Iron-manganese mineralization in Eocene deposits of Parashka skyba (Skybov nappe, Ukrainian Carpathians)

Keywords: morphotype, ore layer, variegated horizon, iron manganese mineralization, Skybov nappe, Ukrainian Carpathians

Abstract

Formulation of the problem. Modern advances in oceanographic studies of sedimentogenesis and orogenesis open up opportunities for in-depth study of rocks by fold-nappe systems, including the Carpathian region.

Review of previous research. On the territory of the Carpathians in flysch complexes researchers have mainly noted the findings of carbonates of manganese and iron nodules.At the same time, flysch complexes contain iron-manganese oxide mineralization.

The purpose of the work was to study the mineral and chemical composition, morphological types of aggregates and the origin of iron-manganese mineralization (IMM) among the Eocene deposits of the Parashka skyba of Skybov nappe in the middle course of the river Opir.

Methods used: Sedimentological, mineralogical, petrogeochemical and X-ray diffractometric analyzes of wall rocks and ore minerals.

Results: The ore mineralization is associated with the Paleocene to Eocene transition strata, which is represented by coarse-grained turbidites and grainites of the Yamna suite and variegated fine- and medium-grained turbidites and hemipelagites of the Manyava suite. IMM are deposited in a main ore bed, ore crusts and scattered in the wall rocks. It is synchronously sedimented with deep-water deposits of the lower bathyal. The оre bed is composited of  concretionary, sinter, brecciated, earthy and sooty aggregates. Concretionary morphotypes have concentric-zonal structure, which is formed by shells with different mineral composition and structural features. Crystalline secretions are observed in the nucleus. The ore substance is represented by X-ray amorphous compounds of iron and manganese hydroxides, among which are minerals of hydrothermal (pyrolusite, psilomelan, todoroquite and bersenite) and hydrogenic (vernadite, buserite) origin. Shells often have columnar, dendrіtic and colomorphic structures typical of hydrothermal formations. Differentiation of mineralization by mineral composition causes significant fluctuations in metal contents in ore aggregates (from 3 to 11.5% of Fe oxides and from 2 to 10% of Mn) and host rocks (from 1.4 to 11.5% of Fe oxides and from 0.12 to 12% Mn). This confirms the endogenous origin of ore-bearing fluids. On the diagram of the ratios of the main components of iron-manganese formations of different zones of modern oceans by E. Bonatti, the geochemical composition of the ore mineralization of the Nad’yamne variegated horizon falls into the fields of both hydrothermal and hydrothermal-hydrogen origin. Mineralogical and geochemical features of ore mineralization indicate that the main source of metals on the seabed were hydrothermal vents. Direct deposition of ore mineral phases and deposition of oxide and hydroxide compounds from metal-enriched bottom waters occurred as a result of reaction of hydrothermal fluids with seawater. The formation and functioning of the hydrothermal system was likely caused by the intensification of tectonic movements of the Laramian phase on Paleocene-Eocene boundary, which  also led to restructuring and deepening of the Carpathian paleobasin. An important role in these processes was played by faults in the flysch foundation, which served as channels for circulation of hot fluids. The source of heat and metals could be deep magma, according to authors.

Scientific novelty. Iron-manganese mineralization in the Eocene rocks of the Nad’yamne variegated horizon was characterized for the first time, IMM morphotypes, structural-textural, mineralogical and geochemical features of ore formations and sedimentation and petrographic features of the content rocks were described. The studied features make it possible to propose a hydrothermal model of mineral formation.

Practical significance. The studied features of IMM correlate well with modern and recent formations of pelagic sedimentation. The presence of iron-manganese mineralization in the Eocene Nad’yamne variegated horizon expands the cognitive aspects of the study of the Outer Carpathian basin of the Tethys Ocean and will contribute to the study of other variegated horizons and their geochemical specialization.

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Author Biographies

Larysa Нeneralova, Ivan Franko National University of Lviv

PhD (Geology), Associate Professor

Vladimir Stepanov, Ivan Franko National University of Lviv

PhD (Geology and Mineralogy), Associate Professor

Leonid Khomyak, Ivan Franko National University of Lviv

PhD (Geology), Associate Professor

Oleksandr Koctyuk, Ivan Franko National University of Lviv

PhD (Geology), Associate Professor

Аnton Heneralov, Ivan Franko National University of Lviv

Student

References

Avdonin V.V., Zhegallo E. A., Sergeeva N. E. (2019). Bacterial nature of oxide iron-manganese ores of the World Ocean. Moscow, GEOS, 280. [in Russian]

Andrieieva-Hryhorovych A. Maslun N., Hnylko S., Hnylko O. (2014). On the age and conditions of sedimentation of horizons of variegated argillites in the Paleocene-Eocene sediments of the Ukrainian Carpathians. In: Problems of geology of the Phanerozoic of Ukraine: materials V Scientific conference (October 8–14, 2014). Lviv, Ivan Franko Lviv National University, 3–6. [in Ukrainian]

