CHAPTER 14

The Endangered Global

Atmosphere
AR-RAFI A. SALUAN
Chapter Outline
• Anthropogenic Change in the Atmosphere
• Greenhouse Gases and Global Warming
• Acid Rain
• Ozone Layer Destruction
• Photochemical Smog
• Nuclear Winter
• What is to be done?
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• There is a very strong connection between life forms on earth and the
nature of earth’s climate, which determines its suitability for life.
• As proposed by James Lovelock, a British chemist, this forms the basis of
the Gaia hypothesis, which contends that the atmospheric O2/CO2
balance established and sustained by organisms determines and maintains
earth’s climate and other environmental conditions.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• Ever since life first appeared on earth, the atmosphere has been influenced
by the metabolic processes of living organisms. When the first primitive
life molecules were formed approximately 3.5 billion years ago, the
atmosphere was very different from its present state.
• At that time, it was chemically reducing and thought to contain nitrogen,
methane, ammonia, water vapor, and hydrogen, but no elemental oxygen.
These gases and water in the sea were bombarded by intense, bond-
breaking ultraviolet radiation which, along with lightning and radiation
from radionuclides, provided the energy to bring about chemical reactions
that resulted in the production of relatively complicated molecules,
including even amino acids and sugars.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• From this rich chemical mixture, life molecules evolved. Initially, these
very primitive life forms derived their energy from fermentation of organic
matter formed by chemical and photochemical processes, but eventually
they gained the capability to produce organic matter by photosynthesis,
and the stage was set for the massive biochemical transformation that
resulted in the production of almost all the atmosphere’s oxygen.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC
• The oxygen initially produced by photosynthesis was probably quite toxic
to primitive life forms. However, much of this oxygen was converted to
iron oxides by reaction with soluble iron(II):

• The enormous deposits of iron oxides thus formed provide convincing

evidence for the liberation of free oxygen in the primitive atmosphere.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• Eventually enzyme systems developed that enabled organisms to mediate

the reaction of waste-product oxygen with oxidizable organic matter in the
sea. Later this mode of waste-product disposal was utilized by organisms
to produce energy for respiration, which is now the mechanism by which
non-photosynthetic organisms obtain energy.

• In time, oxygen accumulated in the atmosphere, providing an abundant

source of O2 for respiration. It had an additional benefit in that it enabled
the formation of an ozone shield against solar ultraviolet radiation. With
this shield in place, the earth became a much more hospitable environment
for life, and life forms were enabled to move from the protective
surroundings of the sea to the more exposed environment of the land.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC
• Other instances of climatic change and regulation induced by organisms
can be cited. An example is the maintenance of atmospheric carbon
dioxide at low levels through the action of photosynthetic organisms (note
from Reaction 14.1.1 that photosynthesis removes CO2 from the
atmosphere). But, at an ever accelerating pace during the last 200 years,
another organism, humankind, has engaged in a number of activities that
are altering the atmosphere profoundly.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC
• The effects of human activities and the anthrosphere on the atmosphere are summarized
below:

 Industrial activities, which emit a variety of atmospheric pollutants including SO2,

particulate matter, photochemically reactive hydrocarbons, chlorofluorocarbons, and
inorganic substances (such as toxic heavy metals)
 Burning of large quantities of fossil fuel, which can introduce CO2 , CO, SO2, NOx,
hydrocarbons (including CH4), and particulate soot, polycyclic aromatic hydrocarbons,
and fly ash into the atmosphere
 Transportation practices, which emit CO2, CO, NOx, photochemically reactive (smog
forming) hydrocarbons, and polycyclic aromatic hydrocarbons
 Alteration of land surfaces, including deforestation
 Burning of biomass and vegetation, including tropical and subtropical forests and
savanna grasses, which produces atmospheric CO2, CO, NOX, and particulate soot and
polycyclic aromatic hydrocarbons
 Agricultural practices, which produce methane (from the digestive tracts of domestic
animals and from the cultivation of rice in waterlogged anaerobic soils) and NO 2 from
bacterial denitrification of nitrate-fertilized soils.
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• These kinds of human activities have significantly altered the atmosphere,

particularly in regard to its composition of minor constituents and trace
gases.

