Environmental Fate of Cl-PFPECAs: Accumulation of Novel and Legacy Perfluoroalkyl Compounds in Real-World Vegetation and Subsoils

Per- and polyfluoroalkyl substances (PFAS) are globally distributed and potentially toxic compounds. We report accumulation of chloroperfluoropolyethercarboxylates (Cl-PFPECAs) and perfluorocarboxylates (PFCAs) in vegetation and subsoils in New Jersey. Lower molecular weight Cl-PFPECAs, containing 7–10 fluorinated carbons, and PFCAs containing 3–6 fluorinated carbons were enriched in vegetation relative to surface soils. Subsoils were dominated by lower molecular weight Cl-PFPECAs, a divergence from surface soils. Contrastingly, PFCA homologue profiles in subsoils were similar to surface soils, likely reflecting temporal-use patterns. Accumulation factors (AFs) for vegetation and subsoils decreased with increasing CF2, 6–13 for vegetation and 8–13 in subsoils. In vegetation, for PFCAs having CF2 = 3–6, AFs diminished with increasing CF2 as a more sensitive function than for longer chains. Considering that PFAS manufacturing has transitioned from long-chain chemistry to short-chain, this elevated vegetative accumulation of short-chain PFAS suggests the potential for unanticipated PFAS exposure levels globally in human and/or wildlife populations. This inverse relationship between AFs and CF2-count in terrestrial vegetation is opposite the positive relationship reported in aquatic vegetation suggesting aquatic food webs may be preferentially enriched in long-chain PFAS. AFs normalized to soil–water concentrations increased with chain length for CF2 = 6–13 in vegetation but remained inversely related to chain length for CF2 = 3–6, reflecting a fundamental change in vegetation affinity for short chains compared to long.