1. Define air pollution.

Air pollution occurs when the air contains gases, dust, fumes or odour in harmful
amounts. That is, amounts which could be harmful to the health or comfort of humans
and animals or which could cause damage to plants and materials.
The substances that cause air pollution are called pollutants. Pollutants that are
pumped into our atmosphere and directly pollute the air are called primary pollutants.
Primary pollutant examples include carbon monoxide from car exhausts and sulfur
dioxide from the combustion of coal.
Further pollution can arise if primary pollutants in the atmosphere undergo
chemical reactions. The resulting compounds are called secondary pollutants.
Photochemical smog is an example of this.
2. What are the compositions of Earths atmosphere?
A. Nitrogen - 78% - Dilutes oxygen and prevents rapid burning at the earth's surface.
Living things need it to make proteins. Nitrogen cannot be used directly from the air. The
Nitrogen Cycle is nature's way of supplying the needed nitrogen for living things.
B. Oxygen - 21% - Used by all living things. Essential for respiration. It is necessary for
combustion or burning.
C. Argon - 0.9% - Used in light bulbs.
D. Carbon Dioxide - 0.03% - Plants use it to make oxygen. Acts as a blanket and prevents
the escape of heat into outer space. Scientists are afraid that the buring of fossil fuels such
as coal and oil are adding more carbon dioxide to the atmosphere.
E. Water Vapor - 0.0 to 4.0% - Essential for life processes. Also prevents heat loss from
the earth.
F. Trace gases - gases found only in very small amounts. They include neon, helium,
krypton, and xenon.
CONSTITUEN
T
Nitrogen
Oxygen
Argon
Carbon Dioxide
Neon
Helium
Methane
Krypton
Hydrogen
Nitrous Oxide

CHEMICAL
SYMBOL
N2
O2
Ar
CO2
Ne
He
CH4
Kr
H2
N2O

MOLE PERCENT
78.084
20.947
0.934
0.035
0.00182
0.00052
0.00017
0.00011
0.00005
0.00003

Xenon
Ozone

Xe
O3

0.00001
trace to
0.00080

3. Temperature structure and Atmospheric region

The vertical distribution of temperature, pressure, density, and composition of the
atmosphere constitutes atmospheric structure. These quantities also vary with season and
location in latitude and longitude, as well as from night to day; however under the topic
of atmospheric structure, the focus is on the average variations with height above sea
level.
Atmospheric layers are characterized by variations in temperature resulting
primarily from the absorption of solar radiation; visible light at the surface, near
ultraviolet radiation in the middle atmosphere, and far ultraviolet radiation in the upper
atmosphere.

The Earth's atmosphere has layers, which are actually characterized by how the
temperature of the atmosphere changes with altitude.
The Different Levels of the Atmosphere are:
Troposphere: This is the lowest atmospheric layer and is about seven miles (11 km) thick.
Most clouds and weather are found in the troposphere. The troposphere is thinner at the
poles (averaging about 8km thick) and thicker at the equator (averaging about 16km
thick). The temperature decreases with altitude.
Stratosphere: The stratosphere is found from about 7 to 30 miles (11-48 kilometers)
above the Earths surface. In this region of the atmosphere is the ozone layer, which
absorbs most of the harmful ultraviolet radiation from the Sun. The temperature increases

