Non-target discovery of emerging PFAS homologues in Dagang Oilfield: Multimedia distribution and profiles in crude oil

Per- and polyfluoroalkyl substances (PFASs) are applied in oil exploitation activity. In this study, non-target and suspect target analyses with high-resolution mass spectrometry were used for identification of novel PFASs in the oilfield environment. A total of thirty-seven PFAS homologues belonging to eight classes were identified as level 4 or above, which partly explained the amount of potential unknown PFAS-precursors that were indicated by total oxidisable precursor assay in our previous study. Hydrogen-substituted and ether-substituted homologues were the main identified PFASs, and seven of them were newly reported homologues. C1-C3 perfluoroalkane sulphonic acids (PFSAs) were also for the first time identified in the oilfield. The sediment-water partitioning coefficients of most identified PFAS homologues positively correlate with their predicted octanol-water partitioning coefficients while those of C1-C3 PFSAs may have elevated sediment partitioning potential as also previously observed for ultra-short chain C2-C3 perfluoroalkyl carboxylic acids. The crude oil and sludge samples were further examined with the target and identified PFAS profiles. An annual flux of 10.4 kg/y via oil production was estimated in Dagang Oilfield with 16.6 % not from the target PFASs. This demonstrates that oil exploitation activities can be a significant underlying source of PFASs to the environment.