Preferential Partitioning of Per- and Polyfluoroalkyl Substances (PFAS) and Dissolved Organic Matter in Freshwater Surface Microlayer and Natural Foam

Per- and polyfluoroalkyl substances (PFAS) are surfactants that can accumulate in the surface microlayer (SML) and in natural foams, with potential elevated exposure for organisms at the water surface. However, the impact of water chemistry on PFAS accumulation in these matrices in freshwater systems is unknown. We quantified 36 PFAS in water, the SML, and natural foams from 43 rivers and lakes in Wisconsin, USA, alongside measurements of pH, cations, and dissolved organic carbon (DOC). PFAS partition to foams with concentration ranging 2300–328,200 ng/L in waters with 6–139 ng/L PFAS (sum of 36 analytes), corresponding to sodium-normalized enrichment factors ranging 7000. Similar enrichment is observed for DOC (∼70). PFAS partitioning to foams increases with increasing chain length and is positively correlated with DOC. Modest SML enrichment is observed for PFOS (1.4) and FOSA (2.4), while negligible enrichment is observed for other PFAS and DOC due to low specific surface area and turbulent conditions that inhibit surfactant accumulation. However, DOC composition in the SML is distinct from bulk water, as assessed using high-resolution mass spectrometry. This study demonstrates that natural foams in unimpacted and impacted waters can have elevated PFAS concentrations, whereas SML accumulation in surface waters is limited.