Abstract
The bitumen shale facies in the Paleocene Palana Formation serves as a key oil-shale resource in the Bikaner–Nagaur Basin, Western India. It has a high organic matter concentration, which provides the necessary foundation for significant oil accumulation. Therefore, the purpose of this work is to characterize the molecular structure of kerogen within the Palana oil shale facies in order to assess the potential of shale oil resources and comprehend the mechanisms of hydrocarbon generation. In this study, comprehensive chemical analyses, including elemental analysis (CHNS), FTIR, TG/DTA, Py-GC, and kinetics of the kerogen decomposition, incorporated with microscopic investigation, were employed to decipher the elemental composition and molecular structure of Palana’s kerogen. The microscopic analysis of kerogen indicates that the Palana oil shale sediments are characterized by high abundance marine organic matter assemblages, including bituminite, fluorescence AOM, and algae, consistent with the presence of hydrogen-rich kerogen. The predominance of hydrogen-enriched kerogen, primarily classified as Type II, with moderate-to-low sulfur content is substantiated by the kerogen’s elemental profile and molecular structure. This includes a high hydrogen-to-carbon atomic ratio (H/C ˃1.40), low sulfur-to-carbon atomic ratio (S/C < 0.04), and predominance of aliphatic compounds with relatively low concentrations of aromatic compounds. The petroleum type of the Palana’s kerogen is corresponding to P–N–A oils with high wax content, and it is released at a subsurface temperature regime of 107 to 153 °C, which is consistent with the computed vitrinite reflectance values of 0.62–1.07%VRo, as demonstrated by the bulk and compositional kinetic results. The highlight results of the elemental composition and molecular structure provide a strong basis for further in-situ conversion processes and development of the shale oil system, as well as the mechanism of petroleum generation in the oil shale of the Palana Formation.
Similar content being viewed by others
Data availability
The datasets generated or analysed during the current study available from the corresponding author on reasonable request.
References
Hackley, P. C. & Ryder, R. T. Organic geochemistry and petrology of Devonian shale in eastern Ohio: Implications for petroleum systems assessment. AAPG Bull. 105(3), 543–573 (2021).
Jarvie, D. M., Hill, R. J., Ruble, T. E. & Pollastro, R. M. Unconventional shale-gas-systems: The Mississippian barnett shale of north-central Texas as one model for thermogenic shale-gas assessment. AAPG Bull. 91, 475–499 (2007).
Sohail, G. M., Radwan, A. E. & Mahmoud, M. A review of Pakistani shales for shale gas exploration and comparison to north American shale plays. Energy Rep. 8, 6423–6442 (2022).
van Krevelen, D. W. Coal: Typology, Chemistry, Physics, Constitution 36, 173 (Elsevier, Amsterdam, 1961)
Lille, U., Heinmaa, I. & Pehk, T. Molecular model of Estonian Kukersite kerogen evaluated by 13C MAS NMR spectra. Fuel 2003(82), 799–804 (2003).
Lai, Z., Tian, Y., Gao, S. & Xu, G. Mechanism of kerogen pyrolysis in terms of chemical structure transformation. Fuel 199, 504–511 (2017).
Pan, S. et al. Molecular structure and electronic properties of oil shale kerogen: An experimental and molecular modeling study. Energy Fuels 2018(32), 12394–12404 (2018).
Hillier, J. L., Fletcher, T. H., Solum, M. S. & Pugmire, R. J. Characterization of macromolecular structure of pyrolysis products from a Colorado Green river oil shale. Ind. Eng. Chem. Res. 52, 15522–15532 (2013).
Yan, J. W., Jiang, X. M., Han, X. X. & Liu, J. G. A. TG-FTIR investigation to the catalytic effect of mineral matrix in oil shale on the pyrolysis and combustion of kerogen. Fuel 104, 307–317 (2013).
Fletcher, T. H. et al. Characterization of macromolecular structure elements from a Green river oil shale. II. Characterization of pyrolysis products by 13C NMR, GC/MS, and FTIR. Energy Fuels 28, 2959–2970 (2014).
Zheng, M. et al. Pyrolysis of Liulin coal simulated by GPU-based ReaxFFMD with cheminformatics analysis. Energy Fuels 28, 522–534 (2014).
