LU 4 Atmospheric Chemistry

STK2123 Environmental Chemistry I
Faculty of Resource Science and Technology, Universiti Malaysia Sarawak

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STK 2123 Environmental Chemistry I
LU 4 Atmospheric Chemistry
4.1 Introduction
4.1.1 The physical properties of atmosphere
The atmosphere contains several different layers that can be defined according to air
temperature or chemical composition.
Troposphere is the layer from the surface of the earth to approximate 11 kilometers.
This layer contains about 75% of the total mass of atmosphere.
It is characterized by the density of its air and an average vertical temperature change of 6
o
C per kilometer. The lowest temperature of troposphere is 55 oC which is at the top of
this layer.
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Water vapor in the troposphere plays a major in regulating air temperature because it
absorbs solar energy and thermal radiation from earths surface.
The troposphere, extending from 11 to 20 kilometers, is an isothermal layer where

temperature remains constant over a distance of 9 kilometers.
All the weather phenomena occur within the troposphere, although turbulence may extend
into the lower portion of the stratosphere.
Above the troposphere, is the stratosphere which extent from 20 to 48 kilometers above
the earths surface.
In the stratosphere, temperature increases with altitude because ozone found in this layer.
Ozone (O3) plays important rule in absorbing UV sunlight and finally creating heat energy.
So that, the temperature in stratosphere is higher than troposphere.
Ozone primarily found in the temperature at varying concentration between the altitude of
10 to 50 kilometers.
Ozone absorbs the bulk of UV radiation in wavelength from 290 nm to 320 nm.
These wavelengths are harmful to life because they can be absorbed by the nucleic acid in
the cell and cause cancer in human skin.
Mesosphere, a layer extending from approximate 50 km to 80 km, is characterized by

decreasing the temperatures, which reach 83 to 73 oC at an altitude of 80 km.
Concentration of ozone and water vapor in this layer are negligible. Hence the temperature
is lower than that of the troposphere and stratosphere.
At very high altitude, the residual gases begin to stratify according to molecular mass,
because of the gravitational separation.
Above mesosphere is another isothermal layer called mesopause.
Thermosphere is located above the mesosphere and separated from it by the mesospause
transition layer.
The upper boundary of the layer extends to heights of perhaps 960 to 1000 km and it is
relatively undefined.
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The temperature in thermosphere generally increases with the altitude up to 700 to 1200
o
C. Increasing temperature is due to the absorption of intense solar radiation by the limited
amount of remaining molecular oxygen.
At an altitude of 100 to 200 km, the major atmospheric components are still nitrogen and
oxygen but they are widely separated.
Exosphere is the most distant atmospheric region from earths surface.
4.1.2 Energy transfer in the atmosphere and global climate
4.1.2.1 Understanding of sea breeze and land breeze
Important concept gained from sea and land breeze is air flows from high pressure to
lower pressure.
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4.1.2.2 The factors that influence the temperature of a location
In Equator, the sun ray comes at 90o to the earth; therefore, the concentration of sun ray
received will be highest.
In season region, sun ray come with 45o where the concentration of sun ray has been
reduced to 0.7 if compared to equator.
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In North Pole or South Pole, sun ray will come at 30o from the earth surface, therefore, the
concentration of the sun ray can reduce to 0.5 compare to Equator.
From figure above, the thickness of the atmosphere will be increased with increasing of
latitude.
So that, the solar radiation must pass through them before reach to the surface of the earth,
thus, most of the sun ray has been filtered out in the atmosphere before the sun ray reach
to North and South Pole.
As conclusion, the reception of the sun ray decrease when the latitude increases.
4.1.2.3 Earths Energy Budget
Rnet = (Kin Kout) + (Lin Lout)

Rnet = net radiation, K = shortwave radiation, L = longwave radiation
Solar energy derived from the sun will be received by the earth surface and it will modify
both short and long wave radiation in reflection.
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Earth surfaces that absorb a lot of energy (low albedo) tend to be warmer (emit more long
wave radiation)
(figure is taken from: NASA homepage)

From the previous pictures in pages 4, 5 and 6, we know that the temperature of a location
is generally influenced by three factors:
How concentrated of the sun ray will be reached to that area.
The thickness of the atmosphere that the solar rays must pass through.
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The value of albedo of the material that located in that area.
4.1.2.4 Simple model of global circulation
The first model will be found on the following simplifying assumptions:
1. The earth is not rotating in space.

