The Antarctic Ozone Hole

The figure shows the substantial decrease in ozone in the 14-20 km range after polar sunrise. For the Antarctic the data show there was little depletion before the 1980s. For the Arctic, there is substantial interannual variability owing to the temperature of the stratosphere 

Earth Probe TOMS Total Ozone, September 16, 2000 

Lowest values of ozone measured from satellite each year in the ozone hole. Global average ozone is about 300 Dobson Units. Before 1980 ozone less than 200 Dobson Units was rarely seen. In recent years ozone near 100 Dobson Units has become normal in the ozone hole. Ozone in the year 2002 ozone hole was higher than we have come to expect because of unusually high temperatures in the Antarctic stratosphere (from NASA data) 

In 1986 and 1987, a huge international expedition was mounted to examine the chemistry and meteorology that leads to the polar ozone loss. Many different measurements were made using satellites, aeroplanes and ground-based instruments. The results showed some stark 

Growth of the average area of the ozone hole from 1979 to 2003. The ozone hole is defined as the area for which ozone is less than 220 Dobson Units, a value rarely seen under normal conditions. It shows that the ozone in this area hardly occurred at all in 1980, but by year 2000 covered an area larger than North America, 26.5 million km (from NASA data) 

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Ozone has received increased attention for its occurrence and function in the Earth s atmosphere.For example the decreasing ozone concentration in the stratospheric ozone layer, becoming most obvious with the Antarctic ozone hole. 

The Antarctic ozone hole is the result of anthropogenic release of trace gases into the atmosphere (CFCs in particular), causing a decrease in stratospheric ozone and a subsequent increase in solar ultraviolet radiation reaching the earth s surface. 

As discussed in Chapter 12, the CIO dimer is a central species in the chemistry of the Antarctic ozone hole. Table 4.32 gives the recommended absorption cross sections (DeMore et al., 1997). The photodissociation can, in principle, proceed by two paths ... 

There are also important differences in the gas-phase chemistry of the Antarctic ozone hole compared to the chemistry at midlatitudes. One is the formation and photolysis of the CIO dimer. In the Antarctic spring, recycling of CIO back to chlorine atoms via reaction (27) with oxygen atoms does not play a major role because of the relatively small oxygen atom concentrations at the low UV levels at that time. Molina and Molina (1987) proposed that the formation of a dimer of CIO could, however, lead to regeneration of atomic chlorine through the following reactions ... 

In short, the heterogeneous chemistry that drives the Antarctic ozone hole can occur not only on solid surfaces but also in and on liquid solutions containing combinations of HN03, H2S04, and HzO. As discussed in the following section, it is believed that this is why volcanic eruptions have such marked effects on stratospheric ozone on a global basis. 

Indeed, these reactions play an important role in the Antarctic ozone hole and they have important implications for control strategies, particularly of the bromi-nated compounds. For example, Danilin et al. (1996) examined the effects of ClO -BrO coupling on the cumulative loss of O-, in the Antarctic ozone hole from August 1 until the time of maximum ozone depletion. Increased bromine increased the rate of ozone loss under the denitrified conditions assumed in the calculations by converting CIO to Cl, primarily via reactions (31b) and (31c) (followed by photolysis of BrCl). Danilin et al. (1996) estimate that the efficiency of ozone destruction per bromine atom (a) is 33-55 times that per chlorine atom (the bromine enhancement factor ) under these conditions in the center of the Antarctic polar vortex, a 60 calculated as a global average over all latitudes, seasons, and altitudes (WMO, 1999). 

Angel I, J. K., Reexamination of the Relation between Depth of the Antarctic Ozone Hole, and Equatorial QBO and SST, 1962-1992, Geophys. Res. Lett., 20, 1559-1562 (1993b). 

Brasseur, G. P., X. Tie, P. J. Rasch, and F. Lefevre, A Three-Dimensional Simulation of the Antarctic Ozone Hole Impact of Anthropogenic Chlorine on the Lower Stratosphere and Upper Troposphere, J. Geophys. Res., 102, 8909-8930 (1997). 

