ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-13-1329-2013 High temporal resolution Br<sub>2</sub>, BrCl and BrO observations in coastal Antarctica Buys Z. 1 2 Brough N. 1 Huey L. G. 3 Tanner D. J. 3 von Glasow R. 2 Jones A. E. 1 British Antarctic Survey, NERC, High Cross, Madingley Road, Cambridge, UK University of East Anglia, School of Environmental Sciences, Norwich, UK Georgia Institute of Technology, School of Earth and Atmospheric Sciences, Atlanta, USA 01 02 2013 13 3 1329 1343 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/13/1329/2013/acp-13-1329-2013.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/13/1329/2013/acp-13-1329-2013.pdf

There are few observations of speciated inorganic bromine in polar regions against which to test current theory. Here we report the first high temporal resolution measurements of Br<sub>2</sub>, BrCl and BrO in coastal Antarctica, made at Halley during spring 2007 using a Chemical Ionisation Mass Spectrometer (CIMS). We find indications for an artefact in daytime BrCl measurements arising from conversion of HOBr, similar to that already identified for observations of Br<sub>2</sub> made using a similar CIMS method. Using the MISTRA model, we estimate that the artefact represents a conversion of HOBr to Br<sub>2</sub> of the order of several tens of percent, while that for HOBr to BrCl is less but non-negligible. If the artefact is indeed due to HOBr conversion, then nighttime observations were unaffected. It also appears that all daytime BrO observations were artefact-free. Mixing ratios of BrO, Br<sub>2</sub> and BrCl ranged from instrumental detection limits to 13 pptv (daytime), 45 pptv (nighttime), and 6 pptv (nighttime), respectively. We see considerable variability in the Br<sub>2</sub> and BrCl observations over the measurement period which is strongly linked to the prevailing meteorology, and thus air mass origin. Higher mixing ratios of these species were generally observed when air had passed over the sea-ice zone prior to arrival at Halley, than from over the continent. Variation in the diurnal structure of BrO is linked to previous model work where differences in the photolysis spectra of Br<sub>2</sub> and O<sub>3</sub> is suggested to lead to a BrO maximum at sunrise and sunset, rather than a noon-time maxima. This suite of Antarctic data provides the first analogue to similar measurements made in the Arctic, and of note is that our maximum measured BrCl (nighttime) is less than half of the maximum measured during a similar period (spring-time) in the Arctic (also nighttime). This difference in maximum measured BrCl may also be the cause of a difference in the Br<sub>2</sub> : BrCl ratio between the Arctic and Antarctic. An unusual event of trans-continental air mass transport appears to have been responsible for severe surface ozone depletion observed at Halley over a 2-day period. The halogen source region appears to be the Bellingshausen Sea, to the west of the Antarctic Peninsula, with the air mass having spent 3 1/2 days in complete darkness crossing the continent prior to arrival at Halley.

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