Batch experiments with the lead sulphide ore mineral galena were carried out in order to get information about the oxidation mechanisms and to contribute to the understanding of field data, especially those obtained from the mining-affected sites. Results indicate that oxygen and sulphur isotopes of dissolved sulphate may be useful tools for the investigation of galena oxidation mechanisms. However, some methodological modifications are necessary to obtain sufficient sulphate yields, which are a prerequisite for the reduction of the analytical uncertainty. Surface and hydrochemical investigations indicated that galena was dissolved non-oxidatively during the experiment at initial pH 2, whereas the oxidative dissolution of galena dominated in experiments at initial pH 6 and 8. No isotope results could be obtained from the experiment at initial pH 2 due to the low sulphate production. The oxidative dissolution of galena resulted in somewhat higher sulphate yields. Thus, the oxygen isotope composition of sulphate produced from galena oxidation could be determined for the first time. Oxygen in sulphate derived largely from water molecules; but minor amounts of molecular oxygen could be also observed. Both molecular oxygen and ferric iron may act as oxidants of galena. A variety of intermediate reactions allow for a variable oxygen isotope composition of sulphate. Sulphur isotopes of sulphate showed an enrichment of (32)S in sulphate (relative to galena), which increases with increasing pH. Sulphur isotope enrichment processes may be associated with the formation of anglesite.