Polar stratospheric clouds, ozone depletion

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). 

A detailed analysis of the atmospheric measurements over Antarctica by Anderson et al. (19) indicates that the cycle comprising reactions 17 -19 (the chlorine peroxide cycle) accounts for about 75% of the observed ozone depletion, and reactions 21 - 23 account for the rest. While a clear overall picture of polar ozone depletion is emerging, much remains to be learned. For example, the physical chemistry of the acid ices that constitute polar stratospheric clouds needs to be better understood before reliable predictions can be made of future ozone depletion, particularly at northern latitudes, where the chemical changes are more subtle and occur over a larger geographical area. 

Toon, O. and Turco, R. (1991). Polar stratospheric clouds and ozone depletion. Scient. Am. 264, 68. 

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During the dark, polar winter the temperature drops to extremely low values, on the order of-80°C. At these temperatures, water and nitric acid form polar stratospheric clouds. Polar stratospheric clouds are important because chemical reactions in the stratosphere are catalyzed on the surface of the crystals forming these clouds. The chemical primarily responsible for ozone depletion is chlorine. Most of the chlorine in the stratosphere is contained in the compounds hydrogen chloride, HCl, or chlorine nitrate, CIONO. Hydrogen chloride and chlorine nitrate undergo a number of reactions on the surface of the crystals of polar stratospheric clouds. Two important reactions are ... 

The finding that the heterogeneous chemistry that occurs on polar stratospheric clouds also occurs in and on liquid solutions in the form of liquid aerosol particles and droplets in the atmosphere provided a key link in understanding the effects of volcanic eruptions on stratospheric ozone in both the polar regions and midlatitudes. As discussed herein, the liquid particles formed from volcanic emissions are typically 60-80 wt% H2S04-H20, and hence the chemistry discussed in the previous section can also occur in these particles (Hofmann and Solomon, 1989). We discuss briefly in this section the contribution of volcanic emissions to the chemistry of the stratosphere and to ozone depletion on a global scale. For a brief review of this area, see McCormick et al. (1995). 

Prather, M. J., More Rapid Polar Ozone Depletion through the Reaction of HOCI with HCI on Polar Stratospheric Clouds, Nature, 355, 534-537 (1992). 

After the discovery of the Antarctic ozone hole" in 1985, atmospheric chemist Susan Solomon led the first expedition in 1986 specifically intended to make chemical measurements of the Antarctic atmosphere by using balloons and ground-based spectroscopy. The expedition discovered that ozone depletion occurred after polar sunrise and that the concentration of chemically active chlorine in the stratosphere was 100 times greater than had been predicted from gas-phase chemistry. Solomon s group identified chlorine as the culprit in ozone destruction and polar stratospheric clouds as the catalytic surface for the release of so much chlorine. 

O. B. Toon and R. P. Turco. Polar Stratospheric Clouds and Ozone Depletion, Scientific American, June 1991 A. J. Prenni and M. A. Tolbert, Studies of Polar Stratospheric Cloud Formation, Acc. Chem. Res. 2001,... 

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. 

These clouds form over Antarctica during the cold winter months. Ozone depletion in the Arctic is less severe because it generally does not get cold enough for the polar stratospheric clouds to form. 

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... 

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