacts nearly every aspect of modern life. The progression has
not always been smooth, and there have been significant missteps along the way. However,
the harnessing of chemistry in the interest of society has brought us to a modern age unimag-
inable by our ancestors. Toward the end of the 20th century, the field of green chemistry was
born from a recognition of those missteps and a desire to minimize the impact of human so-
ciety, and especially of human industry, on our natural environment. The core philosophy
can be expressed in various ways, with lists of principles and metrics. The goal is always
the same: benign by design.
Societal impact on the environment presents us with multiple pressing problems, which
can be addressed by various means. All things considered, it would be preferable if chemical
solutions could be found before political solutions are required. This could entail, for
example, a reimagining of an existing technology (e.g., the electric car, biodegradable plas-
tics), a means to reduce the environmental impact (e.g., solvent-free synthesis, exhaust plume
scrubbers), or a technology to remove existing pollutants (e.g., CO2 sequestration, bioreactor
landfills). By finding a way for companies to profit from the mitigation of pollution, green
chemists can encourage society to adopt these changes much more quickly and completely
than would a reluctant culture enforced by governmental policies. This is not to minimize
the importance of effective policies to control pollution; as we have seen, these efforts are crit-
ical to solving national- and global-scale problems. However, one of the goals of green chem-
istry must be to better facilitate widespread adoption of these new technologies and new
methodologies by making them acceptable for everyone.
1. INTRODUCTION
PROBLEMS 15
PROBLEMS
1. Calculate the atom economy and E-factor of the following processes:
2. Reactions A and B are two different methods producing the same product P. Reaction
A has a theoretical atom economy of 100% with an actual yield of 65% for the product.
Reaction B only possesses 85% atom economy, with 95% actual yield for the product.
Which reaction is greener, that is, generates less waste considering 100% conversion of
A and B?
3. Research the similarities and differences between environmental quotient and life cycle
assessment.
4. Select any chemical product and design a green pathway for it considering the com-
plete process (all details from finding/manufacturing starting materials, other compo-
nents, minimizing environmental impact, etc.). Show your work in a flowchart from
the beginning of the manufacturing phase to the likely fate of the product/postproduct
in the environment.
1. INTRODUCTION
16 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS
5. Solar panels are a popular product marketed widely to offer consumers the opportu-
nity to harness the energy of the sun. Research the manufacturing process of solar
panels and prepare an in-depth analysis on the cost and environmental impact of their
production. Compare the environmental impact of generating energy using solar
panels through the complete lifetime of these panels with that of the same amount en-
ergy generated by a coal-based power plant.
6. Several times in this chapter, the smoke from coal burning was mentioned as being
especially damaging to the environment and to human health. Research what com-
pounds in coal smoke are primarily responsible for these effects.
7. John Evelyn’s Fumifugium detailed the health impacts of coal burning in 17th century
London and was written to request intervention by the Parliament and the King.
Investigate the alarming health statistics that led to his appeal.
8. How does an increase in pastoral agriculture result in an increase in methane emis-
sions? What about rice cultivation?
9. The history of environmental pollution is often the history of unanticipated
consequences. Two excellent examples of this are the stories of DDT and CFCs.
a. In 1948, the Nobel Prize in medicine was awarded for the invention of DDT to
combat disease in the aftermath of World War II. Why was DDT so effective in this
role? What is it about DDT that made its widespread use so problematic?
b. CFCs were one of the “miracle” inventions of the 20th century, replacing toxic and/
or flammable gases in a variety of applications. What were some of these applica-
tions and what were the gases that they replaced?
10. A staggering variety of organic pollutants were found in the soil, water, and air
samples taken from Love Canal in 1977. One of the highest concentrations was of
benzene. Research the toxicity of benzene, including its mode of action and its
mandated concentration limits in the environment.
11. Analyze the 1997 Kyoto Protocol and 2015 Paris Agreement and describe the major
points in both. By comparing the two, summarize the development that occurred
during the nearly 20 years that passed between the two agreements.