Huang, Y., Han, X. & Jiang, X. Characterization of Dachengzi oil shale fast pyrolysis by curie-point pyrolysis-GC-MS. Oil Shale 32, 134–150 (2015).
Eglinton, T. I., Larter, S. R. & Boon, J. J. Characterisation of kerogens, coals and asphaltenes by quantitative pyrolysis mass spectrometry. J. Anal. Appl. Pyrolysis 20, 25–45 (1991).
Li, S. H., Ma, X. Q., Liu, G. C. & Guo, M. X. A. TG−FTIR investigation to the co-pyrolysis of oil shale with coal. J. Anal. Appl. Pyrolysis 120, 540–548 (2016).
Singh, A. et al. Paleoenvironment of Eocene lignite bearing succession from Bikaner–Nagaur Basin, western India: Organic petrography, palynology, palynofacies and geochemistry. Int. J. Coal Geol. 181, 87–102 (2017).
Shukla, A. et al. Paleo-wildfire signatures revealing co-occurrence of angiosperm-gymnosperm in the early Paleogene: Evidences from woody charcoal and biomarker analysis from the Gurha lignite mine, Rajasthan, India. Int. J. Coal Geol. 265, 104164 (2023).
Zhu, B., Kid, W. S. F., Rowley, D. B., Currie, B. S. & Shafique, N. Age of initiation of the India–Asia collision in the east-central Himalaya. J. Geol. 113, 265–285 (2005).
Acharyya, S. K. Evolution of the Himalayan Paleogene foreland basin, influence of its litho-packet on the formation of thrust related domes and windows in the eastern Himalayas—A review. J. Asian Earth Sci. 31, 1–17 (2007).
Kumar, V. & Chandra, R. Geology and evolution of Nagaur-Ganganagar basin with special reference to salt and potash mineralization. Geol. Surv. India 62, 151 (2005).
Mathews, R. P. et al. Organo-petrographic and geochemical characteristics of Gurha lignite deposits, Rajasthan, India: Insights into the palaeovegetation, palaeoenvironment and hydrocarbon source rock potential. Geosci. Front. 11, 965–988 (2020).
Singh, A. K. et al. Geochemical and organic petrographic characteristics of high bituminous shales from Gurha mine in Rajasthan, NW India. Sci. Rep. 10, 22108 (2020).
Hakimi, M. H. et al. High sulphur oil of Type II kerogen of the oil shales from Western Central Jordan based on molecular structure and kinetics. Sci. Rep. 14, 19033 (2024).
Schopf, J. M. Field Description and Sampling of Coal Beds 67 (US Government Printing Office, 1960).
Durand, B. & Nicaise, G. Procedures for Kerogen Isolation. In Kerogen Insoluble Organic Matter from Sedimentary Rocks (ed. Durand, B.) 35–53 (Editions Technip, 1980).
Taylor, G. H., Teichmüller, M., Davis, A., Diessel, C. F. K., Littke, R. & Robert, P. Organic Petrology. (Gebrüder Borntraeger, Berlin, Stuttgart, 1998).
Donahue, J. C. & Rais, E. A. Proximate analysis of coal. J. Chem. Educ. 86(2), 222 (2009).
Horsfield, B. Practical criteria for classifying kerogens: Some observations from pyrolysis-gas chromatography. Geochim. Cosmochim. Acta 53, 891–901 (1989).
Weiss, H.M., Wilhelms, A. & Mills, N. NIGOGA—The Norwegian Industry Guide to Organic Geochemical Analyses [online]. Edition 4.0. Accessed 16 Nov, 2021. https://www.npd.no/globalassets/1-npd/regelverk/rapportering/bronner/eng/guide-organic-geochemical-analyses.pdf. (2000)
Ganz, H. & Kalkreuth, W. Application of infrared spectroscopy to the classification of kerogen-types and the evaluation of source rock and oil shale potentials. Fuel 66, 708–711 (1987).
Ganz, H. H. & Kalkreuth, W. IR classification of kerogen type, thermal maturation, hydrocarbon potential and lithological characteristics. J. Southeast Asian Earth Sci. 5, 19–28 (1991).
