Earth Hour Special

Stratospheric ozone acts as a shield, which protects the Earth's surface from the sun's ultraviolet
radiation. Hence a decrease in stratospheric ozone will result in an increase in UV-B radiation, which will
have negative impacts on human health such as suppressed immune system, serious sunburn,
cataracts, reduced vitamin D synthesis, skin cancer and will also inhibit photosynthesis in plants.
However, ozone being toxic to the living system, elevated tropospheric ozone is associated with
persistent decrease in lung function, pneumonia, influenza, asthma and decrease in crop yield apart from
increase in air temperature, as it is a green house gas.


Earths Atmosphere

Atmosphere is the medium for life on the surface of the planet and is the1 transition zone
between Earth and Space. It comprises of a mixture of gases exposed to the electromagnetic
spectrum of the sun. The atmosphere does not have a well defined outer boundary, but its density
decreases progressively with altitude and ultimately merges with the space environment. The
atmosphere can be divided into different regions on the basis of temperature profile. In the lowermost
region from the ground to about 15 km (~17 km at the tropics), it is found that the temperature
decreases with height. This region is called the Troposphere. The height at which this temperature
reaches a minimum is called Tropopause, signifying the end of Troposphere. The region above the
Tropopause from 15 to 55 km is called the Stratosphere. Here the temperature increases with height.
Heating of this region is caused by the absorption of ultraviolet radiation from the Sun by ozone.
Stratopause signifies the end of Stratosphere.

Atmospheric Ozone

Ozone is a relatively unstable molecule found in the Earth's atmosphere, which is made up
of three atoms of oxygen and constitutes a tiny fraction of the atmosphere (approx. 3 molecules of
ozone for every 10 million air molecules). One of the most important constituents in the stratosphere
is ozone, because it is the only atmospheric species that effectively absorbs ultraviolet solar radiation
from 200 to 300 nm, thus protecting plant and animal life from exposure to harmful radiation.
About 90% of ozone is found in the stratosphere and the remaining 10% in the troposphere.
The only process known to produce a significant amount of ozone in the stratosphere is the photolysis
of molecular oxygen by ultraviolet radiation followed by recombination of atomic oxygen with
molecular oxygen. The band dissociation energy of oxygen is 5.1 eV, which corresponds to a
wavelength of 242.4 nm.
Atmospheric ozone is continuously destroyed by the action of ultraviolet, visible and near
infrared radiation. The threshold for ozone dissociation is 1.1 eV corresponding to a wavelength of
1180 nm. Hence ozone dissociation can take place at all levels in the atmosphere right down to the
surface. In the troposphere, ozone is produced photo chemically through the standard OH - CO NO
reaction. The amount of ozone in the atmosphere depends on a balance between processes that

create ozone and those that destroy it. An upset in the ozone balance can have serious consequences
for life on the Earth. Absorption of sunlight by ozone in the ultraviolet wavelength range is responsible
for stratospheric heating, and determines the temperature structure of the middle atmosphere.
Changes in middle atmospheric ozone concentrations result in an altered radiative input to the
troposphere and to the Earths surface, with implications on the energy balance and the chemical
composition of the lower atmosphere. Thus there is a great need to monitor the atmospheric ozone
concentration.


Figure 1: Vertical ozone profile. Figure 2: Depth of penetration of the solar
UV irradiance (incident on the top of the Earth's
atmosphere), as allowed by the ozone layer.

Two factors, which are necessary for the production of stratospheric ozone, are presence of
molecular oxygen and intensity of solar UV irradiation with wavelength < 240 nm. At high altitudes
the solar intensity is high but the concentration of oxygen molecules is low. At low altitudes, there are
plenty of oxygen molecules but less radiation to dissociate it. Somewhere in between a compromise is
reached between the two factors, which maximizes the production of ozone at around 25 30 km
altitude. The formation of ozone layer in this manner was first explained by Chapman.



