Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

南海北部琼东南盆地浅表层沉积物的地球化学特征及对沉积环境的指示*

南海北部琼东南盆地海底存在着巨型麻坑, 现有研究多认为其形成主要与海底流体渗漏有关。目前对琼东南盆地深海沉积物地球化学特征及麻坑区的生物地球化学过程等尚不清楚。文章选取南海北部琼东南盆地C14、C19两个站位岩心样品, 进行了总硫(TS)、总碳(TC)、总有机碳(TOC)、铬还原性硫化物(CRS)及其δ³⁴S_CRS值测试, 并结合总氮/总碳(TN/TOC)比值和已发表的孔隙水中SO₄^2-浓度等进行了地球化学特征分析。研究表明: C14站位以3.91m bsf (below seafloor)为界, 上下分别存在有机质参与的硫酸盐还原反应(OSR)和甲烷厌氧氧化作用(AOM)驱动的硫酸盐还原反应(SR); 3.91m bsf以上的部位沉积物的TS、TC含量均低于3.91m bsf以下部位, 且沉积物孔隙水中SO₄^2-浓度由3.91m bsf以上的缓慢凹型减少变成3.91m bsf以下的线性减少, 说明该处成为沉积物中地球化学特征分界的明显标志; 在3.91m bsf以下, 受到甲烷渗漏的影响。C19站位沉积物中TS与TC含量由浅到深逐渐增加, 但与TN/TOC比值变化呈现几乎相反趋势, 即整个岩心以OSR为主, 并呈现出有机质早期成岩阶段的沉积现象。C14和C19两个站位柱状沉积物的δ³⁴S_CRS值变化范围分别为-50.2‰~-46.9‰和-50.1‰~-42.0‰ (V-CDT标准), 均显示出了较为偏负的硫同位素值, 表明研究区主要的生物化学过程是在相对开放体系下硫酸盐还原作用的结果, 综合说明该研究区麻坑的甲烷流体已经喷发, 目前可能处于衰退期, 甚至已经不活跃, 该结果与前人的认识基本一致。     

Rare earth element characteristics of the carboniferous Huanglong Formation dolomites in eastern Sichuan Basin,southwest China: Implications for origins of dolomitizing and diagenetic fluids

Marine dolostones of Carboniferous Huanglong Formation constitute major gas reservoir rocks in eastern Sichuan Basin. However, the investigation with respect to sources of dolomitizing and diagenetic fluids is relatively underexplored. The current study attempts to investigate the REE characteristics of dolomites using seawater normalization standard, and therefore discusses the origins of dolomitizing and diagenetic fluids, on the basis of continuous 47.33-m-long core samples from the second member of Huanglong Formation (C₂h₂) in eastern Sichuan Basin. Low Th, Sc, and Hf concentrations (0.791 × 10⁻⁶, 4.751 × 10⁻⁶, and 0.214 × 10⁻⁶, respectively), random correlation between total REE concentration (ΣREE) and Fe or Mn abundance, and seawater-like Y/Ho ratios (mean value of 45.612) indicate that the carbonate samples are valid for REE analysis. Based on petrographic characteristics, four dolomite types are identified, including micritic-sized dolomite (type Dol-1), fine-to medium-sized dolomite (type Dol-2), medium-to coarse-sized dolomite (type Dol-3), and coarse-to giant-sized saddle dolomite (type Dol-4). Dol-1 dolomites, characterized by positive Ce anomaly (mean value of 6.398), light REE (LREE) enrichment, and heavy REE (HREE) depletion with mean LREE/HREE ratio of 12.657, show micritic calcite-like REE patterns, indicating seawater origin of their dolomitizing fluids. Dol-1 dolomites were formed in sabkha environment whereas the dolomitizing fluids originated from evaporative brine water due to their micritic crystal sizes and tight lithology. Dol-2 dolomites, particularly subtype Dol-2a barely developing vuggy porosity, also show micritic calcite-like REE patterns, suggesting their dolomitizing fluids were seawater or seawater-derived fluids. This inference is confirmed by low Fe and Mn concentrations, which range from 651 μg/g to 1018 μg/g (mean value of 863 μg/g) and 65 μg/g to 167 μg/g (mean value of 105 μg/g), respectively, whereas homogenization temperatures (T_h, mean value of 103 °C) indicate that Dol-2 dolomites were formed under burial environment. Dol-3 dolomites, in form of cements of Dol-2 dolomites, show similar REE patterns to their host minerals (i.e., Dol-2 dolomites), indicating their parent source was possibly derived from Dol-2 dolomites. Dol-3 dolomites have high Fe and Mn concentrations with mean values of 3346 μg/g (ranging from 2897 μg/g to 3856 μg/g) and 236 μg/g (ranging from 178 μg/g to 287 μg/g), respectively, indicating the involvement of meteoric water. Meanwhile, it confirms that the dissolution in Dol-2 dolomites was caused by meteoric water leaching. Positive Eu anomalies (mean value of 1.406) in Dol-4 dolomites, coupled with high homogenization temperatures (mean value of 314 °C), suggest that Dol-4 dolomites precipitated from hydrothermal fluids. High Fe and Mn concentrations (mean values of 2521 μg/g and 193 μg/g, respectively) in Dol-4 dolomites likely results from interactions of hydrothermal fluids with deep burial clastic rocks.