1
Yozgat Bozok University, Faculty of Engineering and Architecture, Department of Geological Engineering, Yozgat
2
Ankara University, Faculty of Engineering, Department of Geology, Ankara
Abstract
Geochemical and mineralogical analyses of the Miocene-aged Çayırhan Oil Shales (ÇOS) reveal a significant presence of sulfur, particularly abundant framboidal pyrite. The formation of framboidal pyrite typically occurs in reducing, sulfur-rich, and microbially active environments, indicating such conditions prevailed during deposition. Sulfur isotope analyses (δ³⁴S) of 25 samples show a wide range of values, from –6.37‰ to +26.55‰, with an average of +13.86‰. This broad range suggests the involvement of multiple sulfur sources, including marine sulfate, freshwater sulfate (potentially through plant uptake), and hydrothermal sulfur. Low δ³⁴S values point to microbial sulfate reduction and freshwater influence, while high values may reflect closed-system conditions or rapid sedimentation. Since framboidal pyrite generally forms via microbial sulfate reduction and subsequent FeS₂ precipitation, its presence in ÇOS strongly supports a biogenic origin. The wide δ³⁴S variation further indicates that environmental factors such as pH and oxygen fugacity (ƒO₂) influenced pyrite formation. According to the literature, positive δ³⁴S values are often linked to slight pH drops, while negative values are associated with higher ƒO₂ levels. In summary, framboidal pyrite formation in the Çayırhan Basin was controlled by a complex interplay of diverse sulfur sources and varying environmental conditions. The isotopic variability reflects both open and closed system behavior in a lacustrine setting, influenced by microbial activity, diagenesis, redox conditions, sedimentation rates, and pH changes.
YAVUZ PEHLİVANLI, B., & KOÇ, Şükrü. (2025). Wide Range Variation of δ³⁴S Isotopes in the Çayırhan Oil Shales: Multiple Sulfur Sources and Environmental Influences. MAS Journal of Applied Sciences, 10(2), 371–384. https://doi.org/10.5281/zenodo.15757478
📄Anderson, T.F., Brumsack, H.J., Walter, L.M., Böttcher, M.E., 1987. Sulfur isotopic composition of pyrite: A tool for understanding ore formation. Geochimica et Cosmochimica Acta, 51(10): 2483–2488.
📄Bazylinski D.A., Frankel, R.B., Heywood, B.R., Mann, S., King, J.W., Donaghay, P. L., Hanson, A.K., 1995. Controlled biomineralization of magnetite (Fe₃O₄) and pyrite (FeS₂) by magnetotactic bacteria. Reviews in Mineralogy and Geochemistry: 30: 485–510.
📄Beveridge, T.J., Ferris, F.G., Fyfe, W.S., 1983. Metal ion binding by bacterial surfaces: Implications for the formation of metal ions in sediments. Chemical Geology: 40: 255–266.
📄Canfield, D.E., Raiswell, R., Westrich, J.T., Reaves, C.M., Berner, R.A., 1998. The use of sulfur isotope fractionation to identify the role of bacterial sulfate reduction in the formation of sedimentary sulfides. Geochimica et Cosmochimica Acta, 52(3): 599–618.
📄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(3–4):199–260.
📄Emery, D., Robinson, A.G., 1993. Inorganic Geochemistry: Application to Petroleum Geology. Blackwell, Oxford, 254.
📄Espitalié, J., Deroo, G., Marquis, F., 1985. Rock-Eval pyrolysis and its applications. Revue de l’Institut Français du Pétrole, 40(5): 563–579.
📄Faure, G., Mensing, T.M. 2005. Isotopes: Principles and applications, Hoboken, NJ: John Wiley and Sons.,3rd ed.: 327–345.
📄Ferris, F.G., Fyfe, W.S., Beveridge, T.J., 1989. Bacteria as nucleation sites for authigenic minerals in a metal-contaminated lake sediment. Chemical Geology, 74(3-4): 149–159.
📄Fisher, Q.J., Hudson, J.D., 1987. Pyrite formation in Jurassic shales: The role of organic matter and iron. Sedimentology, 34(6): 923–934.
📄Garcia-Guinea, J., Martinez-Frías, J., Martinez, R., 1997. Framboidal pyrite and other iron sulfide microtextures in old books. Journal of Materials Science Letters, 16: 1744–1746.
📄Goldhaber, M.B., Kaplan, I.R., 1974. The sulfur cycle. In E. D. Goldberg (Ed.), The Sea, Marine Chemistry, Wiley, Interscience, (5): 569–655.
📄Graham, C.M., Robertson, J.D., 1995. Kinetics and mechanisms of pyrite formation: Constraints from laboratory and field observations. Chemical Geology, 124(1–2): 1–20.
📄Graham, R.C., Ohmoto, H., 1994. Framboidal pyrite formation and sulfur isotope fractionation. Geochimica et Cosmochimica Acta, 58(1): 13–23.
📄Heywood, B.R., Mann, S., Frankel, R.B., 1990. Magnetic properties of bacterial magnetite: Implications for magnetic recording. Proceedings of the Royal Society of London. Series B: Biological Sciences, 239(1296): 107–113.
📄Jarvie, D.M., 1991. Total organic carbon (TOC) analysis. In D. W. Waples and J. W. Whelan (Eds.), Petroleum geochemistry and basin evaluation, AAPG:113–118.