Figure 3: Production and destruction of ozone



The total columnar ozone concentration in the atmosphere is expressed in Dobson Units
(DU). 1 DU is about 2.7 x 10
16
molecules/cm
2
. The total columnar ozone concentration is least (250
DU) at the tropics where it is produced and highest (400 460 DU) at the poles to where it is
transported by the stratospheric circulation known as the Brewer-Dobson circulation. Surface ozone
levels from 120 to 200 parts per billion by volume (ppbv) or more are harmful to human beings. The
ambient air quality standards formulated and adopted by the United States Environment Protection
Agency for ozone is 120 ppbv for 1-hour average and 80 ppbv for 8-hour average.

Environmental issues associated with ozone

The dual role of ozone leads to two important environmental issues. Importance of
monitoring of stratospheric ozone levels on a global basis has increased, in view of the findings of
Molina and Rowland in 1974, that substances called chlorofluorocarbons (CFCs), which are used
extensively in refrigerators, as propellants in aerosol spray cans, in foam manufacture and in solvents
could play a major role in the destruction of stratospheric ozone, and it gave rise to the possibility of a
long term global ozone depletion. Its possible impact on the biosphere put ozone on the center stage
of atmospheric research over the next few decades.



Figure 4: Destruction of stratospheric ozone by CFCs




The discovery of the Antarctic ozone hole in the mid eighties by Farman, Gardiner and
Shanklin, highlighted the gravity of the problem. Every year about 60% of the total amount of
overhead ozone gets depleted over some parts of Antarctica during spring time (August - November).
This is because the winters in Antarctic regions are extremely cold, which leads to the formation of
polar stratospheric clouds (PSCs). Chemical reactions which normally do not occur in the gas phase
occur on the surface of PSCs. These reactions convert inactive forms of chlorine that do not affect
ozone into reactive chlorine species, which can easily get dissociated into chlorine radicals and
catalytically destroy ozone in the presence of weak sunlight during spring time. These reactions are so
fast that a major part of the ozone content over Antarctica between 12 and 20 km is destroyed within
few weeks during spring. The main factors affecting the Antarctic ozone loss are high chlorine and
bromine levels, extremely low temperature during winter, and relative isolation of the polar region
from the mid latitudes by a strong circumpolar wind belt called polar vortex, which restricts the ozone
rich air from the mid latitudes from mixing with the air inside the polar region where ozone loss has
taken place. The vortex in the Antarctic region is stronger, develops lower temperature and persists
longer than the Artic vortex. Therefore the ozone depletion is higher in Antarctic compared to Artic
region.



Figure 5: Ozone abundances in the Antarctic (South Pole) and Artic (North Pole) regions.

The low ozone amount observed over the Antarctic continent from the ground-based
balloon and spectrometer measurements were further validated by NASA's Total Ozone Mapping
Spectrometer (TOMS) on board the Nimbus-7 satellite. These studies led to the United Nations
Environment Programme (UNEP) initiative to protect the ozone layer and a protocol outlining proposed
protective actions followed. The Montreal Protocol, signed in September 1987, was a benchmark treaty
calling for a 50% reduction in CFC production by 2000, and an eventual complete phase-out of ozone-
depleting chemicals. The United States ratified the Montreal Protocol in 1988. The implementation of

Montreal Protocol entered into force in January 1989. A total of 193 nations including India, have since
become parties to the treaty as of June 25, 2008. The Montreal Protocol is widely regarded as one of
the most successful and effective environmental treaties in existence because of its strict targets and
enforcement mechanisms. The concern about elevated tropospheric ozone, which is a key component
of photochemical "smog," and is observed not only in industrial areas and cities but also in rural areas,
is equally alarming.

