Stratospheric photolysis

Stratosphere definition: The region of the atmosphere above the troposphere and
below the mesosphere extending upward from the tropopause to about 30 miles (50 km) above the earth, characterized by little vertical change in temperature and contain ozone layer is called stratosphere.

Photolysis in atmosphere: Photolysis also occurs in the atmosphere as part of a

series of reactions by which primary pollutants such as hydrocarbons and nitrogen oxides react to form secondary pollutants such asperoxyacyl nitrates. This all is causing ozone depletion.

Ozone layer: The ozone layer is a layer in Earth's atmosphere containing relatively
high concentrations of ozone (O3). However, "relatively high," in the case of ozone, is still very small with regard to ordinary oxygen, and is less than ten parts per million, with the average ozone concentration in Earth's atmosphere being only about 0.6 parts per million. The ozone layer is mainly found in the lower portion of the stratosphere from approximately 20 to 30 kilometers (12 to 19 mi) above Earth, though the thickness varies seasonally and geographically. Its function is to filter the dangerous ultra-violet rays. ozone depletion and ozone hole: Each spring in the stratosphere over Antarctica (Spring in the southern hemisphere is from September through November.), atmospheric ozone is rapidly destroyed by chemical processes. As winter arrives, a vortex of winds develops around the pole and isolates the polar stratosphere. When temperatures drop below -78C (-109F), thin clouds form of ice, nitric acid, and sulphuric acid mixtures. Chemical reactions on the surfaces of ice crystals in the clouds release active forms of CFCs. Ozone depletion begins, and the ozone hole appears. Over the course of two to three months, approximately 50% of the total column amount of ozone in the atmosphere disappears. At some levels, the losses approach 90%. This has come to be called the Antarctic ozone hole. In spring, temperatures begin to rise, the ice evaporates, and the ozone layer starts to recover. A single chlorine atom would keep on destroying ozone (thus a catalyst) for up to two years (the time scale for transport back down to the troposphere) were it not for

reactions that remove them from this cycle by forming reservoir species such as hydrogen chloride (HCl) and chlorine nitrate (ClONO2). On a per atom basis, bromine is even more efficient than chlorine at destroying ozone, but there is much less bromine in the atmosphere at present. As a result, both chlorine and bromine contribute significantly to the overall ozone depletion. Laboratory studies have shown that fluorine and iodine atoms participate in analogous catalytic cycles. However, in the Earth's stratosphere, fluorine atoms react rapidly with water and methane to form strongly bound HF, while organic molecules containing iodine react so rapidly in the lower atmosphere that they do not reach the stratosphere in significant quantities. Furthermore, a single chlorine atom is able to react with 100,000 ozone molecules. This fact plus the amount of chlorine released into the atmosphere by chlorofluorocarbons (CFCs) yearly demonstrates how dangerous CFCs are to the environment

Chemical Reactions in the Stratosphere:

Chlorine monoxide is a chemical radical with the formula ClO. It plays an important role in the process of ozone depletion. In the stratosphere, chlorine atoms react with ozone molecules to form chlorine monoxide and oxygen. Cl + O3 ClO + O2 This reaction causes the depletion of the ozone layer. This reaction can go on and the ClO radicals can go on to react as such: ClO + O Cl + O2 Regenerating the chlorine radical. In this way, the overall reaction for the decomposition of ozone is catalyzed by chlorine, as ultimately chlorine remains unchanged. The overall reaction is: O + O3 + 2O2 This has been a significant impact of the use of CFCs on the upper stratosphere. The nonreactive nature of CFC's allows them to pass into the stratosphere, where they undergo photo-dissociation to form Cl radicals. These then readily form chlorine monoxide, and this cycle can continue until two radicals react to form dichlorine dioxide, terminating the radical reaction. Because the concentration of CFCs in atmosphere is very low, the probability of a terminating reaction is exceedingly low, meaning each radical can decompose many thousands of molecules.

