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.

The original aims of this project were to investigate the potential for phytoremediation, with emphasis on metal accumulation, of three contrasting industrial processing wastes. These were tailings material (PT) from the decommissioned Pering Pb/Zn Mine (Reivilo, North West Province, South Africa (SA)), smelter slag (SS) from the Samancor Mnsmelter (Meyerton, Gauteng, SA) and electro-winning waste (EW) from MMC (Nelspruit, Mpumalanga, SA). It became evident, however, early in the project, that the use of metal hyperaccumulating plants was not a viable technology for these wastes. The project objectives were thus adapted to investigate alternative remedial technologies. The use of endemic and adapted grass species was investigated to revegetate the PT. In addition, chemically-enhanced phytoremediation was investigated to induce metal hyperaccumulation by grasses grown in the PT (Part 1). Revegetation of the SS and EW were not considered feasible, thus land disposal of these two Mn-rich processing wastes was investigated (Part 2). Part 1 - Revegetation of tailings from Pering Mine The PT was found to be alkaline (pH > 8.0), and consisted mainly of finely crushed dolomite. It was generally nutrient poor with high amounts of readily extractable Zn. It also had a very high P-sorption capacity. Seven grass species (Andropogon eucomus Nees; Cenchrus ciliaris L.; Cymbopogon plurinodis Stapf ex Burtt Davy; Digitaria eriantha Steud; Eragrostis superba Peyr; Eragrostis tef (Zucc.) Trotter and Fingeruthia africana Lehm) were grown in PT treated with different rates of inorganic fertiliser under glasshouse conditions. The fertiliser was applied at rates equivalent to 100 kg N, 150 kg P and 100 kg K ha-1 (full), half the full rate (half) and no fertiliser (0). Seed of C. ciliaris, C. plurinodis, D. eriantha, E. superba and F. africana were collected from Pering Mine. Seed of A. eucomus was collected from the tailings dam of an abandoned chrysotile asbestos mine. These were germinated in seedling trays and replanted into the pots. A commercial variety of E. tef was tested, but due to poor survival this species was subsequently excluded. The foliage and root biomass of the grasses and concentrations of Ca, Cu, Fe, K, Mg, Mn, Pb and Zn in the foliage were determined. The yield of all the grasses increased with an increase in fertiliser rate, with a significant species by fertiliser interaction (p = 0.002). The highest yield was measured for C ciliaris, followed by D. eriantha (4.02 and 3.43 g porI, respectively), at the full fertiliser application rate. Cymbopogon plurinodis was the third highest yielding species, while the yields of E. superba and F. africana were similar. There were positive linear correlations between foliage yield and fertiliser application rate for all grasses. The root biomass of the grasses also increased with an increase in fertiliser application rate. The interaction between grass species and fertiliser level had a non-significant (p = 0.085) effect on the yield of grasses, though there were significant individual effects of species (p < 0.001) and fertiliser (p < 0.001). Digitaria eriantha had the highest root biomass at each fertiliser application rate, followed by C plurinodis and C ciliaris. Similarly to foliage yield, there were positive linear correlations between root biomass and fertiliser application level. Positive, linear correlations were found between foliage yield and root biomass, though the strength of these varied. The weakest correlation was found for D. eriantha (R2 = 0.42) but this was attributed to a moderately high variance in foliage yield and roots becoming potbound. Generally, nutrient concentrations were within adequacy ranges reported in the literature, except for P concentrations. This was attributed to the high P-sorption capacity of the PT. Zinc concentrations were higher than the recommended range for grasses, and also increased with an increase in fertiliser application rate. This was attributed to the high available Zn concentrations in the PT and improved