Comprehensive Two-Dimensional Gas Chromatography Coupled to Time of Flight Mass Spectrometry: New Biomarker Parameter Proposition for the Characterization of Biodegraded Oil

Abstract

Comprehensive two-dimensional gas chromatography with time of flight mass spectrometry (GC×GC-TOFMS) is an appropriate technique for the elucidation of molecular composition of petrochemical samples, such as biodegraded oils. Biomarkers were separated and identified, and conventional biomarker ratios were determined via gas chromatography-mass spectrometry (GC-MS) and GC×GC-TOFMS. In the extracted ion chromatogram m/z 123 + 177 + 191, coelutions between tricyclic terpanes, hopanes and 25-nor-hopanes with secohopanes were resolved by GC×GC-TOFMS. GC×GC-TOFMS allowed the identification of complete series of 25-nor-hopanes, nor-gammacerane, C29 28-nor-spergulanes and oleanane not identified by using GC-MS. The biomarker ratios from the studied oils indicated that they derived from marine source rock deposited under anoxic conditions. The higher chromatographic resolution and sensitivity achieved by using GC×GC-TOFMS allowed for three new parameters to characterize biodegraded oils. These results indicated the superiority of GC×GC-TOFMS for separation and identification of individual and non-target compounds in severely biodegraded oils.