slightly with altitude in the stratosphere. The highest temperature in this region is about
32 degrees Fahrenheit or 0 degrees Celsius.
Mesosphere: The mesosphere is above the stratosphere. Here the atmosphere is very
rarefied, that is, thin, and the temperature is decreasing with altitude, about 130
Fahrenheit (-90 Celsius) at the top.
Thermosphere: The thermosphere starts at about 55 kilometers. The temperature is quite
hot; here temperature is not measured using a thermometer, but by looking at the motion
and speed of the rarefied gases in this region, which are very energetic but would not
affect a thermometer. Temperatures in this region may be as high as thousands of degrees.
Exosphere: Very high up, the Earth's atmosphere becomes very thin. The region where
atoms and molecules escape into space is referred to as the exosphere. The exosphere is
on top of the thermosphere.
Ionosphere: The ionosphere overlaps the other atmospheric layers, from above the Earth.
The air is ionized by the Suns ultraviolet light. These ionized layers affect the
transmittance and reflectance of radio waves. The ionosphere is broken down into the D,
E and F regions. The breakdown is based on what wavelength of solar radiation is
absorbed in that region most frequently. The D region is the lowest in altitude, though it
absorbs the most energetic radiation, hard x-rays. The D region doesn't have a definite
starting and stopping point, but includes the ionization that occurs below about 90km. E
region peaks at about 105km. It absorbs soft x-rays. The F region starts around 105km
and has a maximum around 600km. It is the highest of all of the regions. Extreme ultraviolet radiation (EUV) is absorbed there.
On a more practical note, the D and E regions reflect AM radio waves back to
Earth. Radio waves with shorter lengths are reflected by the F region. Visible light,
television and FM wavelengths are all too short to be reflected by the ionosphere. So your
t.v. stations are made possible by satellite transmissions.

4. Evolution of Earths gases

The evolution of the atmosphere could be divided into four separate stages:
1. Origin
2. Chemical/ pre-biological era
3. Microbial era, and
4. Biological era.
The first three steps were discussed in detail. The composition of the present atmosphere
however required the formation of oxygen to sufficient levels to sustain life, and required
life to create the sufficient levels of oxygen. This era of evolution of the atmosphere is
called the "Biological Era."
The Biological Era - The Formation of Atmospheric Oxygen
The biological era was marked by the simultaneous decrease in atmospheric carbon
dioxide (CO2) and the increase in oxygen (O2) due to life processes. We need to
understand how photosynthesis could have led to maintenance of the ~20% present-day
level of O2. The build up of oxygen had three major consequences that we should note
here.
Firstly, Eukaryotic metabolism could only have begun once the level of oxygen had built
up to about 0.2%, or ~1% of its present abundance. This must have occurred by ~2 billion
years ago, according to the fossil record. Thus, the eukaryotes came about as a
consequence of the long, steady, but less efficient earlier photosynthesis carried out by
Prokaryotes.
Oxygen increased in stages, first through photolysis (Figure 1) of water vapor and carbon
dioxide by ultraviolet energy and, possibly, lightning: H2O -> H + OH
produces a hydroxyl radiacal (OH) and CO2 -> CO+ O produces an atomic oxygen (O).
The OH is very reactive and combines with the O:
O + OH -> O2 + H
The hydrogen atoms formed in these reactions are light and some small fraction excape to space
allowing the O2 to build to a very low concentration, probably yielded only about 1% of the
oxygen available today.
Secondly, once sufficient oxygen had accumulated in the stratosphere, it was acted on by
sunlight to form ozone, which allowed colonization of the land. The first evidence for vascular
plant colonization of the land dates back to ~400 million years ago.
Thirdly, the availability of oxygen enabled a diversification of metabolic pathways, leading to a
great increase in efficiency. The bulk of the oxygen formed once life began on the planet,
principally through the process of photosynthesis: 6CO2 + 6H2O <--> C6H12O6 + 6O2 where

