从中生代琥珀中检测到脊椎动物化石中的卟啉及其对化石记录中有机保存的意义。

Detection of porphyrins in vertebrate fossils from the Messel and implications for organic preservation in the fossil record.

机构信息

Department of Methodology, Textiles and Medical Technology, RISE Research Institutes of Sweden, Stockholm, Sweden.

Department of Earth Sciences, Uppsala University, Uppsala, Sweden.

出版信息

PLoS One. 2022 Jun 29;17(6):e0269568. doi: 10.1371/journal.pone.0269568. eCollection 2022.

Abstract

Organic molecules preserved in fossils provide a wealth of new information about ancient life. The discovery of almost unaltered complex organic molecules in well-preserved fossils raise the question of how common such occurrences are in the fossil record, how to differentiate between endogenous and exogenous sources for the organic matter and what promotes such preservation. The aim of this study was the in-situ analysis of a well-preserved vertebrate fossil from 48 Ma Eocene sediments in the Messel pit, Germany for preservation of complex biomolecules. The fossil was characterized using a variety of techniques including time-of-flight secondary ion mass spectrometry (ToF-SIMS), scanning electron microscopy/energy dispersive x-ray spectroscopy (SEM/EDX), x-ray diffraction (XRD) and Raman spectroscopy. A suite of organic molecules was detected, including porphyrins, which given the context of the detected signal are most probably diagenetically altered heme originating from the fossil though a microbial contribution cannot be completely ruled out. Diagenetic changes to the porphyrin structure were observed that included the exchange of the central iron by nickel. Further analyses on the geochemistry of the fossil and surrounding sediments showed presence of pyrite and aluminosilicates, most likely clay. In addition, a carbonate and calcium phosphate dominated crust has formed around the fossil. This suggests that several different processes are involved in the preservation of the fossil and the organic molecules associated with it. Similar processes seem to have also been involved in preservation of heme in fossils from other localities.

摘要

保存在化石中的有机分子为古代生命提供了丰富的新信息。在保存完好的化石中发现几乎未改变的复杂有机分子,这引发了一个问题,即在化石记录中这种情况有多常见,如何区分有机质的内源性和外源性来源,以及什么促进了这种保存。本研究的目的是对德国 Messel 坑 48 Ma 始新世沉积物中保存完好的脊椎动物化石进行原位分析,以研究复杂生物分子的保存情况。该化石使用多种技术进行了表征,包括飞行时间二次离子质谱 (ToF-SIMS)、扫描电子显微镜/能量色散 X 射线光谱 (SEM/EDX)、X 射线衍射 (XRD) 和拉曼光谱。检测到了一系列有机分子,包括卟啉,鉴于检测到的信号背景,这些卟啉很可能是化石中微生物来源的腐殖质衍生的、发生了成岩变化的血红素,但也不能完全排除微生物的贡献。观察到卟啉结构发生了成岩变化,包括中心铁被镍取代。对化石和周围沉积物的地球化学进一步分析表明,存在黄铁矿和铝硅酸盐,很可能是粘土。此外,在化石周围形成了以碳酸盐和磷酸钙为主的外壳。这表明有几个不同的过程参与了化石及其相关有机分子的保存。类似的过程似乎也参与了其他地方化石中血红素的保存。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3e8a/9242450/c1ea62f84364/pone.0269568.g001.jpg

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