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Ozone Formation

• Ozone is a molecule of oxygen (O3) that


absorbs certain wavelengths of
biologically damaging ultraviolet light.
• It is the only gas in the atmosphere that
does so and, therefore, is an essential part
of the Earth's ecological balance.
• Sidney Chapman, then a scientist at
Oxford University, was the first person to
explain the dynamics of ozone.
• In 1930, he suggested that oxygen molecules (O2) are
split by cosmic rays into two oxygen atoms.Each of these
atoms then combines with another oxygen molecule to
form ozone.
O2 + UVB → O + O
O + O2 → O3
• He also suggested, however, that the single oxygen
atoms can also destroy ozone by randomly colliding with
O3 molecules and creating two O2 molecules again..
O + O3 → O2 + O2

• Ozone absorbs UVB & converted back to free oxygen &


molecular oxygen.
O3 + UVB → O2+ O2
• The rate of ozone destruction increases with the amount
of ozone present and continues to increase until ozone is
being destroyed and created at the same rate
 Ozone found at the surface of the Earth can be
harmful to humans, plants, and animals. For
example, high ozone amounts at ground level are
known to cause respiratory problems in humans and
can lower yields of certain crops.
 Units used to measure ozone concentration :
 Dobsin unit (DU)- the principle unit for measuring ozone
concentration. One DU is about twenty-seven million
molecules per square centimeter ( the palm of your hand
covers an area of rougly a hundred square centimeters). The
ozone concentration over the US is about 300 DU and the
antarctic hole during the late spring can drop to 117 DU.
 Mixing ratios: within a specified volume, it is a fraction of
the number of molecules of a particular gas divided by the
total number of molecules in that given space. Terms of
usually abreviated, like ppmv for parts-per-million or ppbv
which is parts-per-billion . For example the concentration of
HCl at 3 km is said to be about 0.1 ppbv; this means that if
you selected a volume of air that contained 10 billion
molecules of air, one of those molecules would be an HCl
molecule
http://www.nas.nasa.gov/About/Education/Ozone/ozonelayer.html
What is UVB?

• The shorter the wavelength, the stronger the energy.


http://www.teachersdomain.org/media/po
pup/phy03_img_lpaemspect_popup.html
UVA & UVB
 It is important to distinguish between UVA & UVB.
 UVB wavelength (280-320 nanometer), UVA (320 to
400).
 UVB is more energetic → more dangerous.
 Every 1% decrease in the earths ozone shield is
projected to increases the amount of UV light exposure
to the lower atmosphere by 2%.
 Upon being absorbed by biological tissues, UV radiation
damages protein & DNA molecules at the surfaces of all
living things.
 Ozone shield >99% of UVB in stratosphere.
 The small amount (<1%) of UVB has caused all of
sunburns & > 700,000 cases of skin cancer &
precancerous ailments/year in North America
UV – health effects
• It is now predicted that 1 out of every
3 Australians (especially in
Queensland where ozone shield is
thinest) will develop serious &
perhaps fatal skin cancer in his/her
lifetime.
• 3 types of skin cancer: Basal cell
carcinoma (BCC), Squamous cell
Carcinoma (SCC) & Melanoma.
• Most skin cancer = BCC (75% to
90%), slow growth therefore
treatable.
• SCC ~ 20% of skin cancers. Can be
cured if treated early. Potentially
fatal.
• Melanoma=most deadly form.
Melanoma is often traced to
occasional sunburns during
childhood or adolescence or to
sunburns in people who normally
stay out of sun.
UVB damage to other ecosystems
 Increases in ultraviolet-B radiation (UV-B: 280-320 nm)
associated with the Antarctic ozone hole have been
shown to inhibit the photosynthesis of phytoplankton in
Southern Ocean,
 A 6-12% minimum loss in primary production was
estimated under a well-developed ozone hole. Yet long-
term measurements have shown that ozone depletion
may account for only =<3.8% loss in daily primary
production (=<0.2% loss in annually-averaged, total
primary production).
 This departure from previous predictions is largely due to
the may in part be due to the activation of biomolecular
repair and photoprotective mechanisms
 The overall effect on water column production is still a
matter of debate and continued investigation.
Ozone depleting substances (ODS)
 ODS include CFCs, HCFCs, halons, methyl bromide,
carbon tetrachloride, and methyl chloroform.
 ODS are generally very stable in the troposphere and only
degrade under intense ultraviolet light in the
stratosphere.
 When they break down, they release chlorine or bromine
atoms, which then deplete ozone.
 Ozone Depletion Potential (ODP): a number that refers to
the amount of ozone depletion caused by a substance
 The ODP is the ratio of the impact on ozone of a chemical
compared to the impact of a similar mass of CFC-11. Thus,
the ODP of CFC-11 is defined to be 1.0. Other CFCs and
HCFCs have ODPs that range from 0.01 to 1.0. The halons
have ODPs ranging up to 10. Carbon tetrachloride has an
ODP of 1.2, and methyl chloroform's ODP is 0.11. HFCs have
zero ODP because they do not contain chlorine.
 http://www.epa.gov/ozone/ods.html - classification of ODS.
• UV radiation breaks off a chlorine atom from a CFC molecule.
• The chlorine atom attacks an ozone molecule (O3), breaking it apart and
destroying the ozone
• The result is an ordinary oxygen molecule (O2 ) and a chlorine monoxide
molecule (ClO)
• The chlorine monoxide molecule (ClO) is attacked by a free oxygen atom
releasing the chlorine atom and forming an ordinary oxygen molecule (O2)
• The chlorine atom is now free to attack and destroy another ozone molecule
(O3). One chlorine atom can repeat this destructive cycle thousands of times
The Ozone Hole
• In summer, N2O & methane react with ClO (chlorine monoxide) &
chlorine to trap the chlorine (chlorine reservoirs), preventing much
ozone depletion.
• Antartic winter (June), stratosphere vortex forming.
• Cold temperature cause small amount of moisture & other chemical
present in the stratosphere to form t he SOUTH POLAR
STRATOSPHERIC CLOUDS. The
• The cloud provide surfaces (release molecule chlorine Cl2) from the
chlorine reservoir.
• After winter, sunlight in spring breaks up the clouds.
• UV light the attacks molecule chlorine, releasing free Cl & initiate Cl
cycles.
• In summer, vortex breaks down, ozone-rich air returns to Antartic.
• Ozone-poor air spread all over the southern Hemisphere.
• In 1997, Antartic ozone depletion ~15%-40% below normal & grew
to an area larger than all Europe & North America combined.
• Recent year, green-house effect → weaker vortex → less hole in
Antartic.
Montreal Protocol
• http://ozone.unep.org/Public_Information/4B_PublicInfo_Multi