2. The earths surface is composed of the similar materials.
3. A temperature gradient of hotter air at the equator and colder air at the pole.
4. As describe in following figure, surface air flow is from the poles to the equator.
Simplified One-Cell Global Air Circulation Pattern
(Picture taken from web:www.physicalgeography.net)
4.1.2.5 Three Cell Model of Global Circulation
Planetary rotation would cause the development of three circulation cells in each
hemisphere rather than one.
These three circulations are known as: Hadley Cell; Ferrel Cell and Polar Cell.
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In the new model (refer to figures in page 9), the equator still remains the warmest location
on the earth and assuming the earth is made by only one material as well.
Since equator has greater heat, and acts as zone of thermal lows or known as the
intertropical convergence zone.
The intertropical convergence zone draws in surface air from the subtropics.
When this subtropical air reaches the equator, it rises into the upper atmosphere because of
convergence and convection.
It attains a maximum vertical altitude of about 14 km (top of troposphere), and then begins
flowing horizontally to the North and South Poles.
Coriolis force causes the deflection of this moving air in the upper atmosphere, and by
about 30o of latitude the air begins to flow zonally from left to right if the air moving toward
northern part; and from right to left if the air moving toward southern part in north
hemisphere.
The air will reach a zone (approximately 30o of latitude from equator) named subtropical
jet stream, where the air accumulate at the upper atmosphere.
To compensate for this accumulation, some of the air in the upper atmosphere sinks back
to the surface creating subtropical high pressure zone.
Not 100% of the upper air will sink down from subtropical jet stream, some portion of the
air will continuously flow to approximate 60o latitude from equator.
From subtropical high pressure zone, the surface air flow in two direction: one is toward
to both poles and another one is flow back to equator. The one flow back to equator will
complete the circulation system known as Hadley Cell.
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Simplified Three Cell Global Surface and Air Circulation Pattern
(Picture taken from :www.physicalgeography.net)
3-D Simplified Global Circulation Three Cell Model. (Picture taken from web:
www.geocities.com).
Whereas the surface air moves toward to both poles from subtropical high pressure zone is
also defected by Coriolis force acceleration producing the Westerlies.
Between the latitudes of 30 to 60o north and south, upper air blows toward the poles.
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Once again, Coriolis force deflects the wind to cause the formation of Polar Jet Stream at
roughly 60o north and south.
On the earths surface at 60o north and south latitude, the air from Westerlies collide with
the air flow from the poles. This collision can cause the frontal uplift and create the
Subpolar low at 60o north and south latitude from equator.
A small portion of this uplifted air will flow back to Ferrel Cell when it reaches the top of
troposphere.
Most of the uplifted air is directed to the polar vortex where it moves downward to create
the polar high.
Once again, two assumptions are made under the model of three cells global circulation:
1. The earths surface is composed of the similar materials; and
2. The global reception of solar insolation and loss of longwave radiation cause a
temperature gradient of hotter air at the equator and colder air at the pole.
The earth rotates in the space from left to right. Due to the rotation of the earth, Coriolis
force can be formed.
However, in actual earth surface, it is containing various types of materials for example
water, soil, forest, sand and so on.
The different type of materials on earth surface results the formation of different
phenomena of global circulation, for example monsoon air flow.
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Air circulation resulted from the uneven distribution of land and water on the earth.
Temperatures are low in the troughs (low pressure zone) and high in the peaks (high
pressure zones).
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4.2 Stratospheric chemistry The ozone layer
The stratospheric ozone layer, centered at about 20 km above the surface of the Earth
( Figure ), protects life on Earth by absorbing UV radiation from the Sun.
The natural ozone layer: vertical and latitudinal distribution of the ozone number density (1012
molecules cm-3) at the equinox, based on measurements taken in the 1960s. From Wayne, R.P.,
Chemistry of Atmospheres, Oxford, 1991.
There is an abrupt change in concentrations of several important trace constituents between

the troposphere and stratosphere.
For example, water vapour decreases substantially and O3 increases by up to an order of

magnitude.
This is because there is very little vertical mixing between the relatively moist, ozone-poor
troposphere and the dry, ozone-rich stratosphere.
Within the stratosphere the air is generally neutral or stable with respect to vertical motions.
Also, the removal of aerosols and trace gases by precipitation (wash-out or wet deposition)
is absent in the stratosphere.
Materials that enter the stratosphere can remain there for long periods of time, often as
stratified layers.
4.2.1 Chapman Mechanism
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The presence of a high-altitude ozone layer in the atmosphere was first determined in the
1920s from observations of the solar UV spectrum.
A theory for the origin of this ozone layer was proposed in 1930 by a British scientist,
Sydney Chapman, and is known as the Chapman mechanism. It lays the foundation for
current understanding of stratospheric ozone.
Chapman theory describes how sunlight converts the various forms of oxygen from one
to another, explains why the highest content of ozone occur in the layer between 15 and
50 km, termed the ozone layer.
Chapman proposed a simple chemical scheme for maintaining steady state concentrations
of O3 in an oxygen-only stratosphere.
Chapman proposed that the ozone layer originates from the photolysis of atmospheric O2.
The bond energy of the O2 molecule (498 kJ mol-1) corresponds to the energy of a 240 nm
UV photon; only photons of wavelengths less than 240 nm can photolyze the O2 molecule.
Such high-energy photons are present in the solar spectrum at high altitude (Figure).
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Solar actinic flux at different altitudes, for typical atmospheric conditions and a 30o solar zenith
angle. From DeMore, W.B., et al., Chemical Kinetics and Photochemical Data for Use in
Stratospheric Modeling, JPL Publication 97-4, Jet Propulsion Lab, Pasadena, CA, 1997.
Photolysis of O2 yields two O atoms:
(R1)
where the O atoms are in the ground-level triplet state O(3P), and are highly reactive due
to their two unpaired electrons. They combine rapidly with O2 to form ozone:
(R2)
where M is a third body.
The O3 molecules produced in reaction (R2) go on to photolyze.
Because the bonds in the O3 molecule are weaker than those in the O2 molecule,
photolysis is achieved with lower-energy photons:
(R3)
where O(1D) is the O atom in an excited singlet state and is rapidly stabilized to
O(3P) by collision with N2 or O2.
The combination of atomic oxygen and O3 to form O2 O + O3 2O2 12 The O

