Skip to main content Accessibility help

Isomerization and aromatization of hydrocarbons in sedimentary basins formed by extension

  • A. S. Mackenzie (a1) and D. McKenzie (a2)


Summary. The reactions involved in oil generation are of great economic importance, but remain to be studied in detail. We have investigated the rates of three reactions which occur before and during the early stages of oil formation, and have used the predicted thermal and subsidence history of stretched basins to estimate the six reaction constants. Two of the reactions are isomerization reactions, at C-20 in a sterane and at C-22 in a hopane hydrocarbon. The third reaction converts C-ring monoaromatic to triaromatic steroid hydrocarbons. No single measure of maturity can describe the progress of these reactions. In old basins, such as the North Sea, both isomerization reactions are almost complete before appreciable aromatization has occurred, whereas in young basins, such as the Pannonian Basin in Hungary, aromatization is almost complete before appreciable isomerization of the steranes has occurred. We show that the calculated progress of these reactions agrees well with that observed in both basins if the frequency factors and activation energies are 6 x 10-3 s-1 and 91 kJ mol-1, 0.016 s-1 and 91 kJ mol-1, 1.8 x 1024 s-1 and 200 kJ mol-1 for the isomerization of steranes, of hopanes, and the aromatization of steroid hydrocarbons respectively. The rate of conversion of the R to the S form was taken to be 1.174 and 1.564 times that of the reverse reactions for sterane and hopane isomerizations respectively, and the aromatization reaction was assumed to be irreversible. All three reactions were assumed to be first order and unimolecular. The aromatization rate is consistent with laboratory observations. The rate of hopane isomerization is not, and different reaction mechanisms probably dominate at different temperatures. The same constants can be used to predict the progress of the reactions in basins which have been uplifted by inversion, such as the Lower Saxony Basin in West Germany. The geochemical observations provide estimates of the amount and time of uplift which agree with those from geological studies. Geochemical observations from the eastern part of the Paris Basin suggest that this region has also been uplifted by between 1 and 2 km.



Hide All
Bally, A. W. 1982. Remarks following a paper by J. F. Dewey and W. C. Pitman, ‘Carboniferous-Permian basins of the U.S. continental interibr.’ In The Evolution of Sedimentary Basins (ed. P., Kent, Bott, M. H. P., McKenzie, D. P. and Williams, C. A.). Phil. Trans. R. Soc. A 305, 147–8.
Beaumont, C. 1978. The evolution of sedimentary basins on a viscoelastic lithosphere. Geophys. J. R. astr. Soc. 55, 471–97.
Beaumont, C. 1981. Foreland Basins. Geophys. J. R. astr. Soc. 65, 291329.
Berry, R. S., Rice, S. A. & Ross, J. 1980. Physical Chemistry. New York: John Wiley.
Brunet, M. F. 1981. Etude quantitative de la subsidence du Bassin de Paris. Thèse de Doctorat de 3ème cycle, Univ. Pierre et Marie Curie.
Brunet, M. F. & le Pichon, X. 1982. Subsidence of the Paris Basin. J. geophys. Res. 87, 8547–60.
Budiansky, B. 1970. Thermal and thermoelastic properties of isotropic composites. J. Composite Materials 4, 286–95.
Christie, P. A. F. & Sclater, J. G. 1980. An extensional origin for the Buchan and Witchground Graben in the North Sea. Nature, Lond. 283, 729–32.
Day, G. A., Cooper, B. A., Anderson, G., Burgers, W. F. J., Ronnevik, H. C. & Schoneich, H. 1981. Seismic structure maps of the North Sea. In Petroleum Geology of the Continental Shelf of North-West Europe (ed. Illing, L. V. and Hobson, G. D.), pp. 7684. London: Institute of Petroleum.
Dastillung, M. & Albrecht, P. 1977. ΔSterenes as diagenetic intermediates in sediments. Nature, Lond. 269, 678–9.
Deroo, G. 1967. Influence de la température et de la pression sur la genèse des hydrocarbures. Etude des argiles du Lias du bassin de Paris. Fascicule 1: Reconstitution de l' histoire de l'enfouissement du Toarcien dans le bassin de Paris. Internal report Inst. Fr. Pétr. No. 14427.