Direct GWP-weighted emissions

SROC
SROCFigure
FigureTS
TS-1
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Malaysia – Ozone Treaty Status
Treaty Date of Ratification** Type*
Vienna Convention  29 Aug 1989  (Ac)
Montreal Protocol  29 Aug 1989 (Ac)
London Amendment  16 Jun 1993  (Ac)
Copenhagen Amendment  5 Aug 1993  (Ac)
Montreal Amendment  26 Oct 2001  (R)
Beijing Amendment  26 Oct 2001  (R)

 Notes:
 * R: Ratification / Ac: Accession / At: Acceptance / Ap: Approval / Sc:
Succession
 ** Entry into force (E.I.F.) is after ninety days following the date of
ratification/accession/acceptance/approval for new Parties after the
treaty enters into force.
 E.I.F. for Vienna Convention = 22.9.1988.
E.I.F. for Montreal Protocol = 1.1.1989.
E.I.F. for London Amendment = 10.8.1992.
E.I.F. for Copenhagen Amendment = 14.6.1994.
E.I.F. for Montreal Amendment = 10.11.1999.
E.I.F. for Beijing Amendment = 25.2.2002.
Recent Major Findings
Scientific Assessment of Ozone Depletion (since
1989,1991,1994, 1998 & 2002).
Numerous laboratory investigation, atmospheric
observations, theoretical & modeling studies have
been carried out.
Recent findings (2002):
In the troposphere, total combined effective abundance of
ozone-depleting compounds continues to decline slowly
from the peak at 1992-1994.
Analysis of firn air (air trapped in snow above glaciers)
have confirmed that NON-industrial sources of CFCs,
halons & major chlorocarbons were Insignificant.
The abundance of HCFCs in troposphere continue to
increase – HCFC are among the gases as transition
substitutes for CFCs, halons & chlorinated solvents.
HCFC-22 is still widely used in USA. Europe has banned
HCFC-22 since 1 Jan 2001.
Recent Major Findings- continue
Observations in stratosphere → Total chlorine
(sum of hydrogen chloride HCl & chlorine nitrate
ClONO2) is at/near peak.
Very short-lived (a few months) organic chlorine-,
bromine- & iodine-containing sources gases have
potential to deplete stratosphere ozone but hard
to quantified.
Ozone remains depleted in the midlatitudes of
both hemisphere. The global-average total
column ozone amount (1997-2001) was ~ 3%
below pre-1980 average value. No significant
trends in total column ozone in the tropics (25ºN -
25ºS).
Recent Major Findings- continue

7. A future Artic polar ozone hole similar to the


Antartic appears UNLIKELY.
8. Ozone recovery is expected to linked MAINLY
to decreasing chlorine & bromine loading.
Stratospheric cooling (due mainly to projected
CO2 increase) is predicted to enhance future
ozone increase in the upper stratosphere.
9. Projected increase of other greenhouse gas
(methane & nitrous oxide N2 O) are predicted
to have small chemical effects on the ozone
recovery.
Recovery
• Production of CFCs was banned under the
1987 Montreal Protocol. But some linger on
in old refrigerators, fire extinguishers, air-
conditioning systems and other equipment
up till todate.
• The Antarctic ozone hole will probably take
longer (2065) to heal than was previously
thought (2050).
• Measurements of CFC emissions, taken by
low-flying aeroplanes over the United
States and Canada, suggest that more of
the chemicals are still around than
previously expected The seasonal
• For instance, in 2003 developed nations ozone hole that
still accounted for almost half of the global developed over
emissions of CFCs, even though the Antarctica this
chemicals had been banned more than a year (2005) is
decade earlier
slightly smaller
• The Arctic ozone hole (smaller than the
Antarctic one), could recover by as early as than in
2030, previous years.
© NASA
Other new findings
• New NASA-funded research confirms an old theory that plankton
can indirectly create clouds that block some of the Sun's harmful
rays.
• When plankton are UV-stressed, they try to protect themselves by
producing a compound called dimethylsulfoniopropionate (DMSP).
• Some scientists believe DMSP helps strengthen the plankton's cell
walls.
• DMSP gets broken down in the water by bacteria, and it changes
into another substance called dimethylsulfide (DMS).
• DMS then filters from the ocean into the air, where it reacts with
oxygen, to form different sulfur compounds.
• Sulfur in the DMS sticks together in the air and creates aerosols for
water to condense on → clouds are formed.
• So, indirectly, plankton help create more clouds, and more clouds
mean less direct light reaches the ocean surface.
• This relieves the stress put on plankton by the Sun's harmful UV
rays.