Advanced oxidation processes may transform unknown PFAS in groundwater into known products.

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated organic contaminants classified as persistent in the aquatic environment. Early studies using targeted analysis approaches to evaluate the degradation of PFAS by advanced oxidation processes (AOP) in real water matrices may have been misinterpreted due to the presence of undetected or unknown PFAS in these matrices. The aims of the present study were to (1) screen selected commercially available AOPs (UV, UV + HO, O/HO) and UV photocatalysis in a pilot system using commercially used and novel photocatalysts (TiO, boron nitride [BN]) for removing PFAS contaminants and (2) evaluate their role on the conversion of non-detected/unknown to known PFAS compounds in real groundwater used as drinking water supplies. Results indicated that, while AOPs have the potential to achieve removal of the EPA method 533 target PFAS compounds (PFDA [100%], PFNA [100%], PFOA [85-94%], PFOS [25-100%], PFHxS [3-100%], PFPeS [100%], PFBS [100%]), AOPs transformed non-detected/unknown longer-chain PFAS compounds to detectable shorter-chain ones under very high-dose AOP operating conditions, leading to an increase in ∑PFAS concentration ranging from 95% to 340%. As emerging PFAS treatment processes transition from lab-scale investigations of target PFAS to pilot testing of real water matrices, studies will need to consider impact of the presence of non-target long-chain PFAS to transform into targeted PFAS compounds. A promising approach to address the potential risks and unforeseen consequences could involve an increased reliance on adsorbable organic fluorine (AOF) analysis before and after advanced oxidation process (AOP) treatment.