Automated\nAnalysis of Petroleum- and Plastic-Derived\nFuels by Gas Chromatography Coupled with Field Ionization Mass Spectrometry

Gas chromatography combined with field ionization mass\nspectrometry\n(GC × FIMS) was introduced more than 20 years ago. Despite the\nfield ionization method’s unique capability to produce mostly\nmolecular ions, it remained a niche technique. In this work, we present\na renewed look at the comprehensive two-dimensional separation combining\ngas chromatographic retention and time-of-flight mass separation of\nthe molecular ions generated by field ionization. Automated data processing,\nincluding noise removal, peak picking, and differentiation of nearly\nisobaric hydrocarbon and sulfur species, has been developed. Repeatability\nand robustness of GC × FIMS identifications are discussed as\nwell as limitations with quantification. To evaluate the method performance,\nthe resulting speciation of petroleum-derived samples using GC ×\nFIMS is compared to measurements performed using comprehensive two-dimensional\ngas chromatography (GC × GC) and Fourier transform ion cyclotron\nresonance mass spectrometry (FT-ICR MS). Then, the GC × FIMS\nmethod is demonstrated on a variety of samples representing the petroleum\nhydrocarbon value chain. With a constant method and automated processing\nparameters, the detailed compositional characterization is obtained\nfor (i) a wide range of petroleum fractions from naphtha to vacuum\ngas oil, (ii) refinery intermediates, such as light cycle oil and\nan aromatic bottom stream, (iii) commercial fuel, and (iv) plastic-waste-derived\npyrolysis oil. Due to automated data processing, a comprehensive compositional\nanalysis is available within 80 min, regardless of the sample type.\nThereby, the presented method can be highlighted as a valuable tool\nfor the swift and detailed characterization of diverse hydrocarbon\nmixtures.