A detailed evaluation of geochemical properties of oil shale samples from the outcrops of the Lower Miocene upper layer in the Dubrava area, Aleksinac basin, Serbia, was performed. For that purpose X-ray diffraction (XRD) analysis, Rock Eval pyrolysis, gas chromatography-mass spectrometry (GC-MS) analysis of biomarkers and conventional pyrolysis in an autoclave were used.
Most of the samples have similar mineral compositions with predominance of clay and feldspar minerals. Three samples are characterised by an elevated content of carbonates, and among them one sample has a notable prevalence of this mineral group. This sample also demonstrated certain differences in biomarker distribution.
In most samples organic matter (OM) consists predominantly of type I and II kerogens, showing high oil generative potential, whereas three samples, which contain type II kerogen with a certain input of type III kerogen, demonstrated potential to produce both, oil and gas. The OM of all samples is immature and corresponds to the vitrinite reflectance of ca. 0.40%. Biomarker patterns along with Rock-Eval data indicated a strong contribution of aquatic organisms such as green and brown algae and bacteria with some influence of higher plants OM. The organic matter was deposited in a reducing lacustrine alkaline brackish to freshwater environment under warm climate conditions. Preservation of OM was governed by stratification of the water column rather than its height. Tectonic movements that caused the regional tilting of an investigated area and supported minor marine ingression and influx of fresh water played an important role in formation of the sediments.
Conventional pyrolytic experiments confirmed that these sediments at the catagenetic stage could be a significant source of liquid hydrocarbons.
1. Ercegovac, M., Grgurović, D., Bajc, S., Vitorović, D. Oil shale in Serbia: geological and chemical-technological investigations, actual problems of exploration and feasibility studies. In: Mineral Material Complex of Serbia and Montenegro at the Crossings of Two Millenniums (Vujić, S., еd.). Margo-Art, Belgrade, 2003, 368–378 (in Serbian, with English abstract).
2. Jelenković, R., Kostić, A., Životić, D., Ercegovac, M. Mineral resources of Serbia. Geol. Carpath., 2008, 59(4), 345–361.
3. Ercegovac, M., Vitorović, D., Kostić, A., Životić, D., Jovančićević, B. Geology and Geochemistry of the Aleksinac oil shale deposit (Serbia). In: Book of Abstracts Joint 61st ICCP/26th TSOP Meeting “Advances in Organic Petrology and Organic Geochemistry”, September 19–26, 2009, Gramado, Brazil, P13, p. 6.
4. Skala, D., Bastić, M., Jovanović, J., Rahimian, I. Pyrolysis of oil shale in a microretorting unit. Fuel, 1993, 72(6), 829–835.
https://doi.org/10.1016/0016-2361(93)90087-I
5. Obradović, J., Djurdjević-Colson, J., Vasić, N. Phytogenic lacustrine sedimentation – oil shales in Neogene from Serbia, Yugoslavia. J. Paleolimnol., 1997, 18(4), 351–364.
https://doi.org/10.1023/A:1007907109399
6. Čokorilo, V., Lilić, N., Purga, J., Milisavljević, V. Oil shale potential in Serbia. Oil Shale, 2009, 26(4), 451–462.
https://doi.org/10.3176/oil.2009.4.02
7. Tissot, B. P., Welte, D. H. Petroleum Formation and Occurrence, 2nd ed. Springer-Verlag, Heidelberg, 1984.
https://doi.org/10.1007/978-3-642-87813-8
8. Peters, K. E., Walters, C. C., Moldowan, J. M. The Biomarker Guide, Vol. 2: Biomarkers and Isotopes in Petroleum Exploration and Earth History, Second edition. Cambridge University Press, Cambridge, 2005.
