Characterization of asphaltic oil occurrences from the southeastern margin of the Basque-Cantabrian Basin, Spain


  • P. MARÍN Department of Geochemistry, Petrology and Geological Prospecting, University of Barcelona. C/ Martí i Franquès s/n, 08028-Barcelona, Spain.
  • G. MÁRQUEZ Departmento de Ingeniería Minera, Mecánica y Energética, Universidad de Huelva. C/ La Rábida s/n, 21819-Huelva, Spain.
  • J.R. GALLEGO Departmento de Explotación y Prospección de Minas, Universidad de Oviedo. C/ Gonzalo Gutiérrez Quirós, 33600-Mieres, Spain.
  • A. PERMANYER Department de Geologia, Petrologia i Prosprecció Geològica, Universitat de Barcelona. C/ Martí i Franquès s/n, 08028-Barcelona, Spain.



Asphaltic oil occurrences, Basque-Cantabrian Basin, Álava sector, Ayoluengo oil field, Biodegradation


A geochemical investigation has been undertaken on biodegraded hydrocarbons in outcropping reservoirs of the south-eastern margin of the Basque-Cantabrian Basin (Álava sector). The aims of the study were the characterization of the geochemical features and biodegradation level of these hydrocarbons, and the evaluation of their resemblance to oils from the Ayoluengo onshore oil field by means of isotopic analyses and gas chromatography-mass spectrometry techniques. Most of the samples lack of n-alkanes, isoprenoids, low molecular weight aromatic compounds, steranes, homohopanes, diasteranes and triaromatic steroids whereas hexacyclic and heptacyclic alkanes appear as key compounds although some structures were not totally elucidated. Thermal maturity has been assessed with several parameters and thus a calculated-equivalent vitrinite reflectance value of around 0.8% was estimated. In addition, gammacerane content, diasterane-to-sterane ratio and C35 to C34 hopanes ratio suggested that the Álava oil shows were derived from a carbonate rock deposited in a reducing, water-stratified and possibly hypersaline environment. Isotopic signature and other data confirmed that these hydrocarbons are not genetically related to the oils from Ayoluengo and, consequently, their origin has to be associated with a yet unknown source rock in the basin.


Ábalos, B., Alkorka, A., Iríbar, V., 2008. Geological and isotopic constraints on the structure of the Bilbao anticlinorium (Basque–Cantabrian Basin, North Spain). Journal of Structural Geology, 30, 1354-1367.

Agirrezabala, L.M., Dorronsoro, C., Permanyer, A., 2008. Geochemical correlation of pyrobitumen fills with host mid-Cretaceous Black Flysch Group (Basque-Cantabrian Basin, western Pyrenees). Organic Geochemistry, 39, 1185-1188.

Alonso, J.L., Pulgar, J.A., Pedreira, D., 2007. El relieve de la Cordillera Cantábrica. Enseñanza de las Ciencias de la Tierra, 15(2), 151-163.

Alonso-Zarza, A.M., Armenteros, I., Braga, J.C., Muñoz, A., Pujalte, V., Ramos, E., 2002. Tertiary. In: Gibbons, W., Moreno, T. (eds.). The Geology of Spain. London, Geological Society, 293-334.

Alvarez de Buergo, E., García, A., 1996. Cálculo de reservas remanentes de hidrocarburos en zonas estructuralmente complejas: aplicación al campo de Ayoluengo, 1ª parte. Geogaceta, 20, 161-164.

ASTM, 2004. Standard Test Method for Sediment in Fuel Oils by the Centrifugation Method: Annual Book of the American Society for Testing Materials Standards, v. 05.01 and 05.02. West Conshohocken, Pennsylvania, ASTM International.

Barnolas, A., Pujalte, V., 2004. La cordillera Pirenaica. In: Vera, J.A. (ed). Geología de España. Madrid, Sociedad Geográfica Española-Instituto Geológico y Minero de España, 231-344.

Bennett, B., Larter, S., 2000. Quantitative separation of aliphatic and aromatic hydrocarbons using silver ion-silica solid-phase extraction. Analytical Chemistry, 72(5), 1039-1044.

Bennett, B., Larter, S.R., 2008. Biodegradation scales: applications and limitations. Organic Geochemistry, 39, 1222-1228.

