Accumulation and trophic transfer of per- and polyfluoroalkyl substances (PFAS) in estuarine organisms determined via stable isotopes

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants in estuaries. In this study, 19 PFAS were quantified in surface waters, sediments, marine invertebrates (aquatic worms, Eastern oysters, and blue crab), and forage fish (Atlantic silverside, four-spine stickleback, mummichog, sheepshead minnow, and rainwater killifish) in an aqueous film forming foam (AFFF)-contaminated estuary, Georgica Pond (NY, USA). Carbon and nitrogen stable isotopes (δ¹³C and δ¹⁵N) were used to determine trophic position of organisms and to identify modes of PFAS exposure. The influence of salinity (8 to 26 practical salinity units, PSU) on the relative and absolute abundance of PFAS in all matrices was also investigated. Eleven long- and short-chain perfluoroalkyl acids (PFAAs) were found to have bioaccumulation potential (bioaccumulation factor, BAF; biota-sediment accumulation factor, BSAF) and were positively correlated with relative trophic position. Among these, long-chain PFAAs (perfluorohexanesulfonic acid, PFHxS; perfluorooctane sulfonic acid, PFOS; perfluorooctanoic acid, PFOA; perfluorononanoic acid, PFNA) were the greatest contributors to total body burden and bioaccumulated in all organisms, with PFOS (log BAF = 3.55 ± 0.83) and PFNA (log BAF = 3.17 ± 0.46) having the highest mean values of all compounds. PFOS was present in all biota samples and concentrations significantly increased with food web trophic position (ranging from 0.18 to 777 μg kg⁻¹). Perfluorobutane sulfonic acid (PFBS) was also ubiquitous among all organisms, bioaccumulating in both invertebrate and vertebrate species. Total PFAS concentrations in aquatic worms were significantly higher in lower salinity water while the PFAS profile of Eastern oysters shifted from predominately perfluorocarboxylic acids (66 % of total composition) to perfluorosulfonic acids (62 %) as the ecosystem transitioned from low (9 PSU) to high (25 PSU) salinity. Collectively, this study demonstrates the utility of applying δ¹³C and δ¹⁵N to determine bioaccumulation patterns of both legacy PFAS and short-chain replacement compounds and underscores how shifts in salinity can alter the concentration and speciation of PFAS in estuaries.