• Major effects have been the following:

Increased acidity in the atmosphere
Production of pollutant oxidants in localized areas of the lower
troposphere*
Elevated levels of infrared-absorbing gases (greenhouse gases)
Threats to the ultraviolet-filtering ozone layer in the stratosphere
Increased corrosion of materials induced by atmospheric pollutants
14.1. ANTHROPOGENIC CHANGE IN THE ATMOSPHEREC

• In 1957 photochemical smog was only beginning to be recognized as a

serious problem, acid rain and the greenhouse effect were scientific
curiosities, and the ozone-destroying potential of chlorofluorocarbons had
not even been imagined. In that year, Revelle and Suess prophetically
referred to human perturbations of the earth and its climate as a massive
“geophysical experiment.” The effects that this experiment may have on
the global atmosphere are discussed in this chapter.
14.2. GREENHOUSE GASES AND GLOBAL
WARMING
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• This section deals with infrared-absorbing trace gases (other than water
vapor) in the atmosphere that contribute to global warming.
• These gases produce a “greenhouse effect” by allowing incoming solar
radiant energy to penetrate to the earth’s surface while reabsorbing infrared
radiation emanating from it. Levels of these “greenhouse gases” have
increased at a rapid rate during recent decades and are continuing to do so.
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• Concern over this phenomenon has intensified since about 1980. This is
because ever since accurate temperature records have been kept, the 1980s
were the warmest 10-year period recorded and included several record
warm years. In general, the 1990s continued the warming trend. All
months in 1998 except for October (which missed by about 0.1°C) set
record monthly temperature highs, and 1998 was the warmest year on
record as of 1999.
14.2. GREENHOUSE GASES AND GLOBAL WARMING

• Figure 14.1 shows global temperature trends since 1880. In addition to

being a scientific issue, greenhouse warming of the atmosphere has also
become a major policy, political, and economic issue.
• The analysis of fossil ice provides evidence of past variations in
temperature. One characteristic of ice that indicates the temperature at
which it was deposited is conductivity, which declines with declining
temperature of ice formation.
• The other characteristic is the ratio, which is higher with increasing
temperature of ice formation.
 14.2. GREENHOUSE GASES AND GLOBAL WARMING
• *It is known that CO2 and other greenhouse gases such as
CH4, absorb infrared radiation by which earth loses heat.
• The levels of these gases have increased markedly since
about 1850 as nations have become industrialized and
forest lands and grasslands have been converted to
agriculture.
• Shown in the next figure (Figure 14.2) is the per capita
carbon dioxide emissions which are highest for
industrialized countries, and development of countries
with high populations, such as China and India, can be
expected to add large quantities of carbon dioxide to the
atmosphere in the future.
• CFCs, were not even introduced into the atmosphere
until the 1930s.
2018 rankings by per capita emissions
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• Although the levels of these gases are well known, their effects on global
temperature and climate are much less certain. The phenomenon has been
the subject of much computer modeling.
• Most models predict global warming of at least 3.0o and up to 5.5oC
occurring over a period of just a few decades.
• These estimates are sobering because they correspond to the approximate
temperature increase since the last ice age 18,000 years past, which took
place at a much slower pace of only 1 or 2oC per 1000 years.
• Such warming would have profound effects on rainfall, plant growth, and
sea levels, which might rise as much as 0.5-1.5m
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• Carbon dioxide is the gas most commonly thought of as a greenhouse gas;
it is responsible for about half of the atmospheric heat retained by trace
gases.
• It is produced primarily by the burning of fossil fuels, and deforestation
accompanied by burning and biodegradation of biomass. On a
molecule-for molecule basis, methane (CH4) is 20-30 times more effective
in trapping heat than is CO2.
• Other trace gases that contribute are CFCs and N2O.
• The potential of such gas to cause greenhouse warming may be expressed
by a global warming potential (GWP) which is a function of both the
infrared sorption characteristics and lifetime of the gas.
14.2. GREENHOUSE GASES AND GLOBAL WARMING

• Analyses of gases trapped in polar ice samples indicate the preindustrial

levels of CO2 and CH4 in the atmosphere were approx. 260ppm and 0.70
ppm respectively.
• Over the last 300 years, these levels have increased to current values of
around 360 ppm, and 1.8 ppm; most of the increase by far has taken place
at an accelerating pace over the last 100 years.
• About half of the increase in CO2 in the last 300 years can be attributed to
deforestation, which still accounts for approximately 20 percent of the
annual increase in this gas. CO2 is increasing by about 1 ppm per year.
14.2. GREENHOUSE GASES AND GLOBAL WARMING

• Methane is going up at a rate of almost 0.02 ppm/yr.