9. Huizinga, B. J., Aizenshtat, Z. A., Peters, K. E. Programmed pyrolysis-gas chromatography of artificially matured Green River kerogen. Energ. Fuel., 1988, 2, 74–81.
https://doi.org/10.1021/ef00007a011
10. Stojanović, K., Šajnović, A., Sabo, T. J., Golovko, A., Jovančićević, B. Pyrolysis and catalyzed pyrolysis in the investigation of a Neogene shale potential from Valjevo-Mionica basin, Serbia. Energ. Fuel., 2010, 24(8), 4357–4368.
https://doi.org/10.1021/ef100466f
11. Petrović, M. Reserve Report for the Aleksinac Oil Shale – "Dubrava" Field. JP PEU, Resavica, 2012 (in Serbian).
12. Ercegovac, M. Geology of Oil Shale. Građevinska knjiga, Belgrade, 1990 (in Serbian).
13. Perunović, T., Stojanović, K., Simić, V., Kašanin-Grubin, M., Šajnović, A., Erić. V., Schwarzbauer, J., Vasić, N., Jovančićević, B., Brčeski, I. Organic geochemical study of the lower Miocene Kremna basin, Serbia. Ann. Soc. Geol. Pol., 2014, 84(3), 185–212.
14. Vuković, N., Životić, D., Mendonça Filho, J. G., Kravić-Stevović, T., Hámor-Vidó, M., Mendonça, J. O., Stojanović, K. The assessment of maturation changes of humic coal organic matter – insights from closed-system pyrolysis experiments. Int. J. Coal Geol., 2016, 154–155, 213–239.
https://doi.org/10.1016/j.coal.2016.01.007
15. Kabekkodu, S. N. (ed.). PDF-2 Release 2008. International Centre for Diffraction Data: Newtown Square, PA, 2008.
16. Rao, C. P. Modern Carbonates, Tropical, Temperate, Polar: Introduction to Sedimentology and Geochemistry. University of Tasmania, Hobart, Tasmania, 1996.
17. Müller, G., Irion, G., Förstner, U. Formation and diagenesis of inorganic Ca-Mg carbonates in the lacustrine environment. Naturwissenschaften, 1972, 59(4), 158–164.
https://doi.org/10.1007/BF00637354
18. Guo, L., Jiang, Z., Liang, C. Mineralogy and shale gas potential of Lower Silurian organic-rich shale at the southeastern margin of Sichuan Basin, South China. Oil Shale, 2016, 33(1), 1–17.
https://doi.org/10.3176/oil.2016.1.01
19. Remy, R. R., Ferrell, R. E. Distribution and origin of analcime in marginal lacustrine mudstones of the Green River Formation, south-central Uinta Basin, Utah. Clays Clay Miner., 1989, 37(5), 419–432.
https://doi.org/10.1346/CCMN.1989.0370505
20. Kašanin-Grubin, M. Sedimentology of the Oil Shales Series of the Aleksinac Basin. Master thesis, University of Belgrade, Belgrade, 1996 (in Serbian, with English abstract).
21. Harrison, T. N. Experimental VNIR reflectance spectroscopy of gypsum dehydration: Investigating the gypsum to bassanite transition. Am. Mineral., 2012, 97(4), 598–609.
https://doi.org/10.2138/am.2012.3667
22. Hunt, J. M. Petroleum Geochemistry and Geology, 2nd ed. W. H. Freeman and Company, New York, 1996.
23. Peters, K. E. Guidelines for evaluating petroleum source rock using programmed pyrolysis. AAPG Bull., 1986, 70(3), 318–329.
24. Peters, K. E., Cassa, M. R. Applied source rock geochemistry. In: The Petroleum System - From Source to Trap (Magoon, L. B., Dow, W. G., eds.), AAPG Memoir 60. Tulsa, 1994, 93–120.
25. Peters, K. E., Walters, C. C., Moldowan, J. M. The Biomarker Guide, Vol. 1: Biomarkers and Isotopes in the Environment and Human History, Second edition. Cambridge University Press, Cambridge, 2005.
26. Espitalié, J., Deroo, G., Marquis, F. La pyrolyse Rock-Eval et ses applications. Deuxième Partie. Rev. I. Fr. Petrol., 1985, 40(6), 755–784 (in French, with English abstract).
https://doi.org/10.2516/ogst:1985045
27. Bordenave, M. L., Espitalié, J., Leplat, P., Oudin, J. L., Vandenbroucke, M. Screening techniques for source rock evaluation. In: Applied Petroleum Geochemistry (Bordenave, M. L., ed.). Éditions Technip, Paris, 1993, 217–278.
