Antifeedant biomarkers in Cretaceous sediments from the North Sudetic Basin, Poland

The Late Cretaceous succession of siliciclastic sediment from the Czerna Formation in the North Sudetic Basin (SW Poland) consists of sandstones, dark grey mudstones and shales with coal intercalations. Samples of dark grey mudstone with lignite fragments from the inoperative sandstone quarry in Rakowice Mae, and samples of coals and siltstones from the sandstone quarry in Wartowice, were selected for gas chromatography-mass spectrometry analyses. All samples were thermally immature (the mean vitrinite reflectance (Rr) values did not exceed 0.45%). The samples contained phenolic abietans, including ferruginol and chamaecidin, which act as a defence mechanism against insect and microbial attack in coniferous trees (e.g., Gonzalez, 2015). Therefore, these compounds are widespread in extant coniferous trees (Simoneit et al., 2021) and can be identified in the geological record through their primary and diagenetic products. For instance, ferruginol (natural product), along with its derivatives: simonellite and retene, are present in the Cretaceous sedimentary rocks of the North Sudetic Basin. Another compound identified in the investigated samples is bergamotan. Perry et al. (2003) found that two derivatives of this compound were responsible for the insect antifeedant activity. Moreover, some of the identified compounds, such as chamazulene, are known in medical science for their anti-inflammatory properties (Safayhi et al., 1994). The presence of natural products with antifeedant activity against insects in Cretaceous samples suggests that plants had developed host defence mechanisms tens of millions of years ago. Acknowledgements The authors acknowledge financial support from the Polish National Science Centre (grant 2018/31/N/ST10/01646 to MG). References Gonzalez, M.A., 2015. Aromatic abietane diterpenoids: Their biological activity and synthesis. Natural Product Reports 32, 684704. Perry, N. B., Burgess, E. J., Foster, L. M., Gerard, P. J. (2003). Insect antifeedant sesquiterpene acetals from the liverwort Lepidolaena clavigera. Tetrahedron Letters 44(8), 16511653. Safayhi, H., Sabieraj, J., Sailer, E. R., Ammon, H. P. (1994). Chamazulene: An antioxidant-type inhibitor of leukotriene B4 formation.Planta Medica.60(5), 4103. Simoneit, B. R. T., Rybicki, M., Goryl, M., Bucha, M., Otto, A., Marynowski, L. (2021). Monoterpenylabietenoids, novel biomarkers from extant and fossil Taxodioideae and rocks. Organic Geochemistry, 154, 104172.