References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-8-2985-2008

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

Read

K. A.

¹ Lewis

A. C.

¹ Bauguitte

² Rankin

A. M.

² Salmon

R. A.

² Wolff

E. W.

² Saiz-Lopez

³ Bloss

W. J.

⁴ Heard

D. E.

⁵ Lee

J. D.

¹ Plane

J. M. C.

⁵

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

Department of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK

Department of Chemistry, University of Leeds, Leeds LS2 9JT, UK

17 06 2008

8 11 2985 2997

2008

This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/

This article is available from https://acp.copernicus.org/articles/8/2985/2008/acp-8-2985-2008.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/8/2985/2008/acp-8-2985-2008.pdf

In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid (MSA) were made at Halley Station, Antarctica (75°35' S, 26°19' W) 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-SO42−) measurements showed no correlation with those of DMS (regression R2=0.039, and R2=0.001 respectively) in-line with the complexity of DMS fluxes, alternative 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−3 (9.8±13.2 pptV), however MSA: nss-SO42− 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. These findings have significant atmospheric implications, but may also impact on the interpretation of ice cores which previously relied on the understanding of MSA and nss-SO42− chemistry to provide information on environmental conditions such as sea ice extent and the origins of sulphur within the ice.

References 1

Abram, N. J., Mulvaney, R., Wolff, E. W., and Mudelsee, M.: Ice core records of sea ice variability in the Weddell Sea region of Antarctica, J. Geophys. Res., 112, D15101, https://doi.org/10.1029/2006JD008139, 2007.

Arsene, C., Barnes, I., and Becker, K. H.: FT-IR product study of the photo-oxidation of dimethyl sulfide: Temperature and O2 partial pressure dependence, Phys. Chem. Chem. Phys., 1, 5463–5470, 1999.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes., R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume 1 – gas phase reactions of Ox, HOx, NOx, and SOx species, Atmos. Chem. Phys., 4, 1461–1738, 2004.

Ayers, G. P., Bentley, J. P., Ivey, J. P., and Forgan, B. W.: Dimethylsulphide in marine air at Cape Grim, 41°S, J. Geophys. Res., 102, 21 013–21 021, 1995a.

Ayers, G. P., Cainey, J. M., Gillett, R. W., and Ivey, J. P.: Atmospheric sulphur and cloud condensation nuclei in marine air in the Southern Hemisphere, Phil. Trans. R. Soc. Lond. B, 352, 203–211, 1997.

Ayers, G. P., Gillett, R. W., Ivey, J. P., Schafer, B., and Gabric, A.: Short-term variability in marine atmospheric dimethyl sulphide concentration, Geophys. Res. Lett., 22, 2513–2516, 1995b.

Bardouki, H., Barcellos da Rosa, M., Mihalopoulous, N., Palm, W.-U., and Zetzsch, C.: Kinetics and mechanism of the oxidation of dimethylsulfoxide (DMSO) and methanesulfinate (MSI-) by OH radicals in aqueous medium, Atmos. Environ., 36, 4627–4634, 2002.

Barnes, I., Bastian, V., Becker, K. H., and Overath, R. D.: Kinetic studies of the reactions of IO, BrO, and ClO with DMS, Int. J. Chem. Kinet., 23, 579–591, 1991.

Berresheim, H.: Biogenic sulfur emissions from the Subantarctic and Antarctic Oceans, J. Geophys. Res., 92, 13 245–13 262, 1987.

Berresheim, H. and Eisele, F. L.: Sulfur Chemistry in the Antarctic Troposphere Experiment: An overview of project SCATE, J. Geophy. Res., 103, 1619–1627, 1998a.

Berresheim, H., Huey, J. W., Thorn, R. P., Eisele, F. L., Tanner, D. J., and Jefferson, A.: Measurements of dimethyl sulfide, dimethyl sulfoxide, dimethyl sulfone and aerosol ions at Palmer Station, Antarctica, J. Geophys. Res., 103, 1629–1637, 1998b.

Bloss, W. J., Lee, J. D., Heard, D. E., Salmon, R. A., Bauguitte, S. J.-B., Roscoe, H. K., and Jones, A. E.: Observations of OH and HO2 radicals in coastal Antarctica, Atmos. Chem. Phys. Discuss., 7, 2893–2935, 2007.

