Stability of aqueous Fe(III) chloride complexes and the solubility of hematite between 150 and 300 °C

Three sets of experiments were performed to test the stability and geologic importance of ferric (FeIII) chloride complexes in acidic, Cl-rich solutions at 150–300 °C, p = psat. Experiment Set A used the change in solubility of AgCl(s) in the presence of FeCl3 or FeCl2 to determine the stoichiometry of Fe(III) and Fe(II) chloride complexes at ΣCl = 0.1–3.0 molal. Results show that FeCl4− and FeCl2(aq) are the dominant Fe(III) and Fe(II) species, respectively, at T > 200 °C and ΣCl ≥ 1 m. Set B experiments used the solubility of elemental gold as a redox sensor to determine the aO2 of the FeCl4−/FeCl2(aq) boundary and log K values of +6.56 and +7.19 for the following reaction at 250 and 300 °C, respectively: FeCl2(aq) + ¼O2(g) + 2Cl− + H+ = FeCl4− + ½H2O(l). Ferric chloride complexes are stable under conditions of aCl−, aO2, and pH where gold is soluble as AuCl2−. Set C experiments measured the solubility of hematite in NaCl-HCl solutions at 200–300 °C by preparing a series of silica tubes with identical matrix chemistry (0.9 m NaCl + 0.1 m HCl) and increasing concentration of FeCl3. Hematite saturation was constrained by the tube with the lowest FeCl3 concentration that precipitated hematite at high temperature. Set C results were used to compute log K values of +3.6, +5.2, and + 7.4 for the following reaction at 200, 250 and 300 °C, respectively: 0.5Fe2O3(s) + 4Cl− + 3H+ = FeCl4− + 1.5H2O. Hematite solubility as FeCl4− is independent of redox state, and increases quickly with an increase in temperature, increase in Cl− concentration (power of 4), and decrease in pH (power of 3). Concentrations in excess of 100 mg/L ΣFe are attainable under geologically realistic conditions. Once formed, FeCl4− is an extremely effective oxidizing agent, capable of destabilizing any sulfide mineral and dissolving Fe, Au, and other metals (e.g., Cu, Pt, Pd) as chloride complexes. In deep hydrothermal systems, FeCl4− is a more viable oxidant than dissolved O2 gas, although its presence requires a source area with abundant hematite and a lack of reductants such as organic carbon, sulfides, or silicate minerals containing ferrous iron. Dissolved ferric chloride could be an important and previously overlooked reactant in the formation of certain types of hematite-rich hydrothermal mineral deposits, including iron oxide-copper–gold (IOCG) deposits.