Chemical reactions and conditions of mineral formation at tailings storage facilities of the Russian Far East

Cassiterite-sulfide and polymetallic deposits of the Far Eastern Region (FER) were mined by both openpit and underground methods. This resulted in the emerging numerous mine workings and tailings storage facilities (TSFs) (abandoned without reclamation in latest decades) and the formation of mining technogenic mineralogical systems. Sulfide component of minerals in the mining technogenic system is subjected to hypergenic and technogenic processes (oxidation and hydrolysis reactions). As a result, highly concentrated technogenic solutions are formed, from which minerals of various classes precipitate. In this connection the purpose of this study was formulated as follows: to show the possibility of crystallization of technogenic minerals from micropore technogenic solutions. In achieving this goal the following tasks were solved: to demonstrate the possible reactions of oxidation and hydrolysis of technogenic minerals at the tailings storage facilities; to identify Eh-pH parameters of their precipitation from highly concentrated solutions; to determine their possible associations. The studies involved field observations and computations with the use of “Selector” software package. The study findings allow demonstrating possible chemical reactions and physico-chemical conditions of mineral formation for the following elements: Fe, Cu, Pb, Zn, Sb, Mg, Al, and Ca, including the following classes of minerals: oxides and hydroxides, sulfates, carbonates, arsenates and silicates. The paper presented for the first time the crystallization reactions of secondary minerals (37 ones) and their physico-chemical conditions. It was found that secondary minerals: jarosite, pitticite, siderite, tenorite, poznyakite, antlerite and ktenasite crystallize in the interval of positive temperatures, while scorodite, chalcantite, broshantite, cerussite, starkeyite, epsomite and rostite originate in cryogenic conditions (below 0 ^oC). All other minerals, the possibility of precipitation of which was shown in the paper, crystallized in the whole considered temperature interval, from −25 ^oС to +45 ^oС. Field studies and modeling data on formation of technogenic waters (solutions) and crystallization of secondary minerals on the surface of and inside tailings at the tailings storage facilities of the Far East showed high intensity of technogenic processes. Since the tailings storage facilities were not reclaimed, the process of environmental pollution, including the hydrosphere, would last for many decades.

1. Bulavko N. V. Mineralogy of skarn deposits of the Dalnegorsk ore field (Primorye). Monograph. Vladivostok: Far Eastern Book Publisher; 2000. 219 p. (In Russ.)

2. Zvereva V. P. Ecological impacts of hypergene processes at tin the deposits of the Far East. Monograph. Vladivostok: Dalnauka; 2008. 165 p. (In Russ.).

3. Križáni I., Andráš P., Šlesárová A. Percolation modelling of the dump and settlimg pit sediment at the Banská Štiavnbica ore-field (Western Carpathians, Slovakia). Carpathian Journal of Earth and Environmental Sciences. 2009; 4(1):109–125.

4. Schwartz M. O. Numerical modelling of groundwater vulnerability: The example Namibia. Environmental Geology. 2006;50(2):237–249. https://doi.org/10.1007/s00254-006-0204-6

5. Fernandes H. M., Franklin M. R. Assessment of acid rock drainage pollutants release in the uranium mining site of Pocos de Caldas-Brazil. Journal of Environmental Radioactivity. 2001;54(1):5–25. https://doi.org/10.1016/s0265-931x(00)00163-6

6. Aryafar A., Ardejani F. D. Verification of numerical modeling results using analytical solution for oxygen diffusion process in sulfide waste dump. In: 4th WSEAS/IASME International Conference on Dynamical Systems and Control. Abstracts. Athens: World Scientific and Engineering ACAD and SOC; 2008. P. 25–29.

7. Puura E., I. Neretnieks I., Kirsimae K. Atmospheric oxidation of the pyrite waste rock in Maardu, Estonia. 1 field study and modeling. Environmental Geology. 1999;39:1–19. https://doi.org/10.1007/s002540050432

8. Fernandes H. M., Franklin M. R. Assessment of acid rock drainage pollutants release in the uranium mining site of Pocos de Caldas-Brazil. Journal of Environmental Radioactivity. 2001;54(1):5–25. https://doi.org/10.1016/s0265-931x(00)00163-6

9. Wunderly M. D., Blowes D. W., Frind E. O., Ptacek C. J. Sulfide mineral oxidation and subsequent reactive transport of oxidation products in mine tailings impoundments: A numerical model. Water Resources Research. 1996;32(10):3173–3187. https://doi.org/10.1029/96WR02105

10. Chudnenko K. V. Thermodynamic modeling in geochemistry: theory, algorithms, software, and applications. Monograph. Novosibirsk: Geo Publ.; 2010. 287 p. (In Russ.)

11. Helgeson H. C., Kirkham D. H., Flowers G. C. Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600°C and 5 Kb. American Journal of Science. 1981;281(10):1249–1516. https://doi.org/10.2475/ajs.281.10.1249

12. Tanger J. C., Helgeson H. C. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Revised equations of state for the standard partial molal properties of ions and electrolytes. American Journal of Science. 1988;288(1):19–98. https://doi.org/10.2475/ajs.288.1.19

13. Karpov I. K., Kiselev A. I., Letnikov F. A. Computer modeling of natural mineral formation. Monograph. Мoscow: Nedra Publ.; 1976. 255 p. (In Russ.)

