Preferential Partitioning of Per- and Polyfluoroalkyl Substances in Freshwater Ice.

Millions of lakes worldwide freeze, yet the fate of per- and polyfluoroalkyl substances (PFAS) in ice in freshwater systems is poorly understood. We quantified concentrations of 36 PFAS, dissolved organic carbon (DOC), and inorganic ions in ice and water in seven freshwater lakes to investigate the preferential exclusion of ions during freezing. PFAS concentrations in ice are typically lower than in the water column, demonstrating that these chemicals are excluded from ice as it freezes. However, there is preferential partitioning of both PFAS and DOC relative to cations with average sodium-normalized enrichment factors (EF) ranging from 2.74 for perfluorobutanoate (PFBA; a C4 perfluorocarboxylic acid) to 4.01 for perfluorooctanesulfonate (PFOS; a C8 perfluorosulfonic acid), with a similar EF value of 4.14 for DOC. Laboratory experiments and seasonal measurements of PFAS in the water column indicate that PFAS concentrations in ice are a function of aqueous PFAS concentrations, with lower EF values observed in waters with higher PFAS concentrations. Understanding PFAS behavior in freshwater ice is important for predicting contaminant fate during winter and spring periods, with implications for exposure to PFAS during the winter and release of PFAS when ice melts in freshwater systems.

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 <50 to >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.