Mining activities release arsenopyrite into calcareous soils where it undergoes weathering generating toxic compounds. The research evaluates the environmental impacts of these processes under semi-alkaline carbonated conditions. Electrochemical (cyclic voltammetry, chronoamperometry, EIS), spectroscopic (Raman, XPS), and microscopic (SEM, AFM, TEM) techniques are combined along with chemical analyses of leachates collected from simulated arsenopyrite weathering to comprehensively examine the interfacial mechanisms. Early oxidation stages enhance mineral reactivity through the formation of surface sulfur phases (e.g., S n (2-)/S(0)) with semiconductor properties, leading to oscillatory mineral reactivity. Subsequent steps entail the generation of intermediate siderite (FeCO3)-like, followed by the formation of low-compact mass sub-micro ferric oxyhydroxides (α, γ-FeOOH) with adsorbed arsenic (mainly As(III), and lower amounts of As(V)). In addition, weathering reactions can be influenced by accessible arsenic resulting in the formation of a symplesite (Fe3(AsO4)3)-like compound which is dependent on the amount of accessible arsenic in the system. It is proposed that arsenic release occurs via diffusion across secondary α, γ-FeOOH structures during arsenopyrite weathering. We suggest weathering mechanisms of arsenopyrite in calcareous soil and environmental implications based on experimental data.
Keywords: Arsenic release; Arsenopyrite weathering; Calcareous soil; Electrochemical impedance; Oscillatory mineral reactivity; Surface analysis.