CFCs and related compounds in the atmosphere:

Chlorofluorocarbons (CFCs) and other halogenated ozone depleting substances (ODS) are mainly responsible for man-made chemical ozone depletion. The total amount of effective halogens (chlorine and bromine) in the stratosphere can be calculated and are known as the equivalent effective stratospheric chlorine. CFCs were invented by Thomas Midgley, Jr. in the 1920s. They were used in air conditioning and cooling units, as aerosol spray propellants prior to the 1970s, and in the cleaning processes of delicate electronic equipment. They also occur as byproducts of some chemical processes. No significant natural sources have ever been identified for these compoundstheir presence in the atmosphere is due almost entirely to human manufacture. As mentioned above, when such ozone-depleting chemicals reach the stratosphere, they are dissociated by ultraviolet light to release chlorine atoms. The chlorine atoms act as a catalyst, and each can break down tens of thousands of ozone molecules before being removed from the stratosphere.

Ozone depleting substances:

These are those substances which are used during the break down of ozone layer or photolysis of ozone layer.

Substance

Ozone- depletion potential

chlorofluorocarbon-11 (CFC11) chlorofluorocarbon-12 (CFC12) chlorofluorocarbon-13 (CFC13) chlorofluorocarbon-111 (CFC111) chlorofluorocarbon-112 (CFC112) chlorofluorocarbon-113 (CFC113) chlorofluorocarbon-114 (CFC114) chlorofluorocarbon-115 (CFC115) chlorofluorocarbon-211 (CFC211) chlorofluorocarbon-212 (CFC212) chlorofluorocarbon-213 (CFC213) chlorofluorocarbon-214 (CFC214)

1.0 1.0 1.0 1.0 1.0 0.8 1.0 0.6 1.0 1.0 1.0 1.0

Consequences of ozone layer depletion or stratosphere:

Since the ozone layer absorbs UVB ultraviolet light from the sun, ozone layer depletion is expected to increase surface UVB levels, which could lead to damage, including increase in skin cancer. This was the reason for the Montreal Protocol. Although decreases in stratospheric ozone are well-tied to CFCs and there are good theoretical reasons to believe that decreases in ozone will lead to increases in surface UVB, there is no direct observational evidence linking ozone depletion to higher incidence of skin cancer and eye damage in human beings. This is partly because UVA, which has also been implicated in some forms of skin cancer, is not absorbed by ozone, and it is nearly impossible to control statistics for lifestyle changes in the populace.

Increased UV:
Ozone, while a minority constituent in Earth's atmosphere, is responsible for most of the absorption of UVB radiation. The amount of UVB radiation that penetrates through the ozone layer decreases exponentially with the slant-path thickness and density of the layer. Correspondingly, a decrease in atmospheric ozone is expected to give rise to significantly increased levels of UVB near the surface. Ozone-driven phenolic formation in tree rings has dated the start of ozone depletion in northern latitudes to the late 1700s. Increases in surface UVB due to the ozone hole can be partially inferred by radiative transfer model calculations, but cannot be calculated from direct measurements because of the lack of reliable historical (pre-ozone-hole) surface UV data, although more recent surface UV observation measurement programmes exist UV-215 and more energetic radiation is responsible for creation ozone in the ozone layer from O2 (regular oxygen). UV-215 through UV-280 increases as a result of reduction in stratospheric ozone, but this is insufficient to do more than dissociate the single oxygen bond of ozone, and of course disrupt DNA bonding.

Biological effects: The main public concern regarding the ozone hole has been the effects of
increased surface UV radiation on human health. So far, ozone depletion in most locations has been typically a few percent and, as noted above, no direct evidence of health damage is available in most latitudes. Were the high levels of depletion seen in the ozone hole ever to be common across the globe, the effects could be substantially more dramatic. As the ozone hole over Antarctica has in some instances grown so large as to reach southern parts of Australia, New Zealand, Chile, Argentina, and South, environmentalists have been concerned that the increase in surface UV could be significant. [26] Ozone depletion would change all of the effects of UVB on human health, both positive and negative. UVB (the higher energy UV radiation absorbed by ozone) is generally accepted to be a contributory factor to skin cancer and to produce Vitamin D. In addition, increased surface UV leads to increased tropospheric ozone, which is a health risk to humans

Reference:
http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Case_Studies/Depletion_of_the_Ozo ne_Layer http://en.wikipedia.org/wiki/Ozone_depletion http://en.wikipedia.org/wiki/Ozone_layer http://wiki.seas.harvard.edu/geos-chem/index.php/Stratospheric_chemistry