growth of the grasses at higher fertiliser application rates. It was recommended that C ciliaris and D. eriantha be used for revegetation due to high biomass production and that E. superba be used because of rapid growth rate and high self-propagation potential. Both C plurinodis and F. africana can also be used but are slower to establish, while A. eucomus was not a suitable species for revegetation of the PT. Inorganic fertiliser improved the growth of all these species and is recommended for the initial establishment of the grasses. An experiment was conducted to investigate the potential of inducing metal hyperaccumulation in three grass species (C ciliaris, D. eriantha and E. superba) grown in the PT. Grasses were grown in fertilised tailings for six weeks, then either ethylenediaminetetraacetic acid (EDTA) or diethylentriaminepentaacetic acid (DTPA) was added to the pots at rates of 0, 0.25, 0.5, 1 and 2 g kg-I. Grasses were allowed to grow for an additional week before harvesting. The concentrations of Cu, Pb and Zn were determined in the foliage. The interactive effect of species and chelating agent on the uptake of Cu was marginally significant (p = 0.042) and non-significant for Pb and Zn (p = 0.14 and 0.73, respectively). While the addition of the chelating agents resulted in an increase in Pb uptake by the grasses, it did not induce metal hyperaccumulation in the grasses. This was attributed to the ineffectiveness of the chelating agents in the PT in the presence of competing base cations (mainly Ca). The use of this technology was not recommended. Part 2 - Land disposal of Mn-rich processing wastes Chemical characterisation of the SS showed that it was an alkaline (pH > 9.5), Mn-rich silicate (glaucochroite), that generally·had low amounts of soluble and readily extractable metals. Acidic extractants removed high amounts of Mn, Ca and Mg, attributed to the dissolution of the silicate mineral. The EW was highly saline (saturated paste EC = 6 780 mS m,l) with a near-neutral pH. It had high amounts of soluble Mu, NHt+, S, Mg, Ca and Co. The primary minerals were magnetite, jacobsite (MnFe204) and gypsum. The effect of SS and EW on selected chemical properties of six soils was investigated by means of an incubation experiment, and their effect on the yield and element uptake by ryegrass was investigated in selected soils under glasshouse conditions. Five A-horizons (Bonheim (Ba), Hutton (Hu), lnanda (la), Shortlands (Sd) and Valsrivier (Va» and an Ehorizon (Longlands (Lo» were treated with SS at rates of 30, 60, 120,240 and 480 g kg'l and EW at rates of20, 40,80,160 and 320 g kg'l. Soils were incubated at field capacity at 24 QC and sampled periodically over 252 days. The soil pH, both immediately and over time, increased, while exchangeable acidity decreased after the addition of SS to the soils. The pH at the high rates of SS tended to be very high (about 8). The electrical conductivity (EC) of the soils also increased with an increase in SS application rates and over time. The most marked changes tended to occur in the more acidic soils (e.g. la). In the soils treated with EW, there was generally an increase in the pH of the acid soils (e.g. la) while in the more alkaline soils the pH tended to decrease (e.g. Va), immediately after waste application. There was a general decrease in pH over time, with a concurrent increase in exchangeable acidity, due to nitrification processes. The EC of all the soils increased sharply with an increase in EW application rate, attributed to the very saline nature of the EW. Water-soluble Mn concentrations in the soils treated with SS tended to be below measurable limits, except in the acid la. Iron concentrations decreased with an increase in SS application rate and over time for all soils. The water-soluble concentrations of Mn, Ca, Mg and S increased sharply with an increase in EW application rate in all soils. There was also a general increase in Mn concentrations over time. Iron concentrations tended to be low in the EW-treated soils, while Co concentrations increased as EW application rate increased. Exchangeable (EX, 0.05 M CaCh-extractable) concentrations of Fe, Co, Cu, Zn and Ni were low in the SS-treated soils. The concentrations of EX-Mn tended to increase with an increase in SS application rate in the la soil, but generally decreased in the other soils. There was also a decrease over time, attributed to the high pH leading to immobilisation of Mn. The EX-metal concentrations of the EW-treated soils were generally low, except for Mn. The concentrations of EX-Mn increased sharply as EW application rate increased. The contribution of EX-Mn was calculated to range from 209 to 3 340 mg Mn for EW rates of 20 to 320 g kg-I, respectively. In the Lo soil the expected amount of Mn was extracted at the different EW application rates. In the other soils the EX-Mn concentrations were typically higher than expected. This was attributed primarily to the dissolution ofMn from the EW due to the interaction between soil organic matter and the EW. There was generally an increase in EX-Mn concentrations over time, attributed to the decrease in pH of the soils treated with EW. The above-ground biomass production of ryegrass grown in Lo and Hu soils treated with SS increased at low application rates, but decreased again at the highest rates. The reduction in yield was attributed to an increase in soil pH leading to trace nutrient deficiencies. At the lower SS application rates, nutrient concentrations of the ryegrass tended to be within typical adequate ranges reported in the literature. Of concern was the elevated Mn concentration in the ryegrass foliage, though no toxicity symptoms were seen. This was attributed to the dissolution of the silicate mineral due to soil acidification processes and the possible ameliorating effect of high Ca and Si concentrations on Mn toxicity. The growth of ryegrass was generally poor in the Hu soil treated with EW and it did not survive beyond germination in the Lo soil treated with EW. In the Hu soil plants grew well in the 20 and 40 g kg-I EW treatments, but died at the higher rates. In both cases mortality was thought to be due to the high salinity that resulted in toxicity and osmotic stress in the newly germinated seedlings. The improved growth at the lower rates ofEW, in the Hu soil, was attributed mainly to increased N availability. The concentrations of Mn in the foliage were elevated in the soils treated with EW. A pot experiment was conducted to test the effect of applying either humic acid (HA) or compost (at a rate of 20 g kg-I) with lime (at rates of 0, 5 and 10 Mg ha-I) on the growth and nutrient uptake of ryegrass grown in the Hu soil treated with EW at rates of 0, 10, 20 and 40 g kg-I. A basal P-fertiliser was also applied in this experiment. The highest yields were measured in the treatments receiving either HA or compost at the highest application rate ofEW. The addition oflime did not improve the yield of the HA treatments, but did in the compost treatments. Generally, nutrient concentrations were adequate. The Mn concentrations were markedly lower than expected, and this was attributed to the formation of insoluble Mn-P compounds due to the addition of fertiliser. The effect of either HA or compost on Mn concentrations was not marked, but lime reduced Mn uptake. A leaching column experiment showed that, generally, the Mn was not readily leached through a simulated soil profile, though the addition of compost may enhance mobility. There was also evidence to indicate an increase in salinity and that Co concentrations of the leachate may be a problem. These data suggest that soil organic matter may be a very important factor in determining the release of Mn from the wastes, notably the EW. The land disposal of the SS and EW was not recommended at the rates investigated here, as both showed the potential for Mn accumulation in above-ground foliage, even at low application rates, while high application rates negatively impacted on plant growth. It appears that P-compounds may be beneficial in reducing Mn availability in the EW, but further testing is required. / Thesis (Ph.D.)-University of KwaZulu-Natal, Pietermaritzburg, 2007.

