Microcomponents, Macro- and Mesoporosity, and Genesis Features of Zeolite-Bearing Rocks from the Tatarsko-Shatrashanskoye Deposit (Republic of Tatarstan)

Studies were conducted on the morphology of the void space, structural-textural characteristics, composition, and mineral formation conditions of Upper Cretaceous (Turonian– Santonian stages) carbonate-clay-siliceous zeolite-bearing rocks exploited at the Tatarsko-Shatrashanskoye deposit. The deposit is located in the northern part of the Ulyanovsk-Saratov Depression. The objects of study were zeolite-bearing siliceous marls from the first bed (t-1) of the productive sequence. A total of 40 samples represented by calcined and uncalcined coarsegrained fractions (0.5–1 mm) were examined.

The research was performed using X-ray microtomography (micro-CT) and scanning electron microscopy with energydispersive spectroscopy.

The samples are represented by intergrowths of mineral aggregates and detritus, forming medium-, fine-, and very fine-grained, biogenic, scaly, and lepispheric microstructures. The microcomponent composition includes: a paragenesis of authigenic minerals (Opal-CT, the clinoptilolite-Ca – heulandite-Ca isomorphous series, glauconite, clay minerals, volcanic glasses), defined as “camouflaged pyroclastics”; allothigenic minerals (manganoilmenite, zircon); and fossilized remains of calcareous and siliceous biota (foraminifera, coccolithophores, rhabdoliths, diatoms, stomatocysts).

Calcined and uncalcined samples exhibit similarity in all characteristics, except for secondary cracks and a rounded surface in calcined samples. The morphology of the primary void space is represented by rounded and elongated biovoids (>1 µm) and tortuous intergranular pores (<1 µm), of open and closed types. By size, pore types are divided into mesopores (<25 nm) and macropores (>25 nm), with the latter predominating.

The basis for the unique sorption properties of the zeolitebearing rocks exploited at the Tatarsko-Shatrashanskoye deposit, used in various economic sectors, is their mineral composition in combination with macro- and mesoporosity, and the isomorphism within the clinoptilolite-Ca – heulanditeCa series, which enhances bioorganic sorption.

The formation of the zeolite-bearing rocks is the result of the interaction of endogenous and exogenous processes under the conditions of a stable shelf basin with a developed carbonate buffer system.

1. Afanasyeva N.I., Dmitriev D.A., Zhabin A.V., Zorina S.O. (2006). Sericite rocks of the Voronezh anteclise and the Middle Volga region. Vestnik Voronezhskogo gosudarstvennogo universiteta = Bulletin of Voronezh State University, 2, pp. 68-76. (In Russ.)

2. Akhlystina E.F., Bondarenko N.A., Gutsak V.A., Kurlaev V.I. (1980). Composition, paragenetic relationships and genesis of siliceous rocks of the Upper Cretaceous and Paleogene of the Lower Volga region. Osadochnyye porody i rudy: Materialy nauch. soveshch. = Sedimentary Rocks and Ores: Proceedings of a Scientific Meeting. Kiev, pp. 212–219. (In Russ.)

3. Akhlystina E. F., Ivanov A. V. (2000). Atlas kremnistykh porod mela i paleogena Povolzh’ya = Atlas of Siliceous Rocks of the Cretaceous and Paleogene of the Volga Region. Saratov: Publishing House of the State Educational Institution “College”, 166 p. (In Russ.)

4. Belova T.P. (2023). Kinetics of sorption of gold ions from aqueous solutions by zeolites. Uspekhi sovremennogo yestestvoznaniya = Successes of modern Natural Science, 6, pp. 98-103. (In Russ.) https://doi.org/10.17513/use.38059

5. Belousov P.E., Kailachakov P.E., Rumyantseva A.O. (2024). Mineral resource base of zeolites in Russia. Georesursy = Georesources, 26(4), pp. 260–274. (In Russ.) https://doi.org/10.18599/grs.2024.4.12

6. Belousov P.E. Karelina N.D., Morozov I.A., Rudin M.A., Milyutin V.V., Nekrasova N.A., Rumyantseva A.O., Zakusina O.V., Krupskaya V.V. (2023). Zeolite-containing trepel from the Khotynetsky deposit (Oryol region): mineral composition, sorption properties, conditions of formation. Izvestiya Tomskogo politekhnicheskogo universiteta. Inzhiniring georesursov = Proceedings of Tomsk Polytechnic University. Georesource Engineering, 334(5), pp. 70-84. (In Russ.) https://doi.org/10.18799/24131830/2023/5/4001

