Geochemistry of Miocene evaporites from the Aşkale (Erzurum, Eastern Turkey) area: constraints for paleo-environment

The Aşkale sub - basin hosts Early Miocene evaporites intercalated with clastic sediments and carbonates. Gypsum - and anhydrite - rich evaporite samples are characterized by high CaO and SO4 contents, and low Na2O, K2O, MgO, and B contents. The Sr contents are 228 - 13100 ppm in evaporite samples, 169 - 992 ppm in claystone, 181 - 60090 ppm in marl, and 15150 ppm in limestone. All the samples are also characterized by enrichment in light rare earth elements (REE) with LaN / LuN = 0.667 - 4.243 and have variable CeN / Ce* (0.823 - 1.353) ratios. Measured EuN / Eu* values of the samples display strong and ariable negative and positive Eu anomalies. δ34SCDT and δ18O values of gypsum - and anhydrite samples have wide ranges from 21.30 ‰ to 25.62 ‰, and 11.5 ‰ to 19.1 ‰, respectively. Most of these values  are heavier than expected Miocene marine gypsum composition and may be resulted from reduction and oxidation reactions of sulfide species in brines. 87Sr / 86Sr ratios range from 0.707475 (ΔSW = −169.8) to 0.708175 (ΔSW = −99.8), close to and / or slightly lower than an Early - Miocene marine isotopic composition. Petrochemical and isotopic data indicate that the Aşkale basin evaporites developed in subtropical conditions via multiple marine transgressions onto a shallow platform or lagoonal environment.

___

  • Abdioğlu, E., Arslan, M., Gündoğan, İ., Helvacı, C. 2013. Aşkale (Erzurum) Civarındaki Evaporitlerin Mineralojik, Jeokimyasal ve İzotopik Özellikleri, KD Türkiye. TÜBİTAK Projesi, Proje no: 110Y023.
  • Abdioğlu, E., Arslan, M., Aydınçakır, D., Gündoğan, İ., Helvacı, C. 2015. Stratigraphy, mineralogy and depositional environment of the evaporite unit in the Aşkale (Erzurum) sub - basin, Eastern Anatolia (Turkey). Journal of African Earth Sciences 111, 100-112.
  • Adabi, M. H. 2004. Sedimentary Geochemistry. Arianzamin Publication, Iran.
  • Alptekin, Ö. 1973. Focal Mechanism of Earthquakes in Western Turkey and Their Tectonic Implications. PhD Thesis, New Mexico Institute of Mining and Technology, Socorro, USA.
  • Aydınçakır, D. 2013. Pırnakapan (Aşkale, Erzurum) civarındaki evaporitlerin mineralojik, petrografik ve jeokimyasal incelenmesi. Karadeniz Teknik Üniversitesi, Fen Bilimleri Enstitüsü, Yüksek Lisans Tezi.
  • Bahadori, A., Carranza, E. J. M., Soleimani, B. 2011. Geochemical analysis of evaporite sedimentation in Gachsaran Formation, Zeloi oil field, southwest Iran. Journal of Geochemical Exploration 111, 97- 112.
  • Baysal, O., Ataman, G. 1980. Sedimentology, mineralogy and geochemistry of a sulphate series (Sivas - Turkey). Sedimentary Geology 25, 67-81.
  • Brinkmann, R. 1976. Geology of Turkey. Elsevier, Amsterdam.
  • Burke, W. H., Denison, R. E., Hetherington, E. A., Koepnik, R. B., Nelson, H. F., Otto, J. B. 1982. Variation of seawater 87Sr / 86Sr throughout Phanerozoic time. Geology 10, 516-519.
  • Cendón, D. I., Chivas, A. R., García, A. 2004. Chemistry of the rivers in the Gulf of Carpentaria drainage division and possible correlations with the sedimentary record during lake phases. 17th Australian Geological Convention. Dynamic Earth: Past, Present and Future. Hobart, Australia, 73, 228.
  • Claypool, G. E., Holser, W. T., Kaplan, I. R., Sakai, H., Zak, I. 1980. The age curves of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation. Chemical Geology 28, 199-260.
  • Crockford, P. W., Kunzmann, M., Bekker, A., Hayles, J., Bao, H., Halverson, G. P., Peng, Y., Bui, T. H., Cox, G. M., Gibson, T. M., Wörndle, S., Rainbird, R., Lepland, A., Swanson - Hysell, N. L., Master, S., Sreenivas, B., Kuznetsov, A., Krupenik, V., Wing, B. A. 2019. Claypool continued: Extending the isotopic record of sedimentary sulfate. Chemical Geology 513, 200-225.
