Assessment of PFAS contamination in agricultural soils: Non-target identification of precursors, fluorine mass balance and microcosm studies

Biodegradation of PFAS is examined in eight PFAS precursor-contaminated topsoil samples in order to determine generation rate constants for perfluorocarboxyl acids (PFCA) and to elucidate soil properties affecting these. PFAS were analyzed via both target (HPLC-MS/MS) and non-target (HPLC-QTOF) (semi)quantification. FTMAPs, diPAPs, and diSAmPAP were identified and accounted for > 80 % of the total PFAS burden, which ranged from ∼ 280-9700 ng g^-1. These levels were confirmed by chemical oxidation of precursors (TOP assay) which allowed to close the fluorine mass balance against extractable organic fluorine (EOF). Notably, in some organic carbon rich samples, repeated oxidation was needed to achieve a complete fluorine mass balance. Batch microcosm incubations and total precursor quantification allowed to determine production rate constants of short-chain PFCA, which ranged from 0.02 to 0.50 year^-1 depending on PFAS and soil physicochemical properties. Principal component analysis (PCA) indicated that both acid phosphomonoesterase and, to some extent, microbial biomass influences the production rates of short-chain PFAS in soils. This allowed to assess contamination time scales, indicating that production and thus release of PFAS from precursor decay will continue for years to decades. This bears the risk of contamination of adjacent environmental compartments such as groundwater and surface water bodies.