Global analysis of halogenated trace gases in the UTLS: from long-lived to short-lived substances

In this dissertation, the distribution of chlorinated and brominated substances in the upper troposphere and lower stratosphere is investigated. These substances contribute significantly to the catalytic decomposition of ozone and are involved in the recurrent formation of the polar ozone hole in the Antarctic winter and spring. The Montreal Protocol, a multilateral environmental treaty to protect the ozone layer, has successfully reduced emissions of long-lived chlorine- and bromine-containing substances. Short-lived chlorinated and brominated substances, some of which are natural and anthropogenic in origin, are not regulated by the Montreal Protocol and it can be assumed that their relative contribution to the stratospheric halogen budget will increase, while the contribution of long-lived compounds will steadily decrease. The distribution of long- and short-lived halogenated substances are part of current research. For the upper troposphere and lower stratosphere, the very short-lived substances are particularly important. The lower stratosphere needs special investigation in this respect, since its composition is influenced by different transport processes. The influences on ozone trends in the lower stratosphere are subject to great uncertainties. Especially in the Southern Hemisphere, the number of observations is very limited. In this work, the GhOST (Gas chromatograph for Observational Studies using Tracers) instrument was used during the SouthTRAC measurement campaign on the German HALO (High Altitude and LOng range) research aircraft, providing observations of halogenated hydrocarbons in Antarctic late winter to early spring 2019, a generally poorly sampled region. The polar vortex was, compared to previous years, significantly weaker and shifted towards the eastern South Pacific and South America. From the airborne measurements of chlorinated source gases, inorganic chlorine (the sum of active chlorine and reservoir gases; Cly) could be inferred with the result that Cly within the vortex increased up to 1687 ± 19 ppt at 385 K potential temperature, accounting for about 50 % of the total chlorine within the vortex and only 15 % of the total chlorine in the southern mid-latitudes. A comparison with the Northern Hemisphere could be made using the PGS measurement campaign in the Arctic winter 2015/2016. Under comparable conditions (season and distance from the tropopause), only 40 % of the total chlorine was in the inorganic form within the Arctic polar vortex and about 20 % was found in the mid-latitudes of the Northern Hemisphere. In addition, about 540 ppt more Cly was present in the Antarctic vortex than in the Arctic vortex, exceeding the annual variations previously reported for Antarctica. The mean age of air plays an essential role in the derivation of Cly via the organic source gases, as was done in this work. A new method for determining the mean age of air from observational data has been introduced that accounts for extra-tropical input to the stratosphere in addition to tropical input. This new method was compared with the previously used method, which considered only the tropical input. The new method shows more realistic values especially near the tropopause. On average, the air of the lower stratosphere in the Northern Hemisphere was older than in the Southern Hemisphere by about 0.5 ± 0.3 years. About 65 K above the tropopause, the pattern changed with older air in the mid-latitudes of the Northern Hemisphere, but older air in high latitudes of the Southern Hemisphere, which implies differences in the strength and isolation of the respective polar vortex as well as the wave forcing in the shallow branch of the Brewer-Dobson circulation of the respective hemisphere. This is in good agreement with the distribution of Cly. The difference in the lower stratosphere was not clearly evident with the old method and it can be assumed that investigations of the differences in Cly of Northern and Southern Hemisphere will benefit from the new method. Finally, the global and seasonal distribution of the two most important representatives of the short-lived brominated substances, CH2Br2 and CHBr3, was investigated. For this purpose, two additional HALO measurement campaigns have been used, the 2012 TACTS measurement campaign and the 2017 WISE measurement campaign, as well as the HIAPER Pole-to-Pole Observations (HIPPO) and Atmospheric Tomography (ATom) measurement campaigns. Observations of CH2Br2 show a pronounced seasonality in the free and upper troposphere of both hemispheres with slightly larger values in the Northern Hemisphere. CHBr3, on the other hand, shows a generally higher variability and lower seasonality with larger mixing ratios at mid and high latitudes in the northern hemispheric winter and autumn. A comparison of the lower stratosphere is limited to autumn and spring of both hemispheres due to the limited data basis of the observations. The distributions in each spring are similar (less than 0.1 ppt differences for e.g., CH2Br2). In hemispheric autumn, larger differences are evident with substantially smaller mixing ratios in the southern hemispheric lower stratosphere. This suggests that the transport processes of the two hemispheres may be different and implies that the input of tropospheric air (flushing) to the Northern Hemisphere lowest stratosphere is more efficient than in the Southern Hemisphere. Vertical profiles of CH2Br2 and CHBr3 in the mid-latitudes of both hemispheres and resulting vertical gradients support this conjecture. However, the Southern Hemisphere data set is insufficient to quantify this difference and further measurements are needed.

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