Occurrence and Fate of Fluoroalkyl Sulfonamide-Based Copolymers in Earthworms-Bioavailability, Transformation, and...

To date, considerable knowledge and data gaps regarding the occurrence, environmental levels, and fate of polymeric perfluoroalkyl and polyfluoroalkyl substances (PFAS) exist. In the present study availability, accumulation, and transformation of C4- and C8-fluoroalkylsulfonamide (FASA)-based copolymers were assessed in laboratory-grown earthworms (Eisenia fetida, triplicate of exposure tests and control). Further, a field study on earthworms (18 pooled samples) in sludge-amended soil was conducted to assess the environmental impact of sludge-amended soil with regard to the FASA-based copolymers, together with the applied sludge (n = 3), and the field soils during the period (n = 4). In the laboratory study, the FASA-based copolymers were taken up by the earthworms in concentrations between 19 and 33 ng/g of dw for the C8- and between 767 and 1735 ng/g of dw for the C4-FASA-based copolymer. Higher biota soil accumulation factors (BAFs) were observed for the copolymer with a longer perfluorinated side-chain length (C8, average BAF value of 0.7) compared to the copolymer with a shorter side-chain length (C4, average BAF value of 0.02). Perfluorooctane sulfonamidoacetates (FOSAAs) and perfluorooctane sulfonamide (FOSA), including both branched and linear isomers, were detected after exposure to the C8-FASA-based copolymer. Two metabolites were detected in the earthworms exposed to the C4-FASA-based copolymer: perfluorobutanesulfonamide (FBSA) and perfluorobutanesulfonic acid (PFBS). Although the presence of other monomers or impurities in the copolymer formulation cannot be ruled out, the present laboratory study suggests that the FASA-based copolymers may be an indirect source of lower molecular weight PFAS in the environment through transformation. Elevated levels of C8-FASA-based copolymer were found in the field sludge-amended soil compared to nontreated soil (32 versus 11 ng/g d.w.), and higher concentrations of PFAS in earthworms living in sludge-amended soil compared to nontreated soil (566 versus 103 ng/g d.w.) were observed. These findings imply that the application of sludge is a potential pathway of PFAS to the environment.