  • Çiner, A., Koşun, E., Deynoux, M. 2002. Fluvial, evaporitic and shallow-marine facies architecture, depositional evolution and cyclicity in the Sivas Basin (Lower to Middle Miocene), Central Turkey. Journal of Asian Earth Sciences 21, 147- 165.
  • Dejonghe, L., Demaiffe, D., Weis, D. 1998. Strontium isotope geochemistry of anhydrites and calcite pseudomorphs after anhydrite from Paleozoic formations in Belgium. Chemical Geology 144,63-71.
  • Denison, R. E., Kırkland, D. W., Ewans, R. 1998. Using strontium isotopes to determine the age and origin of anhydrite and gypsum beds. The Journal of Geology 106, 1-7.
  • Emelyanov, E. M., Shimkus, K. M. 1986. Geochemistry and Sedimentology of the Mediterranean Sea. Springer, Paris.
  • Emery, D., Robinson, A. 1992. Inorganic Geochemistry Applications to Petroleum Geology. Blackwell Scientific Publications, Oxford.
  • Faure, G., Powell, J. L. 1972. Strontium Isotope Geology.Springer-Verlag, New York.
  • Gallet, S., Jahn, B. M., Torii, M. 1996. Geochemical characterization of the Luochuan loesspaleosol sequence, China, and paleoclimatic implications. Chemical Geology 133, 67-88.
  • Garrels, R. M., Lerman,A. 1984. Coupling of the sedimentary sulfur and carbon cycles; an improved model. American Journal of Science 284, 989-1007.
  • Gökçe, A., Ceyhan, F. 1988. Sivas güneydoğusundaki Miyosen yaşlı jipsli çökellerin stratigrafisi, yapısal özellikleri ve oluşumu. Cumhuriyet Earth Science Journal 5, 1, 91-113 (in Turkish).
  • Gündoğan, İ. 2000. Geology, Mineralogy-Petrography and Economic Potential of the Upper Miocene Evaporites in The Beypazarı and Çankırı - Çorum Basins. PhD Thesis, The Graduate School of Natural and Applied Sciences, DEU.
  • Gündoğan, İ., Önal, M., Depçi, T. 2005. Sedimentology, petrography and diagenesis of Eocene - Oligocene evaporites: the Tuzhisar Formation, SW Sivas Basin, Turkey. Journal of Asian Earth Sciences 25, 791-803.
  • Gündoğan, İ., Helvacı, C., Sözbilir, H. 2008. Gypsiferious carbonates at Honaz Dağı (Denizli): First documentation of Triassic gypsum in western Turkey and its tectonic significance. Journal of Asian Earth Sciences 32, 49-65.
  • Hasselöv, M., Lyvén, D., Haraldsson, C., Sirinawin, W. 1999. Determation of continous size and trace element distribution of field-flow fractionation with ICPMS. Analytical Chemistry 71, 3497-3502.
  • Helvacı, C. Yağmurlu, F. 1995. Geological setting and economic potential of the lignite and evaporite- bearing Neogene basins of Western Anatolia, Turkey. Israel Journal of Earth Sciences 44, 91- 105.
  • Horner, T. J., Pryer, H. V., Nielsen, S. G., Crockford, P. W., Gauglitz, J. M., Wing, B. A., Ricketts, R. D. 2017. Pelagic barite precipitation at micromolar ambient sulfate, Nature Communications 8, Article number: 1342.
  • Kamber, B. S., Greig, A., Collerson, K. D. 2005. A new estimate for the composition of weathered young upper contitnental crust from alluvial sediments, Queensland, Australia. Geochimica et Cosmochimica Acta 69, 4, 1041-1058.
  • Kasprzyk, A. 2003. Sedimentological and diagenetic patterns of anhydrite deposits in the Badenian evaporite basin of the Carpathian Foredeep, southern Poland. Sedimentary Geology 158, 167-194.
  • Keskin, M. 2003. Magma generation by slab steepening and breakoff beneath a subduction-accretion complex: An alternative model for collision- related volcanism in Eastern Anatolia, Turkey. Geophysical Research Letters 30, 24, 1-4.
  • Ketin, İ. 1966. Tectonic units of Anatolia (Asia Minor). Bulletin of the Mineral Research and Exploration 66, 23-34.