• The comparatively rapid increase in methane levels is attributed to a
number of factors resulting from human activities.
• Among these are direct leakage of natural gas, byproduct emissions from
coal mining and petroleum recovery, and release from the burning of
savannas and tropical forests.
• Biogenic sources resulting from human activities produce large amounts of
atmospheric methane.
These includes methane from :
 Bacteria degrading organic matter such as municipal refuse in landfills
 Methane evolved from anaerobic biodegradation of organic matter in rice
paddies;
 Methane emitted as the result of bacterial action in the digestive tracts of
ruminant animals.
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• In addition to acting as a greenhouse gas, CH4 has significant effects on
atmospheric chemistry.
• It produces atmospheric CO as an intermediate oxidation product and
influences concentrations of atmospheric hydroxyl radicals and ozone.
• In the stratosphere, it produces Hydrogen and H2O, but acts to remove
ozone-destroying chlorine.
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• A term called radioactive forcing is used to describe the reduction in infrared
radiation penetrating outward through the atmosphere per unit increase in the
level of gas in the atmosphere. Using this measure it can be shown that the
radiative forcing of CH4 is about 25 times that of CO2.
• Increases of concentration of methane and several other ghg have such a
disproportionate effect on retention of infrared radiation because their infrared
absorption spectra fill gaps in the overall spectrum of outbound radiation not
covered by much more abundant CO2.
• Therefore, whereas an increase in CO2 concentration has a comparatively small
incremental effect because the gas is already absorbing such a high fraction of
infrared radiation in regions of the spectrum where it absorbs, an increase in the
concentration of methane, CFC, or other ghg has a comparatively larger effect.
• Both positive and negative feedback mechanisms may be involved in
determining the rates at which carbon dioxide and methane build up in the
atmosphere. Laboratory studies indicate that increased CO2 levels in the
atmosphere cause accelerated uptake of this gas by plants undergoing
photosynthesis, which tends to slow the buildup of atmospheric CO2.
• Given adequate rainfall, plants living in a warmer climate that would result
from the greenhouse effect would grow faster and take up more CO2. This
could be an especially significant effect of forests, which have a high
CO2-fixing ability. However, the projected rate of increase in carbon
dioxide levels is so rapid that forests would lag behind in their ability to
fix additional CO2.
• Similarly, higher atmospheric CO2 concentrations will results in
accelerated sorption of the gas by oceans. The amount of dissolved CO2 in
the oceans is about 60 times the amount of CO2 gas in the atmosphere
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• However, the times for transfer of CO2 from the atmosphere to the ocean are of the
order of years.
• Because low mixing rates, the times for transfer of oxygen from the upper
approximately 100-meter layer of the oceans to ocean depths is much longer, of the
order of decades. Therefore, the uptake of CO2 by forests, increases absorption by
oceans will lag behind the emissions of CO2.
• A concern with increased levels of CO2 in the oceans is the lowering of ocean water pH.
• Even though such an effect will be slight, of the order of one tenth to several tenths of a
pH unit, it has potential to strongly impact organisms that live in the ocean.
• Severe drought conditions resulting from climactic warming could cut down
substantially on CO2 uptake by plants.
• Warmer conditions would accelerate release of both CO2 and CH4 by microbial
degradation of organic matter
• Global warming might speed up the rates at which biodegradation adds theses gases to
the atmosphere.
14.2. GREENHOUSE GASES AND GLOBAL WARMING
• Drought is one of the most serious problems that could arise from major
climactic change resulting from greenhouse warming.
• Typically, a three-degree warming would be accompanied by a ten percent
decrease in precipitation. Water shortages would be aggravated, not just
from decreased rainfall, but from increased evaporation as well.
• Increased evaporation results in decreased runoff, thereby reducing water
available for agricultural, municipal, and industrial use.
• Water shortages, in turn, lead to increased demand for irrigation and to the
production of lower quality, higher salinity runoff water and wastewater.
14.3. ACID RAIN
14.3. ACID RAIN
14.3. ACID RAIN
14.3. ACID RAIN