Recommended Reading
1. Anastas PT, Warner JC. Green chemistry: theory and practice. New York: Oxford University Press; 1998.
2. Lancaster M. Green chemistry e an introductory text. 3rd ed. Cambridge: RSC; 2016.
3. Matlack AS. Introduction to green chemistry. 2nd ed. New York: CRC Press, Taylor & Francis; 2010.
4. Kovacs L, Csupor D, Lente G, Gunda T. 100 chemical myths: misconceptions, misunderstandings, explanations. Heidelberg,
New York, Dordrecht, London: Springer Cham; 2014.
5. Li C-J, Anastas PT. Green chemistry: present and future. Chem Soc Rev 2012;41(4):1413e4.
6. vanLoon GW, Duffy SJ. Environmental chemistry: a global perspective. 3rd ed. Oxford: Oxford University Press; 2010.
7. Spiro TG, Purvis-Roberts KL, Stigliani WM. Chemistry of the environment. 3rd ed. California: University Science
Books; 2012.
8. Baird C, Cann M. Environmental chemistry. 5th ed. New York: WH Freeman; 2012.
1. INTRODUCTION
C H A P T E R
2.1
Environmental Chemistry,
Renewable Energy, and Global
Policy
Heather A. Rypkema
Heritage Strategies, INTL, Washington, DC, United States
2.1.1 INTRODUCTION
The future welfare of our planet depends on a thorough understanding of our current tech-
nology and its effects on the environment. Earlier manifestations of mankind, in which the
height of environmental impact consisted of the occasional slaughtering of a large mammal,
had little or no impact on the world that surrounded it. Today, however, almost every aspect
of our lifestyle has a profound effect on the macrocosm of Earth’s ecosystems. Most daily ac-
tivities contribute to this impact in varied, and often unexpected, ways.
Most people realize that the mundane act of driving a car contributes to one’s carbon foot-
print, thereby pouring carbon dioxide into the atmosphere, which contributes to global
warming, more currently enveloped into the phenomenon of climate change. But what
impact does this really have? What is the implicit environmental effect of trading in a tradi-
tional vehicle for a hybridddoes the increased fuel economy and reduced carbon footprint
counterbalance the addition of an otherwise usable vehicle to the exploding mass of metal-
contaminated landfill? And, more generally, what is the difference between global warming
and climate change?
There are national movements to reduce the consumption of bottled water, but why? Most
obviously, there is the economic element of paying $1 or more for a bottle of water, when the
equivalent amount of tap water costs 0.1 cents. Additionally, there is the environmental waste
impact of the plastic container. What are the long-term environmental impacts of the plastic
bottle? In 2015, 11.7 billion gallons of bottled water were consumed in the United States, a
volume that equates to more than 75 billion individual 20-oz bottles, more than 60% of which
ultimately end up in landfills. Furthermore, how much energy is expended just to produce
this packaging? The annual energy cost of producing plastic bottles to contain commercial
Green Chemistry
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It is found on some of the loftiest peaks of the Scottish Highlands;
but in Iceland it overspreads the whole country, flourishing more
abundantly and attaining to a larger growth on the volcanic soil of the
western coast than elsewhere. It is collected triennially, for it requires
three years to reach maturity, after the spots where it thrives have
been cleared. We are told that the meal obtained from it, when
mixed with wheat-flour, produces a greater quantity, though perhaps
a less nutritious quality, of bread than can be manufactured from
wheat-flour alone. The great objection to it is its bitterness, arising
from its peculiar astringent principle, cetraria. However, the Lapps
and Icelanders remove this disagreeable pungency by a simple
process. They chop the lichen to pieces, and macerate it for several
days in water mixed with salt of tartar or quicklime, which it absorbs
very readily; next they dry it, and pulverize it; then, mixed with the
flour of the common knot-grass, it is made into a cake, or boiled, and
eaten with reindeer’s milk.
