Chlorofluorocarbons atmospheric lifetimes

Chlorofluorocarbon (CFC) replacements have recently been used for their lower stability and because they have carbon-hydrogen bonds, which means that their atmospheric lifetime is expected to be much shorter than those of CFCs. The adsorption properties of l,l,2-trichloro-l,2,2-trifluoroethane (CFC 113) and its replacement compounds, l,l-dichloro-2,2,2-trifluoroethane (HCFC123), 1,1-dichloro-l-fluoroethane (HCFC141b), and l,l-dichloro-l,2,2,3,3-pentafluoropropane (HCFC225ca) on four kinds of activated carbons were investigated. The adsorption isotherms of inhalational anesthetics (halothane, chloroform, enflurane, isoflurane, and methoxyflurane) on the activated carbon were measured to evaluate the action mechanism of inhalational anesthesia. The anesthesia of CFC replacements can be estimated by the Freundlich constant N of the adsorption isotherms (Tanada et al., 1997). 

In order to enable the fast discontinuation of the production and use of fully halogenated CFCs, hydro-chlorofluorocarbons were introduced in industry as a transition stage. The atmospheric fate and impact of these hydrochlorofluorocarbons and chlorinated solvents are described in [387]. The authors come to the conclusion, that these compounds, with the exception of 1,1,1-trichIoroethane, make a small or insignificant contribution to the stratospheric ozone depletion, global warming, photochemical smog , acid rain or chloride and fluoride levels in precipitations. The ozone depletion potentials are 10 to 50 times lower than that of CFCll or CFC12, mainly as a consequence of their shorter atmospheric lifetime—some months to 10 years—due to destruction in the atmosphere. 

The chlorofluorocarbons (CFCs) have very long lifetimes in the troposphere. This is a consequence of the fact that they do not absorb light of wavelengths above 290 nm and do not react at significant rates with 03, OH, or N03. In addition to the lack of chemical sinks, there do not appear to be substantial physical sinks thus they are not very soluble in water and hence are not removed rapidly by rainout. While laboratory studies have shown that some of the CFCs decompose on exposure to visible and near-UV present in the troposphere when the compounds are adsorbed on siliceous materials such as sand (Ausloos et al., 1977 Gab et al., 1977, 1978), the lifetimes for CFC-11 and CFC-12 with respect to these processes have been estimated to be 540 and 1800 years, respectively (National Research Council, 1979). Similarly, an observed thermal decomposition when adsorbed on sand appears to be an insignificant loss process under atmospheric conditions. 

The oxidizing properties of the troposphere have a strong influence on the lifetime of chemical compounds in the atmosphere, and hence on the probability for a molecule to reach the middle atmosphere. Most hydrocarbons, for example, including hydrogenated halocarbons, are efficiently destroyed by the OH radical in the troposphere before they can penetrate into the stratosphere. Compounds that are not oxidized in the troposphere (e.g., chlorofluorocarbons) or weakly oxidized (e.g., methane) reach the stratosphere more easily. 

This chapter has outlined the history and conceptual understanding of the processes responsible for ozone depletion by chlorofluorocarbons in the stratosphere. In brief, the long lifetimes of chlorofluorocarbons are reflected in their observed worldwide accumulation in the atmosphere. Their role in stratospheric ozone depletion depends critically on... 

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