1

Air Pollutants and

Global Climate

Hsin Chu
Professor
Dept. of Environmental Engineering
National Cheng Kung University
2
In this chapter we consider three air pollution
problems in which humans may be making
large-scale changes in our planet.
Air pollution laws in the U.S. and most other
countries are based on the assumption that
air pollution is a local matter.
3
Local solutions are not available for global
problems or for problems of pollutants like
acid rain that cross international boundaries.
In addition, some parts of the global climate
overshoot.
They continue to change in the direction they
are changing even after the cause of the
change has been reduced or withdrawn.
4
1. Global Warming
Humans are putting gaseous materials into
the atmosphere that may cause the earths
average temperature to rise.
This is called global warming, or the
greenhouse effect.
5
Example 1
Estimate the average temperature that the earth would have if
it had no atmosphere.
Solution:
The total radiant energy flux from the sun, just outside the
earths atmosphere, is 1.353 kW/m
2
.
The diameter of the earth is 12.7510
6
m so that, if all the
incoming solar energy were absorbed by the earth, the total
heat flow in from the sun would be



2 6 2
2
14
(12.75 10 ) 1.353
4 4
1.73 10
kW
D flux m
m
kW
t t
=
=
6
The total heat radiated to outer space would
be this amount plus the amount produced on
earth by nuclear decay and tidal friction with
the moon, which together are less than 0.1%
of the solar energy inflow and can be safely
ignored.
7
The outward radiation (assuming a zero temperature
for outer space and blackbody radiation), using the
surface area of the earth rather than the projected
area, is


where = the stefan-Boltzmann constant =
5.67210
-11
kW/(m
2
K
4
).
Setting these equal and solving for T, we find 278 K
= 5
o
C. #
2 4 6 2 11 4
2 4
(12.75 10 ) 5.672 10
kW
D T m T
m K
t o t

=
8
This is approximately 10
o
C below the
observed average surface temperature of the
earth, which is about 15
o
C.
Thus, the net effect of having an atmosphere
is to raise the average temperature of the
earth about 10
o
C above the value it would
have with no atmosphere, if the earth
absorbed all incoming sunlight.
9
The earth actually reflects roughly 30% of all
the incoming solar radiation back to outer
space from the tops of clouds, ice surfaces,
oceans, etc. (Technically, the earths albedo
is about 0.3.)
The moon, which has no atmosphere and
hence no clouds, surface water, or ice sheets,
reflects about 12% of its incoming solar
radiation.
10
If the atmosphere let the same amount of
sunlight in as it actually does but did not
prevent the outward flow of radiant heat, then
we should multiply the incoming solar
radiation in Example 1 by 0.7, finding an
average surface temperature of 254 K =
-19
o
C, and a frozen world.
11
Example 2
What fraction of the outgoing radiation from
the earth is blocked by the atmosphere?
Solution:
As just discussed, we assume that 30% of
the incoming solar radiation is reflected away,
and use an average surface temperature
over the whole planet of approximately 15
o
C
= 288.15 K.
12
Setting incoming approximately equal to outgoing and solving
for the fraction emitted, we have






We see that for the earths surface temperature to average
about 15
o
C, the atmospheric outward transmission of radiant
energy must be (0.606/0.7), or 86% of the inward transmission
of solar energy. #
2 4
2 4
14
6 2 11 4
0.7(total solar input)
fraction emitted
0.7(1.73 10 )