Charlson, R. J., Lovelock, J. E., Andreae, M. O., and Warren, S. G.: Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate, Nature, 326, 655–661, 1987.

Comisco, J. C., McClain, R. C., Sullivan, C. W., Ryan, J. P., and Leonard, C. L.: Coastal Zone Color Scanner pigment concentrations in the Southern Ocean and relationships to geophysical surface features, J. Geophys. Res., 98, 2419–2451, 1993.

Cosme, E., Hourdin, F., Genthon, C., and Martinerie, P.: Origin of dimethyl sulfide, non-sea-salt sulfate, and methanesulfonic acid in eastern Antarctica, J. Geophys. Res., 110, D03302, https://doi.org/10.1029/2004JD004881, 2005.

Curran, M. A. J., van Ommen, T. D., Morgan, V. I., Phillips, K. L., and Palmer, A. S.: Ice core evidence for Antarctic sea ice decline since the 1950s, Science, 302, 1203–1206, 2003.

Davis, D. D., Eisele, F., Chen, G., Crawford, J., Huey, G., Tanner, D., Slusher, D., Mauldin, D., Oncley, S., Lenschow, D., Semmer, S., Shetter, R., Lefer, B., Arimoto, R., Hogan, A., Grube, P., Lazzara, M., Bandy, A., Thornton, D., Berresheim, H., Bingemer, H., Hutterli, M., McConnell, J., Bales, R., Dibb, J., Buhr, M., Park, J., McMurry, P., Swanson, A., Meinardi, S., and Blake, D.: An overview of ISCAT 2000, Atmos. Environ., 38, 5363–5373, 2004.

Davison, B., Hewitt, C. N., O'Dowd, C. D., Lowe, J. A., Smith, M. H., Schwikowski, M., Baltensperger, U., and Harrison, R. M.: Dimethyl sulfide, methane sulfonic acid and physiochemical aerosol properties in Atlantic air from the United Kingdom to Halley Bay, J. Geophys. Res., 101, 22 855–22 867, 1996.

Davison, B., O'Dowd, C., Hewitt, C. N., Smith, M. H., Harrison, R. M., Peel, D. A., Wolff, E., Mulvaney, R., Schwikowski, M., and Baltensperger U.: Dimethyl sulfide and its oxidation products in the atmosphere of the Atlantic and Southern Oceans, Atmos. Environ., 30, 1895–1906, 1995.

Falbe Hansen, H., Sørensen, S., Jensen, N. R., Pedersen, T., Hjorth, J.: Atmospheric gas-phase reactions of diemthyl sulphoxide and dimethylsulphone with OH and NO3 radicals Cl atoms and ozone, Atmos. Environ., 34, 1543–1551, 2000.

Frieß, U., Hollwedel, J., Konig-Langlo, G., Wagner, T., and Platt, U.: Dynamics and chemistry of troposphieric bromine explosion events in the Antarctic coastal region, J. Geophys. Res., 109, D06305, https://doi.org/10.1029/2003JD004133, 2004.

Frieß, U., Kreher, K., Johston, P. V., and Platt, U.: Ground-based DOAS measurements of stratospheric trace gases at two Antarctic stations during the 2002 ozone hole period, J. Atmos. Sci., 63(3), 765–777, 2005.

Gondwe, M., Krol, M., Gieskes, W., Klaasen, W., and De Baar, H.: The contribution of ocean-leaving DMS to the global atmospheric burdens of DMS, MSA, SO2, and NSS SO$_4^=$, Global Biogeochem. Cy., 17, 2, 1056, https://doi.org/10.1029/2002GB001937, 2003.

Gondwe, M., Krol, M., Klassen, W., Gieskes, W., and De Baar, H.: Comparison of modeled versus measured MSA:nss SO42- ratios: A global analysis, Global Biogeochem. Cy., 18, GB2006, https://doi.org/10.1029/2003GB002144, 2004.

Hegels, E., Crutzen, P. J., Klupfel, T., Perner, D., and Burrows, J. P.: Global distribution of atmospheric bromine-monoxide from GOME on earth observing satellite ERS-2, Geophys. Res. Lett., 25, 3127–3130, 1998.

