Chlorine reactions, ozone depletion

The chlorine-containing product species (HCl, CIONO2, HOCl) are "inert reservoirs" because they are not directly involved in ozone depletion however, they eventually break down by absorbing solar radiation or by reaction with other free radicals, returning chlorine to its catalytically active form. Ozone is formed fastest in the upper stratosphere at tropical latitudes (by reactions 1 and 2), and in those regions a few percent of the chlorine is in its active "free radical" form the rest is in the "inert reservoir" form (see Figure 3). 

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. 

An overview of the reactions involving trihalomethanes (haloforms) CHXYZ, where X, Y, and Z are halogen atoms, has been given in the context of ozone depletion (Hayman and Derwent 1997). Interest in the formation of trichloroacetaldehyde formed from trichloroethane and tetrachloroethene is heightened by the phytotoxicity of trichloroacetic acid (Frank et al. 1994), and by its occurrence in rainwater that seems to be a major source of this contaminant (Muller et al. 1996). The situation in Japan seems, however, to underscore the possible significance of other sources including chlorinated wastewater (Hashimoto et al. 1998). Whereas there is no doubt about the occurrence of trichloroacetic acid in rainwater (Stidson et al. 2004), its major source is unresolved since questions remain on the rate of hydrolysis of trichloroacetaldehyde (Jordan et al. 1999). 

Abstract Heterogeneous chemical reactions at the surface of ice and other stratospheric aerosols are now appreciated to play a critical role in atmospheric ozone depletion. A brief summary of our theoretical work on the reaction of chlorine nitrate and hydrogen chloride on ice is given to highlight the characteristics of such heterogeneous mechanisms and to emphasize the special challenges involved in the realistic theoretical treatment of such reactions. 

The reaction mechanism shown for ozone depletion includes chorine. Chlorine in this reaction acts as a catalyst. A principal source of this chlorine is from the ultraviolet breakdown of CFC (chlorofluorocar-... 

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 ... 

F. Sherwood Rowland (1927-) and Mario Molina (1943-) predicted the destruction of stratospheric ozone in 1974. Rowland and Molina theorized that inert CFCs could drift into the stratosphere, where they would be broken down by ultraviolet radiation. Once in the stratosphere, the CFCs would become a source of ozone-depleting chlorine. The destruction of ozone by CFCs can be represented by the following series of reactions ... 

It is also clear that during periods of low surface ozone, chlorine atoms are a major reactant for hydrocarbons (e.g., Jobson et al., 1994 Solberg et al., 1996 Ariya et al., 1998). Figure 6.39, for example, shows the measured ratios of isobutane, n-butane, and propane during an ozone depletion event (Jobson et al., 1994). These particular pairs of hydrocarbons were chosen to differentiate chlorine atom chemistry from OH reactions. Thus isobutane and propane have similar rate constants for reaction with Cl but different rate constants for reaction with OH. If chlorine atoms are responsible for the loss of these organics, their ratio should remain relatively constant in the air mass, as indicated by the line marked Cl. Similarly, isobutane and n-butane have similar rate constants for removal by OH but different rate constants for reactions with... 

Fluorine chemistry in the stratosphere was also considered and it was concluded that ozone depletion by chlorine was > 104 more efficient than that by fluorine (Rowland and Molina, 1975 Stolarksi and Rundel, 1975). Since then, the kinetics of reaction of F atoms with 02 to form the F02 radical and its thermal decomposition have been measured (e.g., see Pagsberg et al., 1987 Lyman and Holland, 1988 Ellerman et al., 1994 and review in DeMore et al., 1997). The equilibrium constant for the F-F02 system... 

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). 

De Haan, D. O., I. Flpisand, and F. Stordal, Modeling Studies of the Effects of the Heterogeneous Reaction CIOOCI + HCI - Cl2 + HOOCI on Stratospheric Chlorine Activation and Ozone Depletion, J. Geophys. Res., 102, 1251-1258 (1997). 

Reactions (1), (2) and (4) convert stable chlorine reservoir species, CIONO, and HC1, into the more easily photolyzable species Cl, HOC1, and C1NO, (nitryl chloride), respectively. This unique chemistry of CIONO, and N,0, on the cold surfaces of the PSC-surfaces is taking place due to the low temperatures of 180 to 200 K encountered in the lower stratosphere at altitudes between 15 and 25 km in the polar vortex. At sunrise, after the polar winter, these photolabile species release Cl atoms that initiate the chain destruction of ozone according to the mechanism, which is responsible for the fast ozone depletion event occuring within a few days to several weeks [34,35] ... 

Theoretical and experimental studies of the interactions between water molecules and hydrogen chloride are of fundamental importance for the understanding of the production of stratospheric chlorine molecules which, in turn, take part in the catalytic ozone depletion reactions. This mainly heterogeneous atmospheric reaction begins with the adsorption of the HCl molecules on the surface of water icicles is the source of the stratospheric chlorine atoms in the polar regions380 - 382. Chlorine molecules are photolysed by solar radiation and the resultant chlorine atoms take part in the destruction of the stratospheric ozone. The study of the (H20) HC1 clusters is an important step towards understanding of the behavior of the HCl molecule on the ice surface383- 386. 

With little doubt, the most significant change in our understanding of fluorocarbon induced ozone destruction, both qualitatively and quantitatively, since the Rowland-Molina proposition of radical catalyzed recombination of ozone by Cl and CIO in 1974, is described in a recent paper in Nature by Prather et al. [20]. What that paper defines is the dramatically non-linear dependence of ozone depletion on added chlorine at high levels of total CL = Cl + CIO + HCl + CIONO2 + HOCl. The critical point is that at levels of CL approaching 15 ppbv, CIO titrates NO2 out of the system via the previously described thermolecular reaction... 

Catalytic hydrotreatment is widely used in the petroleum Industry to remove sulfur, nitrogen, and oxygen from crude oil fractions. However, its use to treat chlorocarbons has not been widely reported despite the widespread use of these compounds in industrial and military operations, and despite the negative environmental impact associated with most disposal options. Catalytic hydrotreatment has the potential to be a safe alternative for the treatment of chlorinated wastes and has advantages over oxidative destruction methods such as thermal incineration and catalytic oxidation. Some of these advantages include the ability to reuse the reaction products, and minimal production of harmful byproducts, such as CI2, COCI2, or fragments of parent chlorocarbons. 1,1,1- Trichloroethane was chosen for this research because it is widely used in industry as a solvent and is on the EPA Hazardous Air Pollutant list as a toxic air contaminant and ozone depleter. ... 

Fluorine chemistry in the stratosphere has also been considered and attention has been drawn to the atmospheric chemistry of the FOx radicals. The compounds with O-F bonds have gained interest in connection with the ozone depletion problem. It has been suggested that FO and F02 radicals formed in the atmospheric degradation of hydrofluorocarbons (HFCs) could destroy ozone in chain reaction processes. Experimental studies of this hypothesis led to the conclusion that catalytic cycles involving F, FO, and F02 are irrelevant with respect to the chlorine cycle.8 However, kinetic investigations of the reactions of fluorine atoms with 02 and NOx provide useful information on the fluorine chemistry in the polluted atmosphere. 

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