carbon dioxide and water vapor, in the presence of light, produce organics and oxygen. The
reaction can go either way as in the case of respiration or decay the organic matter takes up
oxygen to form carbon dioxide and water vapor.
Life started to have a major impact on the environment once photosynthetic organisms evolved.
These organisms fed off atmospheric carbon dioxide and converted much of it into marine
sediments consisting of the innumerable shells and decomposed remnants of sea creatures.
While photosynthetic life reduced the carbon dioxide content of the atmosphere, it also started to
produce oxygen. The oxygen did not build up in the atmosphere for a long time, since it was
absorbed by rocks that could be easily oxidized (rusted). To this day, most of the oxygen
produced over time is locked up in the ancient "banded rock" and "red bed" rock formations
found in ancient sedimentary rock. It was not until ~1 billion years ago that the reservoirs of
oxidizable rock became saturated and the free oxygen stayed in the air. The figure illustrates a
possible scenario.
We have briefly mentioned the difference between reducing (electron-rich) and oxidizing
(electron hungry) substances. Oxygen is the most important example of the latter type of
substance that led to the term oxidation for the process of transferring electrons from reducing to
oxidizing materials. This consideration is important for our discussion of atmospheric evolution,
since the oxygen produced by early photosynthesis must have readily combined with any
available reducing substance.
We have been able to outline the steps in the long drawn out process of producing present-day
levels of oxygen in the atmosphere. We refer here to the geological evidence.
Banded Iron Formations
When the oceans first formed, the waters must have dissolved enormous quantities of reducing
iron ions, such as Fe2+. These ferrous ions were the consequences of millions of years of rock
weathering in an anaerobic (oxygen-free) environment. The first oxygen produced in the oceans
by the early prokaryotic cells would have quickly been taken up in oxidizing reactions with
dissolved iron. This oceanic oxidization reaction produces Ferric oxide Fe2O3 that would have
deposited in ocean floor sediments. The earliest evidence of this process dates back to the
Banded Iron Formations, which reach a peak occurrence in metamorphosed sedimentary rock at
least 3.5 billion years old. Most of the major economic deposits of iron ore are from Banded Iron
formations. These formations, were created as sediments in ancient oceans and are found in
rocks in the range 2 - 3.5 billion years old. Very few banded iron formations have been found
with more recent dates, suggesting that the continued production of oxygen had finally exhausted
the capability of the dissolved iron ions reservoir. At this point another process started to take up
the available oxygen.
Red Beds

Once the ocean reservoir had been exhausted, the newly created oxygen found another large
reservoir - reduced minerals available on the barren land. Oxidization of reduced minerals, such
as pyrite FeS2 , exposed on land would transfer oxidized substances to rivers and out to the
oceans via river flow. Deposits of Fe2O3 that are found in alternating layers with other sediments
of land origin are known as Red Beds, and are found to date from 2.0 billion years ago. The
earliest occurrence of red beds is roughly simultaneous with the disappearance of the banded iron
formation, further evidence that the oceans were cleared of reduced metals before O2 began to
diffuse into the atmosphere.
Finally after another 1.5 billion years or so, the red bed reservoir became exhausted too
(although it is continually being regenerated through weathering) and oxygen finally started to
accumulate in the atmosphere itself. This signal event initiated eukaryotic cell development, land
colonization, and species diversification. Perhaps this period rivals differentiation as the most
important event in Earth history.
While photosynthetic life reduced the carbon dioxide content of the atmosphere, it also started to
produce oxygen. The oxygen did not build up in the atmosphere for a long time, since it was
absorbed by rocks that could be easily oxidized (rusted). To this day, most of the oxygen
produced over time is locked up in the ancient "banded rock" and "red bed" rock formations
found in ancient sedimentary rock. It was not until ~1 billion years ago that the reservoirs of
oxidizable rock became saturated and the free oxygen stayed in the air. The figure illustrates a
possible scenario.
We have briefly mentioned the difference between reducing (electron-rich) and oxidizing
(electron hungry) substances. Oxygen is the most important example of the latter type of
substance that led to the term oxidation for the process of transferring electrons from reducing to
oxidizing materials. This consideration is important for our discussion of atmospheric evolution,
since the oxygen produced by early photosynthesis must have readily combined with any
available reducing substance.
We have been able to outline the steps in the long drawn out process of producing present-day
levels of oxygen in the atmosphere. We refer here to the geological evidence.
The Oxygen Concentration Problem
Why does present-day oxygen sit at 20%? This is not a trivial question since significantly lower
or higher levels would be damaging to life. If we had < 15% oxygen, fires would not burn, yet at
> 25% oxygen, even wet organic matter would burn freely.
The Early Ultraviolet Problem
The genetic materials of cells (DNA) are highly susceptible to damage by ultraviolet light at
wavelengths near 0.25 m. It is estimated that typical contemporary microorganisms would be

