Stability and solubility of arsenopyrite, FeAsS, in crustal fluids

The stability and solubility of natural arsenopyrite (FeAsS) in pure water and moderately acid to slightly basic aqueous solutions buffered or not with H₂ and/or H₂S were studied at temperatures from 300 to 450°C and pressures from 100 to 1000 bar. The solubilities of FeAsS in pure water and dilute HCl/NaOH solutions without buffering are consistent with the formation of the As(OH)₃⁰(aq) species and precipitation of magnetite. At more acid pH (pH ≤2), arsenopyrite dissolves either stoichiometrically or with formation of the As-FeAsS assemblage. In H₂S-rich and H₂-rich aqueous solutions, arsenopyrite dissolution results in the formation of pyrrhotite (±pyrite) and iron arsenide(s), respectively, which form stable assemblages with arsenopyrite.Arsenic concentrations measured in equilibrium with FeAsS in slightly acid to neutral aqueous solutions with H₂ and H₂S fugacities buffered by the pyrite-pyrrhotite-magnetite assemblage are 0.0006 ± 0.0002, 0.0055 ± 0.0010, 0.07 ± 0.01, and 0.32 ± 0.03 mol/kg H₂O at 300°C/400 bar, 350°C/500 bar, 400°C/500 bar, and 450°C/500 bar, respectively. These values were combined with the available thermodynamic data on As(OH)₃⁰(aq) (Pokrovski et al., 1996) to derive the Gibbs free energy of FeAsS at each corresponding temperature and pressure. Extrapolation of these values to 25°C and 1 bar, using the available heat capacity and entropy data for FeAsS (Pashinkin et al., 1989), yields a value of −141.6 ± 6.0 kJ/mol for the standard Gibbs free energy of formation of arsenopyrite. This value implies a higher stability of FeAsS in hydrothermal environments than was widely assumed.Calculations carried out using the new thermodynamic properties of FeAsS demonstrate that this mineral controls As transport and deposition by high-temperature (>∼300°C) crustal fluids during the formation of magmatic-hydrothermal Sn-W-Cu-(Au) deposits. The equilibrium between As-bearing pyrite and the fluid is likely to account for the As concentrations measured in modern high- and moderate-temperature (150 ≤ T ≤ 350°C) hydrothermal systems. Calculations indicate that the local dissolution of arsenopyrite creates more reducing conditions than in the bulk fluid, which is likely to be an effective mechanism for precipitating gold from hydrothermal solutions. This could be a possible explanation for the gold-arsenopyrite association commonly observed in many hydrothermal gold deposits.