Pyrite oxidation in the presence of hematite and alumina: II. Effects on the cathodic and anodic half-cell reactions.

The oxidative dissolution of pyrite is an important process in the redox recycling of iron (Fe) and is well-known for its role in the formation of acid mine drainage (AMD), which is considered as the most serious and widespread problem after the closure of mines and mineral processing operations. Because this process requires the movement of electrons, common metal oxides in nature that have either semiconducting (e.g., hematite) or insulating (e.g., alumina) properties may have strong effects on it. In this study, changes in the electrochemical behavior of pyrite in the presence of hematite and alumina were investigated. Results showed that the formation of surface-bound species directly influenced the anodic and cathodic half-cell reactions as well as the transfer of electrons between these sites. Pyrite pretreated in the air became anodically more reactive than that pretreated in oxygenated water, but the type of oxidizing media had little effect on the cathodic half-cell reaction. The presence of hematite and alumina during pretreatment also had strong effects on the electrochemical properties of pyrite. Chronoamperometry measurements suggest that hematite and alumina enhanced the anodic half-cell reaction but suppressed the cathodic half-cell reaction of pyrite oxidation. Increased anodic half-cell reaction in the presence of hematite could be attributed to electron "bridging" and catalytic effects of this mineral. In contrast, the effects of alumina on the anodic half-cell reaction were indirect and could be explained by the formation of Fe-oxyhydroxide surface species during pretreatment. Suppression of the cathodic half-cell reaction by both minerals was attributed to their "protective" effect on cathodic sites. Our results also point to the cathodic half-cell reaction as the rate determining-step of the overall oxidative dissolution process.