Oxidation and reduction processes on coal- and mineral-pyrite surfaces have been investigated to better understand the reactions that control the hydrophobicity and flotation behavior of pyrite. The incipient oxidation and reduction reactions were studied using fresh surfaces of pyrite that were created by in situ fracturing electrodes potentiostated at a predetermined potential. Chronoamperometry immediately after fracture and subsequent cyclic voltammetry have established that fresh fracture surfaces of pyrite instantaneously assume a unique potential (referred to as the "stable" potential) at which neither oxidation nor reduction takes place. For Peruvian and Chinese pyrites, the stable potential is -0.28 V (standard hydrogen electrode, SHE) at pH 9.2 and 0 V at pH 4.6. The initial oxidation of pyrite begins at potentials slightly positive of the stable potential and is believed to produce a hydrophobic sulfur-rich species, most likely a polysulfide or metal-deficient sulfide. A rotating ring-disc electrode (RRDE) was employed to study the kinetics and mechanisms of surface reactions on pyrite over moderate potential ranges. Two distinct soluble reduction products (ferrous hydroxide and HS-) and one distinct soluble oxidation product (ferrous hydroxide) were observed on pyrite in alkaline solutions. It is concluded that the initial oxidation of pyrite and the oxidation of ferrous to ferric hydroxide occur in a similar potential range. When the electrode is oxidized, e.g. by polishing, prior to experiments, the initial oxidation of pyrite is masked by the oxidation of ferrous hydroxide, making it difficult to study the oxidation of pyrite itself. (C) 2003 Elsevier Ltd. All rights reserved.