Understanding the impact of pre-digestion thermal hydrolysis process on PFAS in anaerobically digested biosolids

Per- and poly-fluoroalkyl substances (PFAS) present in biosolids are influenced by their source, treatment processes, and the dynamics of water resource recovery facilities (WRRF). Understanding these effects is vital for informed decisions in treatment process selection, however, comprehensive studies are sparse. This study examined the impact of anaerobic digestion (AD) and the addition of a thermal hydrolysis process (THP) before AD on PFAS in the solids stream at a WRRF. Targeted analysis of 58 PFAS (linear and branched) and suspect screening of the solid stream before and after AD as well as THP, with the total PFAS (ΣPFAS) concentrations ranging between 244 and 566 μg/kg_dw. Precursor and intermediate PFAS, mainly di-substituted polyfluoroalkyl phosphate esters (diPAPs) followed by fluorotelomer carboxylic acids (FTCAs), were the dominant contributors (62-96 mol % ΣPFAS) in all 5 sample types. AD impacts were observed both before and after deploying THP altering the relative contribution of different PFAS classes through biotransformation, with an increase in PFCAs and a decrease in diPAPs. However, we observed that THP reduced the % of precursor conversion as well as conversion of the FTCA intermediates in the AD process as evidenced by a substantial increase in FTCAs post-THP + AD and lower PFCA generation compared to AD only. Total PFAS organofluorine (∑F_PFAS) decreased by 28% pre- and post-AD, which on total fluorine (TF) showed a larger reduction to 43%. Fluoride was <3% of the TF in all cases, thus, the greater reduction in TF vs ∑F_PFAS could be volatile losses of PFAS and other non-PFAS F-containing molecules. After THP installation, a 32% decrease in (∑F_PFAS) was observed in the combined THP-AD system whereas adjusted total organofluorine increased by ∼43%. Overall, achieving higher solids handling capacity and energy neutrality with the THP addition did not lead to a significant difference in quantifiable PFAS concentrations compared to AD-only.