Monitoring of atmospheric ozone

There have been significant changes and improvements in the techniques for ozone
measurements since the last few years. Measurement of ozone from satellite platforms, balloon, lidar,
aircraft and ground based platforms involve remote sensing techniques. Vertical profiles of
stratospheric ozone can be obtained with electrochemical sonde by sending balloon borne sensors into
the stratosphere and making direct measurements. In situ surface ozone is measured by
electrochemical method. Dobson Spectrophotometer, Brewer spectrometer and MICROTOPS Sun
photometer are ground-based instruments, which are widely used for measuring the total ozone
content in the atmosphere. A number of remote sensing instruments such as Upper Atmosphere
Research Satellite (UARS), Stratospheric Aerosol and Gas Experiment (SAGE), Solar Back Scatter
Ultraviolet technique (SBUV), Total Ozone Mapping Spectrometer (TOMS), Ozone Monitoring
Instrument (OMI), Microwave Limb Sounder (MLS) aboard NASA's satellites and Global Ozone
Monitoring Experiment (GOME) aboard the ERS-2 (European Remote Sensing) satellite help
researchers to monitor the chemical make-up of the atmosphere. Ever since the discovery of the
ozone hole in 1985, NASA's Total Ozone Mapping Spectrometers on board the Nimbus-7 satellite (from
1978 to 1993), Meteor - 3 satellite (from 1991 - 1994), Advanced Earth-Observing Satellite (from
1996 - 1997) and Earth Probe satellite (from 1996 - 2005) have been key instruments for monitoring
ozone levels throughout the globe. However the limitations in using satellite data is that, it is difficult
to precisely calibrate such instruments. Comparison with the in situ ground-based measurements
provides a check on the accuracy of the satellite measurements and gives a better understanding of
the atmospheric chemistry through computer models.

Variations in atmospheric ozone

Total ozone content (TOC) in the atmosphere exhibits high natural variability in both
space and time. TOC variability at a particular location is strongly influenced by the movement of air
from one region to another. Thus, ozone exhibits temporal variability over hourly, diurnal, synoptic
(35 days), weekly, seasonal, and long-term (520 years) timescales. Variation in atmospheric ozone
content may be due to :
1.Diurnal variation: The variation in ozone content in the upper stratosphere (above 40 km) occurs
with the daily rising and setting of the sun. The diurnal variation indicates a rapid decay at sunrise,
followed by a daytime minimum and a rapid rise at sunset due to recombination of atomic oxygen
forming ozone. The photo dissociation processes within the odd oxygen family governs this daily ozone
cycle. Unlike the diurnal pattern in the upper stratosphere, the diurnal pattern of surface and total
ozone in a typical urban location is low at sunrise; increases to a maximum in the afternoon and
thereafter decreases in the evening. This observed pattern is due to increase in solar radiation from
morning to afternoon hours causing corresponding increase in ozone by photochemical formation. The
NO
X
family mainly governs these small diurnal variations in ozone.
2. Seasonal variability: The annual or seasonal cycle exhibits a general pattern that repeats every
year.
3. Latitudinal variation: The columnar ozone concentration increases with increasing latitude.
4. Transport of air from one region to another due to the effect of weather disturbances, winds and
jet streams.
5. El Nio southern oscillation (ENSO): The El Nio current arises as the ocean and atmosphere
interact to balance earths thermal energy. Normally, the waters of the eastern Pacific Ocean near
South America are quiet cool as a result of upwelling ocean currents. However in an El Nio period,
the Walker Cell (trade winds) weakens, allowing the warmer waters of the western pacific to migrate
eastwards. This change in temperature of the sea surface water causes large-scale shifts in the global
circulation patterns in the troposphere and the lower stratosphere, which in turn affects the transport
of ozone in these regions.
6. Quasi-Biennial Oscillation (QBO): The QBO is an oscillation in the average zonal winds in the
tropical stratosphere. Roughly every 27 to 30 months, the tropical stratospheric winds are observed to
shift from westerly to easterly and then back again. This circulation enters the lower stratosphere in
the tropics and leaves the middle stratosphere in the extra tropics. Air masses having different ozone
concentration are transported between the two latitude regions. This induced (latitude / altitude)
meridional circulation moves ozone poor air into the tropics and ozone rich air out of the tropics during
one phase of QBO and then reverses this process during the other. Ozone in the tropics thus
decreases and then increases as we go through the QBO cycle.
7. Solar ultraviolet variations: The output of solar UV radiation is influenced by magnetically active
regions (sun spots) on the sun. The period when sunspot activity is at its greatest during the 11 year
cycle, is a solar maximum, while the period when sunspot activity is at its least is a solar minimum.
The modulations in the solar UV output have a direct effect on ozone photochemistry and even column
amount of ozone. The production rate of ozone is high when solar activity is at its maximum and it
decreases during solar minimum. Moreover, during solar minimum condition, there is an increase in
low energy cosmic rays in the earths atmosphere, resulting in an increase in NO
x
and decrease in
ozone.
8. Solar storms: Solar storms lead to the ejection of large amount of high-energy protons which
penetrate the earths magnetic field near the poles. These protons penetrate into the atmosphere
causing ionization of air molecules. As the ionized particles recombine, they produce nitrogen and
hydrogen oxides, which can affect ozone through the NO
X
and HO
X
catalytic cycles. These effects are
short lived because the hydrogen oxides, which cause the primary ozone loss, recombine within hours.
The effect of NO
X
can persist for several months.
9. Lightning: Lightning is an important elevated source of NO
X
. The total amount of NO
X
produced by
lightning is proportional to the lightning flash frequency. This increases ozone production potential at
high altitudes.
10. Volcanic eruption: Volcanic eruptions are potential sources of SO
2
, HCl and H
2
O in the lower
stratosphere. SO
2
in the stratosphere gets converted into H
2
SO
4
and condenses into small aerosol
particles, which provide an increased scope for heterophase chemistry and enhanced ozone depletion.

