Chloride and bromide loss from sea-salt particles in southern ocean air

Datasets on aerosol composition in Southern Ocean air at Cape Grim and Macquarie Island, and rainwater composition at Cape Grim, have been analysed for sea-salt components in order to test the validity of the multiphase autocatalytic halogen activation process proposed initially by Sander and Crutzen (1996) and developed fully for clean marine air by Vogt et al. (1996). Four distinct datasets from the two locations were analysed. All four datasets provided consistent evidence in support of three predictions of the autocatalytic model: (1) overall Cl- deficits in sea-salt aerosol were small, difficult to quantify against analytical uncertainty and at most a few percent; (2) Br- deficits were large, averaging -30% to -50% on an annual basis, with strong seasonality ranging from about -10% in some winter samples to -80% or more in some summer samples; and (3) the Br- and Cl- deficits were clearly linked to the availability of strong, S-acidity in the aerosol, confirming the importance of acid catalysis to the dehalogenation process.