Gold mining in the Witwatersrand Basin of South Africa has resulted in soil contamination due to the lack of sufficient environmental management plans for the tailings dumps and remnant footprints. Tailings reclamation as a strategy of reducing pollution in the Central Rand, for instance, has resulted in contamination of water systems by acid mine drainage (AMD). After removal of the tailings dumps, remnant material is left over on the tailings footprints and these contain significant amounts of pollutants that were initially in the tailings. Heavy rainfall during summer dissolves primary minerals and later in the dry season, secondary minerals are precipitated as efflorescent crusts on and nearby tailings dumps as well as footprints due to high evaporation. The efflorescent crusts can redissolve when it rains and form acidic, metal and sulphate-rich solutions due to their soluble characteristics. This study aimed to characterise tailings footprints in areas targeted for human settlements and office spaces to assess their potential to release left over toxic elements such arsenic (As), lead (Pb), copper (Cu) and zinc (Zn). The approach to the study involved characterisation of oxidised and unoxidised tailings material and secondary precipitates on both tailings dumps and footprints. This involved determining the mineralogical composition using Powder X-ray Diffraction (PXRD). Dissolution and leaching studies were also conducted on the material followed by determination of constituent elements using inductively coupled plasma optical emission spectroscopy (ICP-OES) and sulphates using ion chromatography (IC). The leaching solutions used included rainwater; dilute sulphuric acid at pH of 3.0 (a common leachate in such acidic soils); as well as plant exudates such as oxalic and citric acids. The leachate solutions were used to correlate the mineralogical composition of secondary precipitates and tailings footprints. Potential implications on humans following any accidental ingestion of the tailings or contaminated soils were assessed using gastric juices. The ecological risk factors and risk index together with the model to evaluate daily intake and different pathways to humans were used to assess the toxicity caused by exposure to contaminants in the materials. The experimental work was augmented by computer simulations based on geochemical modelling (using the PHREEQC geochemical modelling code) to determine the speciation of elements (and thus their potential lability and bioavailability), dissolution and formation of secondary mineral precipitates in the tailings dumps and footprints. The findings of the PXRD study showed that the mineralogy of the tailings and footprints was dominated by quartz (SiO2) and some minor minerals such as pyrite (FeS2), pyrophyllite (Al2Si4O10(OH)2), chlorite (Mg,Fe)3(Si,Al)4O10), mica (K(Mg,Fe)3 AlSi3O10(F,OH)2) while that of secondary precipitates was dominated by jarosite (KFe3+ 3(OH)6 (SO4)2), goethite (FeOOH), melanterite (FeSO4.7H2O) and gypsum (CaSO4.2H2O). Minerals obtained for the secondary precipitates were corroborated by geochemical modelling. Leaching results using rainwater with pH ranges from 3.5 to 3.9 showed that trace elements are released very slowly from tailings dumps and footprints and in small concentrations during rainy seasons as follows: As (1.5 mg/L-4.5 mg/L), Pb (3.5 mg/L-5.5 mg/L), Cu (4 mg/L-4.8 mg/L) and Zn (23 mg/L-44 mg/L). The release and mobility of Cu, Pb, Zn and As occurs quite markedly when secondary precipitates dissolve, making the immediate impacted environment unfavourable for plant growth and any habits in the vicinity. This was substantiated by simulated dissolutions and assessment of the resulting elemental speciation that pointed to the elements being distributed in bioavailable forms, implying potential uptake by plants (such as vegetables that may be cultivated on such impacted soils). The model was used to evaluate the daily intake and different exposure pathways and the results showed that children may daily intake 48.4 mg kg-1 day-1 and adults‟ 32.8 mg kg-1 day-1 . After 5 years (1825 days) of exposure more harm may be experienced and findings shows that kids are the most victims on these contaminated sites compared to adults. Both children and adults may absorb low levels of these toxic elements daily and after long time of exposure it may cause disease like cancer in their body which may lead to death. Pathways may be through inhalation and accidentally ingesting tailings soil that contain toxic elements. Drawing from the above findings, it will be important that tailings footprints that have been earmarked as land for development (residential or office space) be thoroughly assessed for potential release of toxic elements and high levels of acidity. Further reclamation aimed at reducing these hazards can then be implemented. / College of Agriculture and Environmental Sciences / M. Sc. (Environmental Science)