11. Possible effect of earthquakes: Observed increase in ozone concentration following strong
earthquakes having large magnitude and shallow depth of focus during winter is believed to be mainly
due to the effect of dynamical disturbances and transport processes. The ozone concentration is
normally observed to be low on the day of earthquake, increases gradually after the earthquake,
reaching a maximum within 3 to 11 days and thereafter decreases to its normal value.
12. Catalysts: A catalyst is a substance that facilitates a chemical reaction, but which itself remains
unchanged by the end of the reaction, so that it can take part in a similar reaction again. In the
catalytic process, the ozone molecule is lost while the catalyst (CFCs, chlorine, nitrogen, bromine or
hydrogen) is reformed to potentially destroy another ozone molecule.
13. Forest emissions: Plants emit isoprene (C
5
H
8
) and monoterpene (C
10
H
16
), through their leaves
and needles, in response to stress such as drought, mechanical disturbances such as rain and also
during normal growth. These hydrocarbons emitted from forests react with NO
x
produced from
automobile exhausts and factory byproducts transported from the cities, to produce tropospheric
ozone, which is a pollutant and green house gas.
14. Aircraft emissions: The subsonic aircraft fleet adds NO
X
to the lower most stratosphere, where
large-scale dynamics tend to prevent advection to higher altitudes. The net ozone production rate
increases rapidly with NO
X
until a maximum is reached. At NO
X
concentration > 500 parts per trillion
by volume (pptv), the net rate of ozone production is expected to decrease with increasing NO
X.

Depending on the background concentration of NO
X
, addition of NO
X
from aviation can increase or
decrease the net ozone production rate.
15. Nuclear Testing: During atmospheric testing of nuclear bombs, the temperature within the
fireball of a nuclear explosion is sufficient to convert atmospheric nitrogen and oxygen into nitrogen
oxides.The fireball can then reach the middle stratosphere and deposit the nitrogen oxides, which
could participate in catalytic ozone destruction.
16. Automobile exhaust: Nitrogen oxides and hydrocarbons present in automobile exhaust combine
in the presence of sunlight to produce tropospheric ozone.
17. Emission from fire works: In addition to emitting light in the visible region, flammable
materials present in fireworks emit radiation in the ultraviolet region at high temperature.
Consequences of this are, that the high energy UV radiation are absorbed by molecular oxygen
present in the air, resulting in the splitting of molecular oxygen into atomic oxygen, which in turn
reacts with molecular oxygen to produce ozone.
18. Possible effect of emission from coal fires: When a coal seam is exposed to favorable
conditions (temperature, moisture, oxygen etc.) it ignites spontaneously at low temperature and
continues to burn for tens to hundreds of years, depending primarily on the availability of coal and
oxygen. The smoke plume from these coal fires contain gases such as methane, oxides and dioxides
of carbon, nitrogen and sulphur, some of which act as precursors of tropospheric ozone. Moreover,
when these gases are released into the air, they gradually infiltrate all parts of the atmosphere,
including the stratosphere, where they are broken down by the high levels of solar UV radiation,
freeing extremely reactive NO and OH, which may take part in a complex series of reactions, leading
to stratospheric ozone depletion. Sulphur dioxide is rapidly converted into sulphuric acid aerosol,
increasing the rate of ozone depletion.


