Atmosphere chlorofluorocarbons

In the upper atmosphere, chlorofluorocarbons such as CFC13 absorb sunlight, and subsequently fragment to Cl atoms. The Cl atoms then destroy ozone by the following mechanism ... 

Ho D. T., Schlosser P., Smethie W. M., Jr., and Simpson H. J. (1998) Variability in atmospheric chlorofluorocarbons (CCI3F and CCI2F2) near a large urban area imphcations for groundwater dating. Environ. Sci. Technol. 32,... 

Experience dictates that air pollution problems are not easily rationalized. Well-documented issues such as photochemical smog or the fate of atmospheric chlorofluorocarbons have revealed the potential for chemistry of considerable complexity, and even it seems for a different result (i.e. ozone enrichment or depletion) from not too dissimilar photochemical reactions. Smoke or add gases from combustion processes continue to cause concern, " and informed exchanges highlight the problems of identifying a source even for well-defined emissions. 

N. R. P. Harris,]. C. Farman, and D. W. Fahey, Phys. Rev. Lett., 89,219801 (2002). Comment on Effects of Cosmic Rays on Atmospheric Chlorofluorocarbon Dissociation and Ozone Depletion . 

One of the chief uses of chloromethane is as a starting material from which sili cone polymers are made Dichloromethane is widely used as a paint stripper Trichloromethane was once used as an inhalation anesthetic but its toxicity caused it to be replaced by safer materials many years ago Tetrachloromethane is the starting mate rial for the preparation of several chlorofluorocarbons (CFCs) at one time widely used as refrigerant gases Most of the world s industrialized nations have agreed to phase out all uses of CFCs because these compounds have been implicated m atmospheric processes that degrade the Earth s ozone layer... 

It is the use of LIDAR devices as tools for spectroscopic measurements on the various gases present in the atmosphere which concerns us here. These include ozone, carbon dioxide, the CFCs (chlorofluorocarbons, such as CFC-11, trichlorofluoromethane, and CFC-12, dichlorodifluoromethane, used as refrigerants) and all those molecules regarded as atmospheric pollutants. 

Chlorofluorocarbons (CFCs). Prior to 1978 most aerosol products contained chlorofluorocarbon propeUants. Since that time, the use of chlorinated fluorocarbons for aerosols has been seriously curtailed. These compounds have been impHcated in the depeletion of the ozone (qv) layer and are considered to be greenhouse gases (see Airpollution Atmospheric modeling). 

Production of hydrogen fluoride from reaction of Cap2 with sulfuric acid is the largest user of fluorspar and accounts for approximately 60—65% of total U.S. consumption. The principal uses of hydrogen fluoride are ia the manufacture of aluminum fluoride and synthetic cryoHte for the Hall aluminum process and fluoropolymers and chlorofluorocarbons that are used as refrigerants, solvents, aerosols (qv), and ia plastics. Because of the concern that chlorofluorocarbons cause upper atmosphere ozone depletion, these compounds are being replaced by hydrochlorofluorocarbons and hydrofluorocarbons. 

Most chlorofluorocarbons are hydrolytically stable, CCI2F2 being considerably more stable than either CCl F or CHCI2F. Chlorofluoromethanes and ethanes disproportionate in the presence of aluminum chloride. For example, CCl F and CCI2F2 give CCIF and CCl CHCIF2 disproportionates to CHF and CHCl. The carbon—chlorine bond in most chlorofluorocarbons can be homolyticaHy cleaved under photolytic conditions (185—225 nm) to give chlorine radicals. This photochemical decomposition is the basis of the prediction that chlorofluorocarbons that reach the upper atmosphere deplete the earth s ozone shield. 

Air pollution (qv) problems are characteri2ed by their scale and the types of pollutants involved. Pollutants are classified as being either primary, that is emitted direcdy, or secondary, ie, formed in the atmosphere through chemical or physical processes. Examples of primary pollutants are carbon monoxide [630-08-0] (qv), CO, lead [7439-92-1] (qv), Pb, chlorofluorocarbons, and many toxic compounds. Notable secondary pollutants include o2one [10028-15-6] (qv), O, which is formed in the troposphere by reactions of nitrogen oxides (NO ) and reactive organic gases (ROG), and sulfuric and nitric acids. 

The other global environmental problem, stratospheric ozone depletion, was less controversial and more imminent. The U.S. Senate Committee Report supporting the Clean Air Act Amendments of 1990 states, Destruction of the ozone layer is caused primarily by the release into the atmosphere of chlorofluorocarbons (CFCs) and similar manufactured substances—persistent chemicals that rise into the stratosphere where they catalyze the destruction of stratospheric ozone. A decrease in stratospheric ozone will allow more ultraviolet (UV) radiation to reach Earth, resulting in increased rates of disease in humans, including increased incidence of skin cancer, cataracts, and, potentially, suppression of the immune system. Increased UV radiation has also been shown to damage crops and marine resources."... 

An important effect of air pollution on the atmosphere is change in spectral transmission. The spectral regions of greatest concern are the ultraviolet and the visible. Changes in ultraviolet radiation have demonstrable adverse effects e.g., a decrease in the stratospheric ozone layer permits harmful UV radiation to penetrate to the surface of the earth. Excessive exposure to UV radiation results in increases in skin cancer and cataracts. The worldwide effort to reduce the release of stratospheric ozone-depleting chemicals such as chlorofluorocarbons is directed toward reducing this increased risk of skin cancer and cataracts for future generations. 

The hazard identification step is perhaps the most important, because any hazard not identified will not be considered in the decision process. For example, the impact of chlorofluorocarbons on atmospheric ozone was unknown for much of the period of their use, and this potential hazard was not considered until recent years. 

The question of the fate of chlorofluorocarbons upon their release into the atmosphere IS of great interest at present because of the potential damage to the earth s protective ozone layer caused by the reaction of ozone with photochemically generated chlorine atoms... 

Thus, the mean temperature of the atmosphere, which is about 20°C at sea level, falls steadily to about —55° at an altitude of 10 km and then rises to almost 0°C at 50 km before dropping steadily again to about —90° at 90 km. Concern was expressed in 1974 that interaction of ozone with man-made chlorofluorocarbons would deplete the equilibrium concentration of ozone with potentially disastrous consequences, and this was dramatically confirmed by the discovery of a seasonally recurring ozone hole above Antarctica in 1985. A less prominent ozone hole was subsequently detected above the Arctic Ocean. The detailed physical and chemical conditions required to generate these large seasonal depletions of ozone are extremely complex but the main features have now been elucidated (see p. 848). Several accounts of various aspects of the emerging story, and of the consequent international governmental actions to... 

Despite their instability (or perhaps because of it) the oxides of chlorine have been much studied and some (such as CI2O and particularly CIO2) find extensive industrial use. They have also assumed considerable importance in studies of the upper atmosphere because of the vulnerability of ozone in the stratosphere to destruction by the photolysis products of chlorofluorocarbons (p. 848). The compounds to be discussed are ... 

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