(12.75 10 ) 5.672 10 (288.15 )
0.606
kW
m K
D T
kW
m K
t o
t

~

=

=
13
Clouds block radiation, both inbound and
outbound.
Cloudy days are cool and cloudy nights are
warm relative to clear days and nights at the
same season.
They are more or less equal in their
resistance to incoming and outgoing radiation.
14
The same is not true for clear air, which
contains CO
2
, H
2
O, CH
4
, and some other
gases that can absorb radiant energy.
If the wavelengths of the incoming and
outgoing radiant energies were the same,
then these gases would block equal amounts
in both directions.
But the wavelengths are quite different.
15
Fig. 14.1 (next slide) shows the absorptive
properties of the clear atmosphere (without
clouds, dust, birds, insects) and some
properties of the incoming solar radiation and
the outgoing thermal radiation from the earth.
17
The interaction of a photon with a gas
molecule is quite different from that with a
cloud droplet or with a fine particle.
A gas molecule will absorb a light photon if
the gas molecule can make an internal
rearrangement that requires the same
amount of energy as that carried by the
photon.
18
For wavelengths shorter than about 0.28, the
internal transitions involve shifts of electrons in their
orbitals around the nuclei of one or more of the
atoms that make up the molecule, but not any
change in the relation of one atom to another within
the molecule.
For the wavelengths longer than about 1, the
changes are not within the individual atoms but are
those associated with the vibrations of the various
atoms in the molecule, relative to each other.
19
In the 0.28 to 1 window, the photons have
too little energy to cause shifts of electron
orbitals, and too much energy to be in tune
with intermolecular vibrations.
The H
2
O absorption peaks shown on Fig.
14.1 are caused by the various intermolecular
vibration modes of the water molecule.
20
The lower part of Fig. 14.1 shows the
distribution of energy in sunlight and in the
infrared radiation from the earth.
These are idealized values for blackbody
radiators at 6000 and 288 K, which
correspond roughly to the average surface
temperatures of sun and earth.
21
The quantity plotted is the fraction of the total
emitted energy per micron of wavelength,
which has a higher maximum (14% per
micron) for the sun than for the earth (7% per
micron) because the suns spectrum is
narrower. (Observe the logarithmic scale for
wavelength.)
22
Weins law for blackbody radiatin is



which shows that for the temperature of the suns
surface, about 6000 K, the peak intensity is at 0.50,
corresponding to visible light.
For the earths surface temperature of about 288 K
the peak intensity is 10.3, which is in the infrared
region.
3
max
wavelength of
2.987 10
maximum emission
m K
T

| |
= =
|
\ .
23
Comparing the lower and upper parts of Fig. 14.1,
we see that sunlight comes to the surface practically
unimpeded except for cloudy areas, whereas the
peak radiation from the earth is close to the 8- to 12-
window, which is not as wide nor as completely
open as the window for solar energy.
This is the main reason that the atmosphere is less
transparent for outgoing infrared energy than it is for
incoming solar energy.
24
Fig. 14.1 shows that CO
2
, CH
4
, N
2
O, and
H
2
O all have some absorption in the 8- to 12-
window.
The same is also true for chlorofluorocarbons,
or CFCs.
They are collectively called greenhouse
gases.
25
Human activities are increasing the
concentrations of greenhouse gases in the
atmosphere.
Of these gases, the strongest contributor to
reducing the transparency of the 8- to 12-
window is water vapor.
However, humans do not directly influence its
concentration in the atmosphere, and it is not
normally a part of the discussion of the
greenhouse effect.
26
Fig. 14.2 (next slide) shows a very simplified
view of the interactions and feedback loops
involved in the global temperature.

28
Increasing the global temperature by adding
greenhouse gases will have positive and
negative effects on the albedo by increasing
cloudiness and reducing snow and ice over,
and will further close the IR window by
increasing the average water vapor content
of the atmosphere and the average
cloudiness.
29
Fig. 14.3 (next slide) shows the calculated
relative contributions of the various green-
house gases to the reduction of transparency
of the atmosphere in the 8- to 12- window
for the period 1980 to 1990.

31
If rising temperatures were to melt the ice cap
in Antarctica, the world sea level would rise
several hundred feet, flooding most of the
coastal cities and agricultural areas of the
world.
Temperature increases much smaller than
those needed to melt the ice caps would
cause the deserts and the temperature zones
to extent farther from the equator.
32
Agricultural area that are currently highly
productive would become dryer and hotter,
while sub-Arctic regions would become
warmer and wetter.
The best current estimates are that, for a
business as usual projection of future
emissions of all greenhouse gases, the global
mean temperature will increase by 0.2 to
0.5
o
C (best estimate 0.3
o
C) per decade for
this century.
33
The corresponding projection of world sea
level is for a rise of 3 to 10 cm/decade (best
estimate 6 cm/decade) over the same period.
34
1.1 Carbon Dioxide
CO
2
is a colorless, tasteless gas that
provides the carbonation in soft drinks and
sparkling wines.
It has been part of the earths atmosphere as
long as the earth has had an atmosphere.
The current carbon dioxide concentration in
the world atmosphere is approximately 380
ppm (year of 2006).
35
Geologic records show that the CO
2
content
of the world atmosphere before about A.D.
1750 was 280 10 ppm and did not move out
of that range for hundreds or thousands of
years.
About 1750 humans began to burn increasing
amounts of fossil fuels, and the CO
2
content
of the global atmosphere has risen.
36
Fig. 14.4 (next slide) shows CO
2

concentrations from 1960s to 1990s.
During that period, the annual increase in
CO
2
concentration was 1.5 ppm/yr.
38
Fig. 14.5 (next slide) shows the estimated
reservoirs and flows for carbon on earth (To
convert from carbon to CO
2
multiply by
44/12).
40
The global annual fuel combustion CO
2
emissions
are:




