Flow-modulated comprehensive two-dimensional gas chromatography combined with a high-resolution time-of-flight mass spectrometer: A proof-of-principle study

The present research is focused on the evaluation of a recently developed high-resolution time-of-flight mass spectrometer (HR TOF MS), under the challenging conditions of a flow-modulation comprehensive two-dimensional gas chromatography (FM GC × GC) experiment. The HR TOF MS instrument was operated at a spectral generation frequency of 30 Hz and a mass resolution of ≥25 000 (fwhm). The effluent exiting the second-dimension column was in the range 6-8 mL/min, with part directed to waste to avoid exceeding the maximum pumping capacity of the MS system. An FM GC × GC-HR TOF MS method was developed for the untargeted and targeted analysis of a sample of high complexity, namely, heavy gas oil. With regard to the untargeted results, these were satisfactory in relation to MS database searching and mass accuracies. Considering the targeted data, the high selectivity of the MS system was highlighted by the use of accurate mass extracted-ion-chromatograms with narrow mass windows (±5 and ±1 ppm), for specific classes of polyaromatic sulfur heterocycles (PASHs), namely, benzothiophenes and dibenzothiophenes. Finally, the instrumental performance was also evaluated through the injection of standard solutions of four classes of PASHs.