Recent trends in element speciation analysis of crude oils and heavy petroleum fractions

Medium and heavy crude oils and high-boiling distillation fractions which are increasingly used in petroleum industry contain high concentrations of sulfur and metals. Their behavior in refining processes is critically dependent on the speciation. Recent analytical developments, especially on the level of coupled techniques and high-resolution mass spectrometry, start allowing the speciation of individual metal compounds in crude oil known for its extreme complexity. These developments include: (i) GC stationary phases of high thermal stability and the high-temperature interfaces with ICP-MS and TOF-MS; (ii) high-efficiency microcolumn gel-permeation chromatography with detection by sector-field ICP-MS; (iii) thin layer chromatography coupling with laser ablation ICP-MS detection; and (iv) two-dimensional separation protocols increasing the purity of heteroelement containing fractions. Progress in electrospray and atmospheric-pressure photoionization Fourier Transform MS allows resolutions of above 1,000,000 to be achieved making it possible to identify by accurate mass measurement individual sulfur and metal species directly in crude oils.