England, P. C. 1981. Constraints on continental lithospheric extension. Eos 62, 1022 (abstract).
England, P. C. & Richardson, S. W. 1980. Erosion and the age dependence of continental heat flow. Geophys. J. R. astr. Soc. 62, 421–37.
Ensminger, A., Albrecht, P., Ourisson, G. & Tissot, B. 1977. Evolution of polycyclic alkanes under the effects of burial (early Toarcian shales, Paris Basin). In Advances in Organic Geochemistry 1975 (ed. R., Campos and J., Gõni), pp. 4552: Madrid: ENADIMSA.
Ensminger, A., Joly, G. & Albrecht, P. 1978. Rearranged steranes in sediments and crude oils. Tetrahedron Lett. 18, 1575–8.
Ensminger, A., Van Dorsselaer, 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 (ed. B., Tissot and F., Bienner), pp. 245–60. Paris: Editions Technip.
Espitalié, J., Laporte, J. L., Madec, M., Marquis, F., Leplat, P., Paulet, J. & Boutefeu, A. 1977. Méthode rapide de caractérisation des roches mères de leur potentiel pétrolier et de leur degré d'évolution. Revue Inst. fr. Pétrole 32, 2342.
Gaskell, S. J. & Eglinton, G. 1976. Sterols of a contemporary lacustrine sediment. Geochim. cosmochim. Acta 40, 1221–8.
Glasstone, S., Laidler, K. J. & Eyring, H. 1941. The Theory of Rate Processes. New York: McGraw-Hill.
Goy, G. 1979. Les ‘schistes cartons' (Toarcien Inférieur) du bassin de Paris. Thése de Doctorat ès Sciences, Univ. Pierre et Marie Curie.
Gutsche, C. D. & Pasto, D. J. 1975. Fundamentals of Organic Chemistry, pp. 507–19. New Jersey: Prentice Hall.
Hoffmann, C. F., Mackenzie, A. S., Lewis, C. A., Maxwell, J. R., Oudin, J. L., Vandenbroucke, M. & Durand, B. (in the press). A biological marker study of coals, shales and oils of Mahakam Delta, Kalimantan. Chem. Geol.
Hood, A., Gutjahr, C. C. M. & Heacock, R. L. 1975. Organic metamorphism and the generation of petroleum. Bull. Am. Ass. Petrol. Geol. 59, 986–96.
Hunt, J. M. 1979. Petroleum Geochemistry and Geology. San Francisco: W. H. Freeman.
Hussler, G., Chappe, B., Wehrung, P. & Albrecht, P. 1981. Identification of C27—C29 ring A monoaromatic steroids in Cretaceous black shales. Nature 294, 556–8.
Jarvis, G. T. & McKenzie, D. P. 1980. Sedimentary basin formation with finite extension rates. Earth Planet. Sci. Lett. 48, 4252.
Jordan, T. 1981. Thrust loads and foreland basin evolution, Cretaceous western United States. Bull. Am. Ass. Petrol. Geol. 64, 2506–20.
Koesoemadinata, R. P. 1978. Sedimentary framework of Tertiary coal basins of Indonesia, In Proceedings of the Third Regional Conference on Geology and Mineral Resources of South East Asia, (ed. P., Natalaya), pp. 621–40. New York: Wiley.
Lopatin, N. V. 1971. Temperature and geologic time as factors in coalification [in Russian]. Akad. Nauk S.S.R. Izv. Ser. Geol. 3, 95106.
Ludwig, B., Hussler, G., Wehrung, P. & Albrecht, P. 1981. C26—C29 triaromatic steroid derivatives in sediments and petroleums. Tetrahedron Lett. 22, 3313–6.
Mackenzie, A. S. 1980. Application of biological marker compounds to subsurface geological processes. Ph.D. thesis, University of Bristol.
Mackenzie, A. S., Brassell, S. C., Eglinton, G. & Maxwell, J. R. 1982. Chemical fossils — the geological fate of steroids. Science 217, 491504.