MESMEG / Department of Mining and Environmental Geology / See the attached abstract below

MENVSC / Department of Ecology and Resource Management / Historically, mining activities have generated vast quantities of abandoned tailings dumps in several regions of South Africa and throughout the world. The management and disposal of huge volumes of tailings dumps has constituted a major challenge to the environment. The current study aims to establish the physicochemical properties and mineralogical characterization of the old copper tailings dump in Musina, to reveal the mobility patterns and attenuation dynamics of potentially toxic or heavy metal species as a function of depth, with a view of assessing their potential environmental impact with respect to surface and ground water systems. This information is crucial in the beneficial utilization of copper tailings in the development of sustainable construction materials as part of reuse approach management system. About twelve tailings samples were collected into polyethylene plastic bags from three established tailings profiles drilled by a hand auger. The collected tailings samples were characterized using standard analytical procedures i.e., X-ray fluorescence (XRF), X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS). The transfer of potentially toxic or heavy metal species from tailings to water was evaluated using the standardized batch leaching test (EN 12457) and speciation-equilibrium calculations on the aqueous extracts performed by MINTEQA2. The leachate concentration of cations in the collected tailings samples was determined by inductively coupled mass spectrometry (ICP-MS) and the leachate concentration of anions was determined by ion chromatography (IC). A modified sequential extraction scheme was applied on the selected tailings samples of the drilled tailings profiles to further understand the mode of occurrence, the geochemical partitioning and distribution, real mobility, and environmental bioavailability of potentially toxic or heavy metal species in the tailings and tailings-soil interface. The extracted fractions or phases from sequential scheme were as follows: (F1) water-soluble fraction, (F2) exchangeable fraction, (F3) carbonate fraction, (F4) iron and manganese hydroxide associated fraction, (F5) organic matter and secondary sulphide associated fraction, (F6) primary sulphide bound fraction, and (F7) residual or silicate fraction. The results obtained from the seven steps sequential extraction scheme were validated by the determination vi of percentage recoveries from pseudo-total digestion or total metal content of the original sample. The distribution of major elements and potentially toxic or heavy metal species in different leachate fractions obtained after each step of sequential extraction of the selected tailings samples was determined by inductively coupled plasma mass spectrometry (ICP-MS). The appraised data was used to reveal the impact of atmospheric oxygen and infiltrating rain-water on the chemistry of copper tailings dump by depth profiles. Macroscopic properties revealed that the abandoned Musina copper tailings are fine to medium coarse grained, and range in color from light/dark gray at the upper or shallow depth of the tailings, to dark reddish-brown at the deeper zone where the tailings are mixed with the underlying soil or soil-interface. The drilled respective tailings profiles were uniform and slightly varied in both mineralogical and bulk chemical compositions with tailings depth. Mineralogical analysis showed the following order of mineralogical composition within the respective tailings profiles: quartz> epidote> chlorite> muscovite> calcite> hematite. Chalcopyrite was the only sulphide mineral observed by optical microscopy, although not identified or quantified by XRD and SEM-EDS analysis. The observed discrete chalcopyrite grains were attributed to the primary mined ore (i.e., chalcopyrite, chalcocite and bornite) during past copper mining activities in Musina. The tailings profiles were characterized by a medium alkaline pH (7.97-8.37) that corresponds very well with the tailings leachates or pore-water pH (8.36-8.46). This pH was constant and slightly varied with tailings depth in the respective tailings profiles. The high abundance of alumino-silicate minerals and traces of carbonates as calcite coupled with low sulphide mineral content, suggested a high neutralization capacity of the tailings which was in common agreement with an alkaline nature of the copper tailings dump. The chemical composition of major elements within the respective tailings profiles followed the order: Si>Al>Fe>Ca>Mg>K>Na, and corresponds very well with the mineralogical