Evaluation of Thin-Layer Chromatography-Laser Desorption Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometric Imaging for Visualization of Crude Oil Interactions.

A light oil was separated into four chromatographic fractions that serve as proxy for SARA fractions. The fractions were (semi)quantified on a rod by TLC-flame ionization detection and characterized on a plate with laser desorption ionization-mass spectrometry imaging (TLC-LDI-MS). Comparisons of (semi)quantitative TLC-FID and qualitative TLC-LDI-MS results showed that LDI-MS was most sensitive for detection of molecules in the polar P1 fraction, and, to some extent, for the aromatics fraction, while no signal was observed for the most polar P2 and saturates fractions. Based on these results, limits of the compositional space, as observed by the laser ionization technique, were evaluated. The molecular speciation between and within the spots of the aromatics and the P1 fractions were analyzed and interpreted in terms of oil-SiO2 versus oil-solvent interactions, as a function of molecular characteristics such as DBE, aromaticity (H/C ratio), heteroatom content, degree of alkylation, and shielding of heteroatoms. In addition, the high oil loading resulted in an interesting bifurcation of the aromatics spot, which implies that oil-oil interactions can be enforced and studied in the TLC model system.