killed in a matter of seconds if exposed to the full intensity of solar radiation at these wavelength.
Today, of course, such organisms are protected by the atmospheric ozone layer that effectively
absorbs light at these short wavelengths, but what happened in the early Earth prior to the
significant production of atmospheric oxygen? There is no problem for the original nonphotosynthetic microorganisms that could quite happily have lived in the deep ocean and in
muds, well hidden from sunlight. But for the early photosynthetic prokaryotes, it must have been
a matter of life and death.
It is a classical "chicken and egg" problem. In order to become photosynthetic, early
microorganisms must have had access to sunlight, yet they must have also had protection against
the UV radiation. The oceans only provide limited protection. Since water does not absorb very
strongly in the ultraviolet a depth of several tens of meters is needed for full UV protection.
Perhaps the organisms used a protective layer of the dead bodies of their brethren. Perhaps this is
the origin of the stromatolites - algal mats that would have provided adequate protection for
those organisms buried a few millimeters in. Perhaps the early organisms had a protective UVabsorbing case made up of disposable DNA - there is some intriguing evidence of unused
modern elaborate repair mechanisms that allow certain cells to repair moderate UV damage to
their DNA. However it was accomplished, we know that natural selection worked in favor of the
photosynthetic microorganisms, leading to further diversification.
Fluctuations in Oxygen
The history of macroscopic life on Earth is divided into three great eras: the Paleozoic, Mesozoic
and Cenozoic. Each era is then divided into periods. The latter half of the Paleozoic era, includes
the Devonian period, which ended about 360 million years ago, the Carboniferous period, which
ended about 280 million years ago, and the Permian period, which ended about 250 million years
ago.
According to recently developed geochemical models, oxygen levels are believed to have
climbed to a maximum of 35 percent and then dropped to a low of 15 percent during a 120million-year period that ended in a mass extinction at the end of the Permian. Such a jump in
oxygen would have had dramatic biological consequences by enhancing diffusion-dependent
processes such as respiration, allowing insects such as dragonflies, centipedes, scorpions and
spiders to grow to very large sizes. Fossil records indicate, for example, that one species of
dragonfly had a wing span of 2 1/2 feet.
Geochemical models indicate that near the close of the Paleozoic era, during the Permian period,
global atmospheric oxygen levels dropped to about 15 percent, lower that the current
atmospheric level of 21 percent. The Permian period is marked by one of the greatest extinctions
of both land and aquatic animals, including the giant dragonflies. But it is not believed that the
drop in oxygen played a significant role in causing the extinction. Some creatures that became
specially adapted to living in an oxygen-rich environment, such as the large flying insects and
other giant arthropods, however, may have been unable to survive when the oxygen atmosphere
underwent dramatic change.
5. Pressure, Density and Mixing Ratio

Mixing Ratio
The mixing ratio CX of a gas X (equivalently called the mole fraction) is defined as the
number of moles of X per mole of air. It is given in units of mol/mol (abbreviation for
moles per mole), or equivalently in units of v/v (volume of gas per volume of air) since
the volume occupied by an ideal gas is proportional to the number of molecules.
Pressures in the atmosphere are sufficiently low that the ideal gas law is always obeyed to
within 1%.
The mixing ratio of a gas has the virtue of remaining constant when the air density
changes (as happens when the temperature or the pressure changes). Consider a balloon
filled with room air and allowed to rise in the atmosphere. As the balloon rises it expands,
so that the number of molecules per unit volume inside the balloon decreases; however,
the mixing ratios of the different gases in the balloon remain constant. The mixing ratio is
therefore a robust measure of atmospheric composition.
Gases other than N2, O2, Ar, and H2O are present in the atmosphere at extremely low
concentrations and are called trace gases. Despite their low concentrations, these trace
gases can be of critical importance for the greenhouse effect, the ozone layer, smog, and
other environmental issues. Mixing ratios of trace gases are commonly given in units of
parts per million volume ( ppmv or simply ppm), parts per billion volume ( ppbv or ppb),
or parts per trillion volume ( pptv or ppt); 1 ppmv = 1x10-6 mol/mol, 1 ppbv = 1x10-9
mol/mol, and 1 pptv = 1x10-12 mol/mol. For example, the present-day CO2
concentration is 365 ppmv (365x10-6 mol/mol).
Table 1-1 Mixing ratios of gases in dry air
Mixing ratio
(mol/mol)

