Analysis of perfluorinated compounds in sewage sludge and hydrochar by UHPLC LTQ/Orbitrap MS and removal assessment during hydrothermal carbonization treatment

Wastewater treatment plants have been recognized as important sinks for per- and polyfluoroalkyl substances (PFAS) because of their ineffectiveness in removing them reflecting both water and sewage sludge discharge routes. Hydrothermal treatment represents an alternative technology for treating sludge to recover energy and other valuable products. In this study, 15 PFAS were determined in sludge and hydrochar substrates using sonication-solid phase extraction procedure and analyzed using LC-Orbitrap-High Resolution-MS/MS. The method was fully validated, exhibiting very good linearity, recoveries in the range of 48 to 126 %, low detection and quantification limits with expanded uncertainty and precision below 32 % and 21.9 %, respectively. The method was applied to sludge samples from the WWTP of Ioannina city (Greece), as well as to hydrothermally treated samples under various conditions. The most abundant PFAS were PFHxA (0.5–38.3 ng g−1) and PFOS (4.4–22.1 ng g−1). Finally, the hydrothermally treated sludge samples spiked with PFAS presented removal efficiencies for total PFAS of 86.9 %, 91.8 % and 95.7 % at three spiking levels namely 10, 50 and 200 ng g−1, respectively. Results indicated that PFCAs were almost completely removed, except for PFOA, while the concentrations of PFSAs increased in the produced hydrochar with the formation of several intermediates, as detected by HR-LC-MS/MS. The results of this study demonstrate the effect of hydrothermal treatment to the fate of PFAS in sewage sludge and contribute for further studies on design and scale up of hydrothermal carbonization technology as a management option for safer disposal of municipal wastewater sludge. [Display omitted] •Determination of PFAS in sludge and its hydrochar after hydrothermal carbonization•Sonication-SPE combined to LC-Orbitrap HR MS/MS was optimized and fully validated.•Removal rates were nearly complete for C8-C13 PFCAs and about 70 % for C4-C8 PFSs.•Short-chain PFCAs (C4-C7) were completely degraded during hydrothermal treatment.•Degradation products and pathways during hydrothermal treatment were proposed.