Negative-ion atmospheric pressure ionisation of semi-volatile fluorinated compounds for ultra-high-performance liquid chromatography tandem mass spectrometry analysis

Juan F. Ayala-Cabrera, F. Javier Santos, Encarnación Moyano

In this work, the feasibility of negative-ion atmospheric pressure chemical ionisation (APCI) and atmospheric pressure photoionisation (APPI) for ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) determination of fluorotelomer alcohols (FTOHs), fluorinated octanesulfonamides (FOSAs) and fluorinated octanesulfonamido-ethanols (FOSEs) was evaluated. The study of the effect of mobile phase composition on the atmospheric pressure ionisation of these compounds indicated that methanol/water mixtures provided the best responses in APCI, while acetonitrile/water with a post-column addition of toluene as dopant was the most appropriated mixture in APPI. Under the optimal working conditions, most of the target compounds produced the ion [M-H]- as base peak, although in-source collision-induced dissociation fragment ions in APCI and APPI and superoxide adduct ions [M+O2]-• in APPI were also present. These ions proved to be more useful as precursor ions for MS/MS determination than the adduct ions generated in electrospray. Although the UHPLC-APCI-MS/MS method allowed the determination of these semi-volatile compounds at low concentration levels, the analysis by UHPLC-APPI-MS/MS provided the lowest limits of detection and it was applied to the analysis of water samples in combination with solid-phase extraction. Quality parameters demonstrated the good performance of the proposed method, providing low method limits of detection (0.3-6 ng L-1), good precision (RSD % < 5%) and an accurate quantification (relative error % < 14%). Among the river water samples analysed by the developed method, 4:2 FTOH and N-EtFOSA were determined at 30 and 780 ng L-1, respectively.