The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: An electrochemical study of synthetic pyrite

Abstract

Synthetic pyrite crystals doped with As, Co, or Ni, undoped pyrite, and natural arsenian pyrite from Leadville, Colorado were investigated with electrochemical techniques and solid-state measurements of semiconducting properties to determine the effect of impurity content on pyrite’s oxidation behavior. Potential step experiments, cyclic voltammetry, and AC voltammetry were performed in a standard three-electrode electrochemical cell setup. A pH 1.78 sulfuric acid solution containing 1 mM ferric iron, open to atmospheric oxygen, was chosen to approximate water affected by acid drainage. Van der Pauw/Hall effect measurements determined resistivity, carrier concentration and carrier mobility. The anodic dissolution of pyrite and the reduction of ferric iron half-reactions are taken as proxies for natural pyrite oxidation. Pyrite containing no impurities is least reactive. Pyrite with As is more reactive than pyrite with either Ni or Co despite lower dopant concentration. As, Co, and Ni impurities introduce bulk defect states at different energy levels within the band gap. Higher reactivity of impure pyrite suggests that introduced defect levels lead to higher density of occupied surface states at the solid–solution interface and increased metallic behavior. The current density generated from potential step experiments increased with increasing As concentration. The higher reactivity of As-doped pyrite may be related to p-type conductivity and corrosion by holes. The results of this study suggest that considering the impurity content of pyrite in mining waste may lead to more accurate risk assessment of acid producing potential.