Three major types of trimethyl-alkylbenzenes and significance for the genesis of reservoir bitumens from the northwestern Sichuan Basin, South China

• Three major types of trimethyl-alkylbenzenes were detected in reservoir bitumen. • 2,3,6-TMIPBs and 2,3,6-TMiHB constrain source rock differences. • Trimethyl-alkylbenzene distributions reveal complex oil charging histories. Trimethyl-alkylbenzenes in oil are an important class of molecular marker for determining biological sources, source rock depositional environment and maturity. They can be classified into three major types based on the type of side chain, including trimethyl-isoprenoid-, trimethyl-isohexyl-, and trimethyl- n -alkyl-benzenes. Although they have been studied separately for many years, recent studies have elucidated complicated co-elution of trimethyl-isoprenoid-benzenes and trimethyl- n -alkyl-benzenes on commonly used chromatographic columns. Moreover, simultaneous detections of these three types of trimethyl-alkylbenzenes were rarely reported. Reservoir bitumens, widely distributed along the northwestern margin of the Sichuan Basin, exhibit maturity characteristics that provide crucial insights for regional petroleum exploration in this ancient, giant petroliferous basin. So far, there has been no report on detection of these compounds from these reservoir bitumens, which may have suffered from severe biodegradation resulting in challenges to the understanding of genesis of these bitumens. In this study, asphaltenes, which are resistant to biodegradation, were carefully examined and asphaltene-bound hydrocarbons were compared to free hydrocarbons for the distribution of trimethyl-alkylbenzenes. Three main conclusions were drawn. Firstly, three major types of trimethyl-alkylbenzenes were detected through comparisons with available standards and well-characterized oils. These are 2,3,6-trimethyl-aryl isoprenoids (2,3,6-TMIPBs), 2,3,6-trimethyl-isohexylbenzene (2,3,6-TMiHB, C 15 ), and trimethyl- n -alkylbenzenes (TMnABs, mainly 2,4,5-/2,3,5-, 2,3,6-, 2,3,4-trimethyl series), which show significant differences in concentrations for both free and asphaltene-bound hydrocarbons. Secondly, four groups of reservoir bitumens having distinct isotopic compositions also show large differences in the distributions of 2,3,6-TMIPBs and 2,3,6-TMiHB, providing further constraints on both biological sources and depositional environments for their source rocks. For the major group mainly sourced from the upper Ediacaran to lower Cambrian source rocks, abundant 2,3,6-TMIPBs and isorenieratane were detected. This finding, combined with global distributions of multiple kinds of C 40 aromatic carotenoids (isorenieratane, chlorobactane, okenane) in the upper Ediacaran to lower Cambrian source rocks and their generated oils, indicates that photic zone euxinia was prevalent in ancient oceans, which may be of great significance for biological evolution in this key geological period. Thirdly, the ratios of 2,3,6-TMIPBs and 2,3,6-TMiHB to TMnABs have suggested subtle differences in the maturity of free hydrocarbons and asphaltenes, which can be used to reveal complex genetic processes for these bitumens, including at least two oil charging phases, different degrees of secondary cracking of asphaltenes mainly from early charged oil, and mixing of secondary cracking products with late charged oil from highly mature source rocks. A new ternary diagram, showing relative concentrations of C 15 2,3,6-TMIPB, 2,3,6-TMiHB, and TMnABs, was developed to more clearly elucidate these differences. Overall, this study has shown the great potential of multiple types of trimethyl-alkylbenzenes to understand complicated oil charging histories.