OZONE LAYER AND OZONE HOLE
The ozone layer is a layer in Earth's atmosphere which contains relatively high concentrations of ozone (O3). This layer absorbs 93-99% of the sun's high frequency ultraviolet light, which is potentially damaging to life on earth. Over 91% of ozone in earth's atmosphere is present here. "Relatively high" means a few parts per million—much higher than the concentrations in the lower atmosphere but still small compared to the main components of the atmosphere. It is mainly located in the lower portion of the stratosphere from approximately 15 km to 35 km above Earth's surface, though the thickness varies seasonally and geographically.
The ozone layer was discovered in 1913 by the French physicists Charles Fabry and Henri Buisson. Its properties were explored in detail by the British meteorologist G. M. B. Dobson, who developed a simple spectrophotometer that could be used to measure stratospheric ozone from the ground. Between 1928 and 1958 Dobson established a worldwide network of ozone monitoring stations which continues to operate today (2008). The "Dobson unit", a convenient measure of the total amount of ozone in a column overhead, is named in his honor.
The photochemical mechanisms that give rise to the ozone layer were worked out by the British physicist Sidney Chapman in 1930. Ozone in the earth's stratosphere is created by ultraviolet light (whose wavelength is shorter than 240 nm) striking oxygen molecules containing two oxygen atoms (O2), splitting them into individual oxygen atoms (atomic oxygen); the atomic oxygen then combines with unbroken O2 to create ozone, O3. The ozone molecule is also unstable (although, in the stratosphere, long-lived) and when ultraviolet light between 310 and 200 nm hits ozone it splits into a molecule of O2 and an atom of atomic oxygen, a continuing process called the ozone-oxygen cycle, thus creating an ozone layer in the stratosphere, the region from about 10 to 50 km (32,000 to 164,000 feet) above Earth's surface. About 90% of the ozone in our atmosphere is contained in the stratosphere. Ozone concentrations are greatest between about 20 and 40 km, where they range from about 2 to 8 parts per million. If all of the ozone were compressed to the pressure of the air at sea level, it would be only a few millimeters thick.
Ten percent of the ozone in the atmosphere is contained in the troposphere, the lowest part of our atmosphere where all of our weather takes place. Tropospheric ozone has two sources: about 10 % is transported down from the stratosphere while the remainder is created in smaller amounts through different mechanisms.
The thickness of the ozone layer—that is, the total amount of ozone in a column overhead—varies by a large factor worldwide, being in general smaller near the equator and larger as one moves towards the poles. It also varies with season, being in general thicker during the spring and thinner during the autumn. The reasons for this latitude and seasonal dependence are complicated, involving atmospheric circulation patterns as well as solar intensity.
Since stratospheric ozone is produced by solar UV radiation, one might expect to find the highest ozone levels over the tropics and the lowest over polar regions. The same argument would lead one to expect the highest ozone levels in the summer and the lowest in the winter. The observed behavior is very different: most of the ozone is found in the mid-to-high latitudes of the northern and southern hemispheres, and the highest levels are found in the spring, not summer, and the lowest in the autumn, not winter. During winter, the ozone layer actually increases in depth. This puzzle is explained by the prevailing stratospheric wind patterns, known as the Brewer-Dobson circulation. While most of the ozone is indeed created over the tropics, the stratospheric circulation then transports it poleward and downward to the lower stratosphere of the high latitudes.
The ozone layer is higher in altitude in the tropics, and lower in altitude in the extratropics, especially in the polar regions. This altitude variation of ozone results from the slow circulation that lifts the ozone-poor air out of the troposphere into the stratosphere. As this air slowly rises in the tropics, ozone is produced by the overhead sun which photolyzes oxygen molecules. As this slow circulation bends towards the mid-latitudes, it carries the ozone-rich air from the tropical middle stratosphere to the mid-and-high latitudes lower stratosphere. The high ozone concentrations at high latitudes are due to the accumulation of ozone at lower altitudes.