The reader will not expect to find the tundras of Northern Asia or
the shores of the Polar Sea rich in bud and bloom, yet even these
dreary wastes are not absolutely without floral decoration. Selinum
and cerathium, as well as the poppy and sorrel, andromeda, and
several species of heath, are mentioned by Dr. Kane as blooming in
the neighbourhood of Smith Strait. On the south coast of the Polar
Sea Dr. Richardson found a considerable variety of vegetation. We
noticed, he says, about one hundred and seventy phænogamous or
flowering plants; being one-fifth of the number of species which exist
fifteen degrees of latitude further to the southward. He adds:—The
grasses, bents, and rushes constitute only one-fifth of the number of
species on the coast, but the two former tribes actually cover more
ground than all the rest of the vegetation. The cruciferæ, or cross-
like tribe, afford one-seventh of the species, and the compound
flowers are nearly as numerous. The shrubby plants that reach the
sea-coast are the common juniper, two species of willow, the dwarf-
birch, the common alder, the hippophaë, a gooseberry, the red bear
berry (arbutus uva ursi), the Labrador tea-plant, the Lapland rose,
the bog-whortleberry, and the crowberry. The kidney-leaved oxyria
grows in great abundance there, and occasionally furnished us with
an agreeable addition to our meals, as it resembles the garden-
sorrel in flavour, but is more juicy and tender. It is eaten by the
natives, and must, as well as many of the cress-like plants, prove an
excellent corrective of the gross, oily, rancid, and frequently putrid
meat on which they subsist. The small balls of the Alpine bistort, and
the long, succulent, and sweet roots of many of the astragaleæ,
which grow on the sandy shores, are eatable; but it does not seem
that the Eskimos are acquainted with their use. A few clumps of
white spruce-fir, with some straggling black spruces and canoe-
birches, grow at the distance of twenty or thirty miles from the sea, in
sheltered situations on the banks of rivers.
To sum up:—
What may be called the Arctic climate extends over nearly the
whole of Danish America, the newly-acquired possessions of the
United States, the original Hudson Bay Territory, and Labrador, down
to that unimportant watershed which separates from the tributaries of
Hudson Bay the three great basins of the St. Lawrence, the five
great lakes, and the Mississippi. This line of watershed undulates
between the 52nd and 49th parallels of latitude, from Belle Isle Strait
to the sources of the Saskatchewan, in the Rocky Mountains, where
it inflects towards the Pacific Ocean, skirting on the north the basin
of the Columbia.
Thus bounded on the south, the Arctic lands of America,
including the groups of islands lying to the north and north-east,
cannot occupy less than 560,000 square leagues. They exceed,
therefore, the superficial area of the European lands, estimated at
about 490,000 square leagues.
We propose to divide these lands into two zones or regions, the
wooded and the desert zones: the former, in America, includes the
basins of the Upper Mackenzie, the Churchill, the Nelson, and the
Severn.
In the wooded zone the thermometer does not rise above zero
until the month of May. Then, under the influence of a more genial
temperature, the breath of life passes into the slumbering, inert
vegetation. Then the reddish shoots of the willows, the poplars, and
the birches hang out their long cottony catkins; a pleasant greenness
spreads over copse and thicket; the dandelion, the burdock, and the
saxifrages lift their heads in the shelter of the rocks; the sweet-brier
fills the air with fragrance, and the gooseberry and the strawberry are
put forth by a kindly nature; while the valleys bloom and the hill-sides
are glad with the beauty of the thuja, the larch, and the pine.
The boundary between the wooded zone and the barren would
be shown by a line drawn from the mouth of the Churchill in Hudson
Bay to Mount St. Elias on the Pacific coast, traversing the southern
shores of the Bear and the Slave Lakes. To the north, this barren
zone touches on eternal snow, and includes the ice-bound coasts of
the Parry Archipelago; to the east and the north-east, identity of
climate and uniform character of soil bring within it the greatest part
of Labrador and all Greenland.