atoms produced by this set of reactions undergo numerous collisions with N2 and
O2 molecules, most of which do not result in any permanent products.
Occasionally, however, a three-body collision occurs in which M absorbs the

excess energy of the collision and a stable O3 molecule is produced.
Note that the excess energy acquired by M, which is in the form of thermal energy
that warms the stratosphere, derives primarily from the energy of the incoming
photon, that is, from solar energy.
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Since the concentration of M decreases with increasing altitude, the time constant
for converting O atoms and O2 molecules to O3 increases with altitude (e.g., from
a few seconds at 40 km to 100 s at 50 km).
Stratospheric O3 concentrations exhibit minor diurnal variations (analogous to the day-

to-day variations in weather in the troposphere).
After sunset, both the source and sink of O3 are switched off, the remaining O atoms are
then converted to O3 within a minute or so.
The Chapman reactions reproduce some of the broad features of the vertical distribution
of O3 in the stratosphere. For example, they predict that O3 concentrations should reach
maximum values at an altitude of 25 km.
However, the Chapman reactions overpredict the concentrations of stratospheric O3 by

about a factor of two in the tropics and they underpredict O3 concentration in middle to
high latitudes.
There is an equator-to-pole circulation in the stratosphere, known as the Brewer-Dobson

Circulation, which transports O3 from its primary source in the tropical stratosphere to
higher latitudes.
4.2.2 Stratospheric Ozone
Ozone in the stratosphere is of great importance:

1. It forms a protective shield that reduces the intensity of UV radiation from the Sun
that reaches the Earths surface.
2. Due to the absorption of UV radiation, O3 determines the vertical profile of
temperature in the stratosphere.
3. It is involved in many stratospheric chemical reactions.
In 1881 W.N. Hartley measured the UV radiation reaching the Earths surface and found
a sharp cut-off at = 0.30 m. He correctly attributed this to absorption by O3 in the
stratosphere.
Figure 4.3 below are the results of measurements of O3 . The presence of an ozone layer
between heights of 1530 km is very clear.
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Mean vertical distributions of ozone concentrations based on measurements at different latitudes

(given in degrees).
The O3 layer is highly variable. Its height and intensity change with latitude, season, and
meteorological conditions. The total ozone column abundance [in Dobson units (DU)] is
indicated in the figure.
The O3 layer is highly variable. Its height and intensity change with latitude, season, and
meteorological conditions.
The total ozone column abundance [in Dobson units (DU)] is indicated in the figure. The
largest column densities of O3 in the northern hemisphere occur in polar latitudes in
spring.
At any given point in the atmosphere, the balance between the production and loss of O3
and its flux divergence determines the O3 concentration.
The high concentration at polar and midlatitudes is attributed to meridional transport of

O3 from the equator Much of the change in the total column abundance of O3 is due to
differences in the profiles below 20 km.
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4.2.3 The ozone hole
In the 1970s it was suggested that catalytic cycles involving reactive chlorine (Cl) and
bromine (Br) could be important in the destruction of O3.
The natural sources of Cl and Br in the stratosphere are the destruction of methyl chloride
(CH3Cl) and methyl bromide (CH3Br).
The destruction of stratospheric O3 by the various chemical mechanisms discussed

above, and many other possible mechanisms not discussed here, are not simply additive
because the species in one cycle can react with those in another.
Therefore, advanced numerical models that consider all the known suspects must be used
to unravel the relative importance of the various mechanisms for destroying O3 in the
stratosphere.
This task is complicated further by the fact that concentrations of many of the prime
suspects are changing with time due to anthropogenic emissions.
Most of the catalytic reactions that have been proposed for the removal of stratospheric
odd oxygen are of the form
X + O3 XO + O2
XO + O X + O2

Net: O + O3 2O2
If the concentration of catalyst X is increased significantly by anthropogenic activities,

the balance between the sources and sinks of atmospheric O3 will be disturbed and
stratospheric O3 concentrations can be expected to decrease.
4.2.4 Mechanism of ozone hole
During the austral winter (June-September) stratospheric air over the Antarctic continent
is restricted from interacting with air from lower latitudes by a large-scale vortex
circulation, which is bounded by strongly circulating winds.
Because of the lack of solar heating in the austral winter, the air within the vortex is
extremely cold and therefore slowly sinks.
High-level clouds, called polar stratospheric clouds (PSCs), form in the cold core of the
vortex, where temperatures can fall below 80C.
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In the austral spring, as temperatures rise, the winds around the vortex weaken, and by
November the vortex disappears.
The vortex serves as a giant and relatively isolated chemical reactor in which unique
chemistry can occur.
For example, although the concentrations of O3 in the vortex are normal in August, the
concentrations of ClO in the vortex are ten times greater than just outside the vortex
collar and, by September, O3 concentrations within the vortex decrease dramatically.
There are also sharp decreases in the oxides of nitrogen and water vapour when passing
from the outside to the inside of the vortex collar.
These decreases are due, respectively, to the formation of nitric acid (HNO3), and to the
condensation of water at the very low temperatures inside the vortex.
4.2.5 Polar stratospheric clouds
1. Type I PSCs.
These probably consist of a mixture of liquid and solid particles of nitric acid trihydrate
[HNO3(H2O)3 NAT for short], water and sulfuric acid, which condense at about
78C. These particles are 1 m in diameter, so they sediment very slowly (10 m per
day).
2. Type II PSCs.
These consist of a mixture of ice and water together with some dissolved HNO3 , form
near 85C. Since these particles are > 10 m in diameter, they settle out with
appreciable speeds (1.5 km per day).
3. Type III PSCs.