The first term, the global population, is growing at
about 1.4% per year (population doubles every 50
years), and that growth rate shows little sign of
slowing.
2
2
Global fuel
CO emissions per global per capita
combustion (1)
population fuel use unit of fuel use
CO emissions
| |
| | | || |
|
=
| | |
|
\ .\ .\ .
|
\ .
41
The second term is highly variable from
country to country.
To compare energy uses, we need a proper
standard energy unit.
The most intuitive unit is the minimal energy
intake, as food, that a normal human needs,
about 2750 kcal/day (4 million BTU/yr).
Using it, we can make Table 14.1 (next slide).
43
In the U.S., they use a total of about 79 times
as much fuel as the minimum needed to feed
themselves.
If we had made a similar table for the
average person in the U.S. is 1850, or the
average person in the Third World today, we
would have seen that they used or use
perhaps three to five times the energy they
needed as food.
44
Americans use probably 15 to 30 times as
much fuel per person as they do and live a
much more physically comfortable life.
If the people in the Third world are to live as
Americans do, then world fuel consumption
will grow dramatically.
45
The third term in Eq. (1) depends on the
hydrogen/carbon ratio of the fuel burned.
For equal amounts of energy released, the
relative CO
2
release rates are approximately
coal, 1.0; oil, 0.8; and natural gas, 0.6.
46
It is possible to capture CO
2
from combustion
exhaust gas and prevent its release, but only by
using chemicals like CaO, whose production leads
to the release of more CO
2
.
the only methods we now know to slow or stop the
buildup of CO
2
in the atmosphere are to reduce the
use of fossil fuels and to stop the deforestation of
the tropical rain forests.
Solar, wind, hydroelectric, geothermal, and nuclear
energy release much less CO
2
.
47
1.2 Other Greenhouse Gases,
Aerosols
CFCs are apparently next in greenhouse effect after
CO
2
and will be discussed in next section.
Next in importance is methane, the principal
component of natural gas, which is formed in many
anaerobic biological processes.
It is the principal component of swamp gas, which
is produced by bacterial decay of woody matter, and
is a major component of the waste gases produced
by landfills and sewage treatment plants.
48
It is also emitted by almost all animals; our
domestic dairy and meat cattle and pigs are a
significant worldwide source.
In preindustrial times the world atmosphere
contained ~ 0.7 ppm of methane.
Over the past century that has increased to
~1.7 ppm, and it is increasing by about 0.01
ppm/yr.
49
A methane molecule is roughly 20 times as
strong an infrared absorber as a CO
2

molecule, so that even at this low
concentration methane can play a significant
role.
The remaining important greenhouse gas is
nitrous oxide, N
2
O, which formerly was often
used as a dental anesthetic (laughing gas).
50
N
2
O is not believed to have any harmful
effects as an air pollutant except in its role as
a greenhouse gas.
One N
2
O molecule is roughly 200 times as
effective as one CO
2
molecule in reducing
the transmission in the 8- to 12- window.
51
The sources and sinks for N
2
O are not as
well known as those for the other greenhouse
gases.
There is some concern that the NO
X
control
technologies that reduce NO with NH
3
and its
near chemical relatives may produce
significant amounts of N
2
O.
Table 14.2 (next slide) summarizes current
information on greenhouse gases.
53
The earths average temperature can also be
altered by an increase in the content of fine particles
of the atmosphere.
For atmospheric particles to have effects lasting
more than a few days, they must be injected into the
stratosphere (above about 36,000 ft) because there
is little mixing between the stratosphere and the
troposphere, so that particles in the stratosphere
have life times measured in years.
54
Few human activities place many particles in
the stratosphere.
However, such particles can be injected into
the stratosphere in large quantities by major
volcanic eruptions.
There they cause a lowering of the global
temperature, generally for only a year or two
after the eruption.
55
They lower global temperature because they
are generally close in size to the wavelength
of light (0.4 to 0.7 ) and hence effective in
scattering light and reducing the amount of
incoming sunlight.
However, these particles are much smaller
than the wavelength of outgoing infrared
radiation, and hence less effect in scattering
it.
56
2. Stratospheric Ozone Depletion
and Chlorofluorocarbons
The second global problem concerns the
possible destruction of the stratospheric
ozone layer.
At ground level, O
3
is a strong eye and
respiratory irritant and a major component of
photochemical smog.
It may also act as a greenhouse gas.
57
In the stratosphere, 10 to 20 km above the
earths surface, is a layer of low-density air
containing 300 to 500 ppb of ozone.
Ozone is the only component of the
atmosphere that absorbs significantly at the
wavelength below 0.28 (far ultraviolet).
58
If that ozone layer were removed, we would
expect large amounts of ultraviolet light to
reach the surface of the earth.
The high-energy photons are expected to
cause increased rates of skin cancer in
animals and harmful effects on plants.
Thus ozone is a harmful pollutant at ground
level, but a beneficial ultraviolet shield in the
stratosphere.
59
Destruction of the ozone layer is mostly caused by
elemental chlorine atoms; the mechanism
apparently involves two reactions:
Cl + O
3
ClO + O
2
(2)
ClO + O
3
Cl + 2 O
2
(3)
Other reactions are going on in the stratosphere that
modify and complete with these two, but if we ignore
other reactions, add these two reactions, and cancel
like terms, we see that the overall reaction is:
2 O
3
3 O
2