In Asia the isothermal line of O° descends towards the 55th
parallel of latitude, one lower than in America,—though to the north
of it some important towns are situated, as Tobolsk, lat. 58° 11’;
Irkutsk, lat, 58° 16’; and Yakutsk, lat. 62°.
In Continental Europe, the only Arctic lands properly so called,
and distinguished by an Arctic flora, are Russian Lapland and the
deeply-indented coast of Northern Russia. Far away to the north,
and separated from the continent by a narrow arm of the sea, lie the
three almost contiguous islands known as Novaia Zemlaia (lat. 68°
50’ to 76° N.). And still further north, almost equidistant from the Old
World and the New, lies the gloomy mountainous archipelago of
Spitzbergen (lat. 77° to 81°, and long. 10° to 24°).
The identities between the Arctic dog and the Arctic wolf are so
important that Dr. Kane agrees with Mr. Broderip in assigning to
these animals a family origin. The oblique position of the wolf’s eye
is not uncommon among the Eskimo dogs. Dr. Kane had a slut, one
of the tamest and most affectionate of his team, who had the long
legs, the compact body, the drooping tail, and the wild scared
expression of the eye, which some naturalists have supposed to
distinguish the wolf alone. When domesticated early—and it is easy
to domesticate him—the wolf follows and loves you like a dog. “That
they are fond of wandering proves nothing; many of our pack will
stray for weeks,” says Kane, “into the wilderness of ice; yet they
cannot be persuaded, when they come back, to inhabit the kennel
we have built for them only a few hundred yards off. They crouch
around for the companionship of men.” Both animals howl in unison
alike; and, in most parts, their footprint is the same.
The musk-ox (Ovibos moschatus) is one of the largest of the
Polar ruminants. As its zoological name indicates, it is an
intermediary between the ox and the sheep. Smaller than the former,
larger than the latter, it reminds us of both in its shape and general
appearance. It has an obtuse nose; horns broad at the base,
covering the forehead and crown of the head, and curving
downwards between the eye and ear until about the level of the
mouth, where they turn upwards; the tail is short, and almost hidden
by the thickness of the shaggy hair, which is generally of a dark
brown, and of two kinds, as with all the animals of the Polar Regions;
a long hair, which on some parts of the body is thick and curled, and,
underneath, a fine kind of soft, ash-coloured wool; the legs are short
and thick, and furnished with narrow hoofs, like those of the moose.
The female is smaller than the male, and her horns are smaller. Her
general colour is black, except that the legs are whitish, and along
the back runs an elevated ridge or mane of dusky hair.
The musk-ox, as his name implies, throws out a strong odour of
musk,—with which, indeed, his very flesh is impregnated, so that the
scent is communicated to the knife used in cutting up the animal. Not
the less is he regarded as a valuable booty by the Indians and the
Eskimos, who hunt him eagerly. He wanders in small troops over the
rocky prairies which extend to the north of the great lakes of North
America. He is a fierce-tempered animal, and in defence of his
female will fight desperately.
His general habits resemble strongly those of the reindeer; but
his range appears to be principally limited to Melville Island, Banks
Land, and the large islands to the south-east of the latter.
One of our Arctic explorers describes the musk-oxen as all very
wild in April, and as generally seen in large herds from ten to seventy
in number. In June they were stupidly tame, and seemed to be
oppressed by their heavy coats of wool, which were hanging loosely
down their shoulders and hind-quarters in large quantities; the herds
much smaller, and generally composed of cows and calves.
The heavy coat of wool with which the musk-oxen are provided,
is a perfect protection against any temperature. It consists of a long
fine black hair, and in some cases white (for it is not ascertained that
these oxen change their colour during the winter), with a beautiful
fine wool or fur underneath, softer and richer than the finest alpaca
wool, as well as much longer in the staple. This mantle apparently
touches the ground; and the little creature looks, it is said, like a bale
of black wool, mounted on four short nervous goat-like legs, with two
very bright eyes, and a pair of sharp “wicked-shaped” horns peering
out of one end of it.
THE MUSK-OX.