Bennett, B., Fustic, M., Farrimond, P., Huang, H., Larter, S.R., 2006. 25-Norhopanes: Formation during biodegradation of petroleum in the subsurface. Organic Geochemistry, 37(7), 787-797.

Beroiz, C., Permanyer, A., 2011. Hydrocarbon habitat of the Sedano Trough, Basque-Cantabrian Basin, Spain. Journal of Petroleum Geology, 34(4), 387-410.

Cámara, P., 1997. The Basque Cantabrian Basin, Mesozoic tectono-sedimentary evolution. Mémoires de la Société Géologique de France, 171, 187-191.

Capote, R., Muñoz, J.A., Simón, J.L., Liesa, C.L., Arlegui, L.E., 2002. Alpine Tectonics I. The Alpine System north of the Betic Cordillera. In: Gibbons, W., Moreno, T. (eds.). The Geology of Spain. London, Geological Society, 367- 400.

Carreras-Suárez, F., Ramírez del Pozo, J., 1978. Mapa y memoria explicativa de la Hoja de Eulate (139) del Mapa geológico de España a escala 1:50.000. Madrid, Instituto Geológico y

Minero de España, 36pp.

Connan, J., 1984. Biodegradation of crude oils in reservoirs. In: Brooks, J., Welte, D. (eds.). Advances in Petroleum Geochemistry, Vol. 1. London, Academic Press, 299-335.

Cooper, B.S., Barnard, P.C., 1984. Source-rock and oils of the Central and Northern North Sea. In: Demaison, G., Murris, R.J. (eds.). Petroleum Geochemistry and Basin Evaluation. Tulsa, American Association of Petroleum Geologists, 35, 303-314.

Dorronsoro, C., García, M.R., Grimalt, J.O., 1994. Triterpane distribution in diapir-related asphalts. Fuel, 73, 83-91.

Everitt, B.S., 1993. Cluster Analysis. New York, John Wiley & Sons Inc., 170pp.

Galimov, E.M., 2006. Isotope organic geochemistry. Organic Geochemistry, 37, 1200-1262.

Galimov, E.M., Frik, M.G., 1985. Isotopic method of detection of oil source deposits. Geokhimiya, 10, 1474-1485.

García Sánchez, M.R., 1994. Caracterización geoquímica de bitúmenes naturales en torno al diapiro de Maestu (Álava). Análisis de asfaltenos y resinas. Doctoral Thesis. Universitat de Barcelona, 249pp.

Gómez, M., Vergés, J., Riaza, C., 2002. Inversion tectonics of the Northern margin of the Basque Cantabrian Basin. Bulletin de la Société Géologique de France, 173, 49-59.

Gräfe, K.U., Wiedmann, J., 1993. Sequence stratigraphy in the Upper Cretaceous of the Basco-Cantabrian Basin (northern Spain). Geologische Rundschau, 82, 327-361.

Grantham, P.J., Wakefield, L.L., 1988. Variations in the sterane carbon number distributions of marine source rocks derived crude oils through geological time. Organic Geochemistry, 12, 61-73.

Herron, S.L., Le Tendre, L., 1990. Wireline source rock evaluation in the Paris Basin. In: Huc, A.Y. (ed.). Deposition of Organic Facies. Studies in Geology. Tulsa, American Association of Petroleum Geologists, 30, 57-72.

Huang, W.Y., Meinschein, W.G., 1979. Sterols as ecological indicators. Geochimica et Cosmochimica Acta, 43, 739-745.

Huc, A.Y., 1990. Understanding organic facies: a key to improved quantitative petroleum evaluation of sedimentary basins. In: Huc, A.Y. (ed.). Deposition of Organic Facies. Studies in Geology. Tulsa, American Association of Petroleum Geologists, 30, 1-12.

Hunt, M., 1996. Petroleum Geochemistry and Geology, 2nd Edition. New York, Freeman Editions, 743pp.

Lewan, M.D., 1984. Factors controlling the proportionality of vanadium to nickel in crude oils. Geochimica et Cosmochimica Acta, 48, 2231-2238.

Lewan, M.D., Maynard, J.B., 1982. Factors controlling enrichment of vanadium and nickel in the bitumen of organic sedimentary rocks. Geochimica et Cosmochimica Acta, 46, 2547-2560.