Anykeeva L. Y., Kazakova V. E., Gavrilenko G. M., Rashydov V. A.(2008). Iron-manganese cortical formations of the Western Pacific transition zone. Vestnyk Kraunts. Earth Sciences, 1(11), 10–31. [in Russian]

Astakhova N. V. (2007). Autogenic formations in the Late Cenozoic sediments of the peripheral seas of East Asia.Vladyvostok, Dalnauka, 244. [in Russian]

Afanasyeva Y. M. (1983). Lithogenesis and geochemistry of the flysch formation of the northern slope of the Soviet Carpathians. Kiyv, Nauk. dumka, 183. [in Russian]

Bazylevskaya E. S. (2007). Research of iron-manganese ores of the ocean. Moscow, Nauka,189. [in Russian]

Bilonizhka P. Matkovskyi O. (2010). Smectites in the geological formations of the Ukrainian Carpathians. Miner-al. coll., 2, 3–14. [in Ukrainian]

Bobrovnyk D. P., Petrunyak M. D., Khmelevskyi V. A. (1971). On manganese ore occurrences in the Upper Eocene sediments of the Pokut Carpathians. In: Materials on mineralogy, petrography and geochemistry of sedimentary rocks and ores. Kiyv, Nauk. dumka, 1. 56–67. [in Russian]

Hlushko V. V., Shlapinskyi V. Ye., Kulchytskyi Ya. O., etc. (1994). Study of the geological structure and prospects of oil and gas bearing capacity of the joint zone of Duklyansky, Chornohorsky and Krosnensky cover of the Ukraini-an Carpathians: report on the topic. Lviv, Thematic Party, 136. (funds of SE “Zakhidukrheolohiia”). [in Ukraini-an]

Haievska Yu. (2009). On the mineralogy of the clay fraction of terrigenous rocks of the Eocene Skibova zone of the Ukrainian Carpathians. Mineral. coll., 59, 4, 105–115. [in Ukrainian]

Heneralova L., Stepanov V. (2015). Mineralogical and petrochemical features of rocks of Eocene variegated hori-zons of the Ukrainian Carpathians (on the example of Sushmanets and Manyava suites). Visnyk Lviv. un-tu. Ser. geol., 29, 107–116. [in Ukrainian]

Heneralova L. V., Stepanov V. B. (2018). Iron-manganese mineralization of the Nad’yamne variegated horizon (Skybov nappe, Ukrainian Carpathians). V International Geological Forum “Current issues and prospects for de-velopment of Geology: Science and Production”: materials of the forum, June 18–23, 2018, Odessa. Kiyv : UkrDHRI, 35–38. [in Ukrainian]

Hnylko S., Hnylko О. (2010). Early Eocene agglutinated foraminifera and sedimentological features of flysch for-mation of Monastyretsky and Skibov nappes of the Ukrainian Carpathians. Geology and geochemistry of combus-tible minerals, 1(150), 43–59. [in Ukrainian]

Investigation of manganese and iron-manganese mineralization in different natural environments by scanning electron microscopy. (2012). In: ed. G.N. Baturyn. Moscow, Eslan, 472 p. [in Russian]

Kulish L. I., Kovalchuk M. S., Afanasieva I. M. (2006). Manganese in sedimentary and volcanic-sedimentary com-plexes of the Ukrainian Carpathians In: Lithology and minerals: collection. Science. works of IGN NAS of Ukraine and IGNS NAS and MOE of Ukraine, dedicated. in memory of L.I. Kulish. Nat. acad. Sciences of Ukraine, Institute of Geological Sciences. Kiyv, LOHOS, 37–46. [in Ukrainian]

Senkovskyi, Yu. M., Hryhorchuk, K. H., Koltun, Yu. V., Hnidets V. P. (2018). Lithogenesis of oceanic sedimentary complexes TETIS: Carpathian-Black Sea segment. NAS of Ukraine, Institute of Geology and Geochemistry of Com-bustibles fossil. Kyiv, Naukova dumka, 158 [in Ukrainian]

Lisitsyn A.P. (1991). Processes of terrigenous sedimentation in the seas and oceans. Moscow, Nauka, 271. [in Rus-sian]

Maslov A. V. Krupenyn M. T., Petrov H. A. etc. (2007). Some geochemical features and conditions of formation of fine-grained terrigenous rocks of the Silver and Sylvits series of the Middle Urals. Lithosphere, 2, 3–28. [in Rus-sian]

Murdmaa Y. O. (1987). Facies of the oceans. Moscow, Nauka, 303. [in Russian]

Pylypchuk A. S. (1972). Lithological features and conditions of formation of multicolored Paleogene sediments of the Skibova zone of the Carpathians. In: New data on the geology and oil and gas potential of the USSR. Lviv, Lviv University Press. 6, 101–110. [in Russian]

