Gold and iron oxide associations under supergene conditions: An experimental approach

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-The interaction of gold hydroxo-chloro complexes with iron oxides (ferrihydrites, goethites) during coprecipitation experiments is investigated. Chemical analyses of solids and solutions are coupled with a detailed characterization of the iron oxides with various methods, including X-ray diffraction, High Resolution Transmission Electron Microscopy (HRTEM), and Mössbauer spectroscopy. HCl solutions containing varying amounts of AuCl4- and ferric nitrate were titrated to neutral or alkaline pH, resulting in the coprecipitation of gold and iron oxide phases (ferrihydrite or goethite). Reference titrations were performed in the absence of iron. Most of the gold was removed from solution in the presence of iron oxides whereas gold remained dissolved in the reference samples. In association with iron oxides two forms of gold have been identified by HRTEM and 197Au Mössbauer spectroscopy: metallic gold as well as chloro and/or hydroxo combined gold. This combined gold is in a trivalent state as the primary product which means that a reduction process is not a necessary step for the adsorption of gold species on iron oxides. Metallic gold characterized in these products by means of HRTEM consists mainly of colloids ranging from 3 60 nm in diameter embedded in the ferrihydrite matrix, as isolated particles or as particles associated with goethite laths. The smallest metallic gold particles detected would be almost invisible to classical observation techniques used for solid phases. In our experiments, oxidation-reduction reactions between Fe2+ and Au3+ are responsible for the presence of metallic gold observed on the iron phases. Photochemical reactions may also take part in the reduction process. Colloidal gold and gold complexes could be associated to the iron oxides by strong electrostatic interactions. Our results suggest that poorly ordered iron oxides are highly efficient in trapping gold from solutions thanks to their high surface area, and favor gold precipitation during the first stage of the low temperature genesis of ironrich Au-containing systems.

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