Influence of Water Concentrations of Perfluoroalkyl Acids (PFAAs) on Their Size-Resolved Enrichment in Nascent Sea Spray Aerosols

Perfluoroalkyl acids (PFAAs) are persistent organic substances that have been widely detected in the global oceans. Previous laboratory experiments have demonstrated effective enrichment of PFAAs in nascent sea spray aerosols (SSA), suggesting that SSA are an important source of PFAAs to the atmosphere. In the present study, the effects of the water concentration of PFAAs on their size-resolved enrichment in SSA were examined using a sea spray simulation chamber. Aerosolization of the target compounds in almost all sizes of SSA revealed a strong linear relationship with their water concentrations (p < 0.05, r(2) > 0.9). The enrichment factors (EF) of the target compounds showed no correlation with their concentrations in the chamber water, despite the concentrations varying by a factor of 500 (similar to 0.3 to similar to 150 ng L-1). The particle surface-area-to-volume ratio appeared to be a key predictor of the enrichment of perfluoroalkyl carboxylic acids (PFCAs) with >= 7 perfluorinated carbons and perfluoroalkanesulfonic acids (PFSAs) with >= 6 perfluorinated carbons in supermicron particles (p < 0.05, r(2) > 0.8), but not in submicron particles. The different enrichment behaviors of PFAAs in submicron and supermicron particles might be a result of the different production mechanisms of film droplets and jet droplets. The results suggest that the variability in seawater concentrations of PFAAs has little influence on EFs and that modeling studies designed to quantify the source of PFAAs via SSA emissions do not need to consider this factor.

Automated summary

Perfluoroalkyl acids (PFAAs) are enriched in sea spray aerosols (SSA) with a strong linear relationship to water concentration. The particle surface-area-to-volume ratio is a key predictor of PFAAs enrichment in supermicron particles, while the differences in enrichment behaviors between submicron and supermicron particles are likely due to different production mechanisms. Seawater concentrations of PFAAs have little influence on enrichment factors (EFs) in SSA emissions.