Distinctive adsorption and transport behaviors of short-chain versus long-chain perfluoroalkyl acids in a river sediment

Perfluoroalkyl acids (PFAAs) embrace perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and other concerning chemicals of different chain length and terminal moieties. PFAAs can leach from municipal wastewater facilities as point sources discharging into rivers and receiving streams. In this study, we investigated the adsorption and transport behaviors of six select PFAAs in a Hudson River (USA) sediment in both batch and mesocosm studies. The adsorption capacities single and dual solute systems followed the order: PFBA < PFHxA ≈ PFBS < PFHxS < PFOA << PFOS. Mesocosm experiment that receives a continuous point source discharge of a mixture of these six PFAAs reached equilibrium after 4 weeks of operation. Total adsorbed PFAAs in the sediment was extracted and analyzed, following PFHxS (0.85 mg, 20.4%) ≈ PFBS (0.92 mg, 21.7%) < PFOA (1.02 mg, 27.3%) ≈ PFHxA (1.04 mg, 29.8%) < PFBA (1.12 mg, 30.1%) << PFOS (1.55 mg, 39.2%). PFOS showed highest adsorption, concentrating on the surface layer. Noticeably, two short-chain PFAAs, PFBA and PFHxA, were found with high vertical mobility, partitioning into deeper sediment. Two hotspots for PFAA sediment contamination were formed near the sediment surface downstream from the point source, providing new prospects to guide PFAA sediment cleanup and monitoring. Graphical abstract.