Screening of semifluorinated n-alkanes by gas chromatography coupled to dielectric barrier discharge ionization mass spectrometry.

RATIONALE: The potential of an atmospheric pressure ionization source based on a dielectric barrier discharge in helium for the hyphenation of gas chromatography and mass spectrometry (GC/DBDI-MS) has been demonstrated only recently and for a limited range of compounds. Due to its 'soft' ionization properties and the possibility to choose from a variety of atmospheric pressure ionization MS instruments, GC/DBDI-MS has the potential to be an interesting alternative to 'classic' GC/MS techniques.

METHODS: The hyphenation of GC with DBDI-MS at atmospheric pressure is used for the determination of semifluorinated n-alkanes in ski wax samples.

RESULTS: Different to perfluorinated n-alkanes, which are typically detected as [M - F + O]- and [M - F]- , semifluorinated n-alkanes can be detected both in positive mode as [M - 3H + nO]+ and [M - H + nO]+ (n = 0, 1, 2, and 3) ions, as well as in negative mode as a fragment ion representing the fluorinated part of the respective semifluorinated n-alkane. The method allowed the sensitive detection of semifluorinated n-alkanes with achievable limits of detection (LODs) in the single digit pg range injected on column. To examine the applicability of the GC/DBDI-MS method, semifluorinated n-alkanes were determined in fluorinated ski waxes. Results were confirmed by complimentary GC/electron ionization MS measurements.

CONCLUSIONS: The unique SFA ionization patterns serve for complementary unambiguous identification of semifluorinated n-alkane species in positive mode and screening of contained n-alkanes fluorinated chain lengths in negative mode.