No abstract

The chemical reactions of dry-disposed ash dump, ingressed oxygen, carbon dioxide, and infiltrating rainwater affect mineralogical transformation, redistribution, and migration of chemical species. Composite samples of weathered coal fly ash taken at various depths and fresh coal fly ash were examined using organic petrographic, X-ray diffraction, X-ray fluorescence techniques, and successive extraction procedures. Results obtained show relative enrichment of glass, Al-Fe-oxides, calcite, and tridymite in the weathered CFA, but the fresh CFA is enriched in mullite, inertinite, maghemite, and ettringite. The enrichment of the weathered CFA in amorphous glass suggests higher reactivity when compared to fresh CFA. The evident depletion of soluble oxides in the weathered CFA is attributed to flushing of the soluble salts by percolating rainwater. Comparative enrichment of examined elements in water-soluble, exchangeable, reducible, and residual fractions of the weathered CFA is partly due to the slow release of adsorbed chemical species from the alumina-silicate matrix and diffusion from the deeper sections of the particles of coal fly ash. Sodium and potassium show enrichment in the oxidisable fraction of fresh CFA.

Large volumes of disposed mine tailings abound in several regions of South Africa, as a consequence of unregulated, unsustainable long years of mining activities. Tailings dumps occupy a large volume of valuable land, and present a potential risk for aquatic systems, through leaching of potentially toxic chemical species. This paper reports on the evaluation of the geochemical processes controlling the mobility of potentially toxic chemical species within the tailings profile, and their potential risk with regard to surface and groundwater systems. Combination of X-ray fluorescence (XRF), X-ray diffraction (XRD), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) techniques, show that the tailing profiles are uniform, weakly altered, and vary slightly with depth in both physical and geochemical properties, as well as mineralogical composition. Mineralogical analysis showed the following order of abundance: quartz > epidote > chlorite > muscovite > calcite > hematite within the tailings profiles. The neutralization of the dominant alumino-silicate minerals and the absence of sulfidic minerals, have produced medium alkaline pH conditions (7.97-8.37) at all depths and low concentrations of dissolved Cu (20.21-47.9 µg/L), Zn (0.88-1.80 µg/L), Pb (0.27-0.34 µg/L), and SO 4 2− (15.71-55.94 mg/L) in the tailings profile leachates. The relative percentage leach for the potentially toxic chemical species was low in the aqueous phase (Ni 0.081%, Cu 0.006%, and Zn 0.05%). This indicates that the transport load of potentially toxic chemical species from tailings to the aqueous phase is very low. The precipitation of secondary hematite has an important known ability to trap and attenuate the mobility of potentially toxic chemical species (Cu, Zn, and Pb) by adsorption on the surface area. Geochemical modelling MINTEQA2 showed that the tailings leachates were below saturation regarding oxyhydroxide minerals, but oversaturated with Cu bearing mineral (i.e., cuprite). Most of the potentially toxic chemical species occur as free ions in the tailings leachates. The precipitation of secondary hematite and cuprite, and geochemical condition such as pH of the tailings were the main solubility and mobility controls for the potentially toxic chemical species, and their potential transfer from tailings to the aqueous phase.