ADVISOR:

Prof. Dariuosh Mola

Author:

Seyednurolah Hajhoseini

Changes in
Stratospheric Ozone
13 Changes in Stratospheric Ozone :

The changes occurring in the stratosphere’s protective layer of ozone are closely linked to the
greenhouse problem just discussed. Many of the same gases are involved, including CFCs, halons,
methane, and nitrous oxide, as well as aerosols and ozone itself. Some of the gases that enhance the
greenhouse effect, such as methane, actually reduce stratospheric ozone depletion, so the two problems
really must be considered together.

Ozone has the unusual characteristic of being beneficial when it is in the stratosphere protecting us
from exposure to ultraviolet radiation, while ozone formed near the ground in photochemical smog
reactions is harmful to humans and other living things.

Ozone Column Distributions By Altitude :

If all of the atmospheric ozone overhead at any given spot on the Earth were to be brought down to
ground level so that it would be subjected to 1 atm of pressure, it would form a layer only a few
millimeters thick. In fact, one of the common methods of expressing the total amount of ozone overhead
is in terms of Dobson units (DU).

1 DU = a layer of ozone 0.01 mm thick at 1 atm of pressure at 0°C. At midlatitudes, the ozone overhead
is typically about 350 DU (3.5 mm at 1 atm); near the equator, it is closer to 250 DU. During the annual
appearance of the ozone hole over Antarctica, the ozone column drops below 100 DU.

The Ultraviolet (UV) Portion of the Solar Spectrum

Ozone (o 3) is continuously being created in the stratosphere by photochemical reactions powered by

short wavelength ultraviolet (UV) radiation, while at the same time it is continuously being removed by
other photochemical reactions that convert it back to diatomic oxygen molecules (o 2) . The rates of
creation and removal at any given time and location dictate the concentrations of ozone present.

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 The energy required to drive some of these photochemical reactions comes from sunlight penetrating the
atmosphere. it is convenient to consider such electromagnetic radiation in some contexts as a wave phenomenon and
in others as a packet of energy called a photon.
The energy content of a single photon is the proportional to its frequency, and inversely proportional to its
wavelength:

where

λ = wavelength (m)
v = frequency (s-1)
c = the speed of light (2.997925 * 108 m/s)
h = Planck’s constant (6.626218 * 10-34 J s)
E = the energy of one photon (J)

photons with shorter wavelengths have higher energy content.

In the context of stratospheric ozone depletion ,only the UV portion of the spectrum that is of interest. Photons
associated with those shorter wavelengths can have sufficient energy to break apart molecules, initiating
photochemical reactions. Molecules that are dissociated by UV light are said to have undergone photolysis. The
energy required to drive photochemical reactions is often expressed as an amount of energy per mole of gas under
standard conditions. If we assume the energy required under stratospheric conditions is not much different, we can
easily derive the maximum wavelength that a photon must have to cause photolysis. A single photon (with sufficient
energy) can cause photolysis in one molecule. And since there are Avogadro’s number of molecules in one mole of
gas, we can convert energy needed per mole into the energy that one photon must have, as follows:

Now we can use (47) to solve for the wavelength.

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 The most important wavelength in the context of stratospheric ozone depletion are in the 100 to 400 nm portion
of the ultraviolet (UV) spectrum. It is called ultraviolet since wavelengths just above 400 nm are violet in color and
visible to the human eye.
The wavelengths above 700 are called infrared, since 700 nm is the edge of the red portion of the visible spectrum .

About 99 percent of the incoming solar UV that makes it through the atmosphere is UV-A (320 to 400 nm). It is
sometimes referred to as “black light” since it is invisible to the human eye, though some animals can use it for
vision.

UV-A
Hazardous:
1. penetrates deeply into human skin
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2. causing tanning (but little skin reddening)

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3. DNA damage
4. photoaging (toughening of the skin, wrinkles)
5. possibly skin cancer
Benefit: Some exposure to UV-A benefits human health by helping to induce the formation of vitamin D.

UV-B
Hazardous :
1. UV-B radiation (280–320 nm) poses the greatest danger to human health.
2. reddening of the skin (erythema)
3. reduction of vitamin-D synthesis in the short term
4. in the long term
a) cause of skin cancer
b) cataracts
c) suppression of the immune system

UV-C
Hazardous
1. Photons within the UV-C portion of the spectrum (100 to 280 nm) readily destroy DNA
which makes them extremely dangerous

Benefit:
artificially created UV-C be used as a very effective disinfectant for water treatment and other germicidal
applications.

