References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-9-7361-2009

Latitudinal variation in the multiphase chemical processing of inorganic halogens and related species over the eastern North and South Atlantic Oceans

Keene

W. C.

¹ Long

M. S.

¹ Pszenny

A. A. P.

² ³ ⁶ Sander

⁴ Maben

J. R.

¹ Wall

A. J.

³ ⁷ O'Halloran

T. L.

¹ ⁸ Kerkweg

⁴ ⁹ Fischer

E. V.

³ ¹⁰ Schrems

⁵

Department of Environmental Sciences, University of Virginia, Charlottesville, VA 22904, USA

Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH, 03824, USA

Mount Washington Observatory, North Conway, NH, 03860, 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 Science Foundation, Arlington, VA, 22230, 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

02 10 2009

9 19 7361 7385

2009

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/9/7361/2009/acp-9-7361-2009.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/9/7361/2009/acp-9-7361-2009.pdf

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. 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. Median aerosol pHs inferred from HCl phase partitioning with super-μm size fractions ranged from ~3.0 for EURO to ~4.5 for ITCZ. Because SO2 solubility over this pH range was low, S(IV) oxidation by hypohalous acids was unimportant under most conditions. Simulations with a detailed multiphase box model indicated that BrCl photolysis and ClO + NO were the major sources for atomic Cl in all regimes. Simulated midday concentrations of Cl atoms ranged from 2.1×104 to 7.8×104 cm−3 in the ITCZ and N-AFR regimes, respectively. Measured particulate Br− (median enrichment factor = 0.25) was greater and volatile inorganic Br less than simulated values, suggesting that the halogen activation mechanism in the model overestimated Br-radical production and processing. Reaction with atomic Br was an important sink for modeled O3 (5% in EURO to 46% in N-AFR). Formation of halogen nitrates accelerated the oxidation of NOx (NO + NO2) primarily via hydrolysis reactions involving S aerosol. Relative to simulations with no halogens, lower NOx coupled with direct reactions involving halogens yielded lower steady state mixing ratios of OH (20% to 54%) and O3 (22% to 62%) and lower midday ratios of OH:HO2 (3% to 32%) in all regimes.

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