Geochemistry of fluorine in halo waters of ore fields of the southeastern part of the Dnipro-Donetsk avlakogen
Abstract
The geochemical features of fluorine and its possible sources in the waters of the hydrothermal ore fields of the Dnipro-Donetsk avlakogen (DDA) are considered. It was established that the formation of anomalies occurs due to the interaction of infiltration waters of the zone of free water exchange and waters of deep formation, which are unloaded along the zones of deep faults. It is substantiated that the water migration of fluorine is determined by the geochemical type of groundwater, the degree of its mineralization, acid-base (pH) and oxidation-reduction (Eh) potentials, the presence of complex-forming elements with which fluorine forms mobile complex compounds, etc.
Formulation of the problem. Fluorine is a typomorphic chemical element that is widely present in groundwater. It forms large-scale, contrasting hydrogeochemical anomalies in various types of hydrothermal ore fields, which are controlled by zones of deep faults - fluorite, mercury, polymetallic, and others.
Presenting main material. Anomalies of the element are also formed in those fault zones, where the processes of modern heat and mass transfer are observed, manifested in the upward discharge of endogenous fluids against the background of increased intensity of the geothermal field. This indicates the probable arrival of fluorine in endogenous fluid flows, which are mixed with formation waters during their upward migration. The most contrasting aureoles of fluorine scattering are established in the zone of hypergenic weathering of fluorite of the Pokrovo-Kyreevsky deposit and in the aureole waters of the Mykytiv mercury ore field, in the rocks of which fluorite mineralization is absent. In them, fluorine, together with other trace elements, forms multicomponent anomalies and is part of the hydrogeochemical association of elements-indicators of hidden mercury mineralization - Hg, As, B, F, (Sb).
Conclusions. 1. Geochemical features of fluorine in the processes of hydrothermal mineralization are caused by both hypogenic and hypergenic factors of its migration and concentration in the hydrolithosphere of the Dnipro-Donetsk avlakogen.
2. The high migration activity of fluorine in fluid systems and, in particular, in groundwater, is determined by numerous mobile forms of the element that exist under different geochemical conditions - in the form of gas, simple anions, complex compounds with metals, silicon, manganese, boron and other chemical elements Fluorine migrates best in alkaline sodium bicarbonate and sodium chloride waters, in which Сl–, Na+ and ОН– ions not only act as a complexing agent, but also provide high ionic strength of aqueous solutions.
3. The high content of fluorine in the waters of the Pokrovo-Kyreivsky fluorite deposit is provided by two different geochemical processes: a) hypergenic physicochemical destruction of CaF2 by gravitational infiltration waters of the zone of free water exchange; b) the influx of fluorine into deep formation waters together with endogenous fluids that are discharged along fault structures at the post-hydrothermal stage of their tectonic activation.
4. Abnormally high concentrations of fluorine in the hydrothermal mercury ore fields of the Mykytivskyi and Druzhkivsko-Kostiantynivskyi deposits, in the rocks of which there is practically no fluorite mineralization, are due to the influx of the element into the mineralization zones from deep fluid flows and underground waters of deep horizons.
5. The main natural sources of fluorine in the waters of hydrothermal deposits of the region are: a) products of hypergenic weathering of hydrothermal mineralization of fluorite; b) flows of endogenous postheterothermal fluids; c) pore solutions of sedimentary rocks of marine origin.
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References
Gavrilenko E.S. (1975). Hydrogeology of the tectonosphere. K., Nauk. Dumka, 195 [in Russian].
Goryainov S.V. (2013). Cenozoic tectonic movements of Eastern Europe. Geology and minerals of the world ocean. 3, 55–56 [in Russian].
Goryainov S.V. (2022). Alpine tectonic movements and salt tectonics of Eastern Ukraine. Visnyk of V. N. Karazin Kharkiv National University, series "Geology. Geography. Ecology", (56), 67-75 [in Ukrainian]. https://doi.org/10.26565/2410-7360-2022-56-04
Zhovinsky E.Ya. (1979). Geochemistry of fluorine in sedimentary formations of the southwest of the East European Platform. Kyiv, Nauk. Dumka, 200 [in Russian].
Zhovynskyi E.Ya., Kryuchenko N.O. (2020). Podilsk fluorite zone (middle Transnistria). K., FOP Kravchenko Y.O., 212 [in Ukrainian].
Zhulid V.A. (1978). Phases of tectogenesis and mineralization of the Donbass according to geological and geo-chemical (isotope) data. Geology and geochemistry of ore occurrences of the Donbass and the northern slope of the Ukrainian Shield. K., Naukova Dumka, 81–87 [in Russian].
Suyarko V.G. (1985). Guidelines for the application of the hydrogeochemical method of prospecting for hidden mineralization in the Donbass and the Dnieper-Donetsk depression. Simferopol, MG Ukrainian SSR, 92 [in Rus-sian].
Panov B.S. (1981). Genetic features and search criteria for fluorite mineralization of the Donbass and the Sea of Azov. Fluorite of Ukraine (search criteria). K., Nauk. Dumka, 20–41 [in Russian].
Panov B.S., Suyarko V.G. (1990). Conditions of formation and weathering features of hidden fluorite mineralization of the Pokrovo-Kireevskoye deposit in the Southern Donbass. Geology and exploration, 5, 70–77 [in Russian].
