Experimental and density functional theory investigation of surface-modified biopolymer for improved adsorption of mixtures of per- and polyfluoroalkyl substances in water

Glutaraldehyde (GTH) cross-linked chitosan (CTN) biopolymer-based and polyethyleneimine (PEI) functionalized (GTHCTNPEI) aerogels were proven promising for removing mixtures of long- and short chain per- and polyfluoroalkyl substances (PFAS) in water. In this study, to further improve the performance of the aerogel for short-chain PFAS and undecafluoro-2-methyl-3-oxahexanoic acid (GenX) removal, GTHCTNPEI aerogel chunks with an average size of 13.4 mm were turned into flakes with an average size of 9.1 mm. The GTHCTNPEI flakes achieved >99 % removal of all target PFAS, including long- and short-chain PFAS and >97 % for GenX after 10 h. In addition, the flakes can be regenerated and reused for at least four cycles. When added to tap water spiked with PFAS at initial concentrations of 30, 70, or 100 ng/L, the flakes removed almost 100 % of all tested PFAS. Mechanistic investigations using density functional theory (DFT) revealed strong stabilizing hydrophobic and electrostatic interactions between the aerogels and PFAS, with GTHCTNPEI to PFAS binding energies ranging between -24.0 – -30.1 kcal/mol for PFOA; -41.3 – -48.5 kcal/mol for PFOS; and -40.5 – -47.3 kcal/mol for PFBS. These results demonstrate the great potential of the flakes for removing PFAS from drinking water, surface water, and groundwater.