Paper spray-atmospheric pressure photoionization-high resolution mass spectrometry for the direct analysis of neutral fluorinated compounds in waterproof impregnation sprays.

In this work, paper spray (PS) is combined with atmospheric pressure photoionization-mass spectrometry (PS-APPI-MS) for the determination of non-polar and low polar compounds, such as the neutral per- and polyfluorinated alkyl substances (PFAS). The proposed PS-APPI-MS method has been developed for the analysis of fluorotelomer alcohols (FTOHs), fluoroctanesulfonamides (FOSAs) and fluorooctane sulfonamido-ethanols (FOSEs), using both negative ion mode and high-resolution mass spectrometry (HRMS). The most critical working parameters (i.e., UV-krypton lamp position, sample drying time, spray dopant solvent and spray voltage) have been evaluated to study both the ionization behaviour and ionization efficiency. The best results were achieved using dopant-assisted PS-APPI-HRMS with toluene as dopant solvent. The most intense ions observed in the mass spectra, [M‒H] for FOSAs and [M+O] for FTOHs and FOSEs, were selected and proposed for fast screening and quantitative analysis of target compounds in waterproof impregnation sprays samples using internal standard calibration method and being able to detect down to μg L levels. The satisfactory values of the method quality parameters (detection capability, repeatability, trueness and linearity) demonstrated the good performance of the PS-APPI-HRMS method and allowed the identification and quantitation of some FTOHs (6:2 FTOH, 7-Me-6:2 FTOH, 8:2 FTOH, 10:2 FTOH) and N-MeFOSE at mg L in some of the waterproof impregnation spray products analyzed. This low-cost PS-APPI-HRMS method allows a fast screening, with minimum sample preparation, of non-polar and low polar compounds simultaneously, which can significantly improve the throughput on routine laboratories.