Simultaneous analysis of perfluoroalkyl and polyfluoroalkyl substances including ultrashort-chain C2 and C3 compounds in rain and river water samples by ultra performance convergence chromatography

- The new UPC2-MS/MS method was developed to measure ultrashort-chain PFASs (C2-C3).
- PFCAs, PFSAs, PFPiAs, PFPAs, diPAPs can be measured in a single analysis.
- The newly developed method help further investigation on these ultrashort-chain PFASs.
- Large contribution of ultrashort-chain PFASs indicates the need of monitoring.

An analytical method using ultra performance convergence chromatography (UPC2) coupled to a tandem mass spectrometer operated in negative electrospray mode was developed to measure perfluoroalkyl and polyfluoroalkyl substances (PFASs) including the ultrashort-chain PFASs (C2-C3). Compared to the existing liquid chromatography tandem mass spectrometry method using an ion exchange column, the new method has a lower detection limit (0.4 pg trifluoroacetate (TFA) on-column), narrower peak width (3-6 s), and a shorter run time (8 min). Using the same method, different classes of PFASs (e.g., perfluoroalkyl sulfonates (PFSAs) and perfluorinated carboxylates (PFCAs), perfluorinated phosphonates (PFPAs) and phosphinates (PFPiAs), polyfluoroalkyl phosphate diesters (diPAPs)) can be measured in a single analysis. Rain (n = 2) and river water (n = 2) samples collected in Toronto, ON, were used for method validation and application. Results showed that short-chain PFAS (C2-C7 PFCAs and C4 PFSA) contributed to over 80% of the detectable PFASs in rain samples and the C2-C3 PFASs alone accounted for over 40% of the total. Reports on environmental levels of these ultrashort-chain PFASs are relatively scarce. Relatively large contribution of these ultrashort-chain PFASs to the total PFASs indicate the need to include the measurement of short-chain PFASs, especially C2 and C3 PFASs, in environmental monitoring. The sources of TFA and other short-chain PFASs in the environment are not entirely clear. The newly developed analytical method may help further investigation on the sources and the environmental levels of these ultrashort-chain PFASs.