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.