Mackenzie, A. S., Hoffmann, C. F. & Maxwell, J. R. 1981. Molecular parameters of maturation in the Toarcian shales, Paris Basin, France. III. Changes in aromatic steroid hydrocarbons. Geochim. cosmochim. Acta 45, 1345–55.
Mackenzie, A. S., Lamb, N. A. & Maxwell, J. R. 1982. Steroid hydrocarbons and the thermal history of sediments. Nature 295, 223–6.
Mackenzie, A. S., Lewis, C. A. & Maxwell, J. R. 1981. Molecular parameters of maturation in the Toarcian shales, Paris Basin, France. IV. Laboratory thermal alteration studies. Geochirn. cosmochim. Acta 45, 2369–76.
Mackenzie, A. S., Leythaeuser, D., Altebäumer, F. -J., Disko, U. & Rullkötter, J. (to be submitted). Molecular measurements of maturity for Lias δ shales in N.W. Germany. Geochim. cosmochim. Acta.
Mackenzie, A. S. & Maxwell, J. R. 1981. Assessment of thermal maturation in sedimentary rocks by molecular measurements. In Organic Maturation Studies and Fossil Fuel Exploration (ed. J., Brooks), pp. 239–54. London: Academic Press.
Mackenzie, A. S., Patience, R. L., Maxwell, J. R., Vandenbroucke, M. & Durand, B. 1980. Molecular parameters of maturation in the Toarcian shales, Paris Basin, France. I. Changes in the configurations of acyclic isoprenoid alkanes, steranes and triterpanes. Geochim. cosmochim. Acta 44, 1709–21.
Magnier, P. L., Oki, T. & Witoelar Kartaadiputra, L. 1975. The Mahakam Delta, Kalimantan, Indonesia. In Proc. 9th World Petroleum Congress 2, 239–50. London: Heyden.
Maxwell, J. R., Mackenzie, A. S. & Volkman, J. R. 1980. Configuration at C-24 in steranes and sterols. Nature, Lond. 286, 694–7.
McKenzie, D. P. 1978. Some remarks on the development of sedimentary basins. Earth Planet. Sci. Lett. 40, 2532.
McKenzie, D. P. 1981. The variation of temperature with time and hydrocarbon maturation in sedimentary basins formed by extension. Earth Planet. Sci. Lett. 55, 8798.
Mégnien, C. et al. 1980. Synthèse géologique du Bassin de Paris, Mémoire B.R.G.M. 101 and 102.
Nwachukwu, S. O. 1976. Approximate geothermal gradients in Niger Delta sedimentary basin. Bull. Am. Ass. Petrol. Geol. 60, 1073–7.
Ourisson, G., Albrecht, P. & Rohmer, M. 1979. The hopanoids: Palaeochemistry and biochemistry of a group of natural products. Pure Appl. Chem. 51, 709–29.
Oxburgh, E. R. & Andrews-Speed, C. P. 1981. Temperature, thermal gradients and heat flow in the southwestern North Sea. In Petroleum Geology of the Continental Shelf of North West Europe (ed. Illing, L. V. and Hobson, G. D.), pp. 141–51. London: Institute of Petroleum.
Petrov, A. A., Pustil'nikova, S. D., Abriutina, N. N. & Kagramonova, G. R. 1976. Petroleum steranes and triterpanes [in Russian]. Neftekhimiia 16, 411–27.
Phillipi, G. T. 1965. On the depth, time and mechanism of petroleum generation. Geochim. cosmochim. Acta 29, 1021–49.
Pomerol, C. 1974. Le Bassin de Paris. In Géologie de la France, vol. 1 (ed. J., Debelmas). Paris: Doin.
Putnis, A. & McConnell, J. D. C. 1980. Principles of Mineral Behaviour. Oxford: Blackwell Scientific Publications.
Reznikov, A. N. 1967. The geochemical conversion of oils and condensates in the catagenesis zone [in Russian]. Geologiya Nefti i Gaza 5, 24–8.
