1School of Chemistry, University of Leeds, Leeds LS2 9JT, UK
2Instituto Nacional de Meteorologia Geofisica (INMG), Delegação de São Vicente, Monte, CP 15, Mindelo, Cape Verde
3Laboratory of Atmospheric and Climate Science, Consejo Superior de Investigaciones Cientificas, 45007 Toledo, Spain
4Department of Chemistry, University of York, York, UK
5Centre for Atmospheric Science, School of Earth, Environment and Environmental Sciences, The University of Manchester, Manchester M13 9PL, UK
Abstract. Although reactive halogen chemistry is well studied in coastal and polar environments, the presence of halogens over the open ocean environment has not been widely reported. The impacts of halogens on the tropical open ocean marine boundary layer (MBL), in particular, are not well characterised. This paper describes observations of iodine monoxide (IO) and bromine oxide (BrO) over eight months in the tropical open ocean MBL, on the north-eastern side of São Vicente (Cape Verde Islands, 16.85° N, 24.87° W). The highest BrO mixing ratio observed was 5.6±1 ppt, while the maximum observed IO mixing ratio was 3.1±0.4 ppt. The average values seen between 09:00–17:00 GMT were ~2.8 ppt for BrO and ~1.5 ppt for IO; these averages showed little variability over the entire campaign from November 2006 to June 2007. A 1-dimensional chemistry and transport model is used to study the evolution of iodine species and quantify the combined impact of iodine and bromine chemistry on the oxidising capacity of the MBL. It appears that the measured fluxes of iodocarbons are insufficient to account for the observed levels of IO, and that an additional I atom source is required, possibly caused by the deposition of O3 onto the ocean surface in the presence of solar radiation. Modelling results also show that the total O3 depletion observed at Cape Verde cannot be explained in the absence of halogen chemistry, which contributes ~45% of the total O3 depletion at the height of measurements (10 m) during summer. The model also predicts that halogens decrease the hydroperoxy radical (HO2) concentration by ~14% and increase the hydroxyl radical (OH) concentration by ~13% near the ocean surface. The oxidation of dimethyl sulphide (DMS) by BrO takes place at a comparable rate to oxidation by OH in this environment. Finally, the potential of iodine chemistry to form new particles is explored and conditions under which particle formation could be important in the remote MBL are discussed.