These mother-of-pearl clouds are produced by the rapid freezing of condensed water in
air flow over topography. However, they are of limited extent and duration and do not
form over the South Pole.
As the particles in PSCs slowly sink, they remove both water and nitrogen compounds
from the stratosphere, referred to as dehydration and denitrification
On the surface of the ice particles that form PSCs, the following heterogeneous reactions
are thought to be important:
ClONO2(g) + HCl(s) Cl2(g) + HNO3(s)
ClONO2(g) + H2O(s) HOCl(g) + HNO3(s)
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HOCl(g) + HCl(s) Cl2(g) + H2O(s)
N2O5(g) + H2O(s) 2HNO3(s)
N2O5(g) + HCl(s) ClNO2(g) + HNO3(s)
[(s) indicates those compounds that are on (or in) ice particles, and (g) indicates species
that are released as gases.]
The above reactions convert the reservoir species ClONO2 and HCl into Cl2 , HOCl and
ClNO2 .
When the Sun rises in the Antarctic spring, these three species are photolyzed rapidly to
produce Cl and ClO
Cl2 + h 2Cl
HOCl + h OH + Cl
ClNO2 + h Cl + NO2
and
Cl + O3 ClO + O2
Ozone is then destroyed efficiently by
ClO + ClO + M (ClO)2 + M
(ClO)2 + h Cl + ClOO
ClOO + M Cl + O2 + M
2Cl + 2O3 2ClO + 2O2

Net: 2O3 + h 3O2
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4.3 Tropospheric chemistry
The troposphere is heated from the ground, which absorbs solar radiation and releases
heat back up in the infrared.
The temperature of the air in this region therefore decreases linearly with altitude, at a
lapse rate of 5 to 7 K km-1, or a little over half a degree per 100 m, as common
knowledge suggests.
The tropopause, situated between 8 km (at high latitudes) and 15 km (at the equator),
marks the end of this linear decrease and the beginning of the stratosphere, where lies the
bulk of atmospheric ozone (the ozone layer).
The presence of ozone is vital for life on Earth, as it absorbs the dangerous part of
incoming ultra-violet radiation. As a result, the stratosphere heats up and has a positive
temperature gradient.
The temperature peaks at the stratopause at approximately 50 km in altitude, then falls

linearly again in the mesosphere, as ozone heating diminishes.
The region of the atmosphere above the mesopause is called the thermosphere and is
radically different from the three lower regions.
It cannot be treated as an electrically neutral medium because energetic solar radiation

ionizes the molecules and atoms to form a plasma of free electrons and ions that interact
with the Earths magnetic field.
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4.3.1 Oxidizing capacity of troposphere

Besides nitrogen, oxygen, inert gases, carbon dioxide and water vapor, troposphere
contains many trace pollutants. Be they emitted by natural or anthropogenic sources, they
heavily influence our climate system.
Natural sources include volcanoes eruptions, swamps, wild animal emissions, forest fires
and dust, while anthropogenic ones include industrial activities, fossil fuel burning, car
usage, emissions from domestic animals and agriculture.
Because of its growing importance, the latter category is very publicized and becoming
common knowledge even amongst the non-scientific community.
Fortunately, the atmosphere has up to now avoided any substantial accumulation of

pollutants, thanks to a remarkable natural ability to cleanse itself.
There are three end removal processes.

1. The first is chemical conversion to non-polluting constituents, such as H2O or O2.
2. The second is dry deposition, whereby gases are absorbed by plants, water or soil. It
is of limited significance because it often only applies to gases in the boundary layer
on a local scale.
3. The third is wet deposition, or removal by precipitation, and is only effective for
species that have enough solubility in water, which is not the case in general.
There are, however, a number of tropospheric species capable of oxidizing these

pollutants so that they become soluble. Although these species are only present in minute
amounts, they constitute the pivot of tropospheric chemistry.
Ironically, the discovery of the oxidizing capacity of the troposphere came relatively late
and through indirect reasoning. In 1970, Pressman and Warneck noted that, although the
emission of CO had been steadily increasing over the 50's and 60's, there was no
repercussion on its tropospheric concentration.
The puzzle was solved a year later when Levy (1971) found a route for the formation of
OH radicals in the troposphere and suggested that they could be a major sink for CO. The
importance of OH radicals and other oxidants as the detergents of the atmosphere has
been recognized ever since. They are, in descending order of importance:
1. The hydroxyl radical OH. Hydroxyl is a short-lived free radical and by far the most
effective scavenger in the troposphere. It is the main oxidant for CO, CH4 and higher
hydrocarbons, H2S (hydrogen sulfide) and SO2 (sulfur dioxide). Its sinks in different
environments.
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2. The nitrate radical NO3. At night, this radical takes over from hydroxyl as the
dominant oxidant in the atmosphere: hydroxyl is formed by photolysis and its
concentration peaks during daytime while NO3 does not survive sunlight.
3. The oxygen atom O(3p). This exited state of the oxygen atom has the ability to
oxidize unsaturated hydrocarbons and other gases containing a double bond such as
CS2 and COS in the upper troposphere.
4. Peroxy and hydroperoxy radicals HO2 and RO2 (where R is an alkyl). HO2 and
RO2 are very much intertwined with hydroxyl in the oxidation cycle. They are not as
efficient as hydroxyl, but react with themselves to form H2O2, an important oxidant in
cloud droplets.
5. Hydrogen peroxide H2O2. This strong acid reacts very efficiently in cloud droplets
and oxidizes a number of trace gases, in particular sulfur dioxide. Highly soluble, it
also accounts for a large part of the excess acidity in rain.
Together, these oxidants determine the lifetime and the abundance of trace species, acting as a
atmospheric regulators. The reverse is also true: the abundance of trace species regulate the
oxidizing capacity of the atmosphere, since an increase in the emission of a given pollutant reduces
the abundance of its principal oxidant. The resulting positive feedback may even eventually lead
to an increase of other pollutants. This underlines the importance of a stable oxidizing capacity in
the troposphere, of prime importance to our environment.
Primary and Secondary Pollutants and their impacts
Primary pollutants are those emitted directly from sources