composition of the tailings, whereby alumino-silicates were the most abundant minerals in the tailings samples. Nevertheless, the solid-phase concentration of metals decreases with increasing tailings depth as Cu>Sr>Zr>Ni>Zn and was incongruent with the mineralogical composition within the respective tailings profiles. The main secondary minerals were calcite and hematite, and their proportion increased with increasing tailings vii depth. In addition, hematite formed coatings on the rims and corners of chlorite as observed from optical microscopy, and retained relatively high amounts of potentially toxic or heavy metals (up to 862 ppm of Cu, up to 36 ppm of Ni, and up to 25 ppm of Zn) at the upper and shallow depth of the respective tailings profiles, where bulk density was high and low porosity. Based on batch leaching tests, the amounts of potentially toxic or heavy metal species released into solution were low (0.27-0.34 μg/L Pb, 0.54-0.72 μg/L Ni, 0.88-1.80 μg/L Zn, and 20.21-47.9 μg/L Cu) and decreases with increasing tailings depth, indicating that, presently, the tailings have a minor impact on heavy metals load transported to the receiving surface and groundwater systems. The low concentration of potentially toxic or heavy metal species in solution is primarily due to their retention by secondary Fe oxide phases (i.e., hematite) and the prevailing medium alkaline pH condition of the tailings leachate or pore-water. The observations are consistent with MINTEQA2 speciation calculations, which predicted the precipitation of secondary phase cuprite (Cu2O) as the main solubility-controlling mineral phase for Cu, Zn, and Ni. Primary factors influencing aqueous chemistry at the site are neutralization and dissolution reactions as a function of pH, precipitation, and sorption into hydrous oxides (hematite and cuprite). Based on sequential extraction results, the leachable concentration of potentially toxic or heavy metal species in the water-soluble, exchangeable and carbonate fractions of the respective tailings profiles was relatively low, except for Cu and Mn. For instance, the leachable concentration of Cu and Mn reached 10.84 mg/kg and 321.7 mg/kg at the tailings-soil interface (3 m) in tailings profile C, respectively. The low concentration of potentially toxic or heavy metal species (Cr, Co, Ni, Zn, Cd, and Pb) in these fractions could be due to the low solubility of minerals bearing these trace elements caused by variations in pore-water pH in the respective tailings profiles. The high concentration of Cu and Mn in these fractions suggests their high mobility and therefore most available for uptake in the environment. Except for Cu>Mn>Cr, the contents of potentially toxic or heavy metal species in the Fe and Mn oxides and organic matter or sulphides bound fractions was low, due to the low viii quantity of these fractions in the tailings, despite their high affinity and sorption capacity for potentially toxic or heavy metal species. Likewise, the residual fraction of the respective tailings profiles contained the highest proportion of potentially toxic or heavy metal species. Although the highest potentially toxic or heavy metal species content was in fractions with limited mobility, care must be taken since any geochemical change or shift in the tailings pH or acidic conditions may cause them to be displaced to more mobile fractions, thereby increasing their mobility and environmental bioavailability. Therefore, physicochemical properties of the tailings including pH and mineralogical composition of the tailings samples were the main substrate controlling the geochemical partitioning and distribution, potential mobility, and environmental bioavailability of potentially toxic or heavy metal species by tailings depth. The knowledge of mobility and eco-toxicological significance of tailings is needed when considering tailings dump disposal or reuse in the environment. The addition of copper tailings at 3 and 28 days successfully improved the compressive strength of cement mortar mixtures incorporating tailings at C5 (5%) and C10 (10%) respectively, although with small margin relative to the control mixture (C0). The maximum strength was 31.15 Mpa attained after 28 curing days, and slightly varied when compared with other compressive strength on copper blended cement mortars mixtures in other countries, used for the development of sustainable construction materials. The chemical composition, physical properties and improved compressive strength on cement mortars mixtures incorporating copper tailings, implies that copper tailings are suitable for the development of sustainable construction materials, thereby ensuring job creation, availability of land for development usage, and the reduction of environmental pollution induced by the abandoned copper tailings dumps.

