Substitution of chloride in sea-salt particles by inorganic and organic anions

Depletion of chloride in sea-salt particles was studied at a site near the Arctic Ocean. The investigation was based on size-segregated particle sampling using a Berner low-pressure impactor. According to the impactor measurements, average chloride losses were close to 100% for submicron particles. However, this is successively less for increasing particle size in the supermicron size range. The main constituents replacing chloride from supermicron sea-salt particles were sulfate and nitrate followed by MSA- and oxalate, and with malonate and succinate giving a minor contribution. Anions of organic dicarboxylic acids became more important for air spending a longer time over the continent. Our analysis suggests that principal mechanisms accumulating sulfate into sea-salt particles are cloud processing and, to a lesser degree, heterogeneous reactions taking place in deliquescent sea-salt particles. Mechanisms for the chloride replacement by nitrate are less clear. The distributions of MSA- and oxalate over the sea-salt particle size range were similar to each other, whereas other organic anions analyzed here had a peak concentration at a somewhat larger particle size. Better understanding on the chemistry associated with sea-salt particles requires investigating not only reactions in deliquescent sea-salt particles, but also the interactions between these particles and clouds.