7. Burov A.I. (1992). The raw material base of natural zeolites in Russia. Sbornik tezisov Prirodnyye tseolity Rossii: Geologiya, fiziko-khimicheskiye svoystva i primeneniye v promyshlennosti i okhrane okruzhayushchey sredy = Collection of abstracts Natural zeolites of Russia: Geology, physico-chemical properties and application in industry and environmental protection. Vol. 1. Novosibirsk: Joint Institute of Geology, Geophysics and Mineralogy SB RAS, pp. 11-14. (In Russ.)

8. Vasilyeva S.Yu. (2014). Equilibrium sorption of α-tocopherol on modified clinoptilolite.Dissertation for the degree of Candidate of Chemical Sciences. Voronezh: Voronezh State University, 137 p. (In Russ.)

9. Danilenko S.A. (1992). Zeolites of the Komsomolsk pyrite deposit and their industrial significance. Sbornik tezisov Prirodnyye tseolity Rossii: Geologiya, fiziko-khimicheskiye svoystva i primeneniye v promyshlennosti i okhrane okruzhayushchey sredy = Collection of abstracts Natural zeolites of Russia: Geology, physico-chemical properties and application in industry and environmental protection. Vol. 1. Novosibirsk: Joint Institute of Geology, Geophysics and Mineralogy SB RAS, pp. 27-29. (In Russ.)

10. Deniskina N. D., Kalinin D. V., Kazantseva L. K. (1980). Noble opals, their synthesis and genesis in nature. Novosibirsk: Nauka, 64 p. (In Russ.)

11. Dmitriev D.A., Zhabin A.V. (2020). On the genesis of glauconite in sedimentary deposits of the Voronezh anteclise. Yevraziyskiy Soyuz Uchenykh = Eurasian Union of Scientists, 1(70), pp. 9-15. (In Russ.)

12. Evdokimova V. A., Karatsuba L. P., Lankin S. V. (2011). The change in the adsorption properties of clinoptilolite as a result of ion exchange of cations. Perspektivnyye materialy = Perspective Materials, 13, pp. 497-500. (In Russ.)

13. Zelenikhin P.V., Galeeva A.G., Islamova R.R., Lopatin O.N., Yarullin R.S., Ilyinskaya O.N. (2023). Hybrid organomineral carriers for therapeutic proteins. Bioorganicheskaya khimiya = Bioorganic Chemistry, 49(2), pp. 178-187. (In Russ.) https://doi. org/10.31857/S0132342323020239

14. Zorina S.O., Afanasyeva N. I., Grevtsev V. A., Naumkina N. I., Mikhailov A. A. (2021). Smectite-containing clays of the Middle Eocene Kiev Formation of the Russian Plate and their genesis. Litologiya i poleznyye iskopayemyye = Lithology and Mineral Resources, 2, pp. 146-155. (In Russ.)

15. Zorina S.O. Khabiryanov L.S., Afanasyeva N.I., Sekerina N.V., Petrovsky I.A., Galiullin B.M., Morozov V.P., Yaskin A.A. (2018). Lithostratigraphy, geochemistry and conditions of formation of Upper Cretaceous sediments of the Mezino-Lapshinovka section (east of the Russian Plate). Uchenye Zapiski Kazanskogo Universiteta = Scientific Notes of Kazan University,160(3), pp. 484-499. (In Russ.)

16. Zorina S.O., Afanasyeva N.I., Zhabin A.V. (2012). Traces of pyroclastics in the Santon-Campanian deposits of the Vishnevoye section (Middle Volga region). Litosfera = Lithosphere, 3, pp. 3-13. (In Russ.)

