Biological markers and stable carbon isotope studies of bitumen impregnating Quaternary sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine)

• Autorzy: Kotarba M. J. , Fabiańska M. , Więcław D. , Kowalski A. , Zych H.
• Języki publikacji: EN

Abstrakty

EN

Biological markers and stable carbon isotopic compositions of bitumen impregnating the Pleistocene and Holocene sediments around the Starunia palaeontological site (Carpathian region, Ukraine) near discovered remnants of a mammoth and three woolly rhinoceroses, and one almost completely preserved rhinoceros carcass found in 1907 and 1929, were investigated. The research was carried out to assess genetic connections between the bitumen and oils from the nearby deep accumulations of the Boryslav-Pokuttya and Skyba units of the Carpathians. Another aim of these geochemical studies was to reveal the secondary geochemical processes (oxidation and biodegradation) influencing the bitumen, and to determine which environments have been favourable or unfavourable for the preservation of large Pleistocene vertebrates. Bitumen included within the near-surface rocks are not genetically connected with residual organic matter present in Quaternary sediments. Geochemical features, such as distributions of pentacyclic triterpanes and steranes, biomarker parameters and isotope composition indicate that all bitumens originate from oil-prone, Type II kerogen with insignificant admixture of terrestrial Type III kerogen in the middle stage of catagenesis. The oils occurring in deep accumulations in the Starunia area were the sole source of bitumen found in the near-surface sediments. Input of immature organic matter to bitumen from Pleistocene and Holocene sediments has not been found. The main factors differentiating the bitumen were: biodegradation, water washing and/or weathering. Additional influence of transport of bitumen by brine was found. The most favourable conditions for preservation of large, extinct mammals within the Pleistocene muds exist in the vicinity of Nos 22 and 23 boreholes, where bitumen is best preserved. The worst conditions were found in the vicinity of Nos 1, 4, 4' and 15 boreholes. Intensification of biodegradation and weathering effects were followed by intensive, chaotic changes of the remnants of large Pleistocene mammals.

Słowa kluczowe

EN

biomarkers; stable carbon isotopes; bitumen content; oil origin; woolly rhinoceros; Starunia palaeontological site; Carpathian region; Ukraine

• Wydawca: Polskie Towarzystwo Geologiczne
• Czasopismo: Annales Societatis Geologorum Poloniae
• Rocznik: 2009
• Tom: Vol. 79, No 3
• Strony: 463--480
• Opis fizyczny: bibliogr. 50 poz., rys., tab.

Twórcy

autor

Kotarba M. J.

autor

Fabiańska M.

autor

Więcław D.

autor

Kowalski A.

autor

Zych H.

• Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Kraków, Poland,

Bibliografia

• Adamenko, O. M., Stelmach, O. R., Zinchuk, M. S. & Kotarba, M. J., 2005. History of petroleum exploration in the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba, M. J. (ed.), Polish and Ukrainian geological studies (2004-2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on En vironmental Changes "Geosphere", Warszawa-Kraków: 53-61.
• Alexandrowicz, S. W., 2004. Starunia and the Quaternary research in the tradition and initiatives of the Polish Academy of Arts and Sciences. Studia i materiały do dziejów Polskiej Akademii Umiejętności, (In Polish, English summary). Polish Academy of Arts and Sciences, Kraków, 3, 261 pp.
• Alexandrowicz, S. W., 2005. The history of Starunia - a palaeontologic site and old ozokerite mine. In: Kotarba, M. J. (ed.), Polish and Ukrainian geological studies (2004-2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa-Kraków: 21-38.
• Barabasz, W., Chmiel, M. J. & Ostafin, M., 2009. Microbiological characteristics of Quaternary sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 439-446.
• Boehm, P. D. & Quinn, J. G., 1973. Solubilization of hydrocarbons by the dissolved organic matter in sea water. Geochimica et Cosmochimica Acta, 37: 2459-2477.
• Bray, E. E. & Ev ans, E. D., 1963. Distribution of n-paraffins as aclue to recognition of source beds. Geochimica et Cosmochimica Acta, 22: 2-15.
• Connan, J., 1984. Biodegradation of crude oils in reservoirs. Advances in Petroleum Geochemistry, 1: 299-335.
• Didyk, B. M., Simoneit, B. R. T., Brassell, S. C. & Eglin ton, G., 1978. Organic geochemical indicators of palaeonvironmental conditions of sedimentation. Nature, 272: 216-222.
• Duliński, M., Różański, K. & Kotarba, M. J., 2005. Isotopic and chemical composition of surface and groundwaters in the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba, M. J. (ed.), Po ish and Ukrainian geological studies (2004- 2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa- Kraków: 187-194.
• Ekweozor, C. M. & Udo, O. T., 1988. The oleananes: origin, maturation and limits of occurrence in Southern Nigeria sedimentary basins. Organic Geochemistry, 13: 131-140.
• Elias, V. O., Simoneit, B. R. T. & Cardoso, J. N., 1997. Even n-alkane predominances on the Amazon Shelf and a north east Pacific hydrothermal system. Naturwissenschaften, 84: 415- 420.
• Ensminger, A., van Dorsselear, A., Spyckerelle, C., Albrecht, P. & Ourisson, G., 1974. Pentacyclic triterpanes of the hopane type as ubiquitous geochemical markers: origin and significance. In: Advances in Organic Geochemistry 1973: 245-260.
• Grimalt, J. & Albaiges, J., 1987. Sources and occurrence of C12-C22 n-alkane distributions with even carbon-number preference in sedimentary environment. Geochimimica et Cosmochimica Acta, 51: 1379-1384.
• Huang, W.-Y. & Meinschein, W. G., 1979. Sterols as ecological indicators. Geochimimica et Cosmochimica Acta, 43: 739- 745.
• Jovancicevic, B., Antić, M. P, Solević, T. M., Vrvić, M. M., Kronimus, A. & Schwarzbauer, J., 2005. Investigation of interactions between surface water and petroleum-type pollut - ants. Environmental Science and Pollution Research, 12: 205-212.
• Koltun, Y. V., Adamenko, O. M., Kotarba, M. J., Dudok, I. V., Pavluk, M. I., Burzewski, W. & Stelmakh, O. R., 2005. Geological setting and petroleum occurrence of the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba, M. J. (ed.), Polish and Ukrainian geological studies (2004-2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa-Kraków: 61-78.
• Korin, S. S., 2005. Miocene salt-bearing Vorotyshcha Beds in the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba M. J. (ed.), Polish and Ukrainian geological studies (2004- 2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa-Kraków: 79-86.
• Kotarba, M. J., 2002. Composition and origin of hydrocarbons satu rating the remnants of woolly rhinoceros from Starunia, the Ukrainian Carpathians. (In Polish, English summary). Przegląd Geologiczny, 50: 531-534.
• Kotarba, M. J. (ed.), 2005. Polish and Ukrainian geological studies (2004-2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmen tal Changes "Geosphere", Warszawa-Kraków, 218 pp.
• Kotarba, M. J., 2009. Interdisciplinary studies at Starunia palaeontological site and vicinity (Carpathian region, Ukraine) in the years 2006-2009: previous discoveries and research, purposes, results and perspectives. Annales Societatis Geologorum Poloniae, 79: 219-241.
• Kotarba, M. J., Alexandrowicz, S. W. & Stachowicz-Rybka, R., 2008a. Historia i pro gram dalszych badań geologicznych na obszarze byłej kopalni ozokerytu i stanowiska paleontologicznego w Staruni. (In Polish). Przegląd Geologiczny, 56: 434-441.
• Kotarba, M. J., Dzieniewicz, M., Mościcki, W. J. & Sechman, H., 2008b. Unique Quaternary environment for discoveries of woolly rhinoceroses in Starunia, fore-Carpathian region, Ukraine: Geochemical and geoelectric studies. Geology, 36: 567-570.
• Kotarba, M. J., Dzieniewicz, M. & Sechman, H., 2005a. Geochemical survey, molecular and isotopic compositions, and genetic identification of near-surface gases from the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba, M. J. (ed.), Polish and Ukrainian geological studies (2004-2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa-Kraków:157-174.
• Kotarba, M. J., Więcław, D., Koltun, Y. V., Lewan, M. D., Marynowski, L. & Dudok, I. V., 2005b. Organic geochemical study and genetic correlations be tween source rocks and hydrocarbons from surface seeps and deep accumulations in the Starunia area, fore-Carpathian region, Ukraine. In: Kotarba, M. J. (ed.), Polish and Ukrainian geological studies (2004- 2005) at Starunia - the area of discoveries of woolly rhinoceroses. Polish Geological Institute and Society of Research on Environmental Changes "Geosphere", Warszawa-Kraków: 125-146.
