Stratospheric chemistry ozone “hole

The ozone hole would almost certainly be much worse if chemists had not studied the reactions of CFCs with atmospheric gases before ozone depletion was discovered. The 1995 Nobel Prize in chemistry was awarded to the three pioneers in this effort. A German chemist, Paul Crutzen, discovered how ozone concentration is regulated in a normal stratosphere, while two Americans, F. Sherwood Rowland and Mario Molina, showed that CFCs can destroy ozone. These studies of molecular reactions allowed quick determination that CFCs are a likely cause of ozone depletion and led to the international restrictions described above. 

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. 

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. 

Arctic stratosphere due to chemistry that is qualitatively similar to that in the Antarctic, an analogous ozone hole is not formed. The major reason for this difference is the different meteorology and dynamics (Schoeberl et al., 1992 Manney and Zurek, 1993 Man-ney et al., 1996). 

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. 

The importance of heterogeneous processes in the chemistry of stratospheric ozone has been dramatically illustrated by the annual appearance of the "Ozone Hole" during the Antarctic spring [1-4]. Heterogeneous reactions on particle surfaces in the polar... 

When the ozone hole was reported in 1985, scientists had made measurements of CFC levels in the stratosphere that supported the hypothesis that CFCs could be responsible for the depletion of ozone. The pure research done only for the sake of knowledge became applied research. Applied research is research undertaken to solve a specific problem. Scientists continue to monitor the amount of CFCs in the atmosphere and the annual changes in the amount of ozone in the stratosphere. Applied research also is being done to find replacement chemicals for the CFCs that are now banned. Read the Chemistry and Society feature at the end of this chapter to learn about research into the human genome. What type of research does it describe ... 

In 1984, a remarkable and totally unpredicted phenomenon was discovered by the British Antarctic Survey, the so-called ozone hole. The discovery of ozone depletion over Antarctica during the spring period provided the first observational support for the possible effect of CFCs on the stratospheric ozone. However, the observation of ozone loss did not indicate its cause. From 1984 to 1988, several theories were postulated from CFC chemistry to atmospheric dynamics or even to cosmic electron fluxes. It was not until 1988, with the results of the 1987 Airborne Antarctic Ozone Expedition, that a probable link with CFCs was established. This prompted the Natural Resources Defense Council, an American pressure group, to sue the EPA to fulfill its 1980 promise to seek legislation to further control the manufacture and use of CFCs in the United States of America. 

In 1985, scientists discovered a large decrease in the atmospheric concentration of ozone over Antarctica. This ozone hole could not be explained with the models used to describe atmospheric chemistry at that time, but it has since been explained in terms of an unexpectedly rapid reformation of chlorine atoms from chlorine compounds such as HCl and CIONO2. The new model suggests that reactions such as the following take place on the surface of ice crystals that form in the cold air of the stratosphere over Antarctica. 

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... 

Halogen Chemistry on PSCs. The cold temperatures that occur in polar winter can lead to formation of clouds within the stratosphere, and there are visual sightings of such Arctic clouds dating back hundreds of years. In the unpopulated Antarctic, the earliest explorers noted unusually colorful high clouds in winter. The term polar stratospheric clouds (or PSCs) was coined by McCormick et al. (1982), who first presented satellite observations of high-altitude clouds in the Antarctic and Arctic stratospheres, but the clouds were considered little more than a scientific curiosity until the ozone hole was discovered. 

Heterogeneous reactions. Knowledge of atmospherically relevant heterogeneous reactions is far from complete. Important reactions probably still remain to be identified and their rates and mechanisms determined. Just as ignorance of heterogeneous chemistry contributed to the failure of stratospheric ozone models to anticipate the formation of the antarctic ozone hole, much still is to be discovered and learned about the role of heterogeneous reactions in the troposphere. 

The ozone hole—understanding of ozone chemistry in the stratosphere heterogeneous chemistry in the atmosphere... 

Shortly thereafter, the effect on stratospheric ozone of chlorine released from human-made (anthropogenic) chlorofluorocarbons was predicted by Mario Molina and F. Sherwood Rowland. For their pioneering studies of atmospheric ozone chemistry, Crutzen, Molina, and Rowland were awarded the 1995 Nobel Prize in Chemistry. It was not until 1985, with the discovery of the Antarctic ozone hole by a team led by the British scientist Joseph Farman, that definitive evidence of the depletion of the stratospheric ozone layer emerged. 

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