Abstract

Raman spectroscopy has been widely used in micropalaeontology and organic geochemistry to identify carbonaceous materials and evaluate their thermal maturity in fossils or metasedimentary rocks. Meanwhile, fossil egg researches have mostly focused on biomineralized calcite, but preserved carbonaceous (or possibly organic) materials inside the eggshells have been usually neglected until recently. Here we report an enigmatic egg from the Wido Volcanics (Upper Cretaceous) of South Korea that was analysed using diverse methods including polarized light microscope (PLM), scanning electron microscope (SEM), electron probe microanalyser (EPMA), electron backscatter diffraction (EBSD), and Raman spectroscopy. The eggshell not only shows the crystallography of archosaurian eggshells but also contains peculiar dark bands, which were previously known as the trait of fossil and modern Crocodyliformes eggshells. Raman spectroscopic analysis showed that the dark bands are mainly due to amorphous carbon, as evidenced by the clear graphite (G) and disordered (D) bands. The result suggests that preserved amorphous carbon in the fossil eggshells can be identified using Raman spectroscopy and Raman parameters may make it possible to compare the thermal maturity of spatiotemporally diverse fossil eggshells. It is apparent that the material of this study is not a dinosaur egg but might belong to a crocodyliform or choristoderan egg, and even other non-dinosaur archosaur can be a candidate as well.

Highlights

  • Along with diverse invertebrate fossils, vertebrate egg fossils are calcium carbonate-based biominerals (Mikhailov, 1997; Cusack and Freer, 2008; Pérez-Huerta et al, 2018)

  • Considering the porosity caused by the vesicles in the outer half of the eggshell, the outer half of A. vesicularis might be influenced by exogenous Mg

  • An enigmatic fossil egg from the Wido Volcanics of South Korea named as Aenigmaoolithus vesicularis has typical archosaurian microstructure and crystallography

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Summary

Introduction

Along with diverse invertebrate fossils, vertebrate egg fossils are calcium carbonate-based biominerals (Mikhailov, 1997; Cusack and Freer, 2008; Pérez-Huerta et al, 2018). Calcium carbonate of fossil eggs provide reproductive paleobiological information of amniotes Amorphous Carbon in Egg Fossil therein; Choi et al, 2019; Yang et al, 2019) and afford paleoenvironmental and taphonomic information overprinted in the eggs (Grellet-Tinner et al, 2010; Montanari et al, 2013; Angst et al, 2015; Moreno-Azanza et al, 2016; Graf et al, 2018; Kim et al, 2019; see Montanari, 2018 and references therein). In all rigid eggshells of modern amniotes, organic materials are certainly a minor and degradable component so that they are rarely preserved in the fossil record (Hirsch, 1996, Table 2; Smith and Hayward, 2010). The majority of the fossil eggshell studies have focused on biominerals rather than preserved carbonaceous (potential organic) matters

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