• Kotarba, M. J. & Koltun, Y. V., 2006. The origin and habitat of hydrocarbons of the Polish and Ukrainian Parts of the Carpathian Province. In: Golonka, J. & Picha, F. J. (eds), The Carpathians and their foreland: Geology and hydrocarbon resources. American Association of Petroleum Geologists Memoir, 84: 395-442.
• Kotarba, M. J. & Stachowicz-Rybka, R., 2008. Wyjątkowe stanowisko paleontologiczne i środowisko osadów plejstoceńskich, w których znaleziono nosorożce włochate w Staruni (Karpaty Wschodnie). (In Polish). Przegląd Geologiczny, 56: 442-452.
• Kotarba, M. J., Sechman, H. & Dzieniewicz, M., 2009a. Distribution and origin of gaseous hydrocarbons and carbon dioxide in the Quater nary sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 403-419.
• Kotarba, M. J., Więcław, D., Toboła, T., Zych, H., Kowalski, A. & Ptak, S., 2009b. Bitumen and salt contents within the Quaternary sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 447-461.
• Kotarba, M. J., Więcław, D., Koltun, Y. V., Marynowski, L., Kuśmierek, J. & Dudok, I. V., 2007. Organic geochemical study and genetic correlation of natu ral gas, oil and Menilite source rocks in the area between San and Stryi rivers (Polish and Ukrainian Carpathians). Organic Geochemistry, 38: 1431-1456.
• Mello, M. R., Telnaes. N., Gaglianone, P. C., Chicarelli, M. I., Brassell, S. C. & Maxwell, J. R., 1988. Organic geochemical characterization of depositional palaeoenvironments of source rocks and oils in Brazilian marginal basin. Organic Geochemistry, 13: 31-45.
• Moldowan, J. M., Dahl, J., Huizinga, J. B., Fago, F. J., Hikey, L. J., Peakmen, T. M. & Tylor, D. W., 1994. The molecular fossil record of oleanane and its relation to angiosperms. Sci-ence, 265: 768-771.
• Mościcki, W. J., Toboła, T. & Zarzyka-Ryszka, M., 2009. Salinity of Quaternary sediments and halophytes at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 391-402.
• MSD, 2000. The Wiley/NBS Regis try of Mass Spectral Data (digital massspecra library). Wiley, New York.
• Palmer, S. E., 1993. Ef fect of biodegradation and water washing on crude oil composition. In: Engel, M. H. & Macko, S. A. (eds), Organic Geochemistry, Principles and Applications. Plenum Press, New York: 511-534.
• Peake, E. & Hodgson, G. W., 1966. Alkanes in aqueous systems. I. Exploratory investigations on the accommodation of C20-C33 n-alkanes indistilled water and occurrence in natural water systems. Journal of the American Oil Chemists' Society, 43: 215-222.
• Peters, K. E., Walters, C. C. & Moldowan, J. M., 2005. The biomarker guide. Biomarkers and isotopes in petroleum exploration and earth history. 2nd Edition. University Press, Cambridge, 1132 pp.
• Philp, R. P., 1985. Fossil Fuel Biomarkers. Application and Spectra. Elsevier Elsevier Science Pub. Co., Inc., New York, NY, 294 pp.
• Sechman, H., Kotarba, M. J. & Dzieniewicz, M., 2009. Surface geochemical survey at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 375-390.
• Seifert, W. K. & Moldowan, J. M., 1978. Application steranes, terpanes and monoaromatics to the matu ration, migration and source of crude oils. Geochimica et Cosmochimica Acta, 42: 77-95.
• Seifert, W. K. & Moldowan, J. M., 1986. Use of biological markers in petroleum exploration. In: Johns, R. B. (ed.), Methodsin Geochemistry and Geophysics, 24: 261-290.
• Shanmugam, G., 1985. Significance of coniferous rain forests and related organic matter in generating commercial quantities of oil, Gippsland Basin, Australia. American Association of Petroleum Geologists Bulletin, 69: 1241-1254.
• Sofer, Z., 1984. Stable carbon isotope compositions of crude oils: application to source depositional environments and petroleum alteration. American Association of Petroleum Geologists Bulletin, 68: 31-49.
• Sokołowski, T. & Stachowicz-Rybka, R., 2009. Chronostratigraphy and changes of environment of Late Pleistocene and Holocene at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 315-331.
• Sokołowski, T., Stachowicz-Rybka, R. & Woronko, B., 2009. Upper Pleistocene and Holocene deposits at Starunia palaeontological site and vicinity (Carpathian region, Ukraine). Annales Societatis Geologorum Poloniae, 79: 255-278.
• Stachowicz-Rybka, R., Granoszewski, W. & Hrynowiecka- Czmielewska, A., 2009. Quaternary environmental changes at Starunia palaeontological site and vicinity (Carpathian region, Ukraine) based on palaeobotanical studies. Annales Societatis Geologorum Poloniae, 79: 279-288.
• ten Haven, H. L., de Leeuw, J. W, Sinninghe Damste, J. S., Schenck, P. A., Palmer, S. E. & Zumberge, J. E., 1988. Application of biological markers in the recognition of palaeohypersaline environments. In: Fleets, A. J., Kelts K. & Tal bot, M. R. (eds), Lacustrine Petroleum Source Rocks. Geological Society Special Publcation no. 40, Geological Society of London: 123-130.
• ten Haven, H. L., Lafargue, E. & Kotarba, M., 1993. Oil/oil and Oil/source rock correlations in the Carpathian Foredeep and the Carpathian Overthrust, South-East Poland. Organic Geochemistry, 20: 935-959.
• Tissot, B., Califet-Debyser, Y., Deroo, G. & Oudin, J. L., 1971. Origin and evolution of hydrocarbons in Early Toarcian shales, Paris Basin, France. American Association of Petroleum Geologists Bulletin, 55: 2177-2193.
• Tissot, B. P. & Welte, D. H., 1984. Petroleum Formation and Occurrence. Springer Verlag, New York, 699 pp.
• Wenger, L. M., Da vis, C. L. & Isaksen G. H., 2002. Multiple controls on petroleum biodegradation and impact on oil quality. SPE Reservoir Evaluation and Engineering, 5: 375-38