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Herman & McQuillan 1985
Herman, J.R. and McQuillan, C.J. (1985). Atmospheric chlorine and stratospheric ozone nonlinearities and trend detection. Journal of Geophysical Research 90: doi: 10.1029/JD090iD03p05721. issn: 0148-0227.

The percent decrease of total stratospheric ozone column content due to the injection of fluorocarbons (F-11 and F-12) has been found to be a nearly linear function of the atmospheric mixing ratio of CIX between 1.2 and 10 parts per billion by volume (ppbv). In contrast, Cicerone et al. (1983) found a broad region of slightly positive change in ozone column content between 10 and 80 km for small CIX perturbations in addition to a nonlinear negative decrease for larger perturbations. The presence of a nonlinear response in column ozone to moderate CIX changes appears to depend strongly on the method of diurnal averaging employed in the calculation. The immediate decrease in ozone column content for our small CIX perturbation results leads to the prediction of an earlier date for possible experimental detection of total ozone trends related to chlorine. For larger CIX perturbations the response in column ozone is nonlinear when the amount of CIX in the stratosphere becomes comparable to or larger than the amount of NOx. On the basis of our time-dependent calculations using a specified rate of fluorocarbon injection obtained from Logan et. (1978), and similar previously obtained results from other models, the first evidence of an ozone decrease induced by CIX may be observable in the vicinity of 40 km by 1987--1990 with present-day satellite instrumentation (Nimbus 7). The actual detection of an ozone decrease by 1990 might be obscured by seasonal and longer-term atmospheric variations. Because of increasing fluxes of several minor constituents (e.g., CH4), possible long-term temperature changes in the stratosphere, and possible secular solar flux changes, observation of an ozone decrease is not necessarily an indicator of damage to ozone caused by atmospheric chlorine. Comparing the percent difference curves near 40 km for the diurnal variation of ozone corresponding to different amounts of CIX may provide a means of distinguishing CIX effects from other atmospheric changes. The change should be detectable when CIX finally reaches 5 ppbv in the upper stratosphere (about 2020). By the year 2020 the total ozone decrease due to CIX should be about 3% (2.5% with increasing methane) and may already pose environmental problems.

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Journal of Geophysical Research
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