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

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 (MS(1)) and data-dependent MS(2) 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 (R(2)>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 MS(1) chromatogram at a narrow MS window (5 part per million).