Comparison of tri-, tetra- and pentacyclic caged hydrocarbons in Australian crude oils and condensates

Abstract

Thermally stable and biodegradation resistant, the tricyclic and pentacyclic diamondoid caged hydrocarbons are commonly used as source and maturity indicators of oils and potential source-rocks, but similar tetracyclic structures appear to have received much less attention. Using two-dimensional (2D) gas chromatography – time of flight mass spectrometry (GC × GC-TOFMS), 29 Australian crude oils and condensates were analysed for the presence of caged C12H18 tetracyclics such as ethanoadamantane and iceane. The thermodynamically more stable 2,4-ethanoadamantane was identified by comparison with a synthesised authentic standard. Three of its bridgehead methyl-substituted isomers, 6-methylethanoadamantane (6-ME), 1-ME and 2-ME, were tentatively assigned based on mass spectral comparison and relative elution order. Further series of non-bridgehead methyl isomers, plus dimethyl isomers, were also inferred based on mass spectra and 2D elution positions. The tri-, tetra and pentacyclic caged hydrocarbons and their methyl-substituted homologues were semi-quantified in the Australian oils. The potential of a novel index, the methylethanoadamantane index (MEI), based on the ratio of the more stable bridgehead isomers divided by the sum of all the methyl substituted isomers (MEI = Σ(6-ME + 1-ME + 2-ME)/ΣTotal methylethanoadamantanes), was explored. A significant positive association was found between the MEI and MAI (r2 = 0.203, p < 0.05) and a significant negative association was found between MEI and MDI (r2 = 0.246, p < 0.05). Stronger relationships were found for other commonly applied diamondoid ratio indices, including Σ Methyl Adamantanes/Σ Methyl Diamantanes (ΣMA/ΣMD) versus ΣMA/ΣME (r2 = 0.781, p < 0.0001, n = 26). The relatively low volatility of the ethanoadamantanes compared to the adamantanes and their likely greater resistance to microbial attack than the ethyladamantanes, may make analysis of these compounds a useful addition to the commonly measured diamondoids.