CO: affects oxygen-carrying capacity of blood (but not at urban concentrations)
NO: secondary reactions
NO2: 5% in urban, much higher for biomass burning
SO2: respiratory constriction (asthma, bronchitis)
NH3: aerosol formation
soot: visibility reduction, PAH is carcinogen
isoprene: emitted from plants, leads to ozone
vanillan: yummy smell from Ponderosa Pine
Secondary pollutants are those formed in the atmosphere by chemical interactions among
primary pollutants and normal atmospheric constituents.
NO2 (95%): lung damage
H2SO4: Aerosol formation, visibility reduction and acid rain
PAN: hurts your eyes, damage to plants
O3: damage to plants & plastics, lung damage (only short-term?)
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4.3.2 Formation of OH radical
The basic ingredients for the formation of hydroxyl are NO and NO2, water vapor, ozone and
radiation at wavelengths shorter than 315 nm: in simple terms, NO2 is very reactive and may
form O3, which in turn may yield hydroxyl. NO2 is mainly created through oxidization of NO,
itself an indirect product of biomass burning, high temperature combustion and microbial actions
in the soil. It is thought that the first two man-made sources represent up to 50% of the total
emissions.
The process for in-situ ozone production by NO2 can be written as
(1)
(2)
(3)
(4)
(5)
Net: (6)
(Wayne, 1991). A similar reaction involving alkyls may be written down by replacing NO2 by
RO2 in the above equations. Below a certain value of [NO]'[O3], it is worth noting that ozone is
actually lost, because the destruction sequence dominates over the generation sequence. The
destruction sequence has the net result
(7)
On average ozone maintains itself in the troposphere at levels between 25 and 30 ppbv. It may be
photolysed at wavelengths around 310 nm to yield an exited O(1D) oxygen atom that reacts with
water vapor to form two OH radicals (if not quenched back to its ground state through a collision
with nitrogen or oxygen molecules):
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(8)
(9)
It is should be pointed out that the quenching process does not constitute a loss of ozone because
almost all ground state oxygen atoms react with oxygen to regenerate ozone with the help of a
third body:
(2)
4.3.3 Oxidation of methane
NOx plays a very important role in the methane oxidation cycle. If it is sufficiently
abundant, it closes the loop of a cycle that regenerates hydroxyl.
In its absence, the cycle terminates abruptly and methane becomes a sink for hydroxyl.
This double role is schematically represented in Figure 6.
Figure 6: Schematic of the CH4 oxidation cycle (from Wayne, 1991). The bold arrows in the first
half of the cycle indicate what happens without NOx, while the thin arrows on the second half
indicate processes that require NOx, and close the loop back to the formation of hydroxyl.
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4.3.4 Oxidation of carbon monoxide

