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.

M.Sc. (Zoology) / Pans are endorheic wetlands, and are abundant in South Africa in a band from the western Free State into Mpumalanga. The pan environment experiences daily and seasonal fluctuations in physico-chemical conditions. The physico-chemical variables are influenced by the local climatological and hydrological conditions, and are all inter-related. An imbalance of one variable can have countless effects on the others. The physico-chemical composition of the water ultimately determines the existence of the biota in such wetlands. Branchiopod crustaceans are a unique group of fauna which have various morphological, physiological and behavioural adaptations which enable them to survive in these variable environments. One such adaptation is the production of dormant egg banks. These eggs reside within the sediment through the dry phase and hatch during a following wet phase when conditions are favourable. Due to the endorheic nature of pans they are more vulnerable to anthropogenic stress. Anthropogenic activities are having profound effects on the integrity of these ecosystems. Agricultural and mining activities have some of the largest influences. The impacts that the following activities have include: the over utilisation of water, decreased periods of inundation, erosion and sedimentation, effluent discharge and direct habitat destruction. Many wetlands as a result are experiencing a rapid loss in biodiversity. Mining activities are on the increase especially in the Highveld region of southern Africa. Many of these wetlands are already (and will be in the future) affected by mining activities, making the effect of acid mine drainage (AMD) on the biota a priority concern. In conjunction with the uniqueness and vulnerability of pan ecosystems it is necessary to find new ways of monitoring such environmental impacts in the shortest time possible with minimal efforts, for the benefit of both the environment and researchers involved. This study therefore aimed to assess the diversity of branchiopod crustaceans hatching from egg banks of selected pans and obtain a reference community structure. It also aimed to assess the impacts AMD could have on the hatching success of branchiopods from these egg banks with the objective to determine whether these egg banks are still viable after exposure. To achieve the stated aims and objectives, sediment samples were collected from selected pans in mining regions of the country. Regions selected included Chrissiesmeer in the Mpumalanga province, Wesselsbron in the Free State province and Delareyville in the North West province. The sediment was used for hatching experiments in the laboratory. Pan sediment was exposed to three different treatments which included two salt solutions (1000 mg/l and 1500 mg/l respectively) and AMD. The salt solutions served as controls while the AMD served as an exposure. The number of nauplii hatching was counted in the controls and compared to the number of nauplii hatching in the AMD. The diversity of nauplii was also assessed and compared between controls and the AMD. The recovery potential of eggs exposed to AMD was also assessed by exposing the sediment treated with AMD to distilled water after its removal to get a better understanding on the effects of AMD at the community level. Results from the control treatments indicated that most pans have a range of taxa hatching that follow patterns of pan succession. Between the 1000 mg/l and 1500 mg/l controls there was no treatment that proved superior to the other. Representatives of all four orders of branchiopoda hatched from the experiments. The North West and Free State pans were the most diverse and had had the greatest abundances of individuals hatching. Spatially all three provinces differed in the diversity of individuals hatching from pans, as there were distinct differences in the taxonomic compositions. Although taxonomic composition of pans grouped together per province, pans from just a single province were largely dissimilar. Results from the AMD treatments indicated that AMD has a negative effect on the hatching ability of branchiopod crustacean eggs. Eggs that were initially exposed to AMD were unable to hatch in its presence. The recovery experiments indicated that recovery after exposure is limited as recovery only occurred in a few pans. The taxonomic composition of nauplii in the pans where recovery took place was altered and less diverse than the taxonomic composition found in the respective control treatments. Overall it was found that hatching experiments can be used as a monitoring tool in lieu of field sampling. Hatching experiments showed that AMD is detrimental to the branchiopod egg banks, inhibiting the ability of eggs to hatch in its presence. Recovery can take place but the recovery potential is low. Since the recovery potential of the egg banks is low, pans which are affected by AMD could experience extinction of the entire branchiopod community in years to come. As branchiopod communities are unique among pans, and serve as an important food source for many aquatic bird species, their extinction will bring about further losses in biodiversity.