The Ozone Layer as a Protective Shield

Ozone formation in the stratosphere can be described by the following pair of reactions.
In the first, atomic oxygen (O) is formed by the photolytic decomposition of diatomic oxygen (o 2) .

hν = A photon
For this dissociation to take place, the photon must have a wavelength of no more than 242 nanometers. Photons
with less energy (longer wavelengths) cannot cause the reaction to take place; all they can do is heat up the molecule
that absorbs them. Photons with higher energy (Shorter wavelengths) than the minimum required use some of their
energy to cause photolysis, and what is left over is dissipated as heat.
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Diatomic oxygen has its maximum absorption at about 140 nm, and it is a very effective absorber of UV-C radiation
between 130 and 180 nm. The atomic oxygen formed by (49) reacts rapidly with diatomic oxygen to form Ozone:
where M represents a third body (usually a nearby molecule) needed to carry away the heat generated in the
reaction. Opposing the preceding ozone formation process is ozone removal by photodissociation:

The absorptance of ozone extends from about 200 to 320 nm and reaches its peak at 255 nm. The reaction shown in
(51) is very effective in removing UV-C radiation and some of the UV-B before it reaches the Earth’s surface. The
preceding combination of reactions (49 to 51) forms a chain in which oxygen atoms are constantly being shuttled
back and forth between the various molecular forms.

Effects of extended Ozone absorption reactions :

1. The absorption and removing most of the short-wavelength (potentially damaging) UV radiation as it tries
to pass through the stratosphere.
2. Heats the stratosphere, causing the temperature inversion, which is what defines the stratosphere, produces
stable atmospheric conditions that lead to long residence times for stratospheric pollutants.

The radiation reaching the Earth’s surface is rapidly reduced for wavelengths less than about 320 nm.
An intact ozone layer shields us from almost all of the UV having wavelengths shorter than about 290 nm.
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Catalytic Destruction of Stratospheric Ozone
The natural formation and destruction of ozone in the stratosphere is being affected by gases that we release into the
atmosphere. In particular, ozone destruction is enhanced by catalytic reactions that can be represented as follows:

X = free radical (Cl, Br, H, OH, or NO) .

The net result destruction of one ozone molecule.
The original catalyst may go on to destroy thousands more ozone molecules before it eventually leaves the
stratosphere.

Characteristics of Chlorofluorocarbons (CFCs) :

-The major source of ozone-destroying chlorine (Cl)
- CFCs have long atmospheric lifetimes because they are inert and non-water-soluble so they aren’t removed in the
troposphere by chemical reactions or rainfall.
- CFCs drift into the stratosphere, where they are exposed to UV radiation, which breaks apart the molecules, freeing
the chlorine.
-CFCs typically require photons in the UV-C range with wavelengths shorter than 220 nm for photolysis.

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CFCs Photolysis:

1. Eventually the second chlorine atom is also released. The freed chlorine then acts as a catalyst as described
by (52):

The chlorine atom makes this loop tens of thousands of times, but eventually it reacts with methane (which is a
potent greenhouse gas ) to become water soluble HCl that can diffuse into the troposphere, where it can be washed
out of the atmosphere by rainfall.

Chlorine that has been incorporated into HCl is inactive; that is, it does not participate in the catalytic
destruction of ozone represented.

In the context of climate change, methane is part of the problem; in the context of ozone depletion,
it is part of the cure.

2. Another way that chlorine is removed from the catalytic chain reaction is by its incorporation into chlorine
nitrate:

%99 of the chlorine in the stratosphere is tied up in these inactive molecules, HCl and ClONO2.
Unfortunately, those inactive molecules are subject to chemical reactions and photolysis that can restore the
chlorine to its active forms, Cl and ClO , especially when there are nearby particles available that provide
platforms upon which the reactions can take place :
-Sulfate aerosols, especially from volcanic eruptions
-clouds of nitric acid ice over the Antarctic
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Bromine Photolysis:
Br in the stratosphere is another potent ozone-depleting gas, as the following reactions suggest:

bromine acts as a catalyst destroying ozone until it eventually combines with methane to form hydrogen bromide
(HBr). Hydrogen bromide deactivates the bromine, but not for long. Photolysis rather quickly decomposes HBr,
sending bromine back into its catalytic loop with ozone.

Potentiality: Br >> Cl Number of stratospheric inactive form: HCl And ClON o2 >> HBr

Bromine Sources:
The main source of bromine in the stratosphere is methyl bromide C H 3 Br :
-50% comes from the oceans
-50% is due to anthropogenic sources:
1. in agriculture to sterilize soil and fumigate some crops after they are harvested
2. biomass burning
3. automobile exhaust emissions when leaded fuels
4. using as a flame retardant in fire extinguishers

The Antarctic Ozone Hole

 Chlorine that has been incorporated into hydrogen chloride (HCl) or chlorine nitrate ( ClON o2 ¿ is
inactive, so it doesn’t contribute to the destruction of ozone. In the Antarctic winter, however, a unique
atmospheric condition known as the polar vortex traps air above the pole and creates conditions that
eventually allow the chlorine to be activated.

Polar Vortex:
 The polar vortex consists of a whirling mass of extremely cold air that forms over the South Pole during the
period of total darkness in the Antarctic winter and effectively isolates the air above the pole from the rest
of the atmosphere until the Antarctic spring arrives in September.
Stratospheric temperatures ≤−90 0 c form polar stratospheric clouds (PSCs)

Reactions on the surfaces of polar PSCs particles formation of chlorine gas (c l 2).
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For example,

Once the sun rises in the Antarctic spring in September, the chlorine gas (c l 2) formed during the darkness of winter
photolytically decomposes into atomic chlorine:

which then destroys ozone by reinitiating the catalytic destruction :

The destruction of ozone as the sun first appears in the Antarctic spring proceeds until the nitric acid ( HN O 3 )

formed in (58) and (60) photolyzes and forms inactive chlorine nitrate ( ClON o2), which stops the ozone
destruction process.

