ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-22199-2011 Short-lived brominated species – observations in the source regions and the tropical tropopause layer Brinckmann S. 1 Engel A. 1 Bönisch H. 1 Quack B. 2 Atlas E. 3 Institute for Atmospheric and Environmental Sciences, Universität Frankfurt/Main, Germany Leibniz-Institut für Meereswissenschaften, Universität Kiel, Germany Rosenstiel School of Marine and Atmospheric Science, University of Miami, USA 05 08 2011 11 8 22199 22245 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-discuss.net/11/22199/2011/acpd-11-22199-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/22199/2011/acpd-11-22199-2011.pdf

We conducted measurements of up to the five important short-lived brominated species in the marine boundary layer (MBL) of the mid-latitudes (List/Sylt, North Sea) in June 2009 and of the tropical Western Pacific during the TransBrom ship campaign in October 2009. For the one-week time series in List mean mixing ratios of 2.0, 1.1, 0.2, 0.1 ppt were analysed for CHBr<sub>3</sub>, CH<sub>2</sub>Br<sub>2</sub>, CHBr<sub>2</sub>Cl and CH<sub>2</sub>BrCl, with maxima of 5.8 and 1.6 ppt for the two main components CHBr<sub>3</sub> and CH<sub>2</sub>Br<sub>2</sub>. Along the cruise track in the Western Pacific (between 41° N and 13° S) mean mixing ratios of 1.0, 0.9, 0.2, 0.1 and 0.1 ppt for CHBr<sub>3</sub>, CH<sub>2</sub>Br<sub>2</sub>, CHBrCl<sub>2</sub>, CHBr<sub>2</sub>Cl and CH<sub>2</sub>BrCl were determined. Air samples with coastal influence showed considerably higher mixing ratios than the samples with open ocean origin. Correlation analyses of the two datasets yielded strong linear relationships between the mixing ratios of four of the five species (except for CH<sub>2</sub>BrCl). Using a combined dataset from the two campaigns, rough estimates of the molar emission ratios between the correlated substances were derived as follows: 9/1/0.3/0.3 for CHBr<sub>3</sub>/CH<sub>2</sub>Br<sub>2</sub>/CHBrCl<sub>2</sub>/CHBr<sub>2</sub>Cl. Additional measurements were made in the tropical tropopause layer (TTL) above Teresina (Brazil, 5.07° S, 42.87° W) in June 2008, using balloon-borne cryogenic whole air sampling technique. Near the level of zero clear-sky net radiative heating (LZRH) at 14.8 km about 2.25 ppt organic bromine was bound to the five short-lived species, making up 13 % of total organic bromine (17.82 ppt). CH<sub>2</sub>Br<sub>2</sub> (1.45 ppt) and CHBr<sub>3</sub> (0.56 ppt) accounted for 90 % of the budget of short-lived compounds in that region. Near the tropopause (at 17.5 km) organic bromine from short-lived substances was reduced to 1.35 ppt, with 1.07 ppt and 0.12 ppt attributed to CH<sub>2</sub>Br<sub>2</sub> and CHBr<sub>3</sub> respectively.

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