CARBONATE-MINERAL/WATER INTERACTIONS IN SULFIDE-RICH MINE TAILINGS

Abstract

The chemical composition and mineralogy of coatings on carbonate minerals from mine tailings have been studied using aqueous geochemical methods, Time-of-Flight Laser-Ionization Mass Spectrometry (TOF-LIMS) and Transmission Electron Microscopy (TEM). The goal is to study major and trace element partitioning between the aqueous and solid phase, and to infer mechanisms that control the concentrations of elements in the pore water of sulfide-rich mine tailings. Pore-water samples and carbonate-mineral grains were collected from four geochemically distinct zones within the tailings. Oxidation of sulfide minerals near the surface results in a large range in pore-water pH (3.85 to 6.98) and aqueous concentrations of metals and sulfate. With increasing depth in the tailings, mineral-water interactions lead to increasing pH, and decreasing concentrations of metals and sulfate. Calculated mineral saturation indices, trends in the abundance of Ca, Fe, Mg and Mn in TOF-LIMS profiles through the secondary coatings, and electron diffraction patterns obtained from the coatings, suggest that precipitation/dissolution of jarosite-group minerals, gypsum, goethite, akaganeite, amorphous Fe oxyhydroxides and siderite control the aqueous Ca, Fe, Na, K and SO4 concentrations. The occurrence of secondary coatings on primary minerals is widespread, and reactions with the secondary minerals, rather than the primary mineral substrate, probably represent the principal controls on trace-element distributions in the pore water. The data indicate that adsorption, surface-complexation and co-precipitation reactions are important controls on the concentrations of trace elements in the pore water. The occurrence of siderite coatings on the surface of ankerite grains suggests that Fe-bearing dolomite-structure carbonate minerals dissolve incongruently. This corroborates inferences made by previous workers that solubility differences between calcite and siderite lead to calcite dissolution and siderite precipitation during acid neutralization. The accumulation of secondary coatings will diminish the rate of mineral-dissolution reactions involving the primary minerals. Consequently, the use of kinetic rate constants obtained from the literature for simulating the dissolution of primary mineral phases such as the carbonates and alumino-silicates will likely overestimate the actual rates.