Serdіukova O.O. (2012). Geochemistry of fluorine in underground waters of the Donetsk folded structure. Visnyk of V. N. Karazin Kharkiv National University, series "Geology. Geography. Ecology", 1033(37), 104–107 [in Ukraini-an]
Serdіukova O.O. (2013). Hydrogeochemical features of fluorine in the zone of hypergenesis of Donbas and some aspects of its influence on the human body. Visnyk of V. N. Karazin Kharkiv National University, series "Geology. Geography. Ecology", 1084(39), 243–246 [in Ukrainian].
Suyarko V.G., Otreshko A.I. (1988). Hydrogeochemical zoning as a criterion for local forecasting of fluorite miner-alization in the Southern Donbas. Geological Journal, 1, 46–49 [in Russian].
Suyarko V.G. (1988). Geochemical features of underground waters of Donbass. Geochemistry, 5, 738–747 [in Rus-sian].
Suyarko V.G. (2006). Groundwater geochemistry of the eastern part of the Dnieper-Donetsk aulacogen. Kharkiv, V.N. Karazin KhNU, 225 [in Russian].
Suyarko V.G., Ishchenko L.V., Serdіukova O.O. (2017). Geochemical features of halo waters of the main types of hydrothermal mineralization of the Donetsk folded structure. Exploration and environmental geochemistry, 1, 44–51 [in Ukrainian].
Shumlyansky V.A. (1983). Cimmerian metallogenic epoch on the territory of Ukraine. K., Naukova Dumka, 220 [in Russian].
Barnes H.L. (1997). Solubilites of the ore minerals in Geochemistry of Hydrothermal Ore Deposits. 3 th. (ed. H.L. Barnes). New York, Wiley–Interscience, 405.
Bartaschuk O., Suyarko V. (2021). Geodynamics of formation of the transition zone between the Dniper-Donets basin and the Donbas foldbelt. Geodynamics, 1 (30), 25–35. https://doi.org/10.23939/jgd2021.02.053
Bertaux J. L., Vandaele A.C., Korabbev O. et al. (2007). A warm layer in Uenus cryosphere and high–altitude measurements of HF, HCL, H2O and HDO. Nature, 450, 646–649. https://doi.org/10.1038/nature05974
Castorina F., Masi U., Gorello I. (2020). Rare earth element and Sr–Nd isotopic evidence for the origin of fluorite from the Silins vein deposit (southestern Sardinia, Italy). Journal of Geochemical Exploration, 215, 535–552. https://doi.org/10.1016/j.apgeochem.2008.04.005
Gonzalez-Partida E., Camprubi A., Carillo-Chavez A. et al. (2019). Giant Fluorite Mineralization in Central Mexi-co by Means of Exceptionally Low, Salinity Fluids: An Unusual Style among MVT Deposits. Minerals, 9 (3),142–151. https://doi.org/10.3390/min9010035
Jardley B.W.D., Banks O.A., Munz L.A. (1992). Halogen composition of fluid inclusion as tracers of crustal fluid behavior. Water. Rock interaction, Kharaka and Maest (edc.), 1137–1140.
Rashid A., Khan S., Zahir S., Jehan S. (2018). Fluoride prevalence in groundwater around a fluorite mining area in the flood plain of the River, Swat, Pakistan. Science of The Total Envizonment, 635, 203-215. https://doi.org/10.1016/j.scitotenv.2018.04.064
Sasmaz A., Sagiroglu A., Javuz F., Akgul B. (2005). Geochemical patterns of the Akdagmadeni (Jozgat, Central Turkey) fluorite deposits and implications. Journal of Earth Sciences. 24 (4), 469-479. https://doi.org/10.1016/j.jseaes.2004.01.003
Sasmaz A., Kryuchenko N., Zhovinsky E. et al. (2018). Major, trace and rare earth elements (REE) geochemistry of different colored fluorites in the Bobrynets region, Ukraine. Ore Geology Reviews, 102, 338–350. https://doi.org/10.1016/j.oregeorev.2018.09.014
Stober I., Zhu J., Bucher K. (2002). Water–Rock Reactions in a Barite–Fluorite Underground Mine, Black Forest (Germany). Water Science and Technology Library, book series (Germany), 40, 171–187.
Suyarko V.G., Ishchenko L.V., Gavrilyuk O.V. (2018). Fluid regime and ore water of bitumo-hudrothermal mineral associations in the conditions of Western Donetsk graben. Visnyk of V. N. Karazin Kharkiv National University, se-ries «Geology. Geography, Ecology», 48, 113–123. https://doi.org/10.26565/2410-7360-2018-48-09
Williams-Jones A.E., Samson I.M., Olivo G. (2000). The genesis of Hydrothermal Fluorite – REE Deposits in the Gallinas Mountains, New Mexico. Economic Geology, 95 (2), 327–341. https://doi.org/10.2113/gsecongeo.95.2.327
Zandg Z., Li G., Su X., Zhuang X. et al. (2021). Geochemical controls on the enrichment of fluorite in the mine wa-ter of the Shendong mining area China. Chemosphere, 284, 131388. https://doi.org/10.1016/j.chemosphere.2021.131388