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Monthly mean total ozone columns over the Northern Hemisphere in March 1997 (a), 2011 (b), and 2020 (c) and the Southern
Hemisphere in October 2016 (d) and 2019 (e).

There is concern that greenhouse effect enhancement could lead to stratospheric cooling, which would make an
Arctic ozone hole more likely.
Ozone Depletion Potential (ODPs)
The ODP of a gas is defined as the change in total ozone per unit mass emission of the gas, relative to the change
in total ozone per unit mass emission of CFC-11.

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Causes of Ozone Layer Depletion
1. Chlorofluorocarbon
2. Nitrogenous Compounds
3. Unregulated Rocket Launches
4. Natural Causes

Impacts of Increased Exposure to UV

action spectrum: The action spectrum provides a quantitative way to express the relative ability of various
wavelengths to cause biological harm.

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 - All of these spectra show increasing damage as wavelength decreases, and they all show significant damage in
the UV-B (280 to 320 nm) region.
-The biologically weighted irradiance shows the critical wavelengths in terms of biological damage between
about 290 and 310 nm (UV-B).
- Shorter wavelengths are effectively blocked by the remaining ozone layer, while longer wavelengths do little
biological damage.
Do Sunscreens Really Work?
Sunscreens that block UV-B, but not UV-A, can give a false sense of security by allowing people to spend more
time exposed to the sun without burning, but skin damage that may lead to skin cancer is occurring nonetheless.

Most of our concern for increasing exposure to UV radiation has focused on the increased probability of
developing skin cancer.

- At lower latitudes, there is more surface-level UV-B, and skin cancer rates increase proportionately. Using such
data, it has been estimated that a 1 percent increase in UV-B is estimated to cause a 0.5 percent increase in the
incidence rate of melanoma and a 2.5 percent increase in nonmelanoma (Armstrong, 1993).
Both types of skin cancer are more prevalent among people with fair complexion than among individuals who have
more of the protective pigment, melanin.
Nonmelanoma is most likely to occur on areas of the skin habitually receiving greatest exposure to the sun,
such as the head and neck.

Melanomas are as common on intermittently exposed parts of the body, such as the trunk and legs, as they
are on the head and neck. Melanomas seem to occur more frequently on individuals who have had severe and
repeated sunburns in childhood. The last observation has led to a hypothesis that melanoma is less related to the
accumulated dose of radiation, as seems to be the case for nonmelanoma, than it is to the pattern of exposure.
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 To help alert the public to the dangers of UV exposure, various versions of a simple index have been created. A
UV-index is a nondimensional, single number, in the range of 0 to 12, that represents an erythemal-weighted
irradiance expected at solar noon (when the sun is at its highest) for the following day.

Political Response to the Ozone Depletion Problem

The political response to warnings of ozone depletion by the scientific community has been unusually effective and
timely. When CFCs were first created in the 1930s they were hailed as wonder chemicals. They replaced toxic,
explosive, and unstable refrigerants and made possible the refrigeration and air conditioning luxuries that we now
take for granted.
A British scientist, James E. Lovelock (later famous for the “Gaia”), began experimenting with CFCs in the
1970s and concluded in 1973 that essentially all of the CFCs ever produced were still in the atmosphere. The first
hint of potential problems came with the publication of Molina and Rowland’s paper in 1974, which warned of the
danger to the stratospheric ozone layer that CFCs presented.
In 1987 an international meeting convened in Montreal that led to the signing of the Montreal Protocol on
Substances that Deplete the Ozone Layer. That Protocol called for a 50 percent reduction in use of CFCs by 1999.
The next year, 1991, Mt. Pinatubo erupted, and the ozone hole grew to record proportions, which led to the
London Amendments to the Protocol in 1992. The phase-out of CFCs was moved up to 1996.
Meanwhile, in the United States, Title VI of the Clean Air Act Amendments of 1990 brought us into
compliance with the London Amendment. Major provisions include the following:

• Two categories of ozone-depleting substances (ODS) were created:

1. Class I chemicals are those with high ozone depletion potentials, which includes CFCs, halons, and carbon
tetrachloride
2. Class II substances have lower ODPs and include the HCFCs.

• Motor vehicle air conditioners received special attention since they had been the largest single source
of CFCs.
• Nonessential products that use ozone-depleting substances such as noise horns, “silly string,” and some
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commercial photographic equipment, are banned.

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• Warning labels are required for products that contain ODS such as refrigerators and foam insulation.
In 1992 production and imports of halons ceased in 1994, and CFCs, methyl chloroform (1,1,1-trichloroethane), and
carbon tetrachloride ceased in 1996. Most HCFCs were eliminated by 2003, but some will still be allowed until
2030.

Ozone Layer Recovery:

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