Details zur Publikation

Kategorie Textpublikation
Referenztyp Zeitschriften
DOI 10.1021/ac070802d
Titel (primär) Simultaneous characterization of perfluoroalkyl carboxylate, sulfonate, and sulfonamide isomers by liquid chromatography-tandem mass spectrometry
Autor Benskin, J.P.; Bataineh, M.; Martin, J.W.
Quelle Analytical Chemistry
Erscheinungsjahr 2007
Department WANA
Band/Volume 79
Heft 17
Seite von 6455
Seite bis 6464
Sprache englisch
Abstract A comprehensive method was developed to simultaneously separate and detect perfluorinated acid (PFA) and PFA-precursor isomers using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A linear perfluorooctyl stationary phase and acidified mobile phase increased separation efficiency, relative to alkyl stationary phases, for the many perfluoroalkyl carboxylate (PFCA), perfluoroalkyl sulfonate (PFSA), and perfluorooctyl sulfonamide (PFOSA) isomers and in combination with their distinct MS/MS transitions allowed full resolution of most isomers in standards. Utilizing the absence of the "9-series" and "0-series" product ions, several perfluorooctane sulfonate (C8F17SO3-, PFOS) isomers were structurally elucidated. In human serum, only perfluorooctane sulfonamide (C8F17SO2NH2, FOSA) and PFOS consisted of significant quantities of branched isomers, whereas PFCAs were predominantly linear. Interferences that coelute with the m/z 499 -> 80 transition of PFOS on alkyl stationary phases were simultaneously separated and identified as taurodeoxycholate isomers, removal of which permitted the use of the more sensitive m/z 80 product ion and a resulting 20-fold decrease in PFOS detection limits compared to the m/z 499 -> 99 transition (0.8 pg versus 20 pg using m/z 80 and 99, respectively). Interferences in human serum which caused a 10-20-fold over-reporting of perfluorohexane sulfonate (C6F13SO3-, PFHxS) concentrations on alkyl stationary phases were also simultaneously separated from linear PFHxS and identified as endogenous steroid sulfates. PFOSA isomers, generated with human microsomes, had different rates of metabolism, suggesting that the perfluoroalkyl branching pattern may affect the biological properties of individual isomers. This fact, and for reasons of improved accuracy and sensitivity, investigators are urged to utilize more efficient separation methods capable of isomer characterization in perfluoroalkyl research
dauerhafte UFZ-Verlinkung https://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=1648
Benskin, J.P., Bataineh, M., Martin, J.W. (2007):
Simultaneous characterization of perfluoroalkyl carboxylate, sulfonate, and sulfonamide isomers by liquid chromatography-tandem mass spectrometry
Anal. Chem. 79 (17), 6455 - 6464 10.1021/ac070802d