Hofmann, D. J and T. Deshler, Stratospheric Cloud Observations during Formation of the Antarctic Ozone Hole in 1989, J. Geophys. Res., 96, 2897-2912 (1991). 

While the growth in stratospheric chlorine should clearly be slowed by the Montreal Protocol agreements, it was still substantial and expected to lead to quite large losses of ozone. This recognition, bolstered by the dramatic appearance of the Antarctic ozone hole, led to further major amendments to the Montreal Protocol. 

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. 

R. S. Stolarski, The Antarctic Ozone Hole, Scientific American, January 1988. The 1995 Nobel Prize in Chemistry was shared by Paul Crutzen, Mario Molina, and F. Sherwood Rowland for their work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone. Their Nobel lectures can be found in P. J. Crutzen, My Life with 03, NO, and Other YZO Compounds, Angew. Chem. lnt. Ed. Engl. 1996,35, 1759 M. J. Molina, Polar Ozone Depletion, ibid., 1779 F. S. Rowland, Stratospheric Ozone Depletion by Chlorofluorocarbons, ibid., 1787. 

There is already one excellent example of our failure to make such a predictive leap—the Antarctic ozone hole. The reason for the failure to anticipate the rapid loss of ozone in the lower stratosphere was a failure to appreciate the potential role of the subtle photochemistry, in particular, the heterogeneous chemistry. Nor did researchers have a full appreciation for the consequences of the air parcels inside the polar vortices being relatively isolated from midlatitude air. Some of these same issues are important in the Arctic region in wintertime, but researchers lack the predictive capability to determine how ozone will ultimately be affected. 

However, even if such measurements were possible, would the uncertainty of the result be small enough to establish that production does indeed balance observed loss of ozone The calculation of ozone loss in the Antarctic ozone hole was shown to have an uncertainty of 35 to 50%. The uncertainty for analyzing whether production balances loss in the midlatitude stratosphere is similarly 35 to 50%. About half of the uncertainty is in the measurements of stratospheric abundances, which are typically 5 to 35%, and half is in the kinetic rate constants, which are typically 10 to 20% for the rate constants near room temperature but are even larger for rate constants with temperature dependencies that must be extrapolated for stratospheric conditions below the range of laboratory measurements. In addition to uncertainties in the photochemical rate constants, there are those associated with possible missing chemistry, such as excited-state chemistry, and the effects of transport processes that operate on the same time scales as the photochemistry. Thus, simultaneous measurements, even with relatively large uncertainties, can be useful tests of our basic understanding but perhaps not of the details of photochemical processes. 

These examples illustrate that an increasing number of trace gases must be measured simultaneously if even limited subsets of stratospheric photochemistry and transport are to be understood. The combined uncertainties will also become less of a constraint as simultaneous measurements of trace gas abundances can be compared to values derived from other observed abundances and simple photochemical relationships. As important is the improved measurement of photochemical parameters from laboratory studies as well as the search and study of other mechanisms that may be occurring in the stratosphere. Concerted effort in all of these categories is required to avert future failure in predicting shifts in stratospheric photochemistry, like the Antarctic ozone hole. 

A third issue is the estimates of ozone loss associated with the polar vortex. Will the Antarctic ozone hole expand and will the Arctic ozone hole begin Can the loss of ozone be better quantified, and what are the zonal asymmetries in the CIO and BrO fields How much additional ozone is lost when the polar vortex breaks up ... 

These issues that have direct bearing on stratospheric ozone, and thus on life on this planet, will not go away. The chlorine burden of the stratosphere will remain sufficient to produce the Antarctic ozone hole for the... 

Functional roles treated above are strictly organismal responses to biotic stresses. The use of chemical means to address physical stresses is largely nonexistent. A notable exception to this is the response many organisms make to harmful ultraviolet (UV) radiation. Sunscreens are small organic molecules which absorb UV radiation so that damage to DNA via cross-linking219 225 is prevented. Production of micosporin-like amino acids (MAA) appears to be widespread in shallow-water Antarctic marine invertebrates and macroalgae,223,224 which may be particularly adaptive at present because of the Antarctic ozone hole. 

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