14. Johnson J. V., Oelkers E. H., Helgeson H. C. SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0–1000 °C. Computers & Geosciences. 1992; 18(7): 899–947. https://doi.org/10.1016/0098-3004(92)90029-Q

15. Kulik D. I., Dmitrieva S. V., Chudnenko K. V. et al. User’s manual for Selector-A. Monograph. Brooklyn-Kiev; 1997. 270 p.

16. Eremin O. V. Calculation of standard Gibbs potentials for complex sulfates. In: Mineralogy and geochemistry of the landscape of mining areas. Recent mineral formation: Proceedings of the II All-Russian Symposium with international participation and VIII All-Russian readings in memory of Academician A.E. Fersman. Book of abstracts. Chita:Express Publ.; 2008. Pp. 98–99 (In Russ.)

17. Yeremin O. V., Vinnichenko S. V., Yurgenson G. A. Estimation of standard Gibbs potentials of copper sulfates by means of linear programming techniques. Vestnik Otdeleniya nauk o Zemle RAN. 2006;(1):19–20. (In Russ.)

18. Savchenko A. V. Physico-chemical modeling of the behavior of minor elements on some geochemical barriers. [PhD thesis in Chemistry]. Vladivostok: 2007; 193 p. (In Russ.)

19. Charykova M. V., Krivovichev V. G., Depmeier B. Thermodynamic of arsenates, selenites and sulfates in the weathering zone of sulfide ores. I. Thermodynamic constants at standard conditions. Zapiski Rossiyskogo Mineralogicheskogo Obshchestva / Proceedings of the Russian Mineralogical Society. 2009;138(6):105–117.

20. Yeriomin O. V. Calculation of standard thermodynamic potentials for Na-zeolites with the use of linear programming problems. International Journal of Geosciences. 2011;2(3):227-230. https://doi.org/10.4236/ijg.2011.23024

21. Horn R. Marine chemistry. Monograph. Мoscow: Mir Publ., 1972, 398 p. (In Russ.)

22. Karpov I. K. Computer physico-chemical modeling in geochemistry. Monograph. Novosibirsk: Nauka Publ.; 1981. 247 p. (In Russ.)

23. Zvereva V. P., Kostina A. M., Lysenko A. I. Origin of hypergeneand technogene minerals in mining technogene systems (a case study of the Dalnegorsk region, Primorye). Zapiski Rossiyskogo Mineralogicheskogo Obshchestva = Proceedings of the Russian Mineralogical Society. 2019;148(2):50–60. https://doi.org/10.30695/zrmo/2019.1482.03

24. Zvereva V., Frolov K. Komsomol’sk Tin Ore District Mining Industrial System and Parameters of Hypergene and Technogenic Mineral Formation Therein (Far East of Russia). Russian Journal of General Chemistry. 2020;90:2552–2562. https://doi.org/10.1134/S1070363220130046

25. Zvereva V., Lysenko A., Frolov K. Modern minerals formation genesis in kavalerovsky tin-ore district technogenic system (Primorsky Krai). Minerals. 2020;10(2):91. https://doi.org/10.3390/min10020091

26. Zvereva V. P., Lysenko A. I. Chemical reactions and conditions of crystallization of man-generic minerals from miner water at deposits of the Far East. Journal of Ecological Chemistry. 2021;30(3):159–164. (In Russ.)

27. Zvereva V. P., Krupskaya L. T. Anthropogenic waters in the Komsomolsk, Kavalerovskii, and Dalnegorsk mining areas of the Far East and their impact on the hydrosphere. Russian Journal of General Chemistry. 2012;82:2244–2252. https://doi.org/10.1134/S1070363212130105

28. Zvereva V. P. Impact of technogenic wastewaters of Kavalerovskii and Dalnegorskii mining districts on the hydrosphere of Primorsky Krai. Russian Journal of General Chemistry. 2019;89(13):2808–2817. https://doi.org/10.1134/S1070363219130115

29. Lazarev N. V., Gadaskina I. D. (eds.). Hazardous Substances in Industry. Handbook for chemists, engineers and doctors]. 7th edition, amended. In three volumes. Volume III: Inorganic and organometallic compounds. Leningrad: Khimiya Publ.; 1977. Pp. 332–333. (In Russ.)

30. Filov V. A. (ed.). Harmful chemical substances. Inorganic compounds of V-VIII groups. Handbook. Leningrad: Khimiya Publ.; 1989. Pp. 250–255. (In Russ.)

31. Zvereva V. P., Krupskaya L. T., Malyuk Ya. N. The influence of Karamkenskoe deposit tailing dump on the region hydrosphere and the dump recultivation (Magadan Region). Russian Journal of General Chemistry. 2013;83:2694–2700. https://doi.org/10.1134/S107036321313015X