Like the methane, the oxidation cycle of carbon monoxide depends on the level of NOx. In high
NOx regions the oxidation sequence is
(3)
(4)
(5)
Again, the transformation of NO into NO2 regenerates a mole of OH radicals for each mole
consumed in the CO oxidation reaction, and there is no net loss of oxidants. In turn, NO2 may be
photolysed to initiate the production of ozone and hydroxyl:
(1)
(2)
The net product of the last five equations can be written
(6)
In unpolluted regions, the sequence is
(3)
(4)
(23)
(7)
Regardless of the levels of NOx, both sequences generate carbon dioxide on a mole to mole
basis. In polluted regions, the oxidation of CO generates (also on a mole to mole basis) ozone, a
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vital precursor to hydroxyl, an oxidant in its own right, as well as a potent greenhouse gas. In
unpolluted regions, on the contrary, the oxidation of CO consumes ozone (Cicerone, 1988).
In conclusion, I wish to underline the fact that methane and carbon monoxide have arguably the
most important roles in the hydroxyl oxidation cycle, itself the main scavenger in the
troposphere. In fact, the simplified equation for OH concentration
(24)
where ki are reactions rates (in s-1) and [NMHC] is the concentration of non-methane
hydrocarbons, is often accurate enough for many practical calculations (Wuebbles and
Tamaresis, 1993).
4.4 Photochemical smog processes
4.4.1 Basic of Photochemical Process
The photochemical reactions that take place during ozone formation are very complex.
Simply state, in the presence of light, oxygen (O2) reacts with nitrogen oxide (NOx) and
volatile organic compounds (VOCs) to produce ozone (O3).
Whereas in dark the process reverse and destroys ozone.
NOX, typically produced by combustion engines (power plants, boilers, heaters, incinerators,
trucks and automobiles), is a mixture of about 90 percent nitrogen oxide (NO) and 10 percent
nitrogen dioxide (NO2). In sunlight, the NO2 reacts with O2 to form O3 and NO.
NO2 + O2 O3 + NO
In a reverse process, NO slowly reacts with O3 and destroys it 24 hours a day, even in the dark,
to make NO2 and O2.
NO + O3 NO2 + O2
In sunlight, VOCs, which typically come from sources such as trees, gasoline, solvents, and
paint, recycle NOX by reacting with NO to produce more NO2, fueling the original reaction to
form more O3.
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VOCs + NO NO2 which leads to NO2+ O2 O3 + NO
Ozone (O3) formation occurs rapidly during daylight hours, but not in the dark. Meanwhile,
the destruction of ozone by NO goes on continuously. That is why O3 concentrations will be
higher during the day and lower at night in urban areas.
Because VOCs recycle NOX, a small amount of NOX can produce a large amount of O3. On
the other hand, VOCs are consumed by the NOX recycling process.
4.4.2 Absorption of Solar Radiation in the Atmosphere
The sun is radiating energy according to its temperature of 5785 K. Much of this is in the UV
and visible range, however, the earth is radiating energy in the infrared range.
The atmosphere absorbs the major of short-wavelength radiation from the sun, and various
processes occur that lead to the re-emission of this energy as infrared radiation.
When a molecule AB absorbs a UV photon, a number of things can occur:
(i) it can be electronically excited (photoexcitation)
(ii) it could fall apart (photodissociation)
(iii) it could ionize (photoionization)
In each case, a number of process can lead to the conversion of the energy to internal energy
of molecules (vibration and rotational), and decay of the vibrations and rotations lead to the
scattering of radiation.
Two types of scattering: (i) Rayleigh Scattering and (ii) Mie Scattering.
For all the molecules smaller than the radiation wavelength, Rayleigh scattering occurs in all
direction and is proportional to (1/4). As a result, the scattering of blue ( ~ 0.4 m) is an
order magnitude (i.e. 10 times) greater than that of red light ( ~ 0.7 m), thus creating the day
time blue sky.
When water droplets or aerosol particles, with similar sizes (0.1 0.5 m radius) to the
radiation wavelength, are present, most of the light scatter forward. This is Mie scattering gives
the grayish appearance of polluted atmosphere.
27
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4.4.3 Reaction of OH Radical
Involved in most of the oxidation process in the troposphere.
The radical is generated by the photochemical absorption of light by ozone and reaction with
water.
O3 + hv O + O2 (290 nm < < 318 nm)

O + H2O 2OH
4.4.4 Oxidative Breakdown of Organic Compounds
With presence of O2, OH radical attack on volatile organic compounds (VOCs) is the primary
source of ROO radicals in the troposphere, and consequently the rates of the OH + VOC
reactions have a strong influence on the local rate of O3 formation. (R = H, organic radical)
OH + RH + O2 ROO + H2O (RH = VOCs)
Or
RH + O R + OH
R + O2 + M ROO + M
In this reaction, atom O is came from the photolysis of O3.
4.4.5 Oxidative Breakdown of Organic Compounds

The rate of ozone generation in a particular region of the troposphere is determined by the
perturbation of the local photostationary state of NOx due to oxidation of NO and NO2.
ROO + NO RO + NO2 (R = H, organic radical)
ROO competing reactions,

ROO + NO2 + M ROONO2 + M
ROO + HOO ROOH + O2
ROO + ROO Products
28
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VOC oxidation during the daytime
4.4.6 The Reaction of NOx in Troposphere
NOx plays a central in ozone production in the troposphere through the photodissociation of
NO2 to produce O atoms, which subsequently react with O2 to produce O3.
The transport of NOx in the troposphere has to be defined on its chemical conversion to the
various forms of nitrogen species, which have different atmospheric lifetimes.
Peroxyacetylnitrate (PAN) is important species for transport of NOx as it has a longer life time
in the atmosphere.
CH3C(O)O2 + NO2 + M CH3C(O)O2NO2 + M
29
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Alkyl nitrates, formed in a secondary channel of the reaction of RO2 with NO, are another
stable form of NOx.
NOx Reaction System in Daytime
30
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4.6 Acid precipitation
Acid rain, or acid deposition, is a broad term that includes any form of precipitation with
acidic components, such as sulfuric or nitric acid that fall to the ground from the
atmosphere in wet or dry forms. This can include rain, snow, fog, hail or even dust that is
acidic.
Forms of Acid Deposition

