Multiple sources of petroleum in the Panyu lower uplift evidenced by catalytic hydropyrolysis of petroleum asphaltenes

Abstract

Catalytic hydropyrolysis (HyPy) is an effective method for the release of covalently bound biomarkers from geo-macromolecules (e.g., kerogen or asphaltenes). It is particularly valuable for samples that lack geochemical proxies resulting from extensive maturation or secondary alteration. In this study, HyPy was carried out on asphaltene fractions isolated from crude oils collected from 10 reservoirs of various depths in the Panyu lower uplift in the central Pearl River Mouth Basin, South China Sea. Significant quantities of biomarkers and polycyclic aromatic hydrocarbons (PAHs) were released, and their molecular and isotopic compositions were obtained. The results suggest that these bound compounds were not affected by secondary alteration processes, such as biodegradation in shallow reservoirs or water washing in deeper ones. The δ¹³C values of the HyPy products were 1.2 ‰–2.2 ‰ more enriched than those of the original bulk oils, and are inconsistent with traditional δ¹³C patterns (the asphaltene fraction generally has the most enriched δ¹³C value among petroleum fractions). These reservoirs, therefore, may represent a composite petroleum system involving contributions from multiple source rocks rather than a single source as previously interpreted. This hypothesis is also supported by the molecular and biomarker signatures of the products, which showed elevated proportions of C₁₁–C₁₆ n-alkanes and C₁₉ tricyclic terpanes, and a marked dominance of 24-ethylcholestanes (ranging from 52 % to 79 % of total steranes), significantly exceeding the C₂₇ and C₂₈ homologues. A substantial input of organic matter from vascular plants, much higher than that of the presumed source rocks of the Eocene Wenchang Formation, was found. Therefore, the earlier petroleum charges to the Panyu lower uplift may be associated with the Eocene–Oligocene Enping Formation interbedded with coaly source rock intervals. In contrast, the maltenes of the oil samples were rich in 4-methylsteranes, dinosteranes, and triaromatic dinosteroids, as well as minor oleananes, which closely resemble the biomarker signatures of lacustrine source rocks from the Eocene Wenchang Formation. These findings support a dual contribution to the petroleum reservoirs across the Panyu lower uplift, where the major oils concerned with the coaly source rocks of the Enping Formation and the lacustrine shale source rocks of the Wenchang Formation were likely responsible for potential large hydrocarbon accumulations.