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Chalcocite Cu2S solubility in aqueous sulfide and chloride fluids. Thermodynamic properties of copper(I) aqueous species and copper transport in hydrothermal systemsстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Trofimov Nikolay D., Tagirov Boris R., Akinfiev Nikolay N., Reukov Vladimir L., Nickolsky Maximilian S., Nikolaeva Irina Yu, Tarnopolskaya Maria E., Afanasyev Andrey A.
- Журнал: Chemical Geology
- Том: 625
- Год издания: 2023
- Издательство: Elsevier BV
- Местоположение издательства: Netherlands
- Первая страница: 121413
- DOI: 10.1016/j.chemgeo.2023.121413
- Аннотация: AbstractThe most important Cu reserves, including ores of porphyry deposits, were formed by Cl- and S-bearing hydrothermal fluids transporting and depositing metals within the magmatic-hydrothermal ore systems. In order to determine the state of Cu in the fluids, we measured the solubility of chalcocite Cu2S at 350 and 450 °C, 500 and 1000 bar. The concentration of H2S varied from 0.08 to 0.4 m [mol⋅(kg H2O)−1], NaOH – from 0 to 0.2 m, NaCl + HCl – from 0.01 to 4 m. The solubility of chalcocite can be described by the reactions:0.5 Cu2S(cr) + 0.5 H2S(aq) = CuHS(aq) log K°CuHS = −3.99 ± 0.07 (350 °C/500 bar)−4.61 ± 0.09 (450 °C/500 bar), −4.26 ± 0.11 (450 °C/1000 bar);0.5 Cu2S(cr) + 0.5 H2S(aq) + HS− = Cu(HS)2− log K°Cu(HS)2- = −0.85 ± 0.08 (350 °C/500 bar)−0.65 ± 0.11 (450 °C/1000 bar);0.5 Cu2S(cr) + HCl(aq) = CuCl(aq) + 0.5 H2S(aq) log K°CuCl = −3.11 ± 0.70 (450 °C/1000 bar);0.5 Cu2S(cr) + HCl(aq) + Cl− = CuCl2− + 0.5 H2S(aq) log K°CuCl2- = 0.33 ± 0.19 (450 °C/1000 bar)These results, together with data of Rubtsova et al. (2023) on the coupled solubility of Cu(cr) and Ag in chloride fluids, demonstrated that a simple extended Debye-Hückel equation describe activity coefficients of charged species at any NaCl concentration up to the solubility limit at near- and supercritical PT-parameters; activity coefficients of neutral species can be calculated with Setchenov parameter equal to zero. The Cu2S(cr) solubility in sulfide-chloride-bearing fluids is consistent with the formation of Cu-Cl complexes which implies that mixed Cu-HS-Cl complexes can be neglected. The experimental values pooled with the reliable literature data were fitted to the HKF (Helgeson-Kirkham-Flowers) model equation of state (EoS). The obtained HKF EoS parameters allow to predict thermodynamic properties of CuHS(aq), Cu(HS)2−, and CuCl(aq) from 25 to 700 °C and from Psat. to 2000 bar, and up to 1000 °C/5000 bar for CuCl2−. The AD (Akinfiev and Diamond) EoS parameters were derived for CuCl(aq). The AD EoS can be used to calculate the CuCl(aq) Gibbs free energy in the low-density fluids (ρH2O < 0.35 g⋅cm−3) up to 700 °C. The obtained thermodynamic data imply that CuCl2− predominates in high-density ore-forming fluids (ρH2O > 0.35 g⋅cm−3) of total chloride content >0.1 wt% up to the NaCl saturation limit. The hydrosulfide complexes are the main forms of Cu occurrence in the fluid with concentration of dissolved chlorides <0.1 wt% equilibrated with silicate mineral assemblages (e.g., K-feldspar-muscovite-quartz, pH is near-neutral). However, their concentration in the presence of Cu-bearing sulfides is low (< 0.5 ppm at 500 °C/1500 bar) and decreases with temperature decreasing.
- Добавил в систему: Николаева Ирина Юрьевна