Abstract Catalytic hydropyrolysis (HyPy) has been widely used in the study of covalently bonded biomarkers from macromolecular organic matter. Current HyPy studies mainly focus on nonpolar aliphatic biomarkers, whereas studies of polar non-volatile heteroatomic compounds are lacking. In this study, heteroatomic compounds in free and bound bitumen released via HyPy of kerogen from three different source rocks were characterised and compared by electrospray ionisation (ESI) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). These analyses suggest that heteroatomic compounds in bound bitumen are better proxies of the original biogenic sources and contain more aromatic structures than in heteroatomic compounds occurring in the free bitumen. From studies of three source rocks, we found that differences in the maturity, depositional environment, and diagenetic conditions seem to have significantly influenced the composition and distribution of heteroatomic compounds in free and bound bitumen. Nitrogen-containing compounds (N1 and N1OX species) in the free bitumen were mainly affected by maturity – only being detected in the rock of highest maturity – although they occurred in similar composition in the bound bitumen of all three rocks. With increasing maturity, nitrogen compounds were partitioned from bound to free bitumen, resulting in compositional differences between these two bitumen types (especially for basic nitrogen compounds). Sulfur-containing compounds (mainly S1, OXS1, and OXS2 species) were mainly influenced by the depositional environment and were abundant in the two rocks from a reducing depositional environment. Their composition was more complex and less saturated in bound bitumen. Oxygen compounds were common to all three rocks, but of highest abundance in the one source rock deposited in a freshwater environment.

中文翻译：

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ESI FT-ICR MS表征来自不同烃源岩的游离和结合沥青中的杂原子化合物

摘要 催化加氢热解 (HyPy) 已广泛用于大分子有机物共价键生物标志物的研究。目前的 HyPy 研究主要集中在非极性脂肪族生物标志物上，而缺乏对极性非挥发性杂原子化合物的研究。在这项研究中，通过电喷雾电离 (ESI) 和傅立叶变换离子回旋共振质谱 (FT-ICR MS) 对三种不同烃源岩中通过干酪根的 HyPy 释放的游离和结合沥青中的杂原子化合物进行了表征和比较。这些分析表明，结合沥青中的杂原子化合物是原始生物来源的更好代表，并且比游离沥青中的杂原子化合物含有更多的芳香结构。通过对三种烃源岩的研究，我们发现成熟度的差异，沉积环境和成岩条件似乎显着影响了游离和结合沥青中杂原子化合物的组成和分布。游离沥青中的含氮化合物（N1 和 N1OX 种类）主要受成熟度的影响——仅在最高成熟度的岩石中检测到——尽管它们在所有三种岩石的结合沥青中的成分相似。随着成熟度的增加，含氮化合物从结合沥青分配到游离沥青，导致这两种沥青类型之间的成分差异（尤其是碱性含氮化合物）。含硫化合物（主要是 S1、OXS1 和 OXS2 物种）主要受沉积环境的影响，并且在还原沉积环境的两种岩石中含量丰富。它们的成分更复杂，结合沥青的饱和度更低。含氧化合物在所有三种岩石中都很常见，但在沉积在淡水环境中的一种源岩中含量最高。