MESMEG / Department of Mining and Environmental Geology / This study entails geochemical and mineralogical characterization of gold tailings of Nestor Mine and Glynn’s Lydenberg Mine of the Sabie-Pilgrim’s Rest goldfields. A total of 35 samples were collected and were analysed for chemical composition (XRF and ICP-MS), mineralogical composition (XRD). In addition, acid-base accounting (ABA) techniques had been conducted to predict the potential for acid mine drainage. Seepage from Nestor tailings dump and water samples from the adjacent Sabie River were also collected and analysed by means of inductively coupled plasma mass spectrometry (ICP-MS) and immediate constituent (IC) -analytical techniques. The study revealed that Sabie-pilgrim’s rest goldfield is characterized by both acid generating and non-acid producing tailings, and this is attributed to variations in the mineralogy of source rocks. Gold occurred within the Black Reef Quartzite Formation in the Nestor Mine and within the Malmani Dolomite in the case of Glynn’s Lydenburg Mine. Mineralogy and bulk geochemical analyses performed in this study showed a clear variation in the chemistry of Nestor Mine and Glynn’s Lydenburg Mine tailings. Predominant oxides in Nestor mine tailings samples are SiO2 (ranging from 66.7-91.25 wt. %; followed by Fe2O3 and Al2O3 (in range of 0.82-15.63 wt. %; 3.21-12.50 wt. % respectively); TiO2 (0.18-10.18 wt. %) and CaO (0.005-3.2 wt. %). Also occurring in small amounts is CaO (0.005-3.2 wt. %), K2O (0.51-2.27 wt. %), MgO (0.005-1.46 wt. %), P2O5 (0.029-0.248), Cr2O3 (0.013-0.042 wt. %) and Na2O (0.005-0.05 wt. %). The samples also contain significant concentrations of As (137-1599 ppm), Cu (34-571 ppm), Cr (43-273 ppm), Pb (12-276 ppm), Ni (16-157 ppm), V (29-255 ppm), and Zn 7-485 ppm). In the Glynn’s Lydenburg Mine tailings SiO2 is also the most dominant oxide ranging between 47.95 and 65.89 w%; followed by Al2O3 (4.31 to 16.19 wt. %), Fe2O3 (8.48 to 11.70 wt %), CaO (2.18 to 7.10 wt. %), MgO (2.74 to 4.7 wt. %). Occurring in small amounts is K2O (1.12-1.70 wt. %), MnO (0.089-0.175 wt. %), P2O5 (0.058-0.144 wt. %) and Cr2O3 (0.015-0.027 wt. %). Arsenic (As), is also occurring in significant amounts (807-2502 ppm), followed by Cr (117-238 ppm), Cu (10-104 ppm), V (56-235 ppm), Ni (45-132 ppm), Pb (13-63 ppm) and Zn (90-240 ppm). Nestor Mine tailings associated with Black Reef Formation mineralization have net neutralizing potential (NPR) <2, hence more likely to generate acid; and their acid potential (AP) ranges 1.56 to 140.31 CaCO3/ton and neutralizing potential (NP) range from -57.75 to -0.3 CaCO3/ton. Glynn’s Lydenburg Mine tailings dump which is vi associated with dolomite mineralization, however, was not leaching acid. Based on acid-base accounting results, these tailings have more neutralizing potential (ranging between 57.6 and 207.88 CaCO3/ton) than acid potential (ranging between 7.5 and 72.1 CaCO3/ton); and their NPR>2, hence unlikely to produce acid. This is confirmed by paste pH which was in the ranges between 7.35 and 8.17. Tailings eroded from Nestor Mine tailings dump were also found to be characterized by high content of metals and oxides, namely, As, Cu, Ni, Pb, V, and Zn with SiO2, Fe2O3 and TiO2. The tailings were observed eroded into the Sabie River where AMD related precipitate (yellow boy) was also observed, indicating further oxidation downstream. Field observations, onsite analyses of water samples and laboratory results revealed that Nestor Mine tailings storage facility discharges acid mine drainage with considerable amounts of Al, As, Cu, Fe, Mn, Zn and SO4 and very low pH exceeding the limit as per South African water quality standards. High concentrations of these metals have toxicity potential on plants, animals and humans. Upon exposure to oxygen and water, tailings from Nestor Mine are more likely to generate acid mine drainage that can cause detrimental effect to the environment and the surrounding communities. Potential pollutants are Fe, Mn, Al, As, Cr, Cu, Ni and Pb. Tailings from Glynn’s Lydenberg showed no potential for acid mine drainage formation. / NRF