Li, M., Riediger, C.L., Fowler, M.G. , Snowdon, L.R., Abrajano JR, T.A., 1996. Unusual polycyclic alkanes in Lower Cretaceous Ostracode Zone sediments and related oils of the Western Canada sedimentary basin. Organic Geochemistry, 25(3/4), 199-209.

Mackenzie, A.S., Maxwell, J.R., 1981. Assesment of thermal maturation in sedimentary rocks by molecular measurements. In: Brooks, J. (ed.). Organic Maturation Studies and Fossil Fuel Exploration. London, Academic Press, 239-254.

Mansuy, L., Philp, R.P., Allen, J., 1997. Source identification of oil spills based on the isotopic composition of individual components in weathered oil samples. Environmental Science and Technology, 31, 3417-3425.

Marín, P., 2002. Caracterización geoquímica de los hidrocarburos en reservorios exhumados de la Cuenca Vasco-Cantábrica. MSc Thesis. Universitat de Barcelona, 23pp.

McKirdy, D.M., Aldridge, A.K., Ypma, P.J.M., 1983. A geochemical comparison of some crude oils from PreOrdovician carbonate rocks. In: Albrecht, P., Bjorøy, M., Cornford, C., de Groot, K., Eglinton, G., Galimov, E., Laythaeuser, D., Pelet, R., Rullkötter, J., Speers, G. (eds.). Advances in Organic Geochemistry, 1981. Chichester, John Wiley & Sons Inc., 99-107.

McKirdy, D.M., Kantsler, A.J., Emmett, J.K., Aldridge, A.K., 1984. Hydrocarbon genesis and organic facies in Cambrian carbonates of the Eastern Officer Basin, South Australia. In: Palacas, J.G., (ed.). Petroleum Geochemistry and Source Rock Potential of Carbonate Rocks. Tulsa, American Association of Petroleum Geologists, 13-31.

Meckenstock, R.U., Morasch, B., Warthmann, R., Schink, B., Annweiler, E., Michaelis, W., Richnow, H.H., 1999. 13C/12C isotope fractionation of aromatic hydrocarbons during microbial degradation. Environmental Microbiology, 1, 409-414.

Moldowan, J.M., Fago, F.J., 1986. Structure and significance of a novel rearranged monoaromatic steroid hydrocarbon in petroleum. Geochimica et Cosmochimica Acta, 50, 343-

Moldowan, J.M., Seifert, W.K, Gallegos, E.J., 1985. Relationship between petroleum composition and depositional environment of petroleum source rocks: Tulsa, American Association of Petroleum Geologists Bulletin, 69, 1255-1268.

Permanyer, A., Márquez, G., Gallego, J.R., 2013. Compositional variability in oils and formation waters from the Ayoluengo and Hontomín fields (Burgos, Spain). Implications for assessing biodegradation and reservoir compartmentalization. Organic Geochemistry, 54, 125-139.

Peters, K.E., Moldowan, J.M., 1991. Effects of source, thermal maturity and biodegradation on the distribution and isomerization of homohopanes in petroleum. Organic Geochemistry, 17, 47-61.

Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide, Vol. 2: Biomarkers and Isotopes in Petroleum Systems and Earth History, 2nd edition. Cambridge, Cambridge University Press, 1132pp.

Poinsot, J., Dessort, D., Adam, P., Lacrampe, G., Trendel, J.M., Albrecht, P., 1995. New and rare biomarkers: saturated C33–C43 polycycloisoprenoids. In: Dorronsoro, C., Grimalt, J.O. (eds.). Organic Geochemistry: Developments and Applications to Energy, Climate, Environment and

Human History. Donostia–San Sebastian, AIGOA, 116-118.

Portero, J.M., Ramírez del Pozo, J., 1979. Mapa y memoria explicativa de la Hoja de Haro (170) del Mapa geológico de España a escala 1:50.000. Madrid, Instituto Geológico y Minero de España, 43pp.

Pujalte, V., 1977. El complejo Purbeck-Wealden de Santander. Estratigrafía y sedimentación. Doctoral Thesis. Universidad del País Vasco, 202pp.

Quesada, S., Robles, S., Rosales, I., 2005. Depositional architecture and transgressive–regressive cycles within Lias backstepping carbonate ramps in the Basque-Cantabrian Basin, northern Spain. Journal of the Geological Society, 162, 531-548.