  • Kornexl, B. E., Gehre, M., Höfling, R., Werner, R. A. 1999. On-line δ18O Measurement of organic and inorganic substances. Rapid Communications in Mass Spectrometry 13, 1685-1693.
  • Krauskopf, K. B. 1979. Introduction to Geochemistry.McGraw-Hill Book Company, New York.
  • Kushnir, J. 1980. The coprecipitation of strontium, magnesium, sodium, potassium, and chloride ions with gypsum: an experimental study. Geochimica et Cosmochimica Acta 44, 1471-1482.
  • Kushnir, J. 1982. The partitioning of seawater cations during the transformation of gypsum to anhydrite. Geochimica et Cosmochimica Acta 46, 433-446. Lloyd, R. M. 1968. Oxygen isotope behavior in the sulphate- water system. Journal of Geophysical Research 73, 6099-6110.
  • Longinelli, A. 1989. Oxygen-18 and sulphur-34 in dissolved oceanic sulphate and phospate. In: Fritz, P., Fontes, J.C. (Eds.), Handbook of Environmental Isotope Geochemistry. The Marine environment. Elseiver, Amsterdam, 219-255.
  • Lu, F. H., Meyers, W. J. 1997. Sr, S, OSO4 isotopes and quantitative models of Messinian gypsum, the Nijar Basin, Spain (Abstract). International Applied Isotope Geochemistry (AIG-2) Conference, Calgary.
  • Lu, F. H., Meyers, W.J. 2003. 87Sr / 86Sr, δ34S and δ18O (SO4) isotopes of Messinian evaporites, modeling and environmental significance. Journal of Sedimentary Research 73, 443-449.
  • Ludden, J. N., Thompson, G. 1979. An evaluation of the behaviour of the REE elements during the weathering of seafloor basalt. Earth and Planetary Science Letters, 43, 85-92.
  • Mason, B., Moore, C. B. 1982. Principles of Geochemistry.Wiley, New York.
  • McArthur, J. M., Howarth, R. J., Bailey, T. R. 2001. Strontium isotope stratigraphy: LOWESS version 3: best fit to the marine Sr - isotope curve for 0- 509 Ma and accompanying look-up table for deriving numerical age. The Journal of Geology 109, 155-170.
  • McKenzi, D. P. 1976. The East Anatolian Fault: a major structure in Eastern Turkey. Earth and Planetary Science Letters 29, 189-193.
  • Menzies, M., Seyfried, W., Blanchard, D. 1979. Experimental evidence of rare earth element immobility in Greenstones. Nature 282, 398-399.
  • Mizutani, Y., Rafter, T.A. 1969. Oxygen isotopic composition of sulfates, 4. Bacterial fractionation of oxygen isotopes in the reduction of sulphate and in the oxidation of sulphur: New Zealand. Journal of Science, 12, 60-68.
  • Müller, D. W., Mueller, P.A. 1991. Origin and age of the Mediterranean Messinian evaporites; implications from Sr isotopes. Earth and Planetary Science Letters 107, 1-12.
  • Müller, G. 1962. Zur Geochemie des Strontiums in Ozeanen evaporites unter besonderer Berücksichtigung der sedimentaren Coelestin lagerstatte von Hemmelte-West (Süd Oldenburg). Geologie 11, 1-90.
  • Nesbitt, H. W., Young, G. M. 1982. Early Proterozoic climates and plate motions inferred from major element chemistry of lutites. Nature 299, 715-717.
  • Ohmoto, H. 1986. Stable isotope geochemistry of ore deposits. In: Valley, J. W., Taylor J.R., H.P., O’Neil, J.R. (Eds.), Stable Isotopes in High Temperature Geological Processes. Reviews in Mineralogy, Mineralogical Society of America, 16, 491-560.
  • Okay, A. I., Tüysüz, O. 1999. Tethyan sutures of northern Turkey. In: Durand, B., Jolivet, L., Horváth, F., Séranne M. (Eds.), The Mediterranean Basins: Tertiary Extension within the Alpine Orogen. Geological Society, London, Special Publications 156, 475-515.
  • Ortí, F., Rosell, L. 2000. Evaporative systems and diagenetic patterns in the Calatayud Basin (Miocene, central Spain). Sedimentology 47, 665-685.