• Chemical reactions such as these play a dominant role in determining the

nature, transport, and fate of acid precipitation. As the result of such
reactions the chemical properties (acidity, ability to react with other
substances) and physical properties (volatility, solubility) of acidic
atmospheric pollutants are altered drastically.
• For example, even the small fraction of NO that does dissolve in water
does not react significantly. However, its ultimate oxidation product,
HNO3, though volatile, is highly water-soluble, strongly acidic, and very
reactive with other materials. Therefore, it tends to be removed readily
from the atmosphere and to do a great deal of harm to plants, corrodible
materials, and other things that it contacts.
14.3. ACID RAIN

• Although emissions from industrial operations and fossil fuel

combustion are the major sources of acid-forming gases, acid rain has
also been encountered in areas far from such sources.
• This is due in part to the fact that acid-forming gases are oxidized to acidic
constituents and deposited over several days, during which time the air
mass containing the gas may have moved as much as several thousand km.
It is likely that the burning of biomass, such as is employed in “slash-and-
burn” agriculture evolves the gases that lead to acid formation in more
remote areas.
• In arid regions, dry acid gases or acids sorbed to particles may be
deposited with effects similar to those of acid rain deposition.
14.3. ACID RAIN
• Acid rain spreads out over areas of several hundred to several thousand
kilometers. This classifies it as a regional air pollution problem compared
to a local air pollution problem for smog and a global one for ozone-
destroying chlorofluorocarbons and greenhouse gases.
• Other examples of regional air pollution problems are those caused by
soot, smoke, and fly ash from combustion sources and fires (forest fires).
• Nuclear fallout from weapons testing or from reactor fires (of which,
fortunately, there has been only one major one to date—the one at
Chernobyl in the Soviet Union) may also be regarded as a regional
phenomenon.
14.3. ACID RAIN
• Acid rain has been observed for well over a century, with many of the
older observations from Great Britain. The first manifestations of this
phenomenon were elevated levels of SO42- in precipitation collected in
industrialized areas.
• More modern evidence was obtained from analyses of precipitation in
Sweden in the 1950s, and of U.S. precipitation a decade or so later. A vast
research effort on acid rain was conducted in North America by the
National Acid Precipitation Assessment Program, which resulted from the
U.S. Acid Precipitation Act of 1980.
• Table 14.1 shows typical major cations and anions in pH-4.25
precipitation. Although actual values encountered vary greatly with time
and location of collection, this table does show some major features of
ionic solutes in precipitation. From the predominance of sulfate anion, it is
apparent that sulfuric acid is the major contributor to acid precipitation.
Nitric acid makes a smaller but growing contribution to the acid present.
Hydrochloric acid ranks third.
• An important factor in the study of acid rain and sulfur pollution involves
the comparison of primary sulfate species and secondary sulfate species
• A low primary-sulfate content indicates transport of the pollutant from
some distance, whereas a high primary-sulfate content indicates local
emissions.*
• This information can be useful in determining the effectiveness of SO2
control in reducing atmospheric sulfate, including sulfuric acid. Primary
and secondary sulfates can be measured using the oxygen-18 content of
the sulfates, which is higher in sulfate emitted directly from a power plant
than it is in sulfate formed by the oxidation of SO2. This technique can
yield valuable information on the origins and control of acid rain.
Ample evidence exists of the damaging effects of acid rain.
The major effects are the following:
14.4. OZONE LAYER DESTRUCTION
14.4. OZONE LAYER DESTRUCTION
14.4. OZONE LAYER DESTRUCTION
• Recall from Section 9.9 that stratospheric ozone, O3, serves as a shield to
absorb harmful ultraviolet radiation in the stratosphere, protecting living
beings on the earth from the effects of excessive amounts of such
radiation. The two reactions by which stratospheric ozone is produced are,

