Pyrite, chalcopyrite and mixed sulfide samples, with and without quartz (5 wt per cent S), were subjected to column leaching to mimic natural weathering (cyclic wetting and drying). The pH and SO4 2- concentration of the column effluent was measured over a period of 78 weeks. The pH of the pyrite-only containing column rapidly decreased and remained under pH 4 after 12 weeks of leaching. The pH calculated assuming a 2:1 ratio of H + generation and SO4 2- release was slightly lower than that measured. However, a reduced H + to SO4 2- ratio of 1:1 is predicted if the release of aqueous Fe 2+ is assumed rather than the formation of Fe(OH)3. The pH of all columns containing only chalcopyrite or a 1:1 mole ratio of chalcopyrite and pyrite remained at or above pH 5 for the duration of the leach even though significant SO4 2- was released. One column containing the same initial surface area of pyrite and chalcopyrite but only approximately 0.10 the mole fraction of S as chalcopyrite maintained a pH of greater than five for the first 56 weeks of leaching and showed sporadic acid production thereafter. It is well established that oxidation of chalcopyrite results in a surface layer of polysulfide material. It is the formation of polysulfide that neutralises the acid produced on S oxidation through to SO4 2-. Hence where polysulfide formation occurs extensively on chalcopyrite the resulting solution pH decrease will be less than that based on SO4 2- production._x000D_
The oxidation rate of sulfide minerals increases with decreasing pH and hence acid formation via sulfide oxidation to SO4 2- causes the subsequent oxidation rate to increase. The addition of calcite (CaCO3)to a pyrite column not only neutralises the acid formed but also decreases the rate of release of sulfate to solution by a factor of approximately 30. This is also the case where chalcopyrite is present mixed with pyrite. The rate of release of sulfate from the mixed sulfide mineral columns (after the initial release of the sulfate already present) was between one-fifth and one-tenth that in the absence of chalcopyrite.