Time and temperature dependences of fractional HCl abundances from airborne data in the Southern Hemisphere during 1994

Abstract

Measurements of HCl and CH₄ taken by the aircraft laser infrared absorption spectrometer (ALIAS) on the ER-2 high-altitude research aircraft during the Southern Hemisphere winter of 1994 have been used to examine the abundance of HCl as a fraction of total inorganic chlorine. The fractional abundance of HCl shows a threshold behaviour as a function of temperature history; on a 10 day timescale, the abundance dropped sharply in those air parcels experiencing a temperature < 195 K, but little or no change was seen in parcels which stayed warmer than this temperature. The behaviour mirrors well the temperature behaviour calculated for the transformation of HCl into reactive forms (Cl₂, HOCl) from laboratory studies of sulfate aerosols and polar stratospheric clouds. During the course of the winter, the fractional abundance of HCl outside the vortex decreased from its values in late May by about a third, while inside it dropped to near zero by early August. Some recovery was evident in October. Examples of the peel-off of low-HCl air equatorward of the wind maximum were evident in early June. Meteorological trajectories are used to show, in a case study of a flight in early August, that air parcels which experienced temperatures of < 195 K, and as a result had low fractional HCl abundances, did so largely poleward of the maximum in the polar night jet stream. Encountering temperatures of < 195 K during the previous 10 days was a necessary and sufficient condition for the transformation of HCl into reactive forms by heterogeneous reactions. The trajectories further showed that air arriving from sub-tropical latitudes had higher fractional HCl abundances than the air in the middle latitudes, and much higher fractions than the air at high latitudes. The resulting picture is one in which the fractional abundance of HCl in air at mid latitudes was the result of mixing of air from sub-tropical latitudes with air mainly from polward of the jet stream core which has experienced temperatures < 195 K. The sensitivity of the fractional abundance of HCl to the assumption that no HCl enters the stratosphere via the tropical tropopause is examined in the light of an observed profile near the equator with a volume fraction of 0.4 ppb HCl, zero ClO and tropospheric mixing ratios of CFCs at the tropical tropopause.