Abstract
Understanding and deciphering processes proceeding near the surface are among the urgent tasks of contemporary mineralogy and geochemistry, which are especially important for resolving ecological challenges and developing principles of rational environmental management. The paper presents systematized data published on thermodynamics of minerals (arsenates, sulfates, selenites, and selenates), which are formed in the weathering zone of sulfide ores, and determines approaches to quantitative physicochemical modeling of their formation conditions. Diagrams of phase and chemical equilibria (Eh-pH, diagrams of solubility) of the subsystems of the model system Fe-Cu-Zn-Pb-Co-Ni-As-Se-S-H2O (Fe2+, Fe3+, Cu2+, Zn2+, Pb2+, Ni2+, Co2+, H+//SeO 2−3 , SeO 2−4 , AsO 3−4 , SO 2−4 , OH−-H2O) are used as a thermodynamic basis for modeling mineral-forming processes in the weathering zone of ore deposits. Seventy-two arsenates, about 70 sulfates, and 7 selenites and selenates have been identified in the framework of this system. The available published values of standard thermodynamic functions of the formation of minerals and chemical compounds are given, as well as the Pitzer equation parameters to describe the sulfate systems, which are substantially specific due to the high solubility of their components.
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Baes, C.F., Reardon, E.J., and Moyer, B.A., Ion Interaction Model Applied to Equilibria in the CuSO4-H2SO4-H2O System, J. Phys. Chem., 1993, vol. 97, pp. 12343–12348.
Charykova, M.V., Krivovichev, V.G., and Depmeier, W., Selenites and Sulfates: the System Ni2+, Co2+ // SeO 2−2 , SO 2−4 -H2O—Thermodynamic Analysis and Geological Applications, Zap. Ross. Mineral-O-va, 2007, Spec. Issue, Crystallogenesis and Mineralogy, no. 7, pp. 246–266.
Charykova, M.V., Krivovichev, V.G., and Depmeier, W., Thermodynamics of Arsenates, Selenites, and Sulfates in Oxidation zones of Sulfide Ores. II. The Systems M1, M2 // SO 2−4 -H2O (M1, M2 = Fe2+, Fe3+, Cu2+, Zn2+, Pb2+, Ni2+, Co2+, H+) at 25°C, Zap. Ross. Mineral-O-va, 2010, vol. 138, no. 1, pp. 3–18 [Geol. Ore Deposits (Engl. Transl.), 2010, Vol. 52 (Spec. Issue 8, Zapiski Russian Mineral. Soc.), pp. 771–780.
Christov, C., Pitzer Ion-Interaction Parameters for Fe(II) and Fe(III) in the Quinary {Na + K + Mg + Cl + SO4 + H2O} System at 298.15 K, J. Chem. Thermodyn., 2004, vol. 36, pp. 223–235.
Chukhlantsev, V.G., Splubility Product of Arsenate Series, Zhurn. Analit. Khimii, 1956, vol. 11, pp. 529–535.
Chukhlantsev, V.G. and Tomashevsky, G.P., Solubility of Selenites of Some Metals, Zh. Anal. Khim., 1957, vol. 12, pp. 296–301.
Davis, A., Ruby, M.V., Bloom, M., Schoof, R., et al., Mineralogic Constraints on the Bioavailability of Arsenic in Smelter-Impacted Soils, Environ. Sci. Technol., 1996, vol. 30, pp. 392–399.
Downes, C.J. and Pitzer, R.S., Thermodynamics of Electrolytes. Binary Mixtures Formed from Aqueous NaCl, Na2SO4, CuCl2, and CuSO4 at 25°C, J. Solution Chem., 1976, vol. 5, pp. 389–398.
Drouet, C. and Navrotsky, A., Synthesis, Characterization, and Thermochemistry of K-Na-H3O Jarosites, Geochim. Cosmochim. Acta, 2003, vol. 67, pp. 2063–2076.
Essington, M.E., Estimation of the Standard Free Energy of Formation of Metal Arsenates, Selenates and Selenites, Soil Sci. Soc. Am. J., 1988, vol. 52, pp. 1574–1579.
Filippov, V.K. and Yakovleva, S.I., Application of Pitzer Method to Calculation of Thermodynamic Functions of the System Me2SO4-CuSO4-H2O (Me = Li, Na, K, Rb, Cs), in Khimiya i termodinamika rastvorov (Chemistry and Thermodynamic of Solutions), Leningrad: Leningrad State Univ., 1982, issue 5, pp. 3–31.
