Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 3 2009 10.5194/acpd-9-11889-2009 http://www.atmos-chem-phys-discuss.net/9/11889/2009/ http://www.atmos-chem-phys-discuss.net/9/11889/2009/acpd-9-11889-2009.html http://www.atmos-chem-phys-discuss.net/9/11889/2009/acpd-9-11889-2009.pdf 11889 11950 2009-05-14 Latitudinal variation in the multiphase chemical processing of inorganic halogens and related species over the eastern North and South Atlantic Oceans W. C. Keene wck@virginia.edu M. S. Long A. A. P. Pszenny R. Sander J. R. Maben A. J. Wall T. L. O'Halloran A. Kerkweg E. V. Fischer O. Schrems Department of Environmental Sciences, University of Virginia, Charlottesville, VA 22904, USA Mount Washington Observatory, North Conway, NH 03860, USA Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH 03824, USA Air Chemistry Department, Max-Planck Institute of Chemistry, 55020 Mainz, Germany Alfred Wegener Institute for Polar and Marine Research, 27515 Bremerhaven, Germany now at: Atmospheric Chemistry Program, National Sciences Foundation, Arlington, VA, USA now at: Department of Geosciences, Pennsylvania State University, University Park, PA 16802, USA now at: Department of Forest Ecosystems and Society, Oregon State University, Corvallis, OR 97330, USA now at: Institute for Atmospheric Physics, University of Mainz, 55020 Mainz, Germany now at: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195, USA Volatile inorganic and size-resolved particulate Cl- and Br-species were measured in near-surface air over a broad range of conditions within four distinct regimes (European – EURO, North African – N-AFR, the Intertropical Convergence Zone – ITCZ, and South Atlantic – S-ATL) along a latitudinal gradient from 51° N to 18° S through the eastern Atlantic Ocean. Processes within each regime were interpreted in conjunction with box-model calculations. Median dry-deposition fluxes of sea salt, oxidized N, and oxidized non-sea-salt S varied by factors of 25, 17, and 9, respectively, among the regimes. Sea-salt production was the primary source for inorganic Cl and Br. Acidification and dechlorination of sea salt primarily by HNO₃ sustained HCl mixing ratios ranging from medians of 82 (ITCZ) to 682 (EURO) pmol mol^−1. Aerosol pHs inferred from HCl phase partitioning with super-μm size fractions (~3 for EURO to the low 4 s for ITCZ) were similar to modeled values. Within all regimes, the dominant sources for atomic Cl were BrCl photolysis and ClO+NO. Maxima in atomic Cl ranged from 2.1 to 7.8×10⁴ cm^−3 in the ITCZ and N-AFR regimes, respectively. Because SO₂ solubility over the aerosol pH range was low, S(IV) oxidation by hypohalous acids was unimportant under most conditions. 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