Full length articleComprehensive three-dimensional gas chromatography mass spectrometry separation of diesel

•Comprehensive Three-Dimensional Gas Chromatography Mass Spectrometry Separation, GC × GC × MS.•Comprehensive two-dimensional gas chromatography, GCxGC.•Field ionization mass spectrometry, FIMS.•Field ionization mass spectrometry data used in separation in addition to GCxGC.•Resolved co-elution in the GCxGC separation.•Detailed separation of complex hydrocarbon mixture.

Diesel, a complex hydrocarbon mixture, was examined using comprehensive two-dimensional gas chromatography (GC × GC) and a field ionization mass spectrometer (FIMS), which preferentially yields molecular ions, providing an extra dimension for component separation. Molecular ions collected at low mass resolution can be assigned an NM-class (Nominal Mass-class) value that does not completely express hydrogen deficiency. In contrast to formulae and Z-class assignments that are possible from ultrahigh mass resolution, NM-class assignments are not unambiguous; however, the separation provided by GC × GC can result in coelution of components that differ in NM-class. Hence, compounds that are unresolved by GC × GC separation can be resolved by FIMS provided they differ in mass. This technique allows for easy, automated data processing, evaluation of coelution on quantitative analysis (e.g., using FID) and the identification of additional chemical species and structures. The development of GC × GC × MS creates new opportunities to improve the ability to determine hydrocarbon composition and structure in complex petroleum and refined petroleum products.