Simultaneous qualitative and quantitative analysis of fluoroalkyl sulfonates in riverine water by liquid chromatography coupled with Orbitrap high resolution mass spectrometry

•Simultaneous qualitative and quantitative analysis of PFSAs by Orbitrap was tested.•Quantification of PFOS isomers based on full-scan MS1 chromatogram.•Competent linear dynamic range and sensitivity were found in the HRMS method.•Accurate mass measurement had advantage on elimination of environmental interferent.•High proportions of the emerging 6:2Cl-PFAES were found in riverine water samples.

In this study, a robust method for quick screening, confirmation and quantification analysis of eight fluoroalkyl sulfonates in surface riverine samples was developed using ultra-high performance liquid chromatography-high resolution mass spectrometer (LC-Orbitrap Tribrid HRMS). Weak anion exchange solid phase extraction was optimized to maximum recover perfluoroalkyl sulfonates (PFSAs), fluorotelomer sulfonates and the emerging 6:2 chlorinated polyfluoroalkyl ether sulfonate at the same time. Both qualitative and quantitative purposes could be achieved by simultaneous acquiring full-scan mass spectrum (MS1) and data-dependent MS2 data. The LC-Orbitrap Tribrid HRMS method showed competent method detection limits for all analytes (7.1–62 pg/L) compared with the triple quadrupole mass spectrometry (LC–MS/MS) quantification method (12–54 pg/L), and satisfactory method validation results were also obtained in linearity (R2 > 0.999), trueness (88–118%), precision (2–17%) and recovery (63–103%). A good correlation (R > 0.999) was found between the sets of quantified PFSA residue concentrations in thirteen estuary river samples by both the LC-Orbitrap Tribrid HRMS (0.2–440 ng/L) and LC–MS/MS (0.1–424 ng/L) methods, indicating that Orbitrap Tribrid HRMS could be used for reliable quantitative analysis purpose. Moreover, the LC-Orbitrap Tribrid HRMS method could also benefit from its high mass resolution characteristic to eliminate potential environment interferents (e.g., taurodeoxycholate) and to quantify all PFSA isomers based on full-scan MS1 chromatogram at a narrow MS window (5 part per million).