  • Ortí, F., Gündoğan, İ., Helvacı, C. 2002. Sodium sulphate deposit of Neogene age: the Kirmir Formation, Beypazarı Basin, Turkey. Sedimentary Geology 146, 305-333.
  • Ortí, F., Rosell, L., Ingles, M., Playà, E. 2007. Depositional models of lacustrine evaporates in the SE margin of the Ebro Basin (Paleogene) NE Spain. Geologica Acta 5, 19-34.
  • Palmer, M. R., Helvacı, C., Fallick, A. E. 2004. Sulphur, sulphate, oxygen and strontium isotope composition of Cenozoic Turkish evaporates. Chemical Geology 209, 341-356.
  • Pandarinath, K., Prasad, S., Gupta, S. K. 1999. A 75 ka record of palaeoclimatic changes inferred from crystallinity of illite from Nal Sarovar, Western India. Journal of the Geological Society of India 54, 515-522.
  • Paytan, A., Kastner, M., Campbell, D., Thiemens, M.H. 1998. Sulphur isotopic composition of Cenozoic seawater sulphate. Science 282, 1459-1462.
  • Playà, E., Ortí, F., Rosell, L. 2000. Marine to non-marine sedimentation in the Upper Miocene evaporites of the Eastern Betics, SE Spain: sedimentological and geochemical evidence. Sedimentary Geology 133, 135-1666.
  • Playà, E., Cendon, D. I., Trave, A., Chivas, A. R., Garcia, A. 2007. Using multiple geochemical proxies to trace origin of gypsum (Gulf of Carpentaria, Australia, -70ka). Geogaceta 42, 135-138.
  • Rees, C. E., Jekins, W.E., Monster, J. 1978. The sulphur isotopic composition of ocean water sulphate. Geochimica et Cosmochimica Acta 42, 377-381.
  • Rosell, L., Orti, F., Kasprzyk, A., Playa, E., Peryt, T. M. 1998. Strontium geochemistry of Miocene primary gypsum; Messinian of southeastern Spain and Sicily and Badenian of Poland. Journal of Sedimentary Research 68, 63-79.
  • Roy, P. D., Smykatz-Kloss, W., Sinha, R. 2006. Late Holocene geochemical history inferred from Sambhar and Didwana playa sediments, Thar Desert, India: comparison and synthesis. Quaternary International 144, 84-98.
  • Roy, P. D., Nagar, Y. C., Juyal, N., Smykatz-Kloss, W., Singhvi, A. K. 2009. Geochemical signatures of Late Holocene paleo - hydrological changes from Phulera and Pokharan saline playas near the eastern and western margins of the Thar Desert, India. Journal of Asian Earth Sciences 34, 275 -286.
  • Rushdi, A. I., McManus, J., Collier, R. W. 2000. Marine barite and celestite saturation in seawater. Marine Chemistry 69, 19-31.
  • Sancay, R. E. 2005. Palynostratigraphic and Palynofacies Investigation of the Oligocene - Miocene Units in the Kars - Erzurum - Muş Sub-Basins (Eastern Anatolia). PhD Thesis, Middle East Technical University.
  • Smykatz-Kloss, W., Roy, P. D. 2010. Evaporite mineralogy and major element geochemistry as tools for paleoclimatic investigations in arid regions: a synthesis. Boletin De La Sociedad Geológica Mexicana 62, 3, 379-390.
  • Sungurlu, O. 1971. İ45a, İ45b, İ46a, İ46b, İ47a, İ47b, paftalarına ait 1 / 50000’lik jeoloji haritaları. TPAO, Ankara.
  • Sverjensky, D. A. 1984. Europium Redox Equilibria in Aqueous Solution. Earth and Planetary Science Letters 67, 70-78.
  • Şahintürk, Ö. 1992. Tercan - Çayırlı Basenleri’nin jeolojisi ve hidrokarbon olanakları, TPAO Arama Grubu Rap. No. 3070, Ankara (in Turkish, unpublished).
  • Şahintürk, Ö., Kasar, S. 1980. Tercan - Çayırlı Baseninin Jeolojisi ve Hidrokarbon Olanakları (Geology and Hydrocarbon Potential of the Tercan-Çayırlı Basin). TPAO Arama Grubu Raporu, no. 1446 (in Turkish, unpublished).
