Gas/particle partitioning behavior of perfluorocarboxylic acids with terrestrial aerosols

Experimentally determined gas/particle partitioning constants, K(ip), using inverse gas chromatography (IGC) are presented for perfluorocarboxylic acids (PFCAs), covering a diverse set of terrestrial aerosols over an ambient range of relative humidity (RH) and temperature. The results are compared to estimated K(ip) values using a recently developed model that has been validated for diverse neutral and ionizable organic compounds. The modeling results consistently underestimate the experimental results. This is likely due to additional partition mechanisms unique for surfactants not being accounted for in the model, namely aggregate formation and water surface adsorption. These processes likely also biased the IGC K(ip) measurements compared to ambient PFCA concentrations. Nevertheless, both the experimental and modeling results indicate that partitioning to terrestrial particles in ambient atmospheres is negligible, though sorption to condensed water can be substantial. This favors rain sequestration as a more important atmospheric removal mechanism than dry particle sequestration. PFCAs found on particle filters during ambient sampling are thus accountable to vapor-phase PFCAs or aqueous-phase PFCAs sorbing directly to the filters, or the trapping of perfluorocarboxylate-salt particles. Further work on understanding the partitioning and speciation of PFCAs in atmospheric water droplets is needed to further quantify and understand their atmospheric behavior. To aid in this, a general RH dependent K(ip) model for surfactants is presented.