Mastalerz, M., Hower, J. C. & Taulbee, D. N. Variations in chemistry of macerals as reflected by micro-scale analysis of a Spanish coal. Geol. Acta 11, 483–493 (2013).
Wang, S., Tang, Y. & Schobert, H. H. FTIR and simultaneous TG/MS/FTIR study of late Permian coals from southern China. J. Anal. Appl. Pyrolysis 100, 75–80 (2013).
Patricia, G. R. O., Blandón, A., Perea, C. & Mastalerz, M. Petrographic characterization, variations in chemistry, and paleoenvironmental interpretation of Colombian coals. Int. J. Coal Geol. 227, 103516 (2020).
Burnham, A. K., Braun, R. L., Gregg, H. R. & Samoun, A. M. Comparison of methods for measuring kerogen pyrolysis rates and fitting kinetic parameters. Energy Fuels 1, 452–458 (1987).
Burnham, A. K., Braun, R. L. & Samoun, A. M. Further comparison of methods for measuring kerogen pyrolysis rates and fitting kinetic parameters. Org. Geochem. 13, 839–845 (1988).
Behar, F., Vandenbroucke, M., Tang, Y., Marquis, F. & Espitalié, J. Thermal cracking of kerogen in open and closed systems: Determination of kinetic parameters and stoichiometric coe fficients for oil and gas generation. Org. Geochem. 26, 321 (1997).
Schenk, H. J., Horsfield, B., Kroos, B., Schaefer, R. G. & Schwochau, K. Kinetics of Petroleum Formation and Cracking. In Petroleum and Basin Evolution (eds Welte, D. H. et al.) 231–269 (Springer Verlag Berlin Heidelberg, 1997).
Inan, S., Alp, U. F., İnan, T., Yalçın, M. N. & Mann, U. Relationship between organic matter, sulphur and phosphate contents in Upper Cretaceous marine carbonates (Karaboğaz Formation, SE Turkey): Implications for early oil generation. J. Petrol. Geol. 33(4), 319–338 (2010).
Thana’Ani, N. A. A., Mustapha, K. A. & Idris, M. Source rock pyrolysis and bulk kinetic modelling of Miocene sedimentary sequences in southeastern Sabah, Malaysia: The variability of thermal maturity to oil-gas producing kerogen. J. Pet. Sci. Eng. 208, 109513 (2022).
Makeen, Y. M. et al. Hydrocarbon generation potential of Oligocene oil shale deposit at Onshore Penyu Basin, Chenor, Pahang, Malaysia. Energy Fuels 33(1), 89–105 (2019).
Pickel, W. et al. Classification of liptinite—ICCP System 1994. Int. J. Coal Geol. 169, 40–61 (2017).
Tyson, R. V. Sedimentary Organic Matter—Organic Facies and Palynofacies 615 (Chapman and Hall, 1995).
Tissot, B. P. & Welte, D. H.. Petroleum Formation and Occurrence 966 (Springer Science & Business Media, 1984)
Sawada, K. & Akiyama, M. Carbon isotope composition of macerals separated from various kerogens by density separation method. J. Jap. Assoc. Petrol. Technol. 59, 244–255 (1994).
Walters, C.C. The Origins of Petroleum in Practical Advances in Petroleum Processing 79–101 (Springer, 2007)
Asiwajul, L., Mustapha, K. A., Abdullah, W. H., Makeen, Y. M. & Hakimi, M. H. Geochemical characterisation and petroleum potential of selected Cenozoic coals from Sarawak basin, Malaysia. J. Pet. Explor. Prod. Technol. 15, 113. https://doi.org/10.1007/s13202-025-01987-9 (2025).
Misra, S., Varma, A. K. & Das, S. K. Thermal controls of lamprophyre sill on hydrocarbon generation outlook of shale beds in Raniganj basin, India. J. Nat. Gas Sci. Eng. 56, 536–548 (2018).
Biswas, S., Varma, A. K. & Kumar, M. Influence of geochemical, organo petrographical and palynofacies assemblages on hydrocarbon generation: A study from upper Oligocene coal and shale of the Makum Coal Basin, Assam, India. Mar. Pet. Geol. 114, 104206 (2020).