Importance of ozone layer
Although the concentration of the ozone in the ozone layer is very small, it is vitally important to life because it absorbs biologically harmful ultraviolet (UV) radiation emitted from the Sun. UV radiation is divided into three categories, based on its wavelength; these are referred to as UV-A, UV-B, and UV-C. UV-C, which would be very harmful to humans, is entirely screened out by ozone at around 35 km altitude. UV-B radiation can be harmful to the skin and is the main cause of sunburn; excessive exposure can also cause genetic damage, as a result problems such as skin cancer. The ozone layer is very effective at screening out UV-B; for radiation with a wavelength of 290 nm, the intensity at Earth's surface is 350 billion times weaker than at the top of the atmosphere. Nevertheless, some UV-B reaches the surface. Most UV-A reaches the surface; this radiation is significantly less harmful, although it can potentially cause genetic damage.
Depletion of the ozone layer allows more of the UV radiation, and particularly the more harmful wavelengths, to reach the surface, causing increased genetic damage to living creatures and organisms.
On January 23, 1978, Sweden became the first nation to ban CFC-containing aerosol sprays that are thought to damage the ozone layer. A few other countries, including the United States, Canada, and Norway, followed suit later that year, but the European Community rejected an analogous proposal. Even in the U.S., chlorofluorocarbons continued to be used in other applications, such as refrigeration and industrial cleaning, until after the discovery of the Antarctic ozone hole in 1985. After negotiation of an international treaty (the Montreal Protocol), CFC production was sharply limited beginning in 1987 and phased out completely by 1996.
On August 2, 2003, scientists announced that the depletion of the ozone layer may be slowing down due to the international ban on CFCs. Three satellites and three ground stations confirmed that the upper atmosphere ozone depletion rate has slowed down significantly during the past decade. The study was organized by the American Geophysical Union. Some breakdown can be expected to continue due to CFCs used by nations which have not banned them, and due to gases which are already in the stratosphere. CFCs have very long atmospheric lifetimes, ranging from 50 to over 100 years, so the final recovery of the ozone layer is expected to require several lifetimes.
Compounds containing C–H bonds are being designed to replace the function of CFC's (such as HCFC), since these compounds are more reactive and less likely to survive long enough in the atmosphere to reach the stratosphere where they could affect the ozone layer.
OZONE HOLE AND OZONE DEPLETION
Ozone depletion describes two distinct, but related observations: a slow, steady decline of about 4 percent per decade in the total amount of ozone in Earth's stratosphere since the late 1970s; and a much larger, but seasonal, decrease in stratospheric ozone over Earth's polar regions during the same period. The latter phenomenon is commonly referred to as the ozone hole. In addition to this well-known stratospheric ozone depletion, there are also tropospheric ozone depletion events, which occur near the surface in polar regions during spring. Ozone levels, over the northern hemisphere, have been dropping by 4% per decade. Over approximately 5% of the Earth's surface, around the north and south poles, much larger (but seasonal) declines have been seen; these are the ozone holes.
Ozone depletion mechanism
Ozone can be destroyed by a number of free radical catalysts, the most important of which are the hydroxyl radical (OH·), the nitric oxide radical (NO·) and atomic chlorine (Cl·) and bromine (Br·). All of these have both natural and anthropogenic (manmade) sources; at the present time, most of the OH· and NO· in the stratosphere is of natural origin, but human activity has dramatically increased the high in oxygen chlorine and bromine. These elements are found in certain stable organic compounds, especially chlorofluorocarbons (CFCs), which may find their way to the stratosphere without being destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl and Br atoms are liberated from the parent compounds by the action of ultraviolet light e.g.
CFCl3 + hν → CFCl2 + Cl
Where 'h' is Planck's constant, 'ν' is frequency of electromagnetic radiation.
The Cl and Br atoms can then destroy ozone molecules through a variety of catalytic cycles. In the simplest example of such a cycle, a chlorine atom reacts with an ozone molecule, taking an oxygen atom with it (forming ClO) and leaving a normal oxygen molecule. A free oxygen atom then takes away the oxygen from the ClO, and the final result is an oxygen molecule and a
chlorine atom, which then reinitiates the cycle. The chemical shorthand for these gas-phase reactions is:
Cl + O3 → ClO + O2
ClO + O → Cl + O2
The net reaction is : O3 + O → 2 O2, the "recombination" reaction given above.
The overall effect is to increase the rate of recombination, leading to an overall decrease in the amount of ozone. For this particular mechanism to operate there must be a source of O atoms, which is primarily the photo dissociation of O3; thus this mechanism is only important in the upper stratosphere where such atoms are abundant. More complicated mechanisms have been discovered that lead to ozone destruction in the lower stratosphere as well.
A single chlorine atom would keep on destroying ozone 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 which contain 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.
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