The mining industry produces vast quantities of overburden and mill tailings. In many instances the disposal of these wastes on the Earth's surface have caused local, and occasionally even regional, water resources to become contaminated. Contamination typically arises from the oxidation of metal sulfide minerals contained within these wastes. Upon oxidation these minerals release sulfate, their associated metal cations and acidity into solution. This study investigated the potential for groundwater contamination arising from a Pb/Zn tailings impoundment in the North West Province of South Africa (Pering Mine). The tailings is composed predominantly of dolomite, which imparts to the material an alkaline pH and a high acid buffering capacity. Acid-base accounting (ABA) established that the capacity of the tailings to buffer acidity surpasses any acid producing potential that could arise from pyrite (FeS2), galena (PbS) and sphalerite (ZnS) oxidation. These minerals account for about 3 to 6% of the tailings by mass. Total elemental analysis (XRF) showed that the material has high total concentrations of Fe (19083 mg kg-I), Zn (5481 mg kg-I), Pb (398 mg kg-I), S (15400 mg kg-I), Al (9152 mg kg-I) and Mn (29102 mg kg-I). Only a very small fraction of this, however, was soluble under saturated conditions. An estimation of potentially available concentrations, using the DTPA extraction method, indicated that high concentrations of Zn (1056 mg kg-I), and moderate concentrations of Pb (27.3 mg kg-I) and Cu (6.01 mg kg-I) could potentially be available to cause contamination. A number of leaching experiments were undertaken to accurately quantify the release of elements from the tailings material. These experiments were aimed at determining the potential for groundwater contamination and also provided a means whereby the long-term release of contaminants could be modelled using the convection-dispersion equation for solute transport. Four leaching treatments were investigated. Two consisted of using distilled water under intermittent and continuous flow, while a third used intermittent flow of deoxygenated distilled water to assess leaching under conditions of reduced oxygen. The.mobilisation of potential contaminants under a worst case scenario was assessed by means of leaching with an acetic acid solution at pH 2.88 (after the US Environmental Protection Agency's toxicity characteristic leaching procedure). The acid buffering potential of the tailings was considerable. Even after 8 months of weekly leaching with 1 pore volume of acetic acid solution the pH of the effluent was maintained above pH 5.90. The protracted acidity caused very high concentrations of Pb, Zn, Mu, Ca, Mg, Hg and S to be released into solution. Leaching the tailings with distilled water also caused the effluent to have noticeable traces of contamination, most importantly from S, Mg, Mu and Zn. In many instances concentrations significantly exceeded guideline values for South African drinking water. Modelling solute transport with the convectiondispersion equation predicted that sol- and Mu contamination could persist for a very long period of time. (±700 years under continuous saturated leaching), while Mg and Zn concentrations would most likely exceed recommended limits for a much shorter period of time (±300 years under the same conditions). In light of the various column leaching experiments it was concluded that seepage from the Pering tailings impoundment could cause groundwater contamination. A drill-rig and coring system were used to collect both tailings and pore-water samples from eight boreholes spread out across the tailings impoundment. These investigations showed that most of the impoundment was aerobic (Eh ranged from +323 to +454 mY) and alkaline (pH 8.0 to 9.5). This chemical environment favours sulfide oxidation and as a consequence high concentrations of S have been released into the pore-water of the impoundment (S concentrations ranged from 211 to 1221 mg r l ). The acidity released as a by-product of sulfide oxidation was being buffered by dolomite dissolution, which in turn was releasing high concentrations of Mg (175 to 917 mg r l ) and Ca (62.6 to 247 mg r l ) into solution. Metal concentrations in the pore-water were low as a result of the strong metal sorbing capacity of the tailings and possible secondary precipitation. The only metal which significantly exceeded recommended limits throughout the impoundment was Hg (concentrations were between 100 and 6000 times the recommended limit of 0.001 mg r l ). Under the current geochemical conditions it is expected that Hg, S and Mg will likely pose the greatest threat to groundwater. The main concerns associated with mine tailings are that of mine drainage and dust blow off..In order to eradicate the latter problem, the tailings impoundment at Pering Mine was covered with a layer of rocks. Modelling the water balance of the impoundment using the computer model HYDRUS-2D showed that the rock cladding has potentially increased the volume of drainage water seeping from the impoundment. In light of the leaching experiments and field work, which proved that water passing through the tailings became enriched with various potentially toxic elements, it is expected that the problem of groundwater contamination around Pering Mine has been further exacerbated by the rock cladding. It was therefore concluded that there would be a strong likelihood of groundwater contamination in the vicinity of the mine. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2006.