• and it is destroyed by photodissociation,

14.4. OZONE LAYER DESTRUCTION
• The concentration of ozone in the stratosphere is a steady-state concentration resulting from
the balance of ozone production and destruction by the above processes.
• A total of about 350,000 metric tons of ozone are formed and destroyed daily. Ozone never
makes up more than a small fraction of the gases in the ozone layer. In fact, if all the
atmosphere’s ozone were in a layer at 273 K and 1 atm, it would be only 3 mm thick!
• Ozone absorbs ultraviolet radiation very strongly in the region 220-330 nm.
• Therefore, it is effective in filtering out dangerous UV-B radiation, 290 nm <l <320 nm.
(UV-A radiation, 320 nm-400 nm, is relatively less harmful and UV-C radiation, < 290 nm
does not penetrate to the troposphere.) If UV-B were not absorbed by ozone, severe damage
would result to exposed forms of life on the earth.
• Absorption of electromagnetic radiation by ozone converts the radiation’s energy to heat and
is responsible for the temperature maximum encountered at the boundary between the
stratosphere and the mesosphere at an altitude of approximately 50 km.
• The reason that the temperature maximum occurs at a higher altitude than that of the
maximum ozone concentration arises from the fact that ozone is such an effective absorber
of ultraviolet light, so that most of this radiation is absorbed in the upper stratosphere where
it generates heat and only a small fraction reaches the lower altitudes, which remain
relatively cool.
14.4. OZONE LAYER DESTRUCTION

• *Increase in UV-B reaching the earth’s surface, which causes harm to :

– Humans
– Animals
– Plants and Agriculture
– The Ocean and Aquatic Ecosystems
14.4. OZONE LAYER DESTRUCTION

Impact on Humans and Animals

• *Damaging health effects primarily with skin, eyes, and immune system
• Reduced air quality
• Human exposure to UV-B depends on
– Individual’s location
– Duration and timing of outdoor activities
– Precautionary behavior
– Skin color and age
14.4. OZONE LAYER DESTRUCTION

Impact on Plants and Agriculture

• *Reduction of air quality reduces crop yields

• Decrease in photosynthetic activity
• Susceptibility to disease
• Changes in plant structure and pigmentation
• Retardation of growth
14.4. OZONE LAYER DESTRUCTION

Impact on Ocean and Aquatic Ecosystems

• Diminishes productivity of the oceans
• Decreases species such as fish and shrimp
• Humans and other consumers are dependent on these higher species
• Populations outside the local ecosystem are potentially at risk
14.4. OZONE LAYER DESTRUCTION
• The major culprit in ozone depletion consists of chlorofluorocarbon (CFC)
compounds, commonly known as “Freons.”*
• Other applications include: solvents, aerosol propellants, and blowing
agents in the fabrication of foam plastics.
• The same extreme chemical stability that makes CFCs nontoxic enables
them to persist for years in the atmosphere and to enter the stratosphere. In
the stratosphere, as discussed in Section 12.7, the photochemical
dissociation of CFCs by intense ultraviolet radiation,

yields chlorine atoms, each of which can go through chain reactions,

particularly the following:
14.4. OZONE LAYER DESTRUCTION

• The net effect of these reactions is catalysis

of the destruction of several thousand
molecules of O3 for each Cl atom produced.
Because of their widespread use and
persistency, the two CFCs of most concern
in ozone destruction are CFC-11 and
CFC-12, CFCl3 , and CF2Cl2.
• Even in the intense ultraviolet radiation of
the stratosphere the most persistent
chlorofluorocarbons have lifetimes of the
order of 100 years.
14.4. OZONE LAYER DESTRUCTION
• The most prominent instance of ozone layer destruction is the so-called
“Antarctic ozone hole” that has shown up in recent years. This
phenomenon is manifested by the appearance during the Antarctic’s late
winter and early spring of severely depleted stratospheric ozone (up to
50%) over the polar region. The reasons why this occurs are related to the
normal effect of NO2 in limiting Cl-atom-catalyzed destruction of ozone
by combining with ClO,
• The most prominent instance of ozone layer destruction is the so-called “Antarctic ozone hole” that
has shown up in recent years. This phenomenon is manifested by the appearance during the
Antarctic’s late winter and early spring of severely depleted stratospheric ozone (up to 50%) over
the polar region. The reasons why this occurs are related to the normal effect of NO 2 in limiting
Cl-atom-catalyzed destruction of ozone by combining with ClO,
14.4. OZONE LAYER DESTRUCTION

• In the polar regions, particularly Antarctica, NOx gases are

removed along with water by freezing in polar stratospheric
clouds at temperatures below -70°C as compounds such as
ClONO2 and HNO3•3H2O.
• During the Antarctic winter, HOCl and Cl2 are generated and
accumulate at the surfaces of the solid cloud particles by the
reactions,
14.4. OZONE LAYER DESTRUCTION

