Does wet precipitation represent local and regional atmospheric transportation by perfluorinated alkyl substances?

Perfluorinated alkyl substances (PFASs) have been found widely in the environment including remote marine locations. The mode of transport of PFASs to remote marine locations is a subject of considerable scientific interest. Assessment of distribution of PFASs in wet precipitation samples (i.e., rainfall and snow) collected over an area covering continental, coastal, and open ocean will enable an understanding of not only the global transport but also the regional transport of PFASs. Nevertheless, it is imperative to examine the representativeness and suitability of wet precipitation matrixes to allow for drawing conclusions on the transport PFASs. In this study, we collected wet precipitation samples including rainfall, surface snow, and snow core from several locations in Japan to elucidate the suitability of these matrixes for describing local and regional transport of PFASs. Rain water collected at various time intervals within a single rainfall event showed high fluxes of PFASs in the first 1-mm deposition. The scavenging rate of PFASs by wet deposition varied depending on the fluorocarbon chain length of PFAS. The depositional fluxes of PFASs measured for continental (Tsukuba, Japan) and open ocean (Pacific Ocean, 1000km off Japanese coast) locations were similar, on the order of a few nanograms per square meter. The PFAS profiles in "freshly" deposited and "aged" (deposited on the ground for a few days) snow samples taken from the same location varied considerably. The freshly deposited snow represents current atmospheric profiles of PFASs, whereas the aged snow sample reflects sequestration of local sources of PFASs from the atmosphere. Post-depositional modifications in PFAS profiles were evident, suggesting reactions of PFASs on snow/ice surface. Transformation of precursor chemicals such as fluorotelomer alcohols into perfluoroalkylcarboxylates is evident on snow surface. Snow cores have been used to evaluate time trends of PFAS contamination in remote environments. Snow collected at various depths from a core of up to 7.7m deep, at Mt. Tateyama (2450m), Japan, showed the highest concentrations of PFASs in the surface layer and the concentrations decreased with increasing depth for most PFASs, except for perfluorobutanesulfonate (PFBS). Downward movement of highly water soluble PFASs such as PFBS, following melting and freezing cycles of snow, was evident from the analysis of snow core.