Guerra, E. and Bestetti, M., Physicochemical Properties of ZnSO4-H2SO4-H2O Electrolytes of Relevance to Zinc Electrowinning, J. Chem. Eng. Data, 2006, vol. 51, pp. 1491–1497.
Hemingway, B.S., Seal, R.R.., and Chou, I.-M., Thermodynamic Data for Modeling Acid Mine Drainage Problems: Compilation and Estimation of Data for Selected Soluble Iron-Sulfate Minerals, USGS Open-File Report, 2002, no. 02-161.
Khodakovsky, I.L., Osadchii, E.G., Devina, O.A., Sergeeva, E.I., Shikina, N.D., Ogorodova, L.P., Polotnyanko, N.A., Echmaeva, E.A., Koroleva, O.N., Kristavchuk, A.V., and Viktorov, V.N., Coordination and Form of Presentation of Experimental Thermodynamic Information in the Joint Database, Elektronnyi Nauchno-Informatsionnyi Zhurnal Vestnik Otdeleniya Nauk o Zemle RAN, 2008, no. 1 (26).
Kogan, V.B., Ogorodnikov, S.K., and Kafarov, V.V., Spravochnik po rastvorimosti. Troinye i mnogokomponentnye sistemy, obrazovannye neorganicheskimi veshchestvami (Handbook on Solubility. Ternary and Multicomponent Systems Formed by Inorganic Compounds), Leningrad: Nauka, 1970.
Krivovichev, V.G., Mineralogicheskii slovar (Mineralogical Glossary), St. Petersburg: St. Petersburg State Univ., 2009.
Krivovichev, V.G. and Charykova, M.V., Termodinamika mineral’nykh ravnovesii v sistemakh s toksichnymi komponentami. 1. Selen (Thermodynamic of Mineral Equilibria in Systems with Toxic Components. 1. Selenium), St. Petersburg: SOLO, 2006.
Krivovichev, V.G., Charykova, M.V., and Depmeier, W., Termodinamika mineral’nykh ravnovesii v sistemakh s toksichnymi komponentami. 2. Mysh’yak (Thermodynamic of Mineral Equilibria in Systems with Toxic Components. 2. Arsenic), St. Petersburg: SOLO, 2007.
Krivovichev, V.G. and Depmeier, W., Selenites and Selenates: Systems Se-S-H2O, Pb-Se-S-H2O, U-Se-HO and U-Se-I-H2O—Thermodynamic Analysis and Geological Applications, Zap. Ross. Mineral. O-va, 2005, vol. 134, no. 4, pp. 1–14.
Kumok, V.N., Kuleshova, O.M., and Karabin, L.A., Proizvedeniya rastvorimosti (Solubility Products), Novosibirsk: Nauka, 1983.
Langmuir, D., Mahoney, J., and Rowson, J., Solubility Products of Amorphous Ferric Arsenate and Crystalline Scorodite (FeAsO4 · 2H2O) and Their Application to Arsenic Behavior in Buried Mine Tailings, Geochim. Cosmochim. Acta, 2006, vol. 70, pp. 2942–2956.
Magalhaes, M.K.F., Pedrosa De Jesus, J.D., and Williams P.A. The Chemistry of Formation of Some Secondary Arsenate Minerals of Cu(II), Zn(II) and Pb(II), Mineral. Mag., 1988, vol. 52, pp. 679–690.
Majzlan, J., Navrotsky, A., McCleskey, R.B., and Alpers, C.N., Thermodynamic Properties and Crystal Structure Refinement of Ferricopiapite, Coquimbite, Rhomboclase and Fe2(SO4)3(H2O)5, Eur. J. Mineral., 2006, vol. 18, pp. 175–186.
Makhmetov, M.Zh. and Gorokhova, L.G., Termicheskaya ustoichivost’ i rastvorimost’ arsenatov (Thermal Stability and Solubility of Arsenates), Alma-Ata: Nauka, 1988.
Marion, G.M., Kargel, J.S., and Catling, D.C., Modeling Ferrous-Ferric Iron Chemistry with Application To Martian Surface Geochemistry, Geochim. Cosmochim. Acta, 2008, vol. 72, pp. 242–266.
