New silica-based adsorbents for water purification: Removal of short- and long-chain perfluoroalkyl sulfonic acids (PFSA) at sub-nanomolar concentrations

Abstract

Perfluoroalkyl acids (PFAAs) are widespread in the aquatic environment and also measurable in ground and drinking water. Because of the insufficient PFAA elimination in conventional water treatment processes, e. g. active carbon based methods, consumers in areas with contaminated water supplies are exposed to an elevated health hazard. For this purpose, the applicability of five differentially fluorinated silica-based adsorbents (HSU00107954-958) to remove the potentially human toxic perfluoroalkyl sulfonic acids(PFSAs) perfluorooctane sulfonic acid (PFOS), perfluorohexane sulfonic acid (PFHxS), and perfluorobutane sulfonic acid (PFBS) from water was investigated with regard to removal efficiencies (REs) and equilibrium loadings. During the adsorbent screening at nanomolar concentrations (20.0–33.4 nmol L−1) maximum REs of 46.9% for PFBS (HSU00107954), 79.4% for PFHxS (HSU00107954), and between 86.5 to 96.7% for PFOS (HSU00107956, and HSU00107954, respectively) have been achieved. Even at picomolar concentrations (< 400 pmol L−1) HSU00107954 was still able to eliminate PFBS and PFHxS with an efficiency of 46.3–51.2% and 79.1–88.2%, respectively. Analyses of the equilibrium loadings of the functionalized adsorbents in the concentration range 40.1 pmol to 3.34 nmol L−1 resulted in appropriate linearized Freundlich isotherms for all investigated PFSA. Compared to literature-based Freundlich adsorption coefficients (KF) for granular activated carbon (GAC), the determined KF values (nmol(1−n) Ln m−2) of the most efficient adsorbents HSU00107956 and HSU00107954 for each PFSA were significantly 8–10 and 50–60 times higher, respectively. These proven increased adsorption capacities relative to activated carbon possibly indicate specific PFSA selectivities of the functionalized macroporous silica adsorbents.