17. Zorina S.O., Nikashin K.I., Sokerin M.Yu. (2020). Geochemical indicators of “camouflaged” pyroclastics in Upper Jurassic-Lower Cretaceous deposits of the East of the Russian Plate. Doklady Rossiyskoy akademii nauk = Reports of the Russian Academy of Sciences, 493(2), pp. 46-50. (In Russ.) https://doi.org/10.31857/S2686739720080228

18. Ilyina O.N. (2023). Development of pavement structures using zeolite from the Tatarsko-Shatrashansky deposit. Vestnik SibADI = SibADI Bulletin, vol. 20(6), pp. 798-807. (In Russ.) https://doi.org/10.26518/2071-7296-2023-20-6-798-807

19. Ilyinskaya O.N., Galeeva A.G., Yakovleva G.Yu., Glukhov M.S., Kolpakov A.I., Lopatin O.N. (2024). Organo-mineral preparation of probiotic bacteria. Voprosy pitaniya = Nutrition Issues, 93(3), pp. 77-78. (In Russ.) https://doi.org/10.33029/0042-8833-2024-93-3s-019

20. Islamova R.R., Yakovleva G. Yu., Tyurin A. N., Ilyinskaya O. N., Lopatin O. N. (2022). Zeolites of the Tatarsko-Shatrashansky deposit as carriers of model albumin for promising adsorption of therapeutic proteins. Zapiski Rossiyskogo mineralogicheskogo obshchestva = Notes of the Russian Mineralogical Society, 151(1), pp. 105-113. (In Russ.) https://doi.org/10.31857/S0869605522010063

21. Itzel-Hernandez G., Hernandez M.A., Portillo R., Petranovskii V.P., Pestryakov A.N., Rubio E. (2018). Hierarchical structure of nanoporeosity of Mexican natural zeolites such as clinoptilolite. Izvestiya Tomskogo politekhnicheskogo universiteta. Inzhiniring georesursov = Bulletin of the Tomsk Polytechnic University. Geo Аssets Engineering, 329(10), pp. 107–117. (In Russ.)

22. Kossovskaya A.G. (1975). Genetic types of zeolites of stratified formations. Litologiya i poleznyye iskopayemyye = Lithology and Minerals, 2, pp. 23-44. (In Russ.)

23. Naumov V.A. (1989). Optical determination of sedimentary rock components. A reference guide. Moscow: Nedra, 349 p. (In Russ.)

24. Nikashin K. I., Zorina S. O. (2021). Volcanogenic material in the Upper Jurassic-Lower Cretaceous deposits of the East of the Russian Plate and its sources. Izvestiya Saratovskogo universiteta = Proceedings of the Saratov University, 21(1). pp. 49-57. (In Russ.) https://doi. org/10.18500/1819-7663-2021-21-1-49-57

25. Pekov I.V., Podlesny A.S. (2004). Mineralogy of the Kukisvumchorr deposit (alkaline pegmatites and hydrothermalites). The Ecost Association. Mineralogical Almanac, issue 7. Moscow: Creative Association Earth, 176 p. (In Russ.)

26. Popova V.I., Kasatkin A.V., Popov V.A., Nikandrov S.N., Makagonov E.P., Kuznetsov A.M., Skoda R. (2020). Zeolite mineralization in pegmatites and late veins of the Vishnevogorsky alkaline carbonatite complex (Southern Urals). Mineralogiya = Mineralogy, 6(1), pp. 3-16. (In Russ.) https://doi.org/10.35597/2313-545X-2020-6-1-1

27. Savko A.D., Sviridov V.A. (2015). Late Cenozoic weathering crust of the Olym−Veduga−Devitsa interfluve (Kursk and Voronezh regions). Vestnik Voronezhskogo gosudarstvennogo universiteta = Bulletin of Voronezh State University, 4, pp. 28-37. (In Russ.)

28. Savchenkov M.F. (2009). Zeolites of Siberia and the Far East: ecological and hygienic aspects. Sibirskiy meditsinskiy zhurnal = Siberian Medical Journal, 2, pp. 15-18. (In Russ.)

29. Tyurin A.N. (2003). Mineralogical and lithological characteristics of zeolite-bearing rocks of the Tatarsko-Shatrashansky deposit. Dissertation for the degree of Candidate of Geological and Mineralogical Sciences. Kazan: Kazan State University, 209 p. (In Russ.)

30. Tyurin A.N., Bakhtin A.I., Gafurov S.Z. (2018). Zeolite-bearing rocks of Tatarstan and their role in the development of the mineral resource base of the republic. Georesursy = Georesources, Special Issue, pp. 2-10. (In Russ.) https://doi. org/10.18599/grs.2018.1

31. Sharafiev D. R., Khatsrinov A. I. (2016). Analysis of consumer properties of natural zeolites in the CIS countries. Vestnik tekhnologicheskogo universiteta = Bulletin of the Technological University. 19(12), pp. 95-98. (In Russ.)

