Miranda Flávia Lima E Cima, Nery do Amaral Diego, Cerqueira José Roberto, Garcia Karina Santos, Queiroz Antônio Fernando de Souza, Machado Maria Elisabete
Programa de Pós graduação Geoquímica: Petróleo e Meio Ambiente, Instituto de Geociências, Universidade Federal da Bahia, Salvador 40170-290, BA, Brazil.
Departamento de Ciências Exatas, Universidade Estadual de Feira de Santana, Feira de Santana 44036-900, BA, Brazil.
ACS Omega. 2024 Sep 5;9(37):38633-38647. doi: 10.1021/acsomega.4c04189. eCollection 2024 Sep 17.
In this study, chromatographic methods were first optimized to ensure the robustness of the identification and quantification of nitrogen markers and biomarkers. Then, the optimal conditions were applied to 14 crude oil samples deposited in distinct paleoenvironments from Brazil, Venezuela, and Colombia to perform an integrated geochemical assessment. Analytical standards, certified reference material, and retention indices were used to confirm the identification of biomarkers and N-markers. The results of geochemical interpretations based on unresolved complex mixture (UCM), pristane/-heptadecane (Pr/-C), and phytane/-octadecane (Ph/-C) ratios and concentrations of carbazole and benzo[]carbazole indicated that all oils are not biodegraded. The Pr/-C, Ph/-C, and Pr/Ph ratios showed that the organic matter that generated the oils from Brazil and Venezuela was deposited under anoxic conditions and Colombia oil reached dysoxic conditions. Some samples present a greater abundance of low- to high-molecular-mass -alkanes, indicating freshwater lakes' organic matter (Brazil oils). In contrast, other samples showed a lower abundance of high-mass -alkanes, suggesting marine and saline lake origins (Colombia and Venezuela oils). The tricyclic/hopane ratio, the ternary diagrams using 1-methylcarbazole, 2-methylcarbazole, and 4-methylcarbazole, and regular steranes C, C, and C suggested a contribution of algae to the formation of kerogen present in the source rocks of all petroleum samples. The high concentrations of carbazole in oils generated by marine organic matter confirm the more positive δC values compared with those generated by lake organic matter (Brazil samples). The use of chemometric tools as principal component analysis exhibited a grouping of samples according to the depositional environment using carbazole and tricyclic/hopane ratio. The integration of all parameters analyzed provides a guide for refined interpretations and differentiation of oils according to their depositional environments.
在本研究中,首先对色谱方法进行了优化,以确保氮标记物和生物标志物鉴定及定量的稳健性。然后,将最佳条件应用于来自巴西、委内瑞拉和哥伦比亚不同古环境中沉积的14个原油样品,以进行综合地球化学评估。使用分析标准品、有证参考物质和保留指数来确认生物标志物和氮标记物的鉴定。基于未解析复杂混合物(UCM)、植烷/正十七烷(Pr/⁃C17)和姥鲛烷/正十八烷(Ph/⁃C18)比率以及咔唑和苯并咔唑浓度的地球化学解释结果表明,所有油样均未发生生物降解。Pr/⁃C17、Ph/⁃C18和Pr/Ph比率表明,生成巴西和委内瑞拉原油的有机质是在缺氧条件下沉积的,而哥伦比亚原油达到了弱氧化条件。一些样品中低至高分子量的正构烷烃丰度较高,表明为淡水湖的有机质(巴西原油)。相比之下,其他样品中高分子量正构烷烃的丰度较低,表明其来源于海洋和盐湖(哥伦比亚和委内瑞拉原油)。三环萜烷/藿烷比率、使用1⁃甲基咔唑、2⁃甲基咔唑和4⁃甲基咔唑的三元图以及规则甾烷C27、C28和C29表明,藻类对所有石油样品源岩中存在的干酪根形成有贡献。海洋有机质生成的原油中咔唑浓度较高,这证实了与湖泊有机质生成的原油(巴西样品)相比,其δ13C值更正。使用主成分分析等化学计量工具,根据咔唑和三环萜烷/藿烷比率,样品按沉积环境进行了分组。对所有分析参数的整合为根据油样的沉积环境进行精细解释和区分提供了指导。