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Zhizn Zemli [Life of the Earth] 47, no 3
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Zhizn Zemli [Life of the Earth] 47, no 3

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DOI

10.29003/m4741.0514-7468.2025_47_3/359-373

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Authors:

Filippov, V.M., Shigaev, V.Yu., Ivanov, A.V.

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Keywords:

Kashpir shales, metal-bearing potential, linear geochemical spectra, Clarke values, metals, multi-element associations, supergene processes.

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Filippov, V.M., Shigaev, V.Yu., Ivanov, A.V., “On Assessing the Me­tal-Bearing Potential of Kashpir Shales (Samara Region) Using Linear Geochemical Spectra”, Zhizn Zemli [Life of the Earth] 47, no 3, 359–373 (2025) (in Russ., abstr. in Engl.). DOI: 10.29003/m4741.0514-7468.2025_47_3/359-373.

On assessing the metal-bearing potentialof Kashpir shales (Samara region) using linear geochemical spectra

This study investigates the metal-bearing potential of Upper Jurassic (Tithonian stage) combustible shales from the Kashpir deposit (Volga Basin) using linear geochemical spectra methodology. Samples from mine workings and natural outcrops were analyzed by energy-dispersive X-ray fluorescence spectrometry (ED-XRF), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results reveal elevated concentrations of Ca (27.5–38.6%) and Fe (20.3–24.3%), indicative of a carbonate-clay composition with pyrite inclusions, characteristic of reducing sedimentation conditions. Excesses over the Clarke values were revealed for Ba, Co, Sr, Ni, and Mo, confirming the industrial potential of these shales as a source of rare and non-ferrous metals. The authors have developed a novel analytical approach based on reference concentrations (maximum and minimum values), enabling assessment of metal enrichment without identifying a dominant ore-forming element–particularly valuable for multi-element systems. The observed differences between mine and surface samples are attributed to post-sedimentary processes (leaching and oxidation). Our findings demonstrate a consistent lithological-geochemical shale type and highlight prospects for their comprehensive exploitation.

Список литературы

  1. Bukina, T.F., Sedimentogenesis and early lithogenesis of Upper Jurassic shale-bearing deposits in the central part of the Volga Basin (Saratov: Saratov University Press, 2013) (in Russian).
  2. Vinogradov, A.P., “Average content of chemical elements in the main types of igneous rocks of the Earth’s crust”, Geochemistry 7, 555–571 (1962) (in Russian).
  3. Vyalov, V.I., Dyu, T.A., Nastavkin, A.V., Shishov, E.P., “Rhenium and associated valuable me­tals in combustible shales of the Volga Basin”, Solid Fuel Chemistry 1, 50–56 (2024) (in Russian).
  4. Grigorev, N.A., Distribution of chemical elements in the upper part of the continental crust (Yekaterinburg: UrO RAN, 2009) (in Russian).
  5. Ivanov, A.V., Yashkov, I.A., Zakharov, E.E., Expeditions in the Volga and Caspian regions. Studies of half a millennium. From the first travelers to the “Floating Universities Flotilla” (Moscow: Russkiy Mir, 2021) (in Russian).
  6. Ilyasov, V.S., Formation conditions of Upper Jurassic combustible shales of the Volga Basin on the example of deposits of the Saratov Volga region (Moscow, 2020) (in Russian).
  7. Istratov, A.A., Myachikov, V.T., Vasilev, S.A., Geological report “Classification and assessment of residual shale reserves of the liquidated Kashpir mine” (Rosgeolfond, 2002) (in Russian).
  8. Kasimov, N.S., Vlasov, D.V., “Clarke values of chemical elements as reference standards in ecogeochemistry”, Bull. of Moscow University. Ser. 5. Geography 2, 7–17 (2015) (in Russian).
  9. Solovov, A.P., Garanin, A.V., “Geochemical spectra of anomalies and establishing differences between similar objects”, Proc. of the 1st thematic session of the Interdepartmental Council on the problem “Scientific foundations of geochemical methods for prospecting mineral deposits” (Alma-Ata: Nauka, 1972) (in Russian).
  10. Shary, S.P., Finite-dimensional interval analysis (Novosibirsk: Izd-vo Instituta matematiki im. S.L. Soboleva SO RAN, 2013) (in Russian).
  11. Yudovich, Ya.E., Ketris, M.P., Geochemistry of black shales (Leningrad: Nauka, 1988) (in Russian).
  12. Yanin, E.P., Oil shales and the environment (ecological consequences of extraction, processing and use) (Moscow: IMGRE, 2003) (in Russian).
  13. Hanor, J.S., “Barite-celestine geochemistry and environments of formation”, Reviews in Minera­logy and Geochemistry 40 (1), 193–275 (2000).
  14. Ketris, M.P., Yudovich, Ya.E. “Estimations of Clarkes for Carbonaceous biolithes: World ave­rages for trace element contents in black shales and coals”, Intern. J. of Coal Geology 78, 135–148 (2009).
  15. Riboulleau, A., Baudin, F., Deconinck, J.-F., Derenne, S., “Depositional conditions and organic matter preservation pathways in an epicontinental environment: the Upper Jurassic Kashpir Oil Shales (Volga Basin, Russia)”, Palaeogeography, Palaeoclimatology, Palaeoecology 197, 171–197 (2003).
  16. Rudnick, R.L., Gao, S., “Composition of the continental crust”, Treatise on Geochemistry 3, 1–64 (2003).
  17. Tribovillard, N., Algeo, T.J., Lyons, T., Riboulleau A. “Trace metals as paleoredox and paleo­productivity proxies: An update”, Chemical Geology 232 (1), 12–32 (2006).
  18. Wedepohl, K.H., “The composition of the continental crust”, Geochimica et Cosmochimica Acta 59 (7), 1217–1232 (1995).