with no net consumption of Cl atoms.
60
Thus one Cl atom can convert many ozone
molecules to ordinary oxygen molecules.
One sees estimates from 10
4
to 10
6
O
3

molecules destroyed by one Cl atom.
This mechanism is often referred to as
catalytic destruction of ozone, because the
chlorine atom acts as a nonconsumed
catalyst for the reaction.
61
Most of the chlorine in the world is in the form
of chemically stable NaCl either dissolved in
the oceans or in underground salt deposits
formed by the evaporation of ancient oceans.
Elemental chlorine, a very reactive chemical,
has a short lifetime in the lower atmosphere
and has few natural ways to get from the
lower atmosphere up to the ozone layer.
62
The only naturally occurring chemical that
can transport much chlorine high enough into
the atmosphere to damage the ozone layer is
methyl chloride, CH
3
Cl, which is produced in
large quantities by biological processes in the
shallow oceans.
Most of it is destroyed in the troposphere, but
an estimated 3% of worldwide methyl
chloride emissions reaches the stratospheric
ozone layer.
63
Chemically active ultraviolet light in the 0.2- to 0.28-
range, which enters the ozone layer but does not
penetrate below It, is strong enough to split up
methyl chloride and the other chlorine compounds,
releasing Cl atoms, which initiate Eq. (2).
Before we had synthetic halogen compounds,
methyl chloride was probably the principal natural
destroyer of the ozone layer; its destruction of the
ozone was in balance with natural production
mechanisms, leading to a steady-state ozone layer.
64
Starting about 1900, humans began releasing
into the atmosphere synthetic chlorine-
containing compounds in significant amounts.
Those like methyl chloride that have
hydrogen atoms can be attacked in the
atmosphere by the OH radical; for this reason
most of them do not survive to reach the
stratosphere.
65
Carbon tetrachloride, CCl
4
, has no hydrogen;
most of it is believed to reach the
stratosphere and to participate in the
destruction of the ozone layer.
CFCs (compounds containing chlorine,
fluorine, and carbon, commonly called Freons)
were first developed by General Motors for
use in household refrigerators.
66
One of their virtues is their chemical inertness;
they are nontoxic, nonflammable, invisible,
tasteless, odorless, non-almost everything
else.
They replaced toxic sulfur dioxide and
ammonia in household refrigerators.
Later, their inertness led to the widespread
use of CFCs as propellants in spray cans and
a blowing agent in the production of plastic
foams.
67
Then in the 1950s we began to use air conditioners
in autos.
The CFCs used as refrigerants in these are much
more likely to leak to the atmosphere than the CFCs
in refrigerators and home air conditioners because
the shaft-sealing problem on belt-driven auto air
conditioners is more difficult than that on electric-
driven refrigerators and home air conditioners.
Auto air conditioners became a major source of CFC
emissions.
68
There are many different CFCs; the two most
widely used are CFC12, CF
2
Cl
2
, and CFC11,
CFCl
3
(the first digit in the number of carbon
atoms, the second is the number of F atoms).
CFCs have no H, so they cannot be attacked
by atmospheric OH.
69
As far as we know, the only process for
removing CFCs from the atmosphere is their
slow transport to the top of the ozone layer,
where they are attacked by shortwave
ultraviolet light and thus destroyed, releasing
their Cl to participate in the reactions with
ozone.
70
Trichloroethane, CH
3
CCl
3
, is not a CFC because it
has hydrogens and thus can be attacked by
atmospheric OH.
But that attack is relatively slow, so that an
estimated 9% of this material that is emitted to the
atmosphere makes its way to the stratosphere and
participates in ozone destruction.
Table 14.3 (next slide) shows the concentrations,
lifetimes, and expected contribution to delivery of
elemental chlorine to the stratosphere for these
chemicals.

