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Zn and Pb solubility and speciation in aqueous chloride fluids at T-P parameters corresponding to granitoid magma degassing and crystallization

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Abstract

The solubility of all possible Zn and Pb species in aqueous chloride fluids was evaluated by means of thermodynamic simulations in systems ZnO(PbO)-aqueous solution of NaCl (KCl, NaCl + HCl) within broad ranges of temperature (600–900°C), pressure (0.7–5 kbar), and chloride concentrations, under parameters corresponding to the crystallization and degassing of granitoid magmas in the Earth’s crust. Our simulation results demonstrate that the addition of Cl to the fluid phase in the form of Na(K)Cl and HCl significantly increases the concentrations of Cl-bearing Zn and Pb complexes and the total concentration of the metals in the solutions in equilibrium with the solid oxides. In Zn-bearing fluids, the Zn(OH) 02 , ZnOH+, and Zn(OH) −3 —hydroxyl complexes and the ZnCl 02 , and ZnCl+ chlorocomplexes, which are predominant at low Cl concentrations (CCl < 0.05–0.1 m) give way to ZnCl 2−4 with increasing CCl, which becomes the predominant Zn species of the fluid at CCl > 0.1–0.5 m throughout the whole temperature range in question and pressures higher than 1 kbar. For Pb-bearing fluids, the T-P-X region dominated by the Pb(OH) 02 , and Pb(OH) −3 hydroxyl complexes is remarkably wider than the analogous region for Zn, particularly at elevated temperatures (≥700°C) in alkaline solutions. An increase in CCl is associated with an increase in the concentration and changes in the speciation of Pb chlorocomplexes: PbCl 02 → PbCl −3 → PbCl 2−4 . The concentrations of Zn and Pb chlorocomplexes increase with increasing pressure, decreasing temperature, and decrease pH with the addition of HCl to the system. It is demonstrated that the solubility of ZnO at any given T-P-X in alkaline solutions with low chloride concentrations are lower than the solubility of PbO. The Zn concentration increases more significantly than with the Pb concentration with increasing CCl and decreasing pH, so that the Zn concentration in acidic solutions is higher than the Pb concentration over broad ranges of temperature, pressure, and Cl concentration. Chloride complexes of Zn (ZnCl 02 , and ZnCl 2−4 ) and Pb (PbCl 02 , and PbCl −3 are proved to be predominant within broad T-P-X-pH ranges corresponding to the parameters under which magmatic fluid are generated. Our simulation results confirm the hypothesis that chlorocomplexes play a leading role in Zn and Pb distribution between aqueous chloride fluids and granitic melts. These simulation results are consistent with experimental data on the Zn and Pb distribution coefficients (D(Zn)f/m and D(Pb)f/m, respectively) between aqueous chloride fluids and granitic melts that demonstrated that (1) D(Zn)f/m and D(Pb)f/m increase with increasing Na and K chloride concentrations in the aqueous fluid, (2) both D(Zn)f/m and D(Pb)f/m drastically increase when HCl is added to the fluid, and (3) (D(Zn)f/m is higher than D(Pb)f/m at any given T-P-X parameters. The experimentally established decrease in D(Zn)f/m and D(Pb)f/m with increasing pressure (at unchanging temperature and Cl concentration) is likely explained by an increase in the alkalinity of the aqueous chloride fluid in equilibrium with granite melt and, correspondingly, a decrease in the Zn and Pb solubility in this fluid.

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Authors and Affiliations

  1. Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul. Kosygina 19, Moscow, 117975, Russia

    O. A. Lukanin, B. N. Ryzhenko & N. A. Kurovskaya

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  1. O. A. Lukanin
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Correspondence to O. A. Lukanin.

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Original Russian Text © O.A. Lukanin, B.N. Ryzhenko, N.A. Kurovskaya, 2013, published in Geokhimiya, 2013, Vol. 51, No. 10, pp. 894–923.

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Lukanin, O.A., Ryzhenko, B.N. & Kurovskaya, N.A. Zn and Pb solubility and speciation in aqueous chloride fluids at T-P parameters corresponding to granitoid magma degassing and crystallization. Geochem. Int. 51, 802–830 (2013). https://doi.org/10.1134/S0016702913090048

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