• where the HCl comes primarily from the reaction of stratospheric methane,
CH4, with Cl• atoms produced from chlorofluorocarbons. The preceding
reactions are aided by the tendency of the HNO3 product to become
hydrogen-bonded with water in the cloud particles. The result of these
processes is that over the winter months photoreactive Cl2 and HOCl
accumulate in the Antarctic stratospheric region in the absence of sunlight
then undergo a burst of photochemical activity when spring arrives as
shown by the following reactions:
14.4. OZONE LAYER DESTRUCTION

• The Cl atoms react to destroy ozone according to Reaction 14.4.6. Under

conditions of Antarctic spring, not enough O• atoms are available to
regenerate Cl atoms from ClO• by Reaction 14.4.7. It is now known that
ClO• forms the ClO-OCl dimer, which regenerates Cl• by the following
reactions:
Chlorofluorocarbon Substitutes and Ozone Depletion
• Currently, the substitutes for ozone-destroying chlorofluorocarbon
compounds are hydrohaloalkanes, compounds that contain at least one
H atom. Each molecule of this class of compounds has an H-C bond that
is susceptible to attack by HO radical in the troposphere, thereby
eliminating the compound with its potential to produce ozone-depleting Cl
atoms before it reaches the stratosphere. *
• The substitutes are either hydrochlorofluorocarbons (HCFCs) or
hydrofluorocarbons (HFCs). The compounds used or proposed for use
include
14.5. PHOTOCHEMICAL SMOG
 14.5. PHOTOCHEMICAL SMOG
• Photochemical smog is a major local or regional air
pollution phenomenon characterized by oxidants,
irritating vapors, and visibility-obscuring particles
that occurs in urban areas where the combination of
pollution-forming emissions and appropriate
atmospheric conditions are right for its formation.

• Although not as great a threat to the global

atmosphere as some of the other air pollutants
discussed in this chapter, smog does pose
significant hazards to living things and materials in
local urban areas in which millions of people are
exposed.
 14.5. PHOTOCHEMICAL SMOG

• The word ‘smog’ comes from two words: smoke and fog.*
• It occurs in urban areas where the combination of
pollution-forming emissions and appropriate atmospheric
conditions are right for its formation.
• It is because of action of sunlight on H-C (Hydrocarbons)
and NOx(Nitrogen Oxides) emitted from internal
combustion engines.
14.5. PHOTOCHEMICAL SMOG

SMOG
PRIMARY POLLUTANTS SECONDARY POLLUTANTS

-VOLATILE HYDROCARBONS -NITROGEN DIOXIDES

-NITROGEN OXIDES -ALDEHYDES
-PAN
-NITRIC ACID
 14.5. PHOTOCHEMICAL SMOG

• Nitrogen Monoxide (NO) is a primary pollutant formed by the combination of

nitrogen and oxygen at high temperatures in internal combustion engines.

• A secondary pollutant (NO2) is formed by the oxidation of NO with Oxygen.

 14.5. PHOTOCHEMICAL SMOG

• In the presence of sunlight (UV radiation) the NO2 is broken up to form oxygen
radicals.

• These oxygen radicals react with O2 to form Ozone. (O3)

• They also react with water to form hydroxyl radicals.

 14.5. PHOTOCHEMICAL SMOG

• Aldehydes are produced in the reaction of free radicals with oxygen.