Eglinton, T. I., Sinninghe Damste, J. S., Kohnen, M. E. L. & de Leeuw, J. W. Rapid estimation of the organic sulphur content of kerogens, coals and asphaltenes by pyrolysis-gas chromatography. Fuel 69, 1394–1404 (1990).
Lehne, E. & Dieckmann, V. The significance of kinetic parameters and structural markers in source rock asphaltenes, reservoir asphaltenes and related source rock kerogens, the Duvernay Formation (WCSB). Fuel 86, 887–901 (2007).
Makeen, Y. M., Abdullah, W. H. & Hakimi, M. H. Source rock characteristics of the Lower Cretaceous Abu Gabra formation in the Muglad Basin, Sudan, and its relevance to oil generation studies. Mar. Pet. Geol. 59, 505–516 (2015).
Behar, F. & Vandenbroucke, M. Chemical modeling of kerogens. Org. Geochem. 11, 15–24 (1987).
Schaefer, R. G., Schenk, H. J., Hardelauf, H. & Harms, R. Determination of gross kinetic parameters for petroleum formation from Jurassic source rocks of different maturity levels by means of laboratory experiments. Org. Geochem. 16, 115–120 (1990).
Baskin, D. K. & Peters, K. E. Early generation and characteristics of a sulfur-rich Monterey kerogen. Am. Assoc. Pet. Geol. Bull. 76, 1–13 (1992).
Hakimi, M. H. et al. Pyrolysis analyses and bulk kinetic models of the Late Cretaceous oil shales in Jordan and their implications for early mature sulphur-rich oil generation potential. Mar. Pet. Geol. 91, 764–775 (2018).
Hakimi, M. H. et al. Geochemistry and organofacies characteristics of organic-rich chalky marl deposits, northern Jordan: Insights into Type II-S source rock. J. Asian Earth Sci. 225, 105040 (2022).
Dembicki, H. Three common source rock evaluation errors made by geologists during prospect or play appraisals. AAPG Bull. 93, 341–356 (2009).
Chen, Z., Liu, X. & Jiang, C. Quick evaluation of source rock kerogen kinetics using hydrocarbon pyrograms from regular Rock-Eval analysis. Energy Fuels 2017(31), 1832–1841 (2017).
Dieckmann, V., Caccialanza, P. G. & Galimberti, R. Evaluating the timing of oil expulsion: About the inverse behaviour of light hydrocarbons and oil asphaltene kinetics. Org. Geochem. 33, 1501–1513 (2002).
Dieckmann, V. Modelling Petroleum Formation From Heterogeneous Source (2005).
Acknowledgements
The authors extend their sincere gratitude to the Department of Geology, University of Malaya, Kuala Lumpur, Malaysia, for providing laboratory support for geochemical experiments.
Funding
).This work was funded by the subsidy allocated to Kazan Federal University for the state assignment project No. FZSM-2026-0033 in the sphere of scientific activities. Alok Kumar gratefully acknowledges the Anusandhan National Research Foundation (ANRF), Government of India, for support through the National Postdoctoral Fellowship (File No. PDF/2023/000040). The support given from the Ongoing Research Funding Program No. (ORF-2026-92), King Saud University, Riyadh, Saudi Arabia, is highly appreciated.
Author information
Authors and Affiliations
Contributions
M.H.H., A.K., A.L., A.M.A., K.A.M., R.P.M., take part in data analysis and interpretation, wrote the main manuscript text, results and discussions, and funding the work. D.K.N., S.M.T.Q., P.K.S., take part in reviewing the manuscript.
Permission
The co-author Dr. Alok Kumar has been taken the prior permission from the VS Lignite Power Private Limited for collecting the studied samples from the Gurha mine.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
About this article
Cite this article
Hakimi, M.H., Kumar, A., Lashin, A. et al. Molecular structure and thermal decomposition kinetics of kerogen from the Paleocene oil-shale facies in the Bikaner–Nagaur Basin, western India. Sci Rep (2026). https://doi.org/10.1038/s41598-026-40152-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41598-026-40152-y


