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Structural characterization and mass spectrometry fragmentation signatures of macrocyclic alkanes isolated from a Sydney Basin torbanite, Australia

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Abstract

Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin (Australia) were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR. Saturated cyclic structures were confirmed by single peaks in the NMR 1H and 13C spectra indicating single forms of H and C atoms exist in these biomarker molecules. This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of (CH2)n. The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research. The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes. The characteristic fragment ions in the macrocyclic alkanes of (M–28)+ and base peaks of m/z 97, 111, 125, etc., can be assigned as being generated by simple α-/i-cleavage and hydrogen rearrangement. These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples.

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Acknowledgements

Hong Lu acknowledges the financial support from The Strategic Priority Research Program of the Chinese Academy of Sciences (XDA14010102), and Chinese National Science Foundation grants (41973069; 41673045).

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Authors and Affiliations

  1. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry and Institutions of Earth Science, Chinese Academy of Sciences, Guangzhou, 510640, China

    Xianxin Meng, Hong Lu & Ping’an Peng

  2. CAS Center for Excellence in Deep Earth Science, Guangzhou, 510640, China

    Xianxin Meng, Hong Lu & Ping’an Peng

  3. University of the Chinese Academy of Sciences, Beijing, 100049, China

    Xianxin Meng

  4. Wuxi Institute of Petroleum Geology, PEPRIS, SINOPEC, 2060 Lihu Rd., Wuxi, 214126, Jiangsu, China

    Zhirong Zhang & John K. Volkman

  5. Key Laboratory of Oil and Gas Resources and Exploration Technology, Ministry of Education, College of Resources and Environment, Yangtze University, Wuhan, 430100, China

    Zhirong Zhang

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  1. Xianxin Meng
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  2. Hong Lu
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Correspondence to Hong Lu or Zhirong Zhang.

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Meng, X., Lu, H., Zhang, Z. et al. Structural characterization and mass spectrometry fragmentation signatures of macrocyclic alkanes isolated from a Sydney Basin torbanite, Australia. Acta Geochim 42, 488–494 (2023). https://doi.org/10.1007/s11631-023-00597-8

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  • DOI: https://doi.org/10.1007/s11631-023-00597-8

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