Evaluation of Quantitative Sulfur Speciation in Gas Oils by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Validation by Comprehensive Two-Dimensional Gas Chromatography

• Published in: Journal of the American Society for Mass Spectrometry 2012-05, Vol.23 (5), p.806-815
• Main Authors: Muller, Hendrik, Adam, Frederick M., Panda, Saroj K., Al-Jawad, Hanadi H., Al-Hajji, Adnan A.
• Format: Article
• Language: English
• Subjects: Analytical Chemistry; Applied sciences; Bioinformatics; Biotechnology; Chemistry; Chemistry and Materials Science; Chromatography; Crude oil, natural gas and petroleum products; Cyclotron resonance; Energy; Exact sciences and technology; Fourier transforms; Fuels; Gas chromatography; Gas oil; Ionization; Ions; Mass spectrometry; Organic Chemistry; Prospecting and production of crude oil, natural gas, oil shales and tar sands; Proteomics; Quantitative analysis; Research Article; Scientific imaging; Speciation; Spectroscopy; Sulfur; Sulfur compounds
• ISSN: 1044-0305; 1879-1123
• DOI: 10.1007/s13361-011-0321-7

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been applied for the quantitative speciation of sulfur containing compounds in gas oil (GO). For this purpose, ionization and mass spectrometric parameters have been studied and optimized with a set of standard compounds and GO samples. Comprehensive two-dimensional gas chromatography (GCxGC) was used as the reference method. To allow a quantitative comparison between FT-ICR MS and GCxGC results for GO samples, FT-ICR MS parameters were optimized and data obtained by both techniques were standardized. Response factors were established for two ionization modes: atmospheric pressure photo ionization (APPI) and electrospray after selective derivatization of sulfur compounds (MeESI). To test the validity of the developed MS methods, a third GO was analyzed and response factors were applied. Comparison with GCxGC results showed good agreement for sulfur families (deviation within 5% and 15% for MeESI and APPI data, respectively). Abundances of individual isomer groups match within 40% in most cases. These results principally demonstrate the suitability of FT-ICR MS for a quantitative analysis of sulfur compounds (by DBE and carbon number distribution pattern) in petroleum middle distillates. This approach has the potential to be extended to higher- and non-boiling petroleum fractions where quantitative speciation is presently not available.