Gas
Nitrogen (N2)

0.78

Oxygen (O2)

0.21

Argon (Ar)

0.0093

Carbon dioxide (CO2)

365x10-6

Neon (Ne)

18x10-6

Ozone (O3)

0.01-10x10-6

Helium (He)

5.2x10-6

Methane (CH4)

1.7x10-6

Krypton (Kr)

1.1x10-6

Hydrogen (H2)

500x10-9

Nitrous oxide (N2O)

320x10-9

Number Density

The number density nX of a gas X is defined as the number of molecules of X per unit
volume of air. It is expressed commonly in units of molecules cm-3 (number of
molecules of X per cm3 of air). Number densities are critical for calculating gas-phase
reaction rates. Consider the bimolecular gas-phase reaction
(R1)
The loss rate of X by this reaction is equal to the frequency of collisions between
molecules of X and Y multiplied by the probability that a collision will result in chemical
reaction. The collision frequency is proportional to the product of number densities
nXnY. When we write the standard reaction rate expression

where k is a rate constant, the concentrations in brackets must be expressed as number

densities. Concentrations of short-lived radicals and other gases which are of interest
primarily because of their reactivity are usually expressed as number densities.
Another important application of number densities is to measure the absorption or
scattering of a light beam by an optically active gas. The degree of absorption or
scattering depends on the number of molecules of gas along the path of the beam and
therefore on the number density of the gas. Consider in this atmosphere an optically
active gas X. A slab of unit horizontal surface area and vertical thickness dz contains
nXdz molecules of X. The integral over the depth of the atmosphere defines
the atmospheric column of X as
This atmospheric column determines the total efficiency with which the gas absorbs or
scatters light passing through the atmosphere. For example, the efficiency with which the
ozone layer prevents harmful solar UV radiation from reaching the Earth's surface is
determined by the atmospheric column of ozone.
The number density and the mixing ratio of a gas are related by the number density of air
na (molecules of air per cm3 of air):

The number density of air is in turn related to the atmospheric pressure P by the ideal gas
law. Consider a volume V of atmosphere at pressure P and temperature T containing N
moles of air. The ideal gas law gives

where R = 8.31 J mol-1 K-1 is the gas constant. The number density of air is related to N
and V by

where Av = 6.023x1023 molecules mol-1 is Avogadro's number. Substituting

equation (1.5) into (1.4) we obtain:

and hence

Partial Pressure
The partial pressure PX of a gas X in a mixture of gases of total pressure P is defined as
the pressure that would be exerted by the molecules of X if all the other gases were
removed from the mixture.Dalton's law states that PX is related to P by the mixing ratio
CX :
For our applications, P is the total atmospheric pressure. Similarly to (1.6) , we use the
ideal gas law to relate PX to nX:

The partial pressure of a gas measures the frequency of collisions of gas molecules with
surfaces and therefore determines the exchange rate of molecules between the gas phase
and a coexistent condensed phase. Concentrations of water vapor and other gases that are
of most interest because of their phase changes are often given as partial pressures.
Cloud formation in the atmosphere takes place when PH2O PH2O,SAT, and it is
therefore important to understand how PH2O,SAT depends on environmental variables.

From the phase rule, the number n of independent variables determining the equilibrium
of c chemical components between a number p of different phases is given by

In the case of the equilibrium of liquid water with its vapor there is only one component
and two phases. Thus the equilibrium is determined by one single independent variable;
at a given temperature T, there is only one saturation vapor pressure PH2O,SAT(T) for
which liquid and gas are in equilibrium.
In weather reports, atmospheric water vapor concentrations are frequently reported as
the relative humidity (RH) or the dew point (Td). The relative humidity is defined as:

so that cloud formation takes place when RH 100%. The dew point is defined as the
temperature at which the air parcel would be saturated with respect to liquid water:

6. Draw carbon, nitrogen and oxygen cycles

Carbon Cycle

Nitrogen Cycle

Oxygen Cycle