Ozone scenario in India

In India, ozone is being monitored since past several years at India Meteorological
Department, a number of research institutes and universities across the country, which include
measurements of total ozone with Dobson and Brewer Spectrometer as well as profiles of ozone from
ozonesonde and surface ozone using electrochemical method. There have also been a number of
major campaigns like INDOEX (Indian Ocean Experiment) and BOBMEX (Bay of Bengal Monsoon
Experiment), which provide insights of seasonal changes in ozone. These measurements show that
although the total ozone content has not changed significantly over the past three decades, there has
been a small reduction in stratospheric ozone and substantial increase in tropospheric (surface) ozone.
Unlike the places located at higher and middle latitudes, where severe ozone depletion has been
reported, the total ozone and stratospheric ozone content in India from satellite measurements show a
negligible decreasing trend from 1979 2005. Thus it is noteworthy to observe that the problem of
ozone depletion is not so alarming in India.

Acknowledgment: The images presented in this article were created by NASA and NOAA and have
been taken from their websites.

Suggested Readings

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[3] Crutzen, P. J., Photochemical reactions initiated by and influencing ozone in unpolluted
tropospheric air. Tellus, 26, 4757, 1974.
[4] Farman, J. C., Gardiner, B. G., and Shanklin, J. D., Large losses of total ozone in Antarctica
reveals seasonal CLO
X
/ NO
X
interactions. Nature, 315, 207 210, 1985.
[5] Ganguly, N. D., Ranjan, R., Joshi, H. P., and Iyer, K. N., Diurnal and seasonal variation of
ozone at Rajkot. Indian Journal of Radio and Space Physics. 35 (3), 181 186, 2006.
[6] Ganguly, N. D., and Iyer, K. N., Long term trend in ozone and erythemal UV at Indian latitudes.
Journal of Atmospheric chemistry, 55 (3), 227 239, 2006.
[7] Ganguly, N. D., Trend of tropospheric ozone in Indian forests from 1980 - 2000. Current
Science, 93 (12), 1835 1839, 2007
[8] Ganguly, N. D., Low level of stratospheric ozone near the Jharia coal field in India, Journal of
Earth System Sciences, 117 (1), 79 82, 2008
[9] Ganguly, N. D., Variation in atmospheric ozone concentration following strong earthquakes.
International Journal of Remote Sensing, 30 (2), 349356, 2009
[10] Mandal, T. K., Beig, G., and Mitra, A. P., Ozone and UV scenario over India. Scientific Report
no.22, Center on Global change, NPL, New Delhi, 2004.

[11] Molina, M. J., and Rowland, F. S., Stratospheric sinks for chlorofluromethanes. Nature,
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[12] Niemeier, U., Granier, C., Kornblueh, L., Walters, S., and Brasseur, G. P., Global impact of
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[13] Prakash, A., Remote sensing - GIS based Geoenvironmental studies in Jharia Coalfield, India,
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India, 194, 1996
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http://pubweb.bnl.gov/users/xujun/www/99post/ch2.htm.
[17] The Stratospheric Ozone Electronic Textbook http://hyperion.gsfc.nasa.gov/
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Dr. Nandita Ganguly is currently a lecturer of Physics at St.Xaviers College,
Ahmedabad. She completed her M.Sc. and M. Phil in Physics from Gujarat
University, Ahmedabad and Ph.D. in Atmospheric Sciences from Saurashtra
University, Rajkot under the guidance of Prof. K. N. Iyer. Her research interests
include the study of atmospheric ozone, aerosols and related fields. She has several
papers in National and International Journals to her credit and is a Fellow of the
Society of Earth Scientists.
Email: ganguly.nandita@gmail.com