Pylypchuk A. S., Vul A. S. (1981). Paleocene-Eocene flysch of the northern slope of the Ukrainian Carpathians - deposits of ancient deep seawater cones of removal. In : Geology of oil and gas reservoirs. Moscow, Nauka, 33–42. [in Russian]

Smirnov B. (2004). Geochemistry of trace elements in the rocks of the Ukrainian Carpathians.In : Carpathian Oil and Gas Province, Rozd. 9. NAS of Ukraine, Institute of Geology and Geochemistry of Combustible Minerals, Na-tional Joint Stock Company “Naftogaz of Ukraine”. Lviv–Kyiv, Ukrainian Publishing Center LLC, 284–306. [in Ukrainian]

Yudovych Ya. E. Ketrys M. P. (2000). Fundamentals of lithochemistry. Sankt-Peterburh, Nauka, 479. [in Russian]

Bąk K. (2007). Organic-rich and manganese sedimentation during the Cenomanian—Turonian boundary event in the Outer Carpathian Basin; a new record from the Skole Nappe, Poland, and a review from other tectonic units. Palaeogeography, Palaeoclimatology, Palaeoecology, 256(1-2), 21–46. https://doi.org/10.1016/j.palaeo.2007.09.001

Bonatti E. (1981). Metal deposits in the oceanic lithosphere. In, The Sea, 7, The oceanic lithosphere (Emiliane C., ed). New York., Willey, 639–686.

Bonatti E., Kraemer T., Rydell H. (1972). Classification and genesis of submarine iron manganese deposits. Іn Fer-romanganese Deposits on the Ocean Floor (Horn D.R., ed.). Washington, National Science Foundation, 149–166.

Wang G., Jansa L., Chu F., Zou C., Sun G. (2015). Composition and origin of ferromanganese crusts from equatori-al western Pacific seamounts. China. Ocean Univ. China. 14 (2).217–227. https://doi.org/10.1007/s11802-015-2391-9

Konstantinova N,. Cherkashov F.G., Hein J. R., Mirão J., Dias L., Madureira P., Kuznetsov V., Maksimov F. (2017).Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean. Ore Geology Reviews. 87. 88–99. https://doi.org/10.1016/j.oregeorev.2016.09.011

Marin E, González F.J., Lunar R., Reyes J., Medialdea T., Castillo-Carrión M., Bellido E., Somoza L. (2018). High-Resolution Analysis of Critical Minerals and Elements in Fe–Mn Crusts from the Canary Island Seamount Prov-ince (Atlantic Ocean). Minerals. 8, 285. https://doi.org/10.3390/min8070285

Liu K. Wang Z. (2021). Geochemistry of rare earth elements and yttrium in ferromanganese crusts from Kocebu Guyot in the Western Pacific. Marine Geology & Quaternary Geology. 2021.41(1), 210–222. https://doi.org/10.16562/j.cnki.0256-1492.2020092101

Wegorzewski A. V., Kuhn T., Dohrmann R., Wirth R., Grangeon S. (2015). Mineralogical characterization of indi-vidual growth structures of Mn-nodules with different Ni+Cu content from the central Pacific Ocean. American Mineralogist. 100 (11–12), 2497–2508. https://doi.org/10.2138/am-2015-5122

Scopelliti G., Russo V.(2021). Petrographic and geochemical characterization of the Middle‒Upper Jurassic Fe–Mn crusts and mineralizations from Monte Inici (north western Sicily): genetic implications. International Journal of Earth Sciences, 110, 559 – 582. https://doi.org/10.1007/s00531-020-01971-0

Marino E., González F.J., Somoza L., Lunar R., Ortega L., Vázquez J. T., Reyes J., Bellido E. (2017). Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic.) Ore Geol., Rev. 87, 41–61. https://doi.org/10.1016/j.oregeorev-2016.10.005

Chen S., Yin X.B., Wang X.Y., Huang X., Ma Y., Guo K., Zeng Z.G.( 2018). The geochemistry and formation of ferro-manganese oxides on the eastern flank of the Gagua Ridge. Ore Geol., Rev. 95, 118–130. https://doi.org/10.1016/j.oregeorev.2018.02.026

Zhong Y., Liu Q., Chen Z., González F. J., Hein J. R., Zhang J., Zhong L.(2019). Tectonic and paleoceanographic conditions during the formation of ferromanganese nodules from the northern South China Sea based on the high-resolution geochemistry, mineralogy and isotopes. Mar. Geol., 410, 146–163. https://doi.org/10.1016/j.margeo.2018.12.006

Published
2022-06-01
Cited
How to Cite
НeneralovaL., Stepanov, V., Khomyak, L., Koctyuk, O., & HeneralovА. (2022). Iron-manganese mineralization in Eocene deposits of Parashka skyba (Skybov nappe, Ukrainian Carpathians). Visnyk of V. N. Karazin Kharkiv National University, Series "Geology. Geography. Ecology", (56), 49-66. https://doi.org/10.26565/2410-7360-2022-56-03