1. Wet Deposition
Wet deposition is what we most commonly think of as acid rain. The sulfuric and
nitric acids formed in the atmosphere fall to the ground mixed with rain, snow, fog,
or hail.
2. Dry Deposition
Acidic particles and gases can also deposit from the atmosphere in the absence of
moisture as dry deposition.
The acidic particles and gases may deposit to surfaces (water bodies, vegetation,
buildings) quickly or may react during atmospheric transport to form larger
particles that can be harmful to human health.
When the accumulated acids are washed off a surface by the next rain, this acidic
water flows over and through the ground, and can harm plants and wildlife, such as
insects and fish.
The amount of acidity in the atmosphere that deposits to earth through dry
deposition depends on the amount of rainfall an area receives.
For example, in desert areas the ratio of dry to wet deposition is higher than an
area that receives several inches of rain each year.
Acid rain results when sulfur dioxide (SO2) and nitrogen oxides (NOX) are emitted into
the atmosphere and transported by wind and air currents. The SO2 and NOX react with
water, oxygen and other chemicals to form sulfuric and nitric acids. These then mix with
water and other materials before falling to the ground.
While a small portion of the SO2 and NOX that cause acid rain is from natural sources
such as volcanoes, most of it comes from the burning of fossil fuels. The major sources
of SO2 and NOX in the atmosphere are:
1. Burning of fossil fuels to generate electricity. Two thirds of SO2 and one fourth of
NOX in the atmosphere come from electric power generators.
2. Vehicles and heavy equipment.
3. Manufacturing, oil refineries and other industries.
31
______________________________________________________________________________
Winds can blow SO2 and NOX over long distances and across borders making acid
rain a problem for everyone and not just those who live close to these sources.
The normal technical measure of acidity is pH, defined as pH = - log (activity of

H+ ions, expressed in mol/L)
For ideal gases, the activity is identical to the concentration (Refer Table)
For dilute solutions of acids and bases in water the activity of H+ ions is very close
to, not identical to, the concentration of those ions.
32
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Rain falling through a perfectly unpolluted atmosphere will arrive at the earth with
a pH of about 5.6 because of the CO2 in the atmosphere, which reacts with
rainwater by these reactions:
CO2 + H2O H2CO3 H+ +HCO3-
Carbonic acid is a weak acid, and the above reaction is reversible with acid concentration
in the rain depending on the concentration of CO2 in the air.
Generally, any rain with pH less than 5.6 is considered acidic, but damage to plants and
animals (or fish) does not begin to become apparent until a pH of about 4.5 or less is
reached.
Although damage to human health has not been shown, acid damage to the ecology and
mountain lakes and forests is apparent.
The harmfulness of acid precipitation to a given area is strongly dependent on the

buffering capacity of the soil.
If the local soil contains significant amounts of limestones, CaCO3, then the acid will
react by:
CaCO3 + H+ Ca2+ + HCO3-
Thus removing the H+ ion.
If the soil contains little limestone, then the observed pH values of the surface waters will
be lower and the biologic effects more pronounced.
The acidity need not act alone on plants and fish.
It is also believed that in some area the increased rainfall acidity has speeded the
dissolution of metals from the soil, e.g. aluminium, thus raising the content of those
metals in the water. These dissolved metals may be the true agents of destruction for fish
or plants.
33
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4.7 Particulates in air pollution
4.7.1 Composition of atmosphere
The air in our atmosphere contains:
(Table source: http://www.ux1.eiu.edu)
From the table above, there are 78% of nitrogen and 21% of oxygen present in the
atmosphere. The remaining 1% is carbon dioxide, argon, sulfur and so on.
Typically, the gases present in this composition is not pure, there are mixture such as
nitrogen oxides, volatile organic compounds such as methane, sulfur compounds and so
on.
The contaminations of the air can be occurred naturally, but mainly are from the
anthropogenic sources.
4.7.2 Nitrogen oxides and its sources
NOx defined as the sum of NO + NO2
34
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NOy defined as the total of all the active nitrogen containing species, e.g NO + NO2 +
HNO3 + PAN + HONO + NO3 + N2O5 + organic nitrates etc. (Note: PAN is defined as
Peroxyacetylnitrate)
The main contribution of various sources to total NOx emissions:

1. On road vehicles (main contribution)
2. Fuel Combustion Electrical utility (Main contribution)
3. Lighting 5 8%
4. Nitrification
4.7.3 Sulfur compounds

90% or more of sulfur in fossil fuels is emitted in the form of sulfur dioxide (SO2) during
combustion, the remainder being primarily in the form of sulfates (SO42-).
Contribution of various sources to the total anthropogenic SO2 emission:

1. Fuel combustion electric utility 60%
2. Fuel combustion industrial 17%
Natural emissions of sulfur compounds to the atmosphere occur from a variety of

sources, including volcanic eruptions, sea spray and a host of biological process.
Most of volcanic sulfur is emitted as SO2, with smaller and highly variable amounts of
hydrogen sulfide and dimethyl sulfide (CH3SCH3).
4.7.4 Total Suspended Particles (TSP), PM10, and PM2.5