Hynes, A. J., Wine, P. J., and Semmes, D. H.: Kinetics and mechanism of OH reactions with organic sulfides, J. Phys. Chem., 90, 4148–4156, 1986.

Hynes, A. J. and Wine, P. J.: The atmospheric chemistry of dimethyl sulfoxide (DMSO) kinetics and mechanism of the OH + DMSO reaction, J. Atmos. Chem., 24, 23–27, 1996.

Ingham, T., Bauer, D., Sander, R., Crutzen, P. J., and Crowley, J. N.: Kinetics and products of the reactions BrO + DMS and Br + DMS at 298K, J. Phys. Chem., 103, 7199–7209, 1999.

Jee J. and Tao, F. M.: Reaction mechanism and kinetics for the oxidation of dimethyl sufide by nitrate radical, Chem. Phys. Lett., 420, 336–339, 2006.

Jefferson, A., Tanner, D. J., Eisele, F. L., Davis, D. D., Chen, G., Crawford, J., Huey, J. W., Torres, A. L., and Berresheim, H.: OH photochemistry and methane sulfonic acid formation in the coastal Antarctic boundary layer, J. Geophys. Res., 103, 1647–1656, 1998.

Jones, A. E., Wolff, E. W., Salmon, R. A., Bauguitte, S. J.-B., Roscoe, H. K., Anderson, P. S., Ames, D., Clemitshaw, K. C., Fleming, Z. L., Bloss, W. J., Heard, D. E., Lee, J. D., Read, K. A., Hamer, P., Shallcross, D. E., Jackson, A., Walker, S., Lewis, A. C., Mills, G. P., Plane, J. M. C., Saiz-Lopez, A., Sturges, W. T., and Worton, D. R.: Chemistry of the antarctic boundary layer and the interface with snow: an overview of the CHABLIS campaign, Atmos. Chem. Phys. Discuss., 8, 5137–5181, 2008.

Jourdain, B. and Legrand, M.: Seasonal variations of atmospheric dimethylsulfide, dimethylsulfoxide, sulfur dioxide, methanesulfonate, and non-sea-salt sulfate aerosols at Dumont d'Urville (coastal Antarctica) (December 1998 to July 1999), J. Geophys. Res., 106, 14 391–14 408, 2001.

Jourdain, B. and Legrand, M.: Year-round records of bulk and size-segregated aerosol composition and HCl and HNO3 levels in the Dumont d'Urville (coastal Antarctica) atmosphere: Implications for sea-salt aerosol fractionation in the winter and summer, J. Geophys. Res., 107, 4645, 2002.

Kreher, K., Johnston, P. V., and Wood, S. W.: Ground-based measurements of tropospheric and stratospheric BrO at Arrival Heights, Antarctica, Geophys. Res. Lett., 24, 23, 3021–3024, 1997.

Legrand, M. and Pasteur, E. C.: Methane sulfonic acid to non sea-salt sulfate ratio in coastal Antarctic aerosol and surface snow, J. Geophys. Res., 103(D9), 10 991–11 006, 1998.

Legrand, M., Sciare, J., Jourdain, B., and Genthon, C.: Subdaily variations of atmospheric dimethylsulfide, dimethylsulfoxide, methanesulfonate, and non-sea-salt sulfate aerosols in the atmospheric boundary layer at Dumont d'Urville (coastal Antarctica) during summer, J. Geophys. Res., 106, 14 409–14 422, 2001.

Liss, P. S., Hatton, A. D., Malin, G., Nightingale, P. D., and Turner, S. M.: Marine sulphur emissions, Philos. T. Roy. Soc. B, 352, 159–168, 1997.

Mauldin-III, R. L., Eisele, F. L., Tanner, D. J., Kosciuch, E., Shetter, R., Lefer, B., Hall, S. R., Nowak, J. B., Buhr, M., Chen, G., Wang, P., and Davis, D.: Measurements of OH, H2SO4, and MSA at the South Pole during ISCAT, Geophys. Res. Lett., 28, 3629–3632, 2001.

Minikin,A., Legrand, M., Hall, J., Wagenbach, D., Kleefeld, C., Wolff, E., Pasteur, E. C., and Ducroz, F.: Sulfur containing species (sulfate and methanesulfonate) in coastal Antarctic aerosol and precipitation, J. Geophys. Res., 103, 10 975–10 990, 1998.

