Department of Earth and Planetary Sciences, Tokyo Institute of Technology, Meguro, Tokyo, 152-8551, Japan.
Earth-Life Science Institute (WPI-ELSI), Tokyo Institute of Technology, Meguro, Tokyo, 152-8550, Japan.
Nat Commun. 2022 Oct 2;13(1):5790. doi: 10.1038/s41467-022-33538-9.
Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a C-C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low C-C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low C-C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic C-C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high C-C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The C-C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.
区分生物成因化合物和非生物成因化合物在资源地质学、生物地球化学和宇宙生命探索中至关重要。稳定同位素传统上被用于区分有机物质的起源,特别是烃类。然而,尽管进行了广泛的研究,非生物成因烃类的明确区分仍然具有挑战性。最近开发的聚类同位素分析提供了更可靠的信息,因为它独立于起始材料的稳定同位素组成。在这里,我们报告了乙烷的 C-C 聚类同位素分析数据,并证明与热成因乙烷相比,非生物合成的乙烷具有明显较低的 C-C 丰度。碰撞频率模型预测了由甲基自由基重组产生的乙烷中观察到的低 C-C 丰度(反聚类)。相比之下,热成因乙烷可能表现出从生物前体继承的近乎随机的 C-C 分布,在新陈代谢过程中发生 C-C 键断裂/重组。此外,我们发现微生物氧化后剩余的乙烷中存在异常高的 C-C 特征。总之,该方法可以区分热成因、微生物改变和非生物成因的烃类。C-C 特征可以为区分地球上和地球外环境中有机分子的起源提供重要的一步。