Miller, D.G., Rard, J.A., Eppstein, L.B., and Robinson, R.A., Mutual Diffusion Coefficients, Electrical Conductances, Osmotic Coefficients, and Ionic Transport Coefficients I ij for Aqueous CuSO4 at 25°C, J. Solution Chem., 1980, vol. 9, pp. 467–496.
Naumov, G.B., Ryzhenko, B.N., and Khodakovsky, I.L., Spravochnik termodinamicheskikh velichin (Thermodynamic Data Handbook), Moscow: Atomizdat, 1971.
Olin, A., Nolang, B., Osadchii, E.G., Ohman, L.-O., and Rosen, E., Chemical Thermodynamics of Selenium, Amsterdam: Elsevier, 2005.
Paige, C.R., Kornicker, W.A., Hileman, O.E., and Snodgrass, W.J., Modeling Solution Equilibria for Uranium Ore Processing: the PbSO4-H2SO4-H2O and PbSO4Na2SO4-H2O Systems, Geochim. Cosmochim. Acta, 1992, vol. 56, pp. 1165–1173.
Pitzer, K.S., Thermodynamics of Electrolytes. I. Theoretical Basis and General Equations, J. Phys. Chem., 1973a, vol. 77, pp. 268–277.
Pitzer, K.S. and Mayorga, G., Thermodynamics of Electrolytes. II. Activity and Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent, J. Phys. Chem., 1973b, vol. 77, pp. 2300–2308.
Pitzer, K.S. and Mayorga, G., Thermodynamics of Electrolytes. III. Activity and Osmotic Coefficients for 2-2 Electrolytes, J. Solution Chem., 1974, vol. 3, pp. 539–546.
Pitzer, K.S., Roy, R.N., and Silvester, L.E., Thermodynamics of Electrolytes. 7. Sulfuric Acid, J. Am. Chem. Soc., 1977, vol. 99, pp. 4930–4936.
Reardon, E.J., Ion Interaction Model Applied to Equilibria in the NiSO4-H2SO4-H2O System, J. Phys. Chem., 1989, vol. 93, pp. 4630–4636.
Reardon, E.J. and Beckie, R.D., Modeling Chemical Equilibria of Acid Mine-Drainage: The FeSO4-H2SO4-H2O System, Geochim. Cosmochim. Acta, 1987, vol. 51, pp. 2355–2368.
Rumyantsev, A.V., Hagemann, S., and Moog, H.C., Isopiestic Investigation of the Systems Fe2(SO4)3-H2SO4-H2O, FeCl3-H2O, and Fe(III)-(Na,K,Mg,Ca)Cln-H2O at 298.15 K, J. Phys. Chem., 2004, vol. 218, pp. 1089–1127.
Seby, F., Potin-Gautier, M., Giffaut, E., et al., A Critical Review of Thermodynamics Data for Selenium Species at 25°C, Chem. Geol., 2001, vol. 171, pp. 173–194.
Termicheskie konstanty veshchestv, T. 1-10 (Thermal Constants of Substances), Glushko, V.P., Ed., Moscow: VINITI, 1965–1982.
Toska, N.J., Smirnov, A., and McLennan, S.M., Application of the Pitzer Ion Interaction Model To Isopiestic Data for the Fe2(SO4)3-H2SO4-H2O System at 298.15 and 323.15 K, Geochim. Cosmochim. Acta, 2007, vol. 71, pp. 2680–2698.
Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Halow, I., Bailey, S.M., Churney, K.L., and Nuttall, R.L., The NBS Tables of Chemical Thermodynamic Properties: Selected Values for Inorganic and C1 and C2 Organic Substances in SI Units, J. Phys. Chem. Ref. Data, 1982, vol. 11,suppl. 2.
Yakhontova, L.K. and Zvereva, V.P., Osnovy mineralogii gipergeneza (Principles of Supergene Mineralogy), Vladivostok: Dal’nauka, 2000.
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Original Russian Text © M.V. Charykova, V.G. Krivovichev, W. Depmeir, 2009, published in Zapiski RMO (Proceedings of the Russian Mineralogical Society), 2009, No. 6, pp. 105–117.
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Charykova, M.V., Krivovichev, V.G. & Depmeir, W. Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores: I. Thermodynamic constants at ambient conditions. Geol. Ore Deposits 52, 689–700 (2010). https://doi.org/10.1134/S1075701510080015
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DOI: https://doi.org/10.1134/S1075701510080015