Direct imaging of coupled dissolution-precipitation and growth processes on calcite exposed to chromium-rich fluids

Abstract

Recent increases in industrial activity have resulted in elevated chromium (Cr) pollution in the natural environment, from the degradation of concrete and the leakage of water from landfills or mine waste. The release of toxic chromate ions into the environment could have harmful consequences. Methods for Cr removal are therefore becoming increasingly important to control the release of this highly toxic metal into the environment. This study examines how chromate (CrO42−) can be incorporated into a new, stable solid phase at a dissolving calcite surface. To study the relationship between solutions containing chromate and calcite, we performed two series of time-lapse atomic force microscopy (AFM) experiments to identify calcite dissolution and growth rates in the presence of chromate. In addition, we conducted complementary experiments in a stirred flow-through reactor to determine the amount of Cr removal from solution. All experiments were performed at room temperature and under a constant initial pH in the range 6–12. During the AFM experiments, we observed calcite dissolution via etch pit formation and propagation. In the presence of chromate, nanoparticles of a new phase nucleated and grew at the calcite surface by a coupled dissolution-precipitation process. In experiments with concentrations above 10 ppm Cr or at pH 10 and higher, we observed many nanoparticle precipitates, while precipitates were rarely observed at lower concentrations of Cr. At pH 10.5, the precipitates covered the calcite surface. This partly passivated further calcite dissolution, an observation confirmed by the low amounts of Cr removal measured in the flow-through experiments. Scanning electron microscopy analysis demonstrated that Cr was associated with the precipitates, indicating that Cr could be captured from solution and trapped in solid nanoparticles in the presence of calcite. However, the passivation of the calcite surface by a new precipitate may eventually slow down Cr sequestration.