  • Şahintürk, Ö., Şaroğlu, F., Çaptuğ, A., Temel, Ö., İlleez, H. İ., Tekin, T. 1997. Ağrı Yöresinin Jeolojisi ve Hidrokarbon Olanakları (Geology and Hydrocarbon Potential of the Ağrı Area). TPAO Arama Grubu Rapor No. 3790, Ankara (in Turkish, unpublished).
  • Şengör, A .M. C. 1980. Türkiye’nin Neotektoniğinin Esasları (Fundamentals of the Neotectonics of Turkey). Publication of Geological Society of Turkey, 2, Ankara (in Turkish).
  • Şengör, A. M. C., Özeren, S., Zor, E., Genç, T. 2003. East Anatolian high plateau as a mantle-supported, N-S shortened domal structure. Geophysical Research Letters 30, 8044.
  • Tarhan, N., Deveciler, E., Karabalık, N. N., Akdoğan, E., Çolak, T., Kar, H. 1992. Aşkale - Çat (Erzurum) Dolayının Jeolojisi (Geology of the Aşkale - Çat (Erzurum) area). Maden Tetkik ve Arama Genel Müdürlüğü, Ankara (in Turkish, unpublished).
  • Tchalenko, J. S. 1977. A reconnaissance of the seismicity and tectonics of the northern border of the Arabian plate (Lake Van Region). Revule de Geographie Physique et de Geologie Dynamiqu 19, 2, 189-208.
  • Tekin, E. 2001. Stratigraphy, Geochemistry and Depositional Environment of the Celestine - bearing gypsiferous Formations of the Tertiary Ulaş - Sivas Basin, East - Central Anatolia (Turkey). Turkish Journal of Earth Sciences 10, 35-49.
  • Tekin, E., Varol, B., Ayyıldız, T. 2010. Sedimentology and paleoenvironmental evolution of Messinian evaporates in the İskenderun - Hatay basin complex, Southern Turkey. Sedimentary Geology 229, 4, 282-298.
  • Tekin, T., Alişan, C., Işık, U., Akça, N., Aras, M., Günal, B. 2000. Aşkale-1 Kuyusu Sonuç Raporu (The Aşkale-1 Final Well Report) TPAO Araştırma Grubu Rapor no: 2514, Ankara (in Turkish, unpublished).
  • Thode, H. G., Monster, J. 1965. Sulphur isotope geochemistry of petroleum, evaporites and ancient seas. In: Young, A., Galley, J.E. (Ed.), Fluids in Subsurface Environments. American Association of Petroleum Geologists, Tulsa, Oklahoma, USA, 4, 367-377.
  • Toulkeridis, T., Podwojewski, P., Clauer, N. 1998. Tracing the source of gypsum in New Caledonian soils by REE contents and S - Sr isotopic compositions. Chemical Geology 145, 61-71.
  • Turekian, K. K. 1964. The marine geochemistry of strontium. Geochimica et Cosmochimica Acta 28, 1479-1496.
  • Türkmen, İ. 2004. Facies and evaporite genesis of the Kuşçular Formation (Lower Paleocene) saline playa complex, Eastern Turkey. Journal of Asian Earth Science 24, 91-104.
  • Ueda, A., Krouse, H.R. 1986. Direct Conversion of Sulphide and Sulphate Minerals to SO2 for Isotope Analysis. Geochemical Journal 20, 209-212.
  • Usdowski, E. 1967. Der Einbau von Sr in Gips und Anhydrit.Ann. Meet. Deutsche Mineral. Gesell., Berlin.
  • Warren, J. K. 2010. Evaporites through time: Tectonic, climatic and eustatic controls in marine and nonmarine deposits. Earth Science Reviews 98, 217-268.
  • Warren, J. K., Kendall, C.G.St.C. 1985. Comparison of marine sabkhas (subaerial) and salina (subaqueous) evaporites: modern and ancient. AAPG Bulletin 69, 1013-1023.
  • Yeşilova, Ç., Helvacı, C., Carrillo, E. 2018. Evaporitic sedimentation in the Southeastern Anatolian Foreland Basin: New insights on the Neotethysclosure. Sedimentary Geology 369, 13-27.
  • Yılmaz, Y. 1993. New evidence and model on the evaluation of the southeast Anatolian orogen. Geological Society of America Bulletin 105, 251-271.
  • Zeybek, B. 2007. Geochemical Studies of Porsuk Formation (Pliocene) Evaporites, Middle Sakarya Region, Central Anatolia, Turkey. MSc thesis, The Graduate School of Natural and Applied Sciences, Ankara University (in Turkish).