Air quality standards for particulate matter in the atmosphere were expressed in term of
the mass of the total suspended particulate matter (TSP).
The standard was then changed to mass of suspended particulates matter less than 10 um
in diameter (PM10) and more recently was modified to include particulate matter less
than 2.5 um in diameter, PM2.5.
Larger particles that are inhaled will be removed in the head or upper respiratory tract.
The respiratory system from the nose through the tracheobronchial region is covered with
a layer of mucus that is continuously moved upward by the motion of small hair like
projections called cilia.
Large particles deposit on the mucus, are moved up, and are ultimately swallowed.
But, particles from fossil fuel combustion are generally much smaller.
35
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These particles can reach the alveolar region where gas exchange occurs. This region is
not coated by the mucus layer, and here clearance time for deposited particles is much
greater than in the upper respiratory tract; hence the potential for health effect is much
greater.
Schematic diagram of human

respiratory tract. (Photo source:
Hinds, W. C. Aerosol Technology.
John Wiley & Sons, Inc.
There has been great interest in airborne particulate matter recently due to the result of a
number of epidemiological studies showing a correlation between increased mortality.
A clear relationship between mortality rates and the concentration of PM2.5 is in direct
proportional.
Example: Schwartz et al. (1996) reported a 1.5% increase total daily mortality with an
increase of 10 ug m-3 in PM2.5.
The fine particles are not only concerned from the point of health effect but also are
responsible for the most of the light scattering, which will cause the visibility reducing.
36
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Example:
One of the common examples is the haze

problem due to forest burning.
(Photo source: www.sixthseal.com)
As a result
People have to suffer with high environmental

temperature, skin and respiratory diseases due
to poor air quality. Again, the visibility also is
being reduced.
(Photo source: http://www.nst.com.my)
Sources of PM10 can be split into (1) nonfugitive dust and (2) fugitive dust sources.
In the sources of nonfugitive dust, it include:

1. Fuel combustion other 15%
2. Non-road engines and vehicles 15%
3. Industrial processes 13%
For fugitive dust sources, it include:

1. Unpaved roads 38%
2. Natural resources 20%
3. Agriculture crops 17%
4. Construction 14%
5. Raved road 9%
Major natural resources refer to biogenic emission, volcanic eruption and wild fires.
37
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The End
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LU 4 Atmospheric Chemistry

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LU 4 Atmospheric Chemistry

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STK2123 Environmental Chemistry I

Faculty of Resource Science and Technology, Universiti Malaysia Sarawak

4.1.1 The physical properties of atmosphere

This layer contains about 75% of the total mass of atmosphere.

The troposphere, extending from 11 to 20 kilometers, is an isothermal layer where

Mesosphere, a layer extending from approximate 50 km to 80 km, is characterized by

Above mesosphere is another isothermal layer called mesopause.

Exosphere is the most distant atmospheric region from earths surface.

4.1.2 Energy transfer in the atmosphere and global climate

4.1.2.1 Understanding of sea breeze and land breeze

4.1.2.3 Earths Energy Budget

Rnet = (Kin Kout) + (Lin Lout)

(figure is taken from: NASA homepage)

4.1.2.4 Simple model of global circulation

The first model will be found on the following simplifying assumptions:

1. The earth is not rotating in space.

Simplified One-Cell Global Air Circulation Pattern

(Picture taken from web:www.physicalgeography.net)

4.1.2.5 Three Cell Model of Global Circulation

Simplified Three Cell Global Surface and Air Circulation Pattern

(Picture taken from :www.physicalgeography.net)

1. The earths surface is composed of the similar materials; and

There is an abrupt change in concentrations of several important trace constituents between

For example, water vapour decreases substantially and O3 increases by up to an order of

4.2.1 Chapman Mechanism

Photolysis of O2 yields two O atoms:

where M is a third body.

The O3 molecules produced in reaction (R2) go on to photolyze.

The combination of atomic oxygen and O3 to form O2 O + O3 2O2 12 The O

Occasionally, however, a three-body collision occurs in which M absorbs the

Stratospheric O3 concentrations exhibit minor diurnal variations (analogous to the day-

However, the Chapman reactions overpredict the concentrations of stratospheric O3 by

There is an equator-to-pole circulation in the stratosphere, known as the Brewer-Dobson

4.2.2 Stratospheric Ozone

Ozone in the stratosphere is of great importance:

Mean vertical distributions of ozone concentrations based on measurements at different latitudes

The high concentration at polar and midlatitudes is attributed to meridional transport of

The destruction of stratospheric O3 by the various chemical mechanisms discussed

If the concentration of catalyst X is increased significantly by anthropogenic activities,

4.2.4 Mechanism of ozone hole

4.2.5 Polar stratospheric clouds

3. Type III PSCs.

ClONO2(g) + HCl(s) Cl2(g) + HNO3(s)

ClONO2(g) + H2O(s) HOCl(g) + HNO3(s)

N2O5(g) + H2O(s) 2HNO3(s)

N2O5(g) + HCl(s) ClNO2(g) + HNO3(s)

Ozone is then destroyed efficiently by

ClO + ClO + M (ClO)2 + M

2Cl + 2O3 2ClO + 2O2

4.3 Tropospheric chemistry

The temperature peaks at the stratopause at approximately 50 km in altitude, then falls

It cannot be treated as an electrically neutral medium because energetic solar radiation

4.3.1 Oxidizing capacity of troposphere

Fortunately, the atmosphere has up to now avoided any substantial accumulation of

There are three end removal processes.

There are, however, a number of tropospheric species capable of oxidizing these

Primary and Secondary Pollutants and their impacts

Primary pollutants are those emitted directly from sources

H2SO4: Aerosol formation, visibility reduction and acid rain

PAN: hurts your eyes, damage to plants

O3: damage to plants & plastics, lung damage (only short-term?)

4.3.2 Formation of OH radical

The process for in-situ ozone production by NO2 can be written as

4.3.3 Oxidation of methane