An examination by GC×GC-TOFMS of organic molecules present in highly degraded oils emerging from Caribbean terrestrial seeps of Cretaceous age

For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier, biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography (GC) both oils appear as unresolved complex mixtures (UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry (GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers’ to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and seco-hopanes, mono- and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes, including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons (PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.