• Nitric Acid is produced when hydroxyl radicals react with NO2

 14.5. PHOTOCHEMICAL SMOG

• Peroxyacytyl nitrate (PAN) is a secondary pollutant that causes respiratory

problems. It is produced by the reaction of peroxide radicals and nitrogen dioxide.
14.5. PHOTOCHEMICAL SMOG
14.5. PHOTOCHEMICAL SMOG
14.5. PHOTOCHEMICAL SMOG
• Effects on human health
Headaches
Eyes, nose and throat irritations
Impaired lung function
Coughing and wheezing
 14.5. PHOTOCHEMICAL SMOG
• PAN cause eyes to water and respiratory
problems, also catalyses formation of
sulfuric acid.
• Ozone in the troposphere is:
– an eye irritant and also irritates respiratory
system
– causes deterioration of rubber
– affects leaves and therefore
growth/damages crop
• Reduced visibility
• Secondary pollutants are toxic to plants
• Corrosion of building materials by acids and
ozone.
14.6. NUCLEAR WINTER
14.6. NUCLEAR WINTER
• Nuclear winter is a term used to describe a catastrophic atmospheric effect that
might occur after a massive exchange of nuclear firepower between major powers.
• The heat from the nuclear blasts and from resulting fires would cause powerful
updrafts carrying sooty combustion products to stratospheric regions.
• This would result in several years of much lower temperatures even during
summertime. There are several reasons for such an effect:
– First of all, the highly absorbent, largely black particulate matter would absorb solar
radiation high in the atmosphere so that it would not reach earth’s surface.
– Cooling would also occur from a phenomenon opposite to that of the greenhouse effect.
That is because outgoing infrared radiation from particles high in the atmosphere would
have to penetrate relatively much less of the atmosphere and, therefore, would be exposed
to much less infrared-absorbing water vapor and carbon dioxide gas. This would deprive
the lower atmosphere of the warming effect of outgoing infrared radiation and would mean
that less infrared would be re-radiated from the atmosphere back to earth’s surface.
– The cooling would also inhibit the evaporation of water, thereby reducing the amount of
infrared-absorbing water vapor in the atmosphere and slowing the process by which
particulate matter is scavenged from the atmosphere by rain.
 14.6. NUCLEAR WINTER
• Conditions similar to those of a nuclear winter
occurred in 1816, “the year without a summer,”
following the astoundingly massive Tambora,
Indonesia volcanic explosion of 1815. Brutally
cold years around 210 B.C. that followed a similar
volcanic incident in Iceland were recorded in
ancient China.
• The June 1991 explosion of the Philippine
volcano Pinatubo, which blasted millions of tons
of material, including 15-30 million tons of sulfur
dioxide, into the atmosphere resulted in an
approximately 0.5°C cooling the following year.
In addition to the direct suffering caused, massive
starvation would result from crop failures
accompanying years of nuclear winter. The
incidents cited above clearly illustrate the climatic
effects of huge quantities of particulate matter
ejected high into the atmosphere.
 14.6. NUCLEAR WINTER
• Evidence exists to suggest that military
explosives can result in the introduction of large
quantities of particulate matter into the
atmosphere.
• For example, carpet bombings of cities, such as
the tragic bombing of Dresden, Germany, near
the end of World War II, have caused huge
firestorms that created their own wind causing a
particle-laden updraft into the atmosphere. Of
course, the effect of a full-scale nuclear exchange
would be manyfold higher.
14.6. NUCLEAR WINTER
• A full-scale nuclear exchange might involve a total of the order of 5,000
megatons of nuclear explosives. As a result, unimaginable quantities of soot
from the partial combustion of wood, plastics, paving asphalt, petroleum,
forests, and other combustibles would be carried to the stratosphere.
• At such high altitudes, tropospheric removal mechanisms for particles are not
effective because there is not enough water in the stratosphere to produce
rainfall to wash particles from the air, and convection processes are very
limited. Much of the particulate matter would be in the µm size range in which
light is reflected, scattered, and absorbed most effectively and settling is very
slow.
• Therefore, vast areas of the earth would be overlain by a stable cloud of
particles and the fraction of sunlight reaching the earth’s surface would be
drastically reduced, resulting in a dramatic cooling effect.
• The extreme heat and pressure in the fireball would result in fixation of nitrogen
by the following reaction:
14.6. NUCLEAR WINTER

• The timing and location of nuclear blasts are very important in

determining their climatic effects. Atmospheric testing of nuclear
weapons, including a 58-megaton monster detonated by the Soviet
Union, have had little atmospheric effect. Such tests were carried out
at widely spaced intervals on deserts, small tropical islands, and
other locations with minimal combustible matter.
• In contrast, military use of nuclear weapons would involve a high
concentration of firepower, both in time and in space, on industrial
and military targets consisting largely of combustibles. Furthermore,
destruction of hardened military sites requires blasts that disrupt
large quantities of soil, rock, and concrete, which are pulverized,
vaporized, and blown into the atmosphere.
14.6. NUCLEAR WINTER
Visitors from Space
• Of all the possible atmospheric catastrophes that can occur, arguably the
most threatening would be one caused by collision of a large asteroid with
earth. Convincing evidence now exists that mass extinctions of species in
the past have resulted from earth being hit by asteroids several kilometers
in diameter. Such an event would cause much the same effects as those
from “nuclear winter,” though with a large asteroid the effects would be
much more pronounced.
14.7. WHAT IS TO BE DONE?

