Ozone polar stratospheric clouds, role

Heterogeneous chemistry occurring on polar stratospheric cloud particles of ice and nitric acid trihydrate has been estabUshed as a dorninant factor in the aggravated seasonal depletion of o2one observed to occur over Antarctica. Preliminary attempts have been made to parameterize this chemistry and incorporate it in models to study ozone depletion over the poles (91) as well as the potential role of sulfate particles throughout the stratosphere (92). 

The discovery of ozone holes over Antarctica in the mid-1980s was strong observational evidence to support the Rowland and Molina hypothesis. The atmosphere over the south pole is complex because of the long periods of total darkness and sunlight and the presence of a polar vortex and polar stratospheric clouds. However, researchers have found evidence to support the role of CIO in the rapid depletion of stratospheric ozone over the south pole. Figure 11-3 shows the profile of ozone and CIO measured at an altitude of 18 km on an aircraft flight from southern Chile toward the south pole on September 21, 1987. One month earlier the ozone levels were fairly uniform around 2 ppm (vol). 

There are several reasons for the dramatic ozone destruction (see Fig. 2.17) low temperatures may have prolonged the presence of polar stratospheric clouds, which play a key role in the ozone destruction, the polar vortex was very stable, there were increased sulfate aerosols from the 1991 Mount Pinatubo volcanic eruption, which also contribute to heterogeneous chemistry, and chlorine levels had continued to increase. These issues are treated in more detail shortly. 

In short, the overall features of the chemistry involved with the massive destruction of ozone and formation of the ozone hole are now reasonably well understood and include as a key component heterogeneous reactions on the surfaces of polar stratospheric clouds and aerosols. However, there remain a number of questions relating to the details of the chemistry, including the microphysics of dehydration and denitrification, the kinetics and photochemistry of some of the C10x and BrOx species, and the nature of PSCs under various conditions. PSCs and aerosols, and their role in halogen and NOx chemistry, are discussed in more detail in the following section. 

While the sulfuric acid is key nucleation precursor in the low troposphere, its contribution to the polar stratospheric chemistry is a lot more modest. Another strong acid-nitric-plays a major role as the dominant reservoir for ozone destroying odd nitrogen radicals (NOj) in the lower and middle polar stratosphere. Nitric acid is an extremely detrimental component in the polar stratosphere clouds (PSCs), where nitric acid and water are the main constituents, whose presence significantly increases the rate of the ozone depletion by halogen radicals. Gas-phase hydrates of the nitric acid that condense and crystallize in the stratosphere play an important role in the physics and chemistry of polar stratospheric clouds (PSCs) related directly to the ozone depletion in Arctic and Antarctic. 

The existence of aerosol surfaces in the stratosphere has been known for many decades, but it was not until the discovery of the Antarctic ozone hole that their role in surface chemistry was recognized. Here the stratospheric sulfate layer and polar stratospheric clouds will be... 

Gas-phase chemistry associated with the ClOj, and NO cycles is not capable of explaining the polar ozone hole phenomenon. Heterogeneous reactions occurring on PSCs play the pivotal role in polar ozone depletion (McElroy et al., 1986 Solomon et al., 1986 Molina, 1991). The ozone hole is sharply defined between about 12 and 24 km altitude. Polar stratospheric clouds occur in the altitude range 10 to 25 km. Ordinarily, liberation of active chlorine from the reservoir species HCl and CIONO2 is rather slow, but the PSCs promote... 

Chlorine CI2, and bromine monochloride BrCl are formed in the reactions of CIONO2, Br0N02, HCl, HBr, HOCl, HOBr in the heterogeneous reaction in the polar stratospheric clouds (see Sect. 6.5), and their photolyses play an important role in the chain reactions of the ozone hole formation. In the troposphere, CI2 is known to be produced in the heterogeneous reactions on sea salts, but observational data is still limited. Bromine Bra is known to be produced by the heterogeneous chain reactions in the tropospheric ozone destruction in the arctic region. Meanwhile, iodine I2 is released from sea weeds in coastal regions. 

While the many heterogeneous reactions in the troposphere so far described plays a complementary role to the homogeneous gas phase reactions, heterogeneous reactions on polar stratospheric cloud (PSC) are of primary importance for the formation of stratospheric ozone hole. 

Peter, T. Cmtzen, P.J., 1993 The Role of Stratospheric Cloud Particles in Polar Ozone Depletion. An Overview , in Journal of Aerosol Science, 24, Suppl. 1 119-120. 

It has become clear only recently that the atmospheric sierosol plays an important role for the climate on earth. It is common to distinguish between direct and indirect effects of the aerosols on the climate. Aerosols effect directly the radiation balance of the earth due to scattering and absorption of electromagnetic radiation (radiative forcing). On the other hand they influence the physics and chemistry of the atmosphere as condensation nuclei for cloud droplets and their chemical reactions with atmospheric trace gases. Though these indirect aerosol effects are difficult to quantify, they are at least as important as the direct radiative forcing. An especially important and complex example for the indirect influence of aerosols on the chemistry and radiation balance of the earth is the role of stratospheric aerosol particles on the polar ozone depletion, which is discussed in more detail below. 

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