Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 4 2007 10.5194/acpd-7-11647-2007 http://www.atmos-chem-phys-discuss.net/7/11647/2007/ http://www.atmos-chem-phys-discuss.net/7/11647/2007/acpd-7-11647-2007.html http://www.atmos-chem-phys-discuss.net/7/11647/2007/acpd-7-11647-2007.pdf 11647 11683 2007-08-08 Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic A. E. Cavender acavende@purdue.edu T. A. Biesenthal J. W. Bottenheim P. B. Shepson Department of Chemistry, Purdue University, West Lafayette, IN, USA Department of Chemistry, York University, Toronto, Ontario, Canada Science and Technology Branch, Environment Canada, Toronto, Ontario, Canada Department of Earth and Atmospheric Science, Purdue University, West Lafayette, IN, USA Purdue Climate Change Research Center, Purdue University, West Lafayette, IN, USA now at: Sciex, Concord, Ontario, Canada Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack) to correctly simulate the VOC chemistry of the Arctic, and that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events. Adams, J. W., Holmes, N. S., and Crowley, J. N.: Uptake and reaction of HOBr on frozen and dry NaCl/NaBr surfaces between 253 and 233 K, Atmos. Chem. Phys., 2, 79–91, 2002. Anastasio, C. and Jordan, A. L.: Photoformation of hydroxyl radical and hydrogen peroxide in aerosol particles from Alert, Nunavut: implications for aerosol and snowpack chemistry in the Arctic, Atmos. Environ., 38, 1153–1166, 2004. Apel, E. C., Riemer, D. D., Hills, A., Baugh, W., Orlando, J., Faloona, I., Tan, D., Brune, W., Lamb, B., Westberg, H., Carroll, M. A., Thornberry, T., and Geron, C. 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