Identification of historical contamination and novel PFAS in wastewater of a fluoropolymer manufacturing plant (Northern Italy)

Per- and polyfluorinated substances (PFAS) are globally distributed due to their ubiquitous use in industrial and consumer products. However, the notoriety of these substances was initially spurred by the high concentrations measured in the surrounding environmental media of industrial producer and user sites. Further, environmental studies around active PFAS production facilities allow us to assess current PFAS emissions and identify possible future PFAS issues. High-resolution mass spectrometry and non-targeted analysis (NTA) are the most appropriate tools to identify the presence of novel PFAS or understudied historical contaminants. In this study, samples of the discharge of a fluoropolymer manufacturing site (Northern Italy) were analyzed by HPLC-Orbitrap. The most recent strategies developed for non-targeted analysis of PFAS in environmental samples (e.g. mass defect filtering, homologous series detection, Kendrick plots) were applied to evaluate the presence of unknown or suspect PFAS. The investigation allowed detection of historical contamination due to sustained use of legacy and emerging PFAS. In addition, unknown or suspect PFAS such as alternative fluorosurfactants, fluorinated monomers and byproducts were also tentatively identified. The presence of some suspected PFAS detected in the water samples was also scrutinized in different environmental matrices collected near the fluoropolymer manufacturing plant to provide the first data on the distribution and fate of the novel suspects. Some of the suspect PFAS were also assessed in air samples collected some kilometers far from the manufacturing plant to gather insight of their possible long-range transport.