32. Yurkov V.V. (2007). The effect of modification on the electrical conductivity and ion exchange properties of clinoptilolite. Dissertation for the degree of Candidate of Physical and Mathematical Sciences. Blagoveshchensk: Blagoveshchensk State Pedagogical University, 139 p. (In Russ.)

33. Yapaskurt O.V. (2008). Genetic mineralogy and stadial analysis of sedimentary rock and ore formation processes. A study guide. Moscow: ESLAN, 356 p. (In Russ.)

34. Anderle K., Wolzt M., Moser G., Keip B., Peter J., Meisslitzer C., Gouya G., Freissmuth M., Tschegg C. (2022) Safety and efficacy of purified clinoptilolite-tuff treatment in patients with irritable bowel syndrome with diarrhea: Randomized controlled trial. World Journal of Gastroenterology, 28(46), pp. 6573-6588. https://doi. org/10.3748/wjg.v28.i46.6573

35. Attanoos R.L., Churg A., Galateau-Salle F., Gibbs A.R., Roggli V.L. (2018). Malignant mesothelioma and its non-asbestos cause. Archives of Pathology & Laboratory Medicine, 142(6), pp. 753–760. https://doi.org/10.5858/arpa.2017-0365-RA.

36. Berger M.J., Hubbell J.H., Seltzer S.M. et al. (2015). NIST XCO database at MuCalcTool. Text: electronic. XCOM: Photon Cross Sections Database. URL: http://physics.nist.gov/PhysRefData/Xcom/Text/XCOM.html (accessed: 16.08.2024).

37. Ferreia L., Fonseca A.M., Botelho G., Aguiar C.A., Neves I.C. (2012). Antimicrobial activity of faujasite zeolites doped with silver. Microporous Mesoporous Materials, 160, pp. 126–132. https://doi.org/10.1016/j.micromeso.2012.05.006

38. Ilinskaya O., Galeeva A., Glukhov M., Kurdy W., Zelinikhin P., Kolpakov A., Yakovleva G., Lopatin O. (2024). New Design and Characteristics of Probiotics Immobilized on a Clinoptilolite-Containing Tuff. Scientia Pharmaceutica, 92, 46. https://doi.org/10.3390/scipharm92030046

39. Ilinskaya O.N., Galeeva A.G., Kharitonova M.A., A. I. Kolpakova, Glukhov M. S., Lopatin O. N. (2023). Probiotics on a Mineral Zeolite-Containing Carrier. Microbiology, 92 (1), pp. 37–40. https://doi.org/10.1134/S002626172360372X

40. Khojaewa V., Lopatin O., Zelenikhin P., Ilinskaya O. (2019). Zeolites as Carriers of Antitumor Ribonuclease Binase. Frontiers in Pharmacology, 10, 442. https://doi.org/10.3389/fphar.2019.00442

41. Khojaewa V., Zelenikhin P., Ilinskaya O., Lopatin O. (2019). Zeolites as carriers of antitumor ribonuclease binase. Frontiers in Pharmacology,10(5), pp. 442-448. https://doi. org/10.3389/fphar.2019.00442

42. Mastinu A., Kumar A., Maccarinelli G., Bonini S.A., Premoli M., Aria F., Gianocelli A., Memo M. (2019). Zeolite clinoptiolite: therapeutic virtues of an ancient mineral. Molecules, 24(8), 1517. https://doi.org/10.3390/molecules24081517

43. Pavelić K., Hadžija M., Bedrica L., Pavelić J., Ðikić I., Katić M., … Čolić M. (2001). Natural zeolite clinoptilolite: new adjuvant in anticancer therapy. Journal of Molecular Medicine, 78(12), pp. 708–720. https://doi. org/10.1007/s001090000176

44. Pavelic K., Katic M., Sverko V. Marotti T., Bosnjak B., Balog T., Stojkovic R., Radacic M. Poljak-Blazi M. (2002). Immunostimulatory effect of natural clinoptilolite as a possible mechanism of its antimetastatic activity. Journal of Cancer Research and Clinical Oncology, 128(1), pp. 37-44. https://doi. org/10.1007/s00432-001-0301-6

45. Pavelic S.K., Medica J.S., Gumbarevic D., Filoševic A., Pržulj N., Pavelic K. (2018). Critical Review on Zeolite Clinoptilolite Safety and Medical Applications in vivo. Frontiers in Pharmacology, 9, 1350. https://doi.org/10.3389/fphar.2018.01350

46.