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2657
2694
2008-02-08
DMS and MSA measurements in the Antarctic boundary layer: impact of BrO on MSA production
K. A. Read
km519@york.ac.uk
A. C. Lewis
S. Bauguitte
A. M. Rankin
R. A. Salmon
E. W. Wolff
A. Saiz-Lopez
W. J. Bloss
D. E. Heard
J. D. Lee
J. M. C. Plane
Department of Chemistry, University of York, Heslington, York, YO19 4RR, UK
British Antarctic Survey, High Cross, Madingley Road, CB3 0ET, Cambridge, UK
Earth and Space Science Division, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109, USA
School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK
Department of Chemistry, University of Leeds, Leeds LS2 9JT, UK
In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid
(MSA) were made at Halley Station, Antarctica (75°35´S, 26°19W)
during February 2004–February 2005 as part of the CHABLIS (Chemistry of the
Antarctic boundary layer and the interface with snow) project. DMS was
present in the atmosphere at Halley all year (average 38.1±43 pptV)
with a maximum monthly average value of 113.6±52 pptV in February
2004 coinciding temporally with a minimum in sea extent. Whilst seasonal
variability and interannual variability can be attributed to a number of
factors, short term variability appeared strongly dependent on air mass
origin and trajectory pressure height. The MSA and derived non-sea salt
sulphate (nss-SO<sub>4</sub><sup>2−</sup>) measurements showed no correlation with those
of DMS (regression <i>R</i><sup>2</sup>=0.039, and <i>R</i><sup>2</sup>=0.001, respectively)
in-line with the complexity of DMS fluxes, conflicting oxidation routes,
transport of air masses and variable spatial coverage of both sea-ice and
phytoplankton. MSA was generally low throughout the year, with an annual
average of 42 ng m<sup>−3</sup> (9.8±13.2 pptV), however MSA:
nss-SO<sub>4</sub><sup>2−</sup> ratios were high implying a dominance of the addition
oxidation route for DMS. Including BrO measurements into MSA production
calculations demonstrated the significance of BrO on DMS oxidation within
this region of the atmosphere in austral summer. Assuming an 80% yield
of DMSO from the reaction of DMS+BrO, an atmospheric concentration of BrO
equal to 3 pptV increased the calculated MSA production from DMS by a factor
of 9 above that obtained when considering only reaction with the hydroxyl
radical.
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