Photochemical Smog and Production of PAN and Ozone

Photochemical form is formed by a complex series of chemical reactions involving sunlight, oxides of
nitrogen, and volatile organic compounds that are present in the atmosphere as a result of air
pollution. These reactions often result in the formation of ground level ozone and certain airborne
particles. The formation of photochemical smog is closely related to the concentration of primary
pollutants in the atmosphere. It is also related to the concentration of secondary pollutants (in some
cases).
Common examples of primary pollutants that contribute towards photochemical smog include oxides
of nitrogen such as nitric oxide, nitrogen dioxide, and nitrous oxide and most VOCs (volatile organic
compounds). Common examples of secondary pollutants that contribute towards the formation of
photochemical smog include aldehydes, tropospheric ozone, and peroxyacyl nitrates (often
abbreviated to PAN).
During peak-traffic hours in the morning, large amounts of nitrogen oxides and volatile hydrocarbons
are released into the atmosphere. These pollutants can be traced to automobile emissions and
industrial discharge. Some of these hydrocarbon pollutants rapidly undergo oxidation by the hydroxyl
groups in the atmosphere, resulting in the formation of peroxy radicals. These peroxy radicals go on
to convert nitric oxide into nitrogen dioxide.

Effects of Photochemical Smog: Photochemical smog has a number of negative effects on the
environment and human beings. The chemicals contained within it, when combined with
hydrocarbons, form molecules which cause eye irritation. The atmospheric radicals interfere with the
nitrogen cycle by stopping ground level ozone from being eliminated. Ground level ozone can prove
to be extremely toxic to human beings. Other negative symptoms associated with photochemical smog
include decreased vision and shortness of breath.
Composition of photochemical smog: Nitric oxide (a nitrogen compound with the formula NO) and
nitrogen dioxide (another nitrogen compound with the chemical formula NO 2) are often produced as
a result of the burning of fossil fuels. These pollutants are also naturally released due to events such
as the eruption of volcanoes and the occurrence of forest fires. However, the vast concentration of
these pollutants in areas that are densely occupied by humans is of great concern. This is because
natural emissions tend to continue to spread over much wider areas. When it is exposed to ultraviolet
radiation, the NO2 molecule is known to undergo a complex series of hydrocarbon reactions to
produce the photochemical smog components. These components include a mixture of ozone,
aldehydes, nitric acid, peroxyacyl nitrates (abbreviation: PANs) and many other secondary pollutants.

Effects of photochemical smog: Photochemical smog is created by the interaction of sunlight with
certain atmospheric chemicals. Ozone is the principal component of air pollution of this kind. Ozone
in the stratosphere protects us from harmful ultraviolet radiation but it is detrimental to human health
when it is present on the ground level.

Photochemical smog control: The most obvious way to minimize photochemical smog levels is to
eliminate the use of fossil fuels by using non-polluting or sustainable sources of electricity, such as
nuclear power, hydropower, and wind power.

Production of PAN and Ozone: PAN is believed formed in the urban atmosphere by those
hydrocarbons which yield acetylperoxy radicals upon photooxidation. Peroxyacyl radicals react
with nitrogen oxides to form peroxyacyl nitrates. Thus a close relationship might be expected to
exist between the occurrence of the primary pollutants, nitrogen oxides and hydrocarbons, with
that of the secondary pollutants, ozone and PAN. Such a relationship is well known for the
nitrogen oxides and ozone; nitric oxide is oxidized to nitrogen dioxide leading to the formation of
ozone (3). It is not the absolute amount of nitrogen oxides which controls the abundance of ozone
but rather the ratio of the nitrogen dioxide to nitric oxide. The mechanisms of PAN formation are
quite different from those of ozone. PAN is the terminal product of a chain of free radical reactions
whereas, with ozone, the generation process is self-perpetuating. In Calgary, the primary
pollutants, nitrogen oxides, carbon monoxide, and hydrocarbons, show similar diurnal
concentration patterns the maximum concentration of each occurs at the same time on a given
day. The hydrocarbon concentrations, however, show far less variation than do the carbon
monoxide and nitrogen oxides, with sufficient hydrocarbons available at all times to participate
in the formation of peroxyacyl radicals.
In the winter months concentrations of primary pollutants are high but the intensity and duration
of solar radiation and the atmospheric temperature are low. Conversely, during the summer, solar
radiation reaches its maximum intensity and duration and temperatures are highest, but
pollutant concentrations are low. During spring and autumn months the possibility exists for the
simultaneous occurrence of high levels of pollutants together with high solar radiation and
temperatures resulting in the generation of PAN. Thus solar radiation is believed to be the limiting
factor in the formation of PAN during the winter months in Calgary (51°N) whereas the
abundance of the primary pollutants, the precursors of PAN, is the limiting factor in the summer
months.
Ozone - PAN relationships: The photochemical oxidants, PAN and ozone, are generated by related
photochemical processes, each usually reaching maximum concentrations simultaneously in the
early afternoon. comparison of the primary pollutant concentrations, with the corresponding
ozone and PAN concentrations, showed the generation of ozone and PAN after a decline in the
overall concentration of nitrogen oxides which corresponded to the conversion of NO to NOz In
some cases, however, PAN maxima occurred coincident with maximum concentrations of the
primary pollutants. On January 27, 1981, high nitrogen oxide concentrations were recorded at
the University, and the maximum PAN concentration of 2.3 ppb occurred simultaneously with a
maximum of 410 ppb nitrogen oxides, both NO and NO2 reaching a maximum at that time.

Generally only one peak in the PAN concentration occurred each day, usually during the
afternoon, but on occasion a second peak occurred later in the day. On August 28 a secondary
PAN maximum occurred at 2400 h. This would suggest either that sufficient peroxyacyl radical
existed to allow the generation of PAN to proceed after dark or that an air mass moved from the
downtown area of the city during the afternoon and returned in the evening to produce a second
PAN peak. Air moves along the river valley in Calgary in response to adiabatic heating and cooling.