72
Some other gases can attack the ozone layer, e.g.,
NO from stratospheric air-planes and relatively inert
N
2
O, if we release much of it at ground level.
NO, released by high-flying aircraft, can contribute
to ozone depletion by the reaction:
NO + O
3
NO
2
+ O
2

which is swift and practically irreversible.
But it is not a catalytic reaction like the chlorine
reaction; one NO molecule only destroys one O
3

molecule.
73
The only method we know to protect the
ozone layer is to limit the emission of those
materials that can harm it.
Many of the proposed substitutes for CFCs
are chlorohydrofluorocarbons, HCFCs, which
contain at least one H atom, and hence are
susceptible to OH attack in the atmosphere.
74
3. Acid Rain
The average acidity of rainfall in Scandinavia,
the northeastern United States and Canada,
and parts of Europe has increased over the
past 40 years.
There seems no question that this change is
primarily due to the increased emissions of
sulfur oxides and nitrogen oxides that have
accompanied the greatly increased economic
activity in or upwind of these regions.
75
The common name for acid precipitation is
acid rain, but the complete description
includes acidic rain, acidic snow or hail, acids
adsorbed on falling dust particles, etc.
The normal technical measure of acidity is pH.
Table 14.4 (next slide) shows pH of various
substances.
77
Rain falling through a perfectly unpolluted
atmosphere will arrive at the earth with a pH of about
5.6 because of the carbon dioxide in the atmosphere,
which reacts with rainwater by these reactions:


H
2
CO
3
is a weak acid, with the acid concentration in
the rain depending on the concentration of carbon
dioxide in the air.
2 2 2 3 3
CO H O H CO H HCO
+
+ +
78
Generally, any rain with a pH less than the
5.6 is considered acidic, but damage to
plants and animals does not begin to become
apparent until a pH of about 4.5 or less is
reached.
The transport distances between emission
and precipitation are generally hundreds of
miles, so that local control seems imossible.
79
Example 3
Table 1.1 shows that the total annual U.S.
emissions of SO
2
in 1997 were 20.4 million tons.
If we assume that 25% of that was in the Midwest-
Ohio Valley area, and that 50% of that came to
ground as acid precipitation in a 1000 km by 1000
km area in the northeastern U.S. and southeastern
Canada, and that the average precipitation over that
area is 1 m/yr, by how much would this sulfur
dioxide (if all converted to H
2
SO
4
) change the pH of
the rainwater?
80
Solution:




An estimated 25% 50% = 12.5% falls on the
affected area.


( )
6 12 11
2
Annual U.S.
20.4 10 18.5 10 2.9 10
SO emissions 64
1 ton = 2000 lbs
mol
ton g mol
g
| |
= = =
|
\ .
( )( )( )
6 6 12 3 15
Annual
area depth 10 10 1 10 10
precipitation
m m m m L
| |
= = = =
|
\ .
81
Each mol of SO
2
produces two mols of H
+
, so the
increase of H
+
above the naturally occuring value is


The original rainfall is assumed to have a pH of 5.6,
or a H
+
concentration of:


Adding these two values, we find an H
+
= 7.48 10
-
5
mol/L, or pH = -log (H
+
) = -log (7.48 10
-5
) = 4.13
#
( )
11
+ 5
15
2 12.5% 2.9 10
increase in H = 7.23 10 /
10 L
mol
mol L

=
5.6 6
10 10 2.51 10 /
pH
H mol L
+
= = =
82
How harmful acid precipitation is to a given
area is strongly dependent on the buffering
capacity of the soil.
If the local soil contains significant amounts
of limestone, CaCO
3
, the acid will react by
CaCO
3
+ H
+
Ca
2+
+ HCO
3
-
thus removing the H
+
ion.
83
It is believed that in some areas the
increased rainfall acidity has speeded the
dissolution of metals from the soil, e.g.,
aluminum, thus raising the content of those
metals in the water.
These dissolved metals may be the true
agents of destruction for fish or plants.