Application of in-source fragmentation to the identification of perfluoropentanoic acid and perfluorobutanoic acid in environmental matrices and human serum by isotope dilution liquid chromatography coupled with tandem mass spectrometry

Abstract

Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is the most common analytical technique for per- and polyfluoroalkyl substances (PFASs) research and monitoring. The PFAS identification requires a minimum of two multiple reaction monitoring (MRM) transition ions as quantifier transition ion and qualifier transition ion, respectively. The second transition ion abundance for perfluoropentanoic acid (PFPeA) and perfluobutanoic acid (PFBA) is too low for practical use. A method using the in-source fragment ions as the precursor ion for MRM or pseudo-MRM has been developed and evaluated for PFPeA and PFBA identification in various environmental abiotic and biotic samples including water, soil, sediment, WWTP sludge, fruits, vegetables, egg, macrophytes, fish, dolphin liver and human serum. The PFPeA qualifier MRM transition ion (m/z = 219 > 69) has been successfully applied in all the matrices with spike recoveries (90–125%), signal to noise ratios (>10) and transition ions ratio variation (80–120%). The PFBA qualifier pseudo-MRM transition ion (m/z = 169 > 169) works well in all the matrices except dolphin liver sample. The interpretation of pseudo-MRM results should be with cautions due to lower specificity compared to MRM. In addition, this project indicated under typical chromatographic conditions the MRM isobaric interference does happen frequently to PFPeA quantifier transition ion (m/z = 263 > 219) in serum and fish composite samples, and to PFBA quantifier transition ion (m/z = 213 > 169) in macrophytes, fish composite and dolphin liver samples.