Py-GC-MS和HyPy-GC-MS技术释放的热解烃与游离烃分子地球化学特征对比

Comparison of molecular geochemical characteristics between free hydrocarbons and pyrolytic hydrocarbons released by Py-GC-MS and HyPy-GC-MS

  • 摘要: 由于受到干酪根/沥青质复杂大分子结构的保护,结合态生物标志物具备抗生物降解、热成熟等后期改造的能力,能够较好地解决游离烃易受干扰、污染和改造的问题,应用价值较高。如何高效、便捷地获取结合态生物标志物,一直是地球化学家重点探索的方向。在线加氢热解—气相色谱—质谱联用技术(HyPy-GC-MS)以氢气为反应气,可高效释放干酪根中的结合态生物标志物,单位产率显著高于Py-GC-MS等传统热解技术。但Py-GC-MS和HyPy-GC-MS两种热解模式,分别从干酪根和沥青质释放的结合态生物标志物,与抽提物中的游离态生物标志物的可比性目前仍不明确。为此,通过选取渤中凹陷三套主力烃源岩所在层系的低熟样品,系统对比可溶抽提物(EOM)中的游离烃,与利用Py-GC-MS、HyPy-GC-MS分别从对应干酪根/沥青质中释放的热解烃。结果表明:干酪根Py-GC-MS产物中的C27规则甾烷占比与游离态差异大,且烯烃占比偏高。相较于Py-GC-MS,HyPy-GC-MS显著提高了烷烃产率及占比,其从干酪根和沥青质释放的产物,与EOM中C27-C29规则甾烷分布特征更为相似,TT23/H30、H29/H30等比值也更为接近,并呈现更低熟特征。因此在低熟烃源岩中,HyPy-GC-MS技术可有效抑制自由基二次反应,更好地保留甾萜烷的完整性和原始地化信息,是获取可靠结合态生物标志物的便捷方法,但其在高成熟度或强改造样品中的普适性需进一步验证。

     

    Abstract: Protected by the complex macromolecular structure of kerogen/asphaltene, bound biomarkers show strong resistance to post-depositional alterations such as biodegradation and thermal maturation, effectively overcoming the issues of easy disturbance, contamination, and alteration of free hydrocarbons, and therefore have high application value. How to efficiently and conveniently obtain bound biomarkers has always been a direction geochemists strive to explore. The on-line hydropyrolysis-gas chromatography-mass spectrometry (HyPy-GC-MS) technology uses hydrogen as the reaction gas and can efficiently release bound biomarkers from kerogens with a higher unit yield than conventional pyrolysis techniques like Py-GC-MS. However, the comparability between bound biomarkers released from kerogens and asphaltenes by Py-GC-MS and HyPy-GC-MS and free biomarkers in extracts remains unclear. Therefore, low-maturity samples from three main source rock strata in the Bozhong Sag were selected. A systematic comparison was made between free hydrocarbons in extractable organic matter (EOM) and pyrolytic hydrocarbons released from the corresponding kerogens/asphaltenes using Py-GC-MS and HyPy-GC-MS. The results showed that the proportion of C27 regular steranes in Py-GC-MS products from kerogens differed significantly from those in the free state, with a higher proportion of alkenes. Compared to Py-GC-MS, HyPy-GC-MS significantly increased the yield and proportion of alkanes. Its products released from kerogens and asphaltenes showed distribution characteristics of C27-C29 regular steranes similar to those in EOM, with ratios like TT23/H30 and H29/H30 closer to the free state and exhibiting low-maturity characteristics. Therefore, in low-maturity source rocks, the HyPy-GC-MS technique can effectively inhibit secondary free radical reactions, better preserve the integrity and original geochemical information of steranes and terpanes, making it a convenient method for obtaining reliable bound biomarkers. However, its universality in high-maturity or strongly altered samples requires further verification.

     

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