• Of all environmental hazards, there is little doubt that major disruptions in

the atmosphere and climate have the greatest potential for catastrophic and
irreversible environmental damage

• On a hopeful note, the bulk of these emissions arise from industrialized

nations which, in principle, can apply the resources needed to reduce them
substantially. The best example to date has been the 1987 “Montreal
Protocol on Substances that Deplete the Ozone Layer,”*. This agreement
and subsequent ones, particularly the Copenhagen Amendment of 1992,
may pave the way for more encompassing agreements covering carbon
dioxide and other trace gases.
• More ominous, however, is the combination of population pressure and
desire for better living standards on a global basis.
• For example, the demand that these two factors place on energy resources,
and the environmental disruption that may result. In many highly
populated developing nations, high-sulfur coal is the most readily
available, cheapest source of energy. It is understandably difficult to
persuade populations faced with real hunger to forego short-term
economic gain for the sake of long-term environmental quality.
• Destruction of rain forests by “slash and-burn” agricultural methods does
seem to make economic sense to those engaged in subsistence farming to
obtain badly needed hard currency, which can be earned by converting
forest to pasture land and exporting fast-food-hamburger beef to wealthier
nations.
• What is to be done?
• First of all, it is important to keep in mind that the atmosphere has a strong
ability to cleanse itself of pollutant species.
– Water-soluble gases, including greenhouse-gas CO2 , acid-gas SO2 , and fine
particulate matter are removed with precipitation. For most gaseous contaminants,
oxidation precedes or 2 . To a larger extent, the most active atmospheric oxidant is
hydroxyl radical, HO accompanies removal processes.
– To a degree, oxidation is carried out by O3 . As illustrated in Figure 9.10, this
atmospheric scavenger species reacts with all important trace gas species except for
CO2 and chlorofluorocarbons. It is now generally recognized that HO • is an almost
universal atmospheric cleansing agent. Given this crucial role of HO • radical, any
pollutants that substantially reduce its concentration in the atmosphere are potentially
troublesome. One concern over carbon monoxide emissions to the atmosphere is the
reactivity of HO • with CO, which could result in removal of HO• from the
atmosphere.
• Of all the major threats to the global climate, it is virtually certain that
humankind will have to try to cope with greenhouse warming and the
climatic effects thereof. The measures to be taken in dealing with this
problem fall into the three following categories:
• Potentially, tax strategy can be very effective in reducing use of
carbonaceous fuels and greenhouse CO2 emissions. This is the rationale
behind the carbon tax, which is tied with the carbon content of various
fuels.

• Another option is to dispose of carbon dioxide to a sink other than the

atmosphere. The most obvious such sink is the ocean; other possibilities
are deep subterranean aquifers and exhausted oil and gas wells.
• A common measure taken against the effects of another atmospheric
hazard, ultraviolet radiation, provides an example of adaptation. This
measure is the use of sunscreens placed on the skin as lotions to filter out
UV-B radiation. The active ingredient of sunscreen must absorb ultraviolet
light effectively, but this is not enough because it is the absorption of
ultraviolet light by skin that makes it so dangerous in the first place.
Therefore, active compounds in sunscreen formulations must also dissipate
the absorbed energy in a harmless way.
• The “tie-in strategy” has been proposed as a sensible approach to dealing with the kinds
of global environmental problems discussed in this chapter. This approach was first
enunciated in 1980.
– It advocates taking measures consisting of “high-leverage actions” which are designed to prevent problems from
occurring and which have substantial merit even if the major problems that they are designed to avoid do not
materialize.

• An example is implementation of environmentally sound substitutes for fossil fuels to

lower atmospheric CO output and prevent greenhouse warming. Even if it turns out that
the greenhouse effect is exaggerated, such substitutes would save the earth from other
kinds of environmental damage, such as disruption of land by strip mining coal or
preventing oil spills from petroleum transport.
• Increased energy efficiency would diminish both greenhouse gas and acid rain
production, while lowering costs of production and reducing the need for expensive and
environmentally disruptive new power plants.

• The implementation of these kinds of tie-in strategies requires some degree of incentive
beyond normal market forces and, therefore, is opposed by some on ideological grounds.
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