References

  1. Bukina, T.F., Sedimentogenesis and early lithogenesis of Upper Jurassic shale-bearing deposits in the central part of the Volga Basin (Saratov: Saratov University Press, 2013) (in Russian).
  2. Vinogradov, A.P., “Average content of chemical elements in the main types of igneous rocks of the Earth’s crust”, Geochemistry 7, 555–571 (1962) (in Russian).
  3. Vyalov, V.I., Dyu, T.A., Nastavkin, A.V., Shishov, E.P., “Rhenium and associated valuable me­tals in combustible shales of the Volga Basin”, Solid Fuel Chemistry 1, 50–56 (2024) (in Russian).
  4. Grigorev, N.A., Distribution of chemical elements in the upper part of the continental crust (Yekaterinburg: UrO RAN, 2009) (in Russian).
  5. Ivanov, A.V., Yashkov, I.A., Zakharov, E.E., Expeditions in the Volga and Caspian regions. Studies of half a millennium. From the first travelers to the “Floating Universities Flotilla” (Moscow: Russkiy Mir, 2021) (in Russian).
  6. Ilyasov, V.S., Formation conditions of Upper Jurassic combustible shales of the Volga Basin on the example of deposits of the Saratov Volga region (Moscow, 2020) (in Russian).
  7. Istratov, A.A., Myachikov, V.T., Vasilev, S.A., Geological report “Classification and assessment of residual shale reserves of the liquidated Kashpir mine” (Rosgeolfond, 2002) (in Russian).
  8. Kasimov, N.S., Vlasov, D.V., “Clarke values of chemical elements as reference standards in ecogeochemistry”, Bull. of Moscow University. Ser. 5. Geography 2, 7–17 (2015) (in Russian).
  9. Solovov, A.P., Garanin, A.V., “Geochemical spectra of anomalies and establishing differences between similar objects”, Proc. of the 1st thematic session of the Interdepartmental Council on the problem “Scientific foundations of geochemical methods for prospecting mineral deposits” (Alma-Ata: Nauka, 1972) (in Russian).
  10. Shary, S.P., Finite-dimensional interval analysis (Novosibirsk: Izd-vo Instituta matematiki im. S.L. Soboleva SO RAN, 2013) (in Russian).
  11. Yudovich, Ya.E., Ketris, M.P., Geochemistry of black shales (Leningrad: Nauka, 1988) (in Russian).
  12. Yanin, E.P., Oil shales and the environment (ecological consequences of extraction, processing and use) (Moscow: IMGRE, 2003) (in Russian).
  13. Hanor, J.S., “Barite-celestine geochemistry and environments of formation”, Reviews in Minera­logy and Geochemistry 40 (1), 193–275 (2000).
  14. Ketris, M.P., Yudovich, Ya.E. “Estimations of Clarkes for Carbonaceous biolithes: World ave­rages for trace element contents in black shales and coals”, Intern. J. of Coal Geology 78, 135–148 (2009).
  15. Riboulleau, A., Baudin, F., Deconinck, J.-F., Derenne, S., “Depositional conditions and organic matter preservation pathways in an epicontinental environment: the Upper Jurassic Kashpir Oil Shales (Volga Basin, Russia)”, Palaeogeography, Palaeoclimatology, Palaeoecology 197, 171–197 (2003).
  16. Rudnick, R.L., Gao, S., “Composition of the continental crust”, Treatise on Geochemistry 3, 1–64 (2003).
  17. Tribovillard, N., Algeo, T.J., Lyons, T., Riboulleau A. “Trace metals as paleoredox and paleo­productivity proxies: An update”, Chemical Geology 232 (1), 12–32 (2006).
  18. Wedepohl, K.H., “The composition of the continental crust”, Geochimica et Cosmochimica Acta 59 (7), 1217–1232 (1995).