Rhead, M. M., Eglinton, G. & Draffan, G. H. 1971. Hydrocarbons produced by the thermal alteration of cholesterol under conditions stimulating the maturation of sediments. Chem. Geol. 8, 277–97.
Royden, L. & Keen, C. E. 1980. Rifting process and thermal evolution of the continental margin of Eastern Canada determined from the subsidence rates. Earth Planet. Sci. Lett. 51, 343–61.
Royden, L., Sclater, J. G. & von Herzen, R. P. 1980. Continental margin subsidence and heat flow: important parameters in the formation of petroleum hydrocarbons. Bull. Am. Ass. Petrol. Geol. 64, 173–87.
Sajgò, Cs. 1980. Hydrocarbon generation in a super thick Neogene sequence in South-east Hungary, a study of the extractable organic matter. In Advances in Organic Geochemistry 1979, (ed. Douglas, A. G. and Maxwell, J. R.), pp. 103–13. Oxford: Pergamon Press.
Schaeflé, J. 1979. Marqueurs biologiques hydroaromatiques de sédiments et pétroles. Thèse de Doctorat ès Sciences. Univ. Louis Pasteur.
Sclater, J. G. and Christie, P. A. F. 1980. Continental stretching — an explanation of the post-early Cretaceous subsidence of the Central Graben of the North Sea. J. geophys. Res. 85, 3711–39.
Sclater, J. G., Royden, L., Horvath, F., Buchfiel, B. C., Semken, S. & Stegna, L. 1980. The formation of the inter-Carpathian Basins determined from subsidence. Earth Planet. Sci. Lett. 51, 139–62.
Seifert, W. K., Carlson, R. M. & Moldowan, J. M. (in the press). Geomimetic synthesis, structure assignment and geochemical correlations. Application of monoaromatized petroleum steranes. In Advances in Organic Geochemistry (ed. M., Bjorøy et al.). Chichester: Wiley.
Seifert, W. K. & Moldowan, J. M. 1980. The effect of thermal stress on source rock quality as measured by hopane stereochemistry. In Advances in Organic Geochemistry 1979, (ed. Douglas, A. G. and Maxwell, J. R.), pp. 229–37. Oxford: Pergamon Press.
Snowdon, L. R. 1979. Errors in extrapolation of experimental kinetic parameters to organic geochemical systems. Bull. Am. Ass. Petrol. Geol. 63, 1128–38.
Steckler, M. S. & Watts, A. B. 1980. The Gulf of Lion: subsidence of a young continental margin. Nature 287, 425–9.
Tissot, B., Durand, B., Espitalié, J. & Combaz, A. 1974. Influence of nature and diagenesis of organic matter in formation of petroleum. Bull. Am. Ass. Petrol. Geol. 58, 499506.
Tissot, B. & Welte, D. H. 1978. Petroleum Formation and Occurrence. Berlin: Springer Verlag.
van Graas, G., Baas, J. M. A., van der Graaf, B. & de Leeuw, J. W. 1982. Theoretical organic geochemistry. I. The thermodynamic stability of several cholestane isomers calculated from molecular dynamics. Geochim. cosmochim. Acta 46, 2399–402.
Waples, D. H. 1980. Time and temperature in petroleum formation: Application of Lopatin's method to petroleum exploration. Bull. Am. Ass. Petrol. Geol. 64, 916–26.
Wood, R. J. 1981. The subsidence history of Conoco well 15/30—1, Central Graben, North Sea. Earth Planet. Sci. Lett. 54, 306–12.
Wood, R. J. 1982. Subsidence in the North Sea. Ph.D. thesis, Cambridge University.
Wood, R. J. & Barton, P. 1983. Crustal thinning and subsidence in the North Sea. Nature 302, 134–6.
Young, A., Monaghan, P. H. & Schweisberger, R. T. 1977. Calculation of ages of hydrocarbons in oils — Physical chemistry applied to petroleum geochemistry. I. Bull. Am. Ass. Petrol. Geol. 61, 573600.
Ziegler, P. A. 1980. Northwestern Europe: Geology and hydrocarbon provinces. Spec. Mem. Can. Soc. Pet. Geol. 6, 653706.


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed