Tracking Neutral Nitrogen Compounds in Subfractions of Crude Oil Obtained by Liquid Chromatography Separation Using Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
Аннотация:Neutral nitrogen compounds have been used as molecular markers for tracking secondary oil migration in geochemistry. However, the distribution of neutral nitrogen compounds in the separation process is not well-characterized because the conventional analytical technique, such as gas chromatography−mass spectrometry (GC−MS), is non-selective for neutral nitrogen and not capable of detecting non-volatile high-molecular-weight compounds. In this paper, a crude oil was subjected to the traditional two-step open-column liquid chromatography (LC) technique to prepare subfractions, which were characterized for their molecular composition of neutral nitrogen compounds by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The results showed that the two-step LC technique produced a low yield of carbazole in the neutral nitrogen fraction. The neutral nitrogen fraction was enriched with low-molecular-weight neutral nitrogen compounds. Most N1 class species with relatively low double-bond equivalent (DBE) values and high carbon numbers were eluted into the aromatic fraction, and a portion of neutral nitrogen compounds was eluted into the amino fraction, which was not expected. Because the neutral nitrogen compounds detected by GC−MS analysis only account for a fraction of total neutral nitrogen compounds, caution should be exercised in interpreting the analytical data obtained from the two-step LC technique. The analytical bias of the separation technique could lead to erroneous geochemical interpretations when a low yield of carbazole in the neutral nitrogen fraction was derived. Negative-ion ESI FT-ICR MS was an effective tool to monitor and evaluate the separation technique for neutral nitrogen compounds in crude oil.
