Petroleum sources in the Xihu Depression, East China Sea: evidence from stable carbon isotopic compositions of individual n-alkanes and isoprenoids

In order to better understand the relative contributions of various source rocks for petroleum in the Xihu Depression, East China Sea Basin, gas chromatography-mass spectrometry analyses of the saturated and aromatic fractions and carbon isotopic analyses of the purified n-alkanes and isoprenoids were performed. The molecular composition and individual n-alkane and isoprenoid carbon isotope compositions were determined for oils and extracts of Paleogene mudstones (TOC: 0.45–2.3%), carbonaceous mudstones (12.7–19.6%), and coals (48–60%) in the Xihu Depression, so as to discriminate the hydrocarbon sources of coals and associated mudstones to the petroleum generated in the basin. Abundant diterpanes (e.g., isopimarane, phyllocladane) are present in all the samples. The differences in the δ ¹³C values of pristane and phytane indicate separate origins for the isoprenoids. A general negative sloping profile with increasing n-alkane carbon chain length was observed in coals, mudstones and oils from the Huangyan oilfield, with individual n-alkane δ ¹³C values between −25.6‰ and −34.4‰. These values are characteristic of the isotopic compositions of C3 plants, and are also typical of fluvial/lacustrine depositional settings. The isotope compositions of individual n-alkanes from the extracts of coals and mudstones correlate with the relative concentration of terrigenous higher plant-derived diterpenoids, which suggests that plant phyla/classes (for example gymnosperm-derived diterpanes versus angiosperm-derived diterpanes) may be a control on the carbon isotope profiles of n-alkanes. For samples dominated by terrigenous organic matter, long chain n-alkanes with a large proportion of gymnosperm input are approximately 2–3‰ enriched in ¹³C relative to those with angiosperm input, regardless of lithology. The connections between the oils, coals, and mudstones allow determination of the patterns and variations for different hydrocarbon contributions, and provide a way of differentiating specific source contributions to petroleum in the Xihu Depression. Oils generated from the coals have heavier δ ¹³C values with increasing chain length within a narrow range (approx. 2–3‰) and have more heterotrophic origins, whereas oils from the mudstones are more depleted in ¹³C with increasing carbon number (n-C _20-31) and have a greater derivation from land plants. The 825B oils in the Huangyan oilfield have a greater angiosperm-sourced hydrocarbon contribution than those of the 825AD oils, which have a greater gymnosperm-sourced hydrocarbon contribution. The tricyclic and tetracyclic diterpanes and the isotopic compositions of individual n-alkanes and isoprenoids may be useful in differentiating contributions of coals and associated mudstones to petroleum.