title: Mass spectral studies of perfluorooctane sulfonate derivatives separated by high-resolution gas chromatography.
abstract: The mass spectral characteristics of perfluorooctane sulfonate (PFOS, C(8)F(17)SO(3)-) isomers present in technical PFOS were obtained using high-resolution gas chromatography (HRGC) combined with mass spectrometry (MS). To make PFOS amenable to HRGC separation, a simple derivatization procedure was developed. The method involved the conversion of PFOS into the iso-propyl ester using iso-propanol as the derivatization reagent under acidic conditions. Mass spectra were generated employing electron ionization (EI) and negative chemical ionization (NCI). Interpretation of fragment ions was possible due to the use of deuterium-labeled iso-propanol as derivatization reagent, which induced mass shifts in the electron ionization (EI) and negative chemical ionization (NCI) mass spectra. HRMS allowed the accurate mass measurement of important EI fragments and confirmed the derivatization reaction as well as the proposed fragmentation pathway involving rearrangement. Moreover, the high resolution provided by HRGC enabled the separation of eleven PFOS isomers present in the technical product. This is an improvement over the previously reported high-performance liquid chromatography (HPLC) separation. A complete identification of all isomers was not possible due to lack of pure reference materials. Finally, the developed derivatization procedure was successfully applied to perfluoroalkyl carboxylates (PFCA) and corresponding fragmentation involving rearrangement of the derivatized PFCA was observed. The described qualitative derivatization offers a promising alternative technique for the separation and identification of isomers of perfluoroalkyl sulfonates and carboxylates by HRGC/MS.
authors.affiliation: Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4057 Basel, Switzerland.
authors.forename: Ingrid
authors.initials: I
authors.lastname: Langlois
authors.forename: Urs
authors.initials: U
authors.lastname: Berger
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Zencak
authors.forename: Michael
authors.initials: M
authors.lastname: Oehme
mesh_terms: D000433:1-Propanol / Q000737:chemistry; D017738:Alkanesulfonic Acids / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D005466:Fluorocarbons / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D007536:Isomerism; D015203:Reproducibility of Results; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods
chemical_list: D017738:Alkanesulfonic Acids; D004952:Esters; D005466:Fluorocarbons; D000433:1-Propanol; C076994:perfluorooctane sulfonic acid