Experimental Study of Gold and Platinum Solubility in a Complex Fluid under Hydrothermal Conditions
Authors: LIKHOIDOV G. G. , PLYUSNINA L. P. , SCHEKA J. A. , EVA T. B. APHANAS 
Published: November 2008

Abstract: The solubility of gold was studied in water and aqueous NaCl (1– 5 m) solutions under oxygen and sulfur buffered conditions between 300–500C at a constant pressure 1 kb. Two buffer assemblages HMP and PPM were used. Analysis of the scatter in measured values in log mAu–mNaCl–T frame fixed linear dependence between log mAu and T at any studied iso‐pleth (mNaCl) in the form of log mAu = a. T(C) + b. Coefficients of the equation were calculated for water and NaCl (1, 3, 5 m) solutions. The maximum solubility characterizes the NaCl‐free system in the presence of HMP. In the case, Au solubility increases from (log mAu) –6. 72 to –5. 04 at 300 and 500C, respectively. In the presence of PPM, maximum of Au solubility was obtained for the 5 mNaCl solution. In a similar manner solubility rises from –6. 54 to –5. 77 at 300 and 500C, accordingly. In studied fO2/fS2 area the behavior of Au solubility testified that: (i) – a composite interaction between chloride and hydrosulfide speciation of gold affects its total solubility; (ii) – in addition of NaCl up to about 1. 5 m the solubility decreases, more pronounced in the presence of HMP; (iii) – the contribution of chloride in total Au solubility is more for PPM despite of lower fO2value, than for HMP.

The solubility of platinum was studied in the Pt–Cl–S–H2O system between 300 and 500C, 1 kb. PPM solid buffer controlled oxidation state, pH and sulfur activity of solutions (H2O, 1 mNaCl and 0. 1 mHCl). Under the conditions, PtS precipitated from the solutions with increasing temperature and acidity. The PtS solubility in the 0. 1 mHCl solutions lowers slightly in the range of 300–500C from –5. 30 to –5. 60 (in log mPt) that is typical to the hydrosulfide species. It was deduced that reducing media, regulated by the PPM assemblage, suppress activity of chloride species of Pt. More oxidizing conditions were modeled in runs using mixtures of Mn(II), Mn(III) and Mn(IV) oxides to buffer the aqueous‐chloride solutions between 300 and 500C, 1 kb. It was found that MnO tends to oxidize at T below 400C forming intermediate Mn‐hydroxides (β–MnOOH, Mn (OH)2 and Mn2(OH)3Cl). These phases are metastable and transfer to Mn3O4 with increasing duration. Generation of the Mn‐hydroxides leads to a change of physical‐chemical parameters of the solutions, such as water activity, pH and Eh. The last results in abrupt increase in the noble metals dissolution. At stable existence of only Mn3O4, the solubility of both Pt and Au lowers to equilibrium values. Essential catalysis effect of Pt on intensity and rate of Mn(II) oxidation was found. The dominant role of chloride of Pt and Au was defined under most oxidized conditions, specified by Mn2O3–MnO2 buffer. So at 400C, dissolved Au (log mAu) increases from –4. 40 in water to –1. 00 in 0. 1 mHCl, and ones of Pt (log mPt) from –4. 80 to –2. 90 accordingly.

Thus, mixing of hydrosulfide and chloride solutions, as well as transformation of the systems to the stable state act upon total solubility of the noble metals.