Removal of per- and polyfluoroalkyl substances by nanofiltration: Effect of molecular structure and coexisting natural organic matter

This study investigates the removal efficiency of anionic, cationic, and zwitterionic per- and polyfluoroalkyl substances (PFAS) by nanofiltration (NF) in the presence of three representative natural organic matter (NOM) types: bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA). In particular, effects of PFAS molecular structure and coexisting NOM on the transmission and adsorption efficiency of PFAS during NF treatment were analyzed. The results indicate that NOM types dominate membrane fouling behavior despite the coexistence of PFAS. SA exhibits the most significant fouling propensity, resulting in maximum water flux decline. NF effectively removed both ether and precursor PFAS. The effects of the three typical NOM on the membrane-passing behavior of PFAS were consistent for all PFAS investigated. Generally, PFAS transmission decreased in the order of SA-fouled > pristine > HA-fouled > BSA-fouled, indicating that the presence of HA and BSA enhanced PFAS removal while SA declined. Furthermore, reduced PFAS transmission was observed with increased perfluorocarbon chain length or molecular weight (MW), regardless of the presence or type of the NOM. The impacts of NOM on PFAS filtration diminished when the PFAS van der Waals radius was > 4.0 Å, MW > 500 Da, polarization > 20 Å, or LogKow > 3. These findings suggest that both steric repulsion and hydrophobic interactions, especially the former, play important roles in PFAS rejection by NF. This study provides insights into the specific applicability and performance of membrane-based processes for eliminating PFAS during drinking and wastewater treatments, and highlighting the importance of coexisting NOM.