28. Dyman, T. S., Palacas, J. G., Tysdal, R. G., Perry, W. J., Pawlewicz, M. J. Source rock potential of middle Cretaceous rocks in Southwestern Montana. AAPG Bull., 1996, 80(8), 1177–1184.
29. Moldowan, J. M., Seifert, W. K., Gallegos, E. J. Relationship between petroleum composition and depositional environment of petroleum source rocks. AAPG Bull., 1985, 69(8), 1255–1268.
30. Volkman, J. K., Zhang, Z., Xie, X., Qin, J., Borjigin, T. Biomarker evidence for Botryococcus and a methane cycle in the Eocene Huadian oil shale, NE China. Org. Geochem., 2015, 78, 121–134.
https://doi.org/10.1016/j.orggeochem.2014.11.002
31. De Rosa, M., Gambacorta, A., Gliozzi, A. Structure, biosynthesis, and physicochemical properties of archaebacterial lipids. Microbiol. Rev., 1986, 50(1), 70–80.
32. Volkman, J. K. A review of sterol markers for marine and terrigenous organic matter. Org. Geochem., 1986, 9(2), 83–99.
https://doi.org/10.1016/0146-6380(86)90089-6
33. Wolff, G. A., Lamb, N. A., Maxwell, J. R. The origin and fate of 4-methyl steroid hydrocarbons. 1. Diagenesis of 4-methyl sterenes. Geochim. Cosmochim. Ac., 1986, 50(3), 335–342.
34. Ourisson, G., Albrecht, P., Rohmer, M. The hopanoids: palaeochemistry and biochemistry of a group of natural products. Pure Appl. Chem., 1979, 51(4), 709–729.
https://doi.org/10.1351/pac197951040709
35. Sofer, Z., Regan, D. R., Muller, D. S. Sterane isomerization ratios of oils as maturity indicators and their use as an exploration tool, Neuquen Basin, Argentina. Book of Proceedings, XII Geological Congress, Buenos Aires, Argentina, 1993, 407–411.
36. Didyk, B. M., Simoneit, B. R. T., Brassell, S. C., Eglinton, G. Organic geochemical indicators of palaeoenvironmental conditions of sedimentation. Nature, 1978, 272, 216–222.
https://doi.org/10.1038/272216a0
37. ten Haven, H. L., de Leeuw, J. W., Rullkötter, J., Sinninghe Damsté, J. S. Restricted utility of the pristane/phytane ratio as a palaeoenvironmental indicator. Nature, 1987, 330, 641–643.
https://doi.org/10.1038/330641a0
38. Fu, J., Sheng, G., Xu, J., Eglinton, G., Gowar, A. P., Jia, R., Fan, S., Peng, P. Application of biological markers in the assessment of paleoenvironments of Chinese non-marine sediments. Org. Geochem., 1990, 16(4–6), 769–779.
39. Adam, P., Schmid, J. C., Mycke, B., Strazielle, C., Connan, J., Huc, A., Riva, A., Albrecht, P. Structural investigation of nonpolar sulfur cross-linked macromolecules in petroleum. Geochim. Cosmochim. Ac., 1993, 57(14), 3395–3419.
https://doi.org/10.1016/0016-7037(93)90547-A
40. Peters, K. E., Cunningham, A. E., Walters, C. C., Jiang, J., Fan, Z. Petroleum systems in the Jiangling-Dangyang area, Jianghan Basin, China. Org. Geochem., 1996, 24(10–11), 1035–1060.
41. Sinninghe Damsté, J. S., Kenig, F., Koopmans, M. P., Köster, J., Schouten, S., Hayes, J. M., de Leeuw, J. W. Evidence for gammacerane as an indicator of water column stratification. Geochim. Cosmochim. Ac., 1995, 59(9), 1895–1900.
https://doi.org/10.1016/0016-7037(95)00073-9
42. Casagrande, D. J. Sulphur in peat and coal. In: Coal and Coal-Bearing Strata: Recent Advances (Scott, A. C., ed.). Geol. Soc. Spec. Publ. 32, London, 1987, 87–105.
https://doi.org/10.1144/GSL.SP.1987.032.01.07
https://doi.org/10.1130/0091-7613(1984)12<365:CMFDFF>2.0.CO;2