The treatment of acid mine drainage (AMD) and circumneutral mine water (CMW) with South African coal fly ash (FA) provides a low cost and alternative technique for treating mine wastes waters. The sulphate concentration in AMD can be reduced significantly when AMD was treated with the FA to pH 9. On the other hand an insignificant amount of sulphate was removed when CMW (containing a very low concentration of Fe and Al) was treated using FA to pH 9. The levels of Fe and Al, and the final solution pH in the AMD-fly ash mixture played a significant role on the level of sulphate removal in contrast to CMW-fly ash mixtures. In this study, a modelling approach using PHREEQC geochemical modelling software was combined with AMD-fly ash and/or CMW-fly ash neutralization experiments in order to predict the mineral phases involved in sulphate removal. The effects of solution pH and Fe and Al concentration in mine water on sulphate were also investigated. The results obtained showed that sulphate, Fe, Al, Mg and Mn removal from AMD and/or CMW with fly ash is a function of solution pH. The presence of Fe and Al in AMD exhibited buffering characteristic leading to more lime leaching from FA into mine water, hence increasing the concentration of Ca(2+). This resulted in increased removal of sulphate as CaSO(4)center dot 2H(2)O. In addition the sulphate removal was enhanced through the precipitation as Fe and Al oxy-hydroxysulphates (as shown by geochemical modelling) in AMD-fly ash system. The low concentration of Fe and Al in CMW resulted in sulphate removal depending mainly on CaSO(4)center dot 2H(2)O. The results of this study would have implications on the design of treatment methods relevant for different mine waters. (C) 2011 Elsevier Ltd. All rights reserved.