📄Jørgensen, B. B., 1979. A theoretical model of the stable sulfur isotope distribution in marine sediments. Geochimica et Cosmochimica Acta, 43(3): 363–374.
📄Kaplan, I.R., Rittenberg, S.C., Wall, J.D., 1963. Carbon isotope fractionation during bacterial sulfate reduction. Journal of General Microbiology, 31(3): 417–425.
📄Koch, R., 1985. Bacterial pyrite formation: A mechanism for early energy conservation. Origins of Life and Evolution of the Biosphere, 15(3): 245–259.
📄Kohn, M.J., Riciputi, L.R., Stakes D., Orange D.L., 1998. Sulfur isotope variability in biogenic pyrite: Reflections of heterogeneous bacterial colonization? American Mineralogist, 83: 1454–1468.
📄Konhauser, K.O., 1997. Bacterial iron biomineralisation in nature. FEMS Microbiology Reviews, 20(3-4): 315–326.
📄Krouse, H.R., McCready, R.G.L., 1979. Sulphur isotope fractionation in sulfide minerals. In P. J. Hood (Ed.), Geophysics and geochemistry in the search for metallic ores, Geological Survey of Canada: 139–174.
📄Ohmoto, H., Goldhaber, M.B., 1997. Sulfur and carbon isotopes. In H. L. Barnes (Ed.), Geochemistry of Hydrothermal Ore Deposits, Wiley.3rd ed.: 517–611.
📄Ohmoto, H., Rye, R.O., 1979a. Isotopes of sulfur and carbon. In H. L. Barnes (Ed.), Geochemistry of Hydrothermal Ore Deposits, Wiley-Intersci, New York, 2nd ed.: 509–567.
📄Papunen, H., 1966. Pyrite textures and sulfur isotopes in black shales. Bulletin of the Geological Society of Finland, 38: 75–91.
📄Peters, K.E., Cassa, M.R., 1994. Applied source rock geochemistry. In L. B. Magoon and W. G. Dow (Eds.), The petroleum system–From source to trap. AAPG, 60: 93–120.
📄Popa, R., Kinkle, B.K., Badescu, A., 2004. Pyrite Framboids as Biomarkers for Iron-Sulfur Systems. Geomicrobiology Journal, 21(3): 193–206.
📄Postgate, J.R., 1963. Versatile medium for the enumeration of sulfate‐re‐ducing bacteria. Applied Microbiology, 11: 265–267.
📄Rickard, D., 1969a. Framboidal pyrite formation. Economic Geology, 64(4): 576–585.
📄Rickard, D., 1969b. The chemistry of iron sulphide formation at low temperatures. Stockholm Contributions in Geology, 20: 49–66.
📄Rickard, D., 1970. The origin of framboids. Lithos, 3(3): 269–293.
📄Schneiderhöhn, H., 1923. Über die Entstehung des Pyrits. Chemie der Erde, 1: 101–135.
📄Schoonen, M.A.A., Barnes, H.L., 1991. Reactions forming pyrite and marcasite from solution: II. Via FeS precursors below 100 °C. Geochimica et Cosmochimica Acta, 55(6): 1505–1514.
📄Subías, I., Yusta, I., Velasco, F., 1997. Sulphur isotope geochemistry of the Tharsis massive sulfide deposit, Iberian Pyrite Belt, Spain. Mineralium Deposita, 32: 165-173.
📄Thode, H.G., Kleerekoper, H., McElcheran, D., 1960. Isotope fractionation in sulfur compounds. Geochimica et Cosmochimica Acta, 20(1): 1–12.
📄Tissot, B.P. and Welte, D.H., 1984. Petroleum Formation and Occurrence. 2nd Edition, Springer-Verlag, Berlin: 699.
📄Ünal Çakır, E., 2020. Sulphur and lead isotope geochemistry of the Dursunbey (Balikesir) lead-zinc deposit. Journal of African Earth Science: 172.
📄Ünal Çakır, E., Gökce, A., Harris, C., 2023. Genesis of Tertiary Akçakışla vein-type Pb-Zn-Cu mineralisation (Central Anatolia, Turkey): Evidence from fluid inclusion and O, H, S, Pb-isotope compositions. Journal of African Earth Sciences: 205.
📄Wächtershäuser, G., 1990. Evolution of the first metabolic cycles. Proceedings of the National Academy of Sciences, 87(1): 200–204.
📄Wehner, H., 1989. Evaluation of source rock potential and maturity using Rock-Eval pyrolysis data. Oil and Gas Journal, 87(45): 63–66.
📄Wilkin, R.T., Barnes, H.L., 1996. Pyrite formation by reactions of iron monosulfides with dissolved inorganic and organic sulfur species. Geochimica et Cosmochimica Acta, 60(21): 4167–4179.
📄Wilkin, R.T., Barnes, H.L., 1997. Formation processes of framboidal pyrite. Geochimica et Cosmochimica Acta, 61(2): 323–339.
📄Yavuz Pehlivanlı, B., 2011. Hırka Formasyonu (Beypazarı, Ankara, Türkiye) Bitümlü şeyllerinin İnorganik element depolanmaları ve organik-inorganik elementler arasındaki kökensel ilişkiler. Doktora Tezi, Ankara Üniversitesi, Fen Bilimleri Enstitüsü, Ankara
📄Zhao, X., Jin, Q., Bethke, C.M., 2003. The influence of pH and redox conditions on sulfur isotope fractionation in microbial sulfate reduction. Geochimica et Cosmochimica Acta, 67(22): 4391–4403.