Abstract In recent times, the limits of traditional Py-GC-MS techniques in evaluating the macromolecular compositions of biopolymers have proved to be more apparent – particularly in those samples containing complex, structurally similar organic molecules, often producing large areas of unresolved complex mixtures (UCM). In this paper, we compare the use of pyrolysis comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (Py-GC×GC-TOFMS) with conventional Py-GC-MS analyses, and attempt to showcase the full potential of this technique by analyzing different fossil organic material – algal-derived Tasmanites, Ordovician microfossil Gloeocapsomorpha prisca and terrestrial plant-derived resin. With all three fossil samples, Py-GC×GC-TOFMS was able to offer a higher degree of compound separation, and detect more complex compounds. Sulphur and oxygen-bearing polar compounds were clearly separated into different homologous series. Thus, this method bypassed the problem created by UCM in traditional Py-GC-MS in the case of G. prisca and Tasmanites, while resolving several biomarkers in the case of resin, and aids in their chemotaxonomic classification. We find that Py-GC×GC-TOFMS provides a greater variety of compounds at enhanced resolution levels than conventional Py-GC-MS methods and is more suited to analyzing samples with larger variety of chemical structures and functional groups with greater confidence, particularly in unknown samples. It can thus provide the analytical capability to better characterize the chemistry of kerogens, which will help assess hydrocarbon source properties, and provide new avenues to interpretation in paleobiological studies.

中文翻译：

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使用 Py-GC×GC-TOFMS 阐明化石生物聚合物的大分子组成

摘要 近年来，传统 Py-GC-MS 技术在评估生物聚合物的大分子组成方面的局限性已被证明更加明显——尤其是在那些含有复杂、结构相似的有机分子的样品中，通常会产生大面积未解析的复杂混合物。 UCM）。在本文中，我们将热解综合二维气相色谱联用飞行时间质谱 (Py-GC×GC-TOFMS) 与常规 Py-GC-MS 分析进行了比较，并试图展示其全部潜力通过分析不同的化石有机材料——藻类来源的塔斯曼石、奥陶纪微化石 Gloeocapsomorpha prisca 和陆生植物来源的树脂，来了解这项技术。对于所有三个化石样品，Py-GC×GC-TOFMS 能够提供更高程度的化合物分离，并检测更复杂的化合物。含硫和含氧的极性化合物被清楚地分为不同的同源系列。因此，该方法在 G. prisca 和 Tasmanites 的情况下绕过了 UCM 在传统 Py-GC-MS 中产生的问题，同时解决了树脂情况下的几种生物标志物，并有助于它们的化学分类学分类。我们发现，与传统的 Py-GC-MS 方法相比，Py-GC×GC-TOFMS 以更高的分辨率提供了更多种类的化合物，并且更适合更有信心地分析具有更多种类化学结构和官能团的样品，尤其是在未知样本。因此，它可以提供更好地表征干酪根化学性质的分析能力，这将有助于评估烃源性质，