Enrichment of poly- and perfluoroalkyl substances (PFAS) in the surface microlayer and foam in synthetic and natural waters

Bench-scale experiments were performed to interrogate poly- and perfluoroalkyl substance (PFAS) enrichment in the water surface microlayer (SML). In initial experiments using electrolyte-only solutions, the perfluorooctane sulfonate (PFOS) and perfluorooctane carboxylate (PFOA) enrichment in the SML were reasonably (with a factor of 2) described by the Gibbs adsorption equation coupled with a Freundlich-based interfacial adsorption model. Enrichment in the SML among perfluorinated sulfonates and perfluorinated carboxylates of varying chain lengths was proportional to their surface activity. The PFOS enrichment factor (EF), defined as the PFAS concentration in the SML divided by the concentration in the bulk water, was 18 in a 200 mg/l NaCl solution. The presence of elevated organic carbon levels in synthetic surface waters inhibited PFAS accumulation in the SML, with resulting EF values of approximately 1 for all PFAS. However, in the presence of elevated organic levels coupled with foam, PFAS enrichment in the foam was observed, with a foam EF of 25 measured for PFOS in synthetic surface waters. PFAS EF values measured in several natural surface waters without foam showed little variation among the waters tested, with PFOS EF values ranging between 6 and 10. Together, these results suggest that PFAS accumulation in the SML is largely controlled by PFAS sorption at the air-water interface for the conditions examined in this study, and the presence of foam with natural organics enhances PFAS uptake at the water surface. [Display omitted] •Interfacial sorption controls PFAS microlayer accumulation in absence of organics.•Natural organics in natural waters reduced PFOS accumulation in the surface microlayer.•Natural organics in naturalwaters enhanced PFOA and 6:2 FtS accumulation in the surface microlayer.