Plane, J. M. C. and Saiz-Lopez, A.: UV-Visible differential optical absorption spectroscopy (DOAS), in: Analytical techniques for atmospheric measurement, edited by: Heard, D. E., Blackwell Publishing, Oxford, 2006.

Preunkert, S., Legrand, M., Jourdain, B., Moulin, C., Belviso, S., Kasamatsu, N., Fukuchi, M., and Hirawake, T.: Interannual variability of dimethylsulfide in air and seawater and its atmospheric oxidation by-products (methanesulfonate and sulfate) at Dumont d'Urville, coastal Antarctica (1999–2003), J. Geophys. Res., 112, D06306, https://doi.org/10.1029/2006JD007585, 2007.

Prospero, J. M., Savoie, D. L., Saltzman, E. S., and Larsen, R.: Impact of oceanic sources of biogenic sulphur on sulphate aerosol concentrations at Mawson, Antarctica, Nature, 350, 221–223, 1991.

Rankin, A. M. and Wolff, E. W.: A year-long record of size-segregated aerosol composition at Halley, Antarctica, J. Geophys. Res., 108(D24), 4775, https://doi.org/10.1029/2003JD003993, 2003.

Read, K. A., Lewis, A. C., Salmon, R. A., Jones, A. E., and Bauguitte, S.: OH and halogen influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer, Tellus B., 59, 22–38, 2007.

Saiz-Lopez, A., Plane, J. M. C., and Shillito, J. A., Bromine oxide in the mid-latitude marine boundary layer, Geophys. Res. Lett., 31, L03111, https://doi.org/10.1029/2003GL018956, 2004.

Saiz-Lopez, A, Mahajan, A. S., Salmon, R. A., Bauguitte, S. J.-B., Jones, A. E., Roscoe, H. K., and Plane, J. M. C.: Boundary Layer Halogens in Coastal Antarctica, Science, 317. 5836, 348–351, https://doi.org/10.1126/science.1141408, 2007.

Savoie, D. L., Prospero, J. M., Larsen, R. J., Huang, F., Izaguirre, M. A., Huang, T., Snowdon, T.H., Custals, L., and Sanderson, C. G.: Nitrogen and sulfur species in Antarctic aerosols at Mawson, Palmer Station and Marsh (King George Island), J. Atmos. Chem., 95–122, 1993.

Simpson, W. R., von~Glasow, R., Riedel, K., Anderson, P., Ariya, P., Bottenheim, J., Burrows, J., Carpenter, L. J., Frieß, U., Goodsite, M. E., Heard, D. E., Hutterli, M., Jacobi, H.-W., Kaleschke, L., Neff, B., Plane, J., Platt, U., Richter, A., Roscoe, H., Sander, R., Shepson, P., Sodeau, J., Steffen, A., Wagner, T., and Wolff, E.: Halogens and their role in polar boundary-layer ozone depletion, Atmos. Chem. Phys., 7, 4375–4418, 2007.

Staubes, R. and Georgii H. W.: Biogenic sulfur compunds in seawater and the atmosphere of the Antarctic region, Tellus, 45B, 127–137, 1993.

Toumi, R.: BrO as a sink for dimethylsulphide in the marine atmosphere, Geophys. Res. Lett., 21, 117–120, 1994.

Von Glasow, R., Sander, R., Bott, A., and Crutzen, P. J.: Modelling halogen chemistry in the marine boundary layer, 2, Interactions with sulfur and cloud-covered MBL, J. Geophys. Res., 107(D17), 4323, https://doi.org/10.1029/2001JD000943, 2002.

Von Glasow, R. and Crutzen, P. J.: Model study of multiphase DMS oxidation with a focus on halogens, Atmos. Chem. Phys., 4, 589–608, 2004.

Wagenbach, D., Ducroz, F., Mulvaney, R., Keck, L., Minikin, A., Legrand, M., Hall, J. S., and Wolff, E. W.: Sea-salt aerosol in coastal Antarctic regions, J. Geophys. Res., 103, 10 961–10 974, 1998.

Wolff, E. W., Legrand, M. R., and Wagenbach, D.: Coastal Antarctic aerosol and snowfall chemistry, J. Geophys. Res., 103, 10 927–10 934, 1998.