Quesada, S., Dorronsoro, C., Robles, S., Chaler, R., Grimalt, J.O., 1997. Geochemical correlation of oil from Ayoluengo field to Liassic black shale units in the southwestern BasqueCantabrian Basin (nothern Spain). Organic Geochemistry, 27, 25-40.

Ramírez del Pozo, J., 1969. Síntesis estratigráfica y micropaleontológica de las facies Purbeck y Wealdense del Norte de España. Madrid, Ediciones CEPSA S.A., 68pp.

Rat, R., 1988. The Basque–Basque-Cantabrian Basin between the Iberian and European plates: Some facts but still many problems. Revista de la Sociedad Geológica de España, 1, 327-348.

Requejo, A.G., Halpern, H.I., 1989. An unusual hopane biodegradation sequence in tar sands from the Pt Arena (Monterey) Formation. Nature, 342, 670-673.

Riolo, J., Hussler, G., Albrecht, P., Connan, J., 1986. Distribution of aromatic steroids in geological samples: their evaluation as geochemical parameters. Organic Geochemistry, 10, 981-990.

Roest, W.R., Srivastava, S.P., 1991. Kinematics of the plate boundaries between Eurasia, lberia and Africa in the North Atlantic from the Late Cretaceus to the present. Geology, 19, 613-616.

Romesburg, H.C., 1984. Cluster Analysis for researches. Belmont, Lifetime Learning Publications, 334pp.

Rullkötter, J., Spiro, B., Nissenbaum, A., 1985. Biological marker characteristics of oils and asphalts from carbonate source rocks in a rapidly subsiding graben, Dead Sea, Israel. Geochimica et Cosmochimica Acta, 49, 1357-1370.

Salamon, J., 1982. Les formations continentales du Jurassique Supérieur–Crétacé Inférieur (Espagne du Nord. Chaînes Cantabrique et NW Ibérique). Dijon, Mémoires Géologiques de l’Université de Dijon, 6, 227pp.

Sanz, R., 1967. The Ayoluengo Field. Seventh World Petroleum Congress Proceedings, 2, 251-258.

Seifert, W.K., Moldowan, J.M., 1978. Application of steranes, terpanes and monoaromatic to the maturation, migration and source of crude oils. Geochimica et Cosmochimica Acta, 42, 77-95.

Seifert, W.K., Moldowan, J.M., Demaison, G.J., 1984. Source correlation of biodegraded oils. Organic Geochemistry, 6, 633-643.

Sinninghe-Damsté, J.S., Kenig, F., Koopmans, M.P., Köster, J, Schouten, S, Hayes, J.M., de Leeuw, J.W., 1995. Evidence for gammacerane as an indicator of water-column stratification. Geochimica et Cosmochimica Acta, 59, 1895-1900.

Sofer, Z., 1984. Stable Carbon Isotope composition of crude oils: application to source depositional environments and petroleum alteration. The American Association of Petroleum

Geologists Bulletin, 68, 31-49.

Sundararaman, P., 1985. High-performance liquid chromatography of vanadyl porphyrins. Analytical Chemistry, 57, 2204-2206.

Sundararaman, P., Hwang, R.J., 1993. Effect of biodegradation on vanadyl porphyrin distribution. Geochimica et Cosmochimica Acta, 57, 2283-2290.

Sundararaman, P., Raedeke, L.D., 1993. Vanadyl porphyrins in exploration: maturity indicators for source rocks and oils. Applied geochemistry, 8, 245-254.

Sundararaman, P., Biggs, W.R., Reynolds, J.G., Fetzer, J.C., 1988. Vanadyl porphyrins, indicators of kerogen breakdown and generation of petroleum. Geochimica et Cosmochimica Acta, 52, 2337-2341.

Talukdar, S.C., Gallango, O., Chin-A-Lien, M., 1986. Generation and migration of hydrocarbons in the Maracaibo Basin, Venezuela: an integrated basin study. Organic Geochemistry, 10, 261-279.

ten Haven, H.L., de Leeuw, J.W., Schenck, P.A., 1985. Organic geochemical studies of a Messinian evaporitic basin, Northern Appenines (Italy) I: hydrocarbon biological markers for a

hypersaline environment. Geochimica et Cosmochimica Acta, 49, 2181-2191.

Tissot, B. and Welte, D.H., 1984. Petroleum formation and occurrence, 2nd edition. Berlin, Springer-Verlag, 699pp.