At the Orieco mine quartz veins carrying sulphides were localized in parts of an extensive fault zone in the Mathinna Beds during late Middle Palaeozoic mineralization.These deposits were subsequently exposed, and oxidation of the sulphides by percolating groundwaters resulted in the formation of gossans at the surface, and replacement close to the permanent water table of the more soluble sulphides by copper sulphides (chalcocite, coveIlite). A restricted zone containing copper oxides (cuprite, tenorite), copper carbonates (malachite, azurite), iron arsenates (scorodite, pharmacosiderite) and possibly rare copper sulphates occurred above the water table.The renewed oxidation of these deposits following mine development has been facilitated by the ready circulation of air and water combined with the formation of large free surfaces ideal for evaporation of aqueous solutions. Under these new conditions of high initial sulphate concentration, low pH, and relatively high Eh, the previously formed mineral assemblage is unstable and numerous Cu (Fe,Zn)-sulphates and Fe (Cu,Pb)-arsenates are presently forming in fractures in the fault zone and on the adit and stope surfaces for some considerable distance from the Sulphide-rich ore shoots. The observed spatial sequence of the major sulphates with respect to the sulphide-rich zones (Le. chalcanthite-antleritebrochantite and langite) is consistent with decreasing sulphate concentration and increasing pH away from the oxidizing sulphides.