MESMEG / Department of Mining and Environmental Geology / The increase in the demand and market price of gold has led to reprocessing of gold tailings in many parts of the world. Mines are recently closing down due to depletion of resources and increasing mining costs leading to the reprocessing of old tailings dams. The cost of rehabilitation is high, and therefore a more convenient way of rehabilitation is required. The most convenient strategy identified here was to reprocess tailings for gold and use waste rocks as construction materials. The tailings residues (waste remaining after reprocessing) will be relocated to a more convenient place to avoid pollution. Gold reprocessing from tailings dams has gained momentum in South Africa especially in the Witwatersrand Basin where there are large volumes of tailings. Gold is being reprocessed from tailings in this area using hydraulic monitors. This study focused on the evaluation of gold and heavy metals within the tailings at Consolidated Murchison Mine tailings in Gravelotte, Limpopo province. Augering was conducted over the tailings up to a depth of 8 m along four sampling Profiles. The first profile had two sampling points, the second profile with three sampling points, the third and fourth profiles consisted of four and five sampling points respectively. Samples were collected at 1 m interval, therefore a total of 112 samples were collected and analysed for heavy metals using X-Ray Fluorescence spectrometry and 84 samples were analysed for gold using fire assaying. Tailings sampling was accompanied with tailings logging, taking note of colour, texture and moisture content. Based on this, the oxidation status of the tailings dam was determined. Oxidation zone of this tailings dam was mainly from top down to a depth of 3 m. The transitional zone was not identified, hence after the oxidation zone, the rest was unoxidized zone. This study established that gold was erratically distributed within the tailings dam with the lowest and highest values of 200 mg/kg and 1880 mg/kg respectively and the average was 670 mg/kg. The tonnage of tailings within the dam was found to be 13 280 310 tons with a total gold amount of 8 897. 81 kg. At the current world market, this interprets to US$ 306 932 396.00 (R 4 281 706 924.20). It was concluded that this tailings dam is economically viable for reprocessing, although previous studies have indicated that it is not possible to extract gold from tailings dams completely. The heavy metal content of Pb, Ni and Cr were found to be high with average values of (ppm); 5631.5, 2062.6 and 1345 v respectively. The metals with the lowest values were Cd, Co and Cu, averaging (ppm); 0.01 ppm, 19.8 ppm and 42.1 ppm respectively. Heavy metal content in soil around the tailings dam was gradually decreasing with distance from the tailings dam. Waste rocks have been used in some parts of the world as sub-base material for engineering construction, hence in this study, a total of 6 waste rock samples were collected using grab sampling method for geostatistical investigation. Such samples were subjected to various geotechnical tests which included particle size distribution analysis (sieve analysis), Atterberg limit tests and laboratory compaction test to determine their suitability for construction. The waste rock material was found to be suitable for road construction as it was classified under Group A-1-a using the AASHTO classification system. The material consisted mainly of rock fragments, gravel and sand material with minor silt/clay. In general, Consolidated Murchison mine waste was found to be suitable for road construction. / NRF

Thesis (M.Sc.(Chemistry)) -- University of Limpopo, 2022 / Water contamination caused by toxic elements has serious human health and ecological implications. The increasing quantity of toxic elements in surface and groundwater is currently an area of greater concern, especially since many industries are discharging their metal containing effluents into freshwater without any adequate treatment. The mineral dissolution in mining regions is highly enhanced by mining and smelting activities. The mine waste and drainage in areas surrounding mines have high levels of toxic element contamination above the permissible limits. Contamination of groundwater by toxic elements such as As, Fe, Mn, Al, Cr, Zn and Co due to operational activities of surrounding mines in the Sekhukhune district was reported by several researchers. Removal of toxic elements from contaminated water is a big challenge. The affected communities need to attain a safe water supply source for daily usage, hence there is an urgent need of technologies for the treatment of water supplies contaminated with these toxic elements to ensure the safety of potable water. The study was undertaken by modifying nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) and investigating the removal of chromium, nickel and lead from anthropogenic contaminated groundwater in the Sekhukhune area, in Limpopo. The as-prepared N-MWCNTs functionalised with metal oxide, thiol and amino functional groups are expected to increase the surface area of the nanocomposite, which can facilitate high adsorption of contaminants from water samples. The adsorption capabilities for the removal of these toxic elements by modified N MWCNTs nanocomposites were investigated in batch studies as a function of different parameters. The parameters studied included pH, contact time, adsorbent dosage, initial concentration, temperature, competing ions and reusability. The optimum condition was then acquired for removal of selected toxic elements from real water studies. The removal efficiencies of the as-prepared nanocomposites were pH dependent and the optimal pH values for adsorption was 5.5, 1.5, 11 and 6 at optimum contact time of 10, 80, 60 and 120 min and dosage of 0.30, 0.35, 0.05 and 0.6 g/L for Cr(III), Cr(VI), Ni(II) and Pb(II), respectively. The prepared nanocomposites were characterised using various techniques such as Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmet-Teller (BET) and thermogravimetric analysis (TGA). The FTIR analysis confirmed the presence of Fe3O4, -SH and -NH2 groups on the functionalised MWCNTs. The PXRD analysis further supported that the synthesized nanocomposites consisted of hexagonal graphite structure of MWCNTs. Furthermore, SEM and TEM results showed that the introduced functional groups were uniformly attached on the surface of the MWCNTs. The BET analysis indicated that the surface area of the modified MWCNTs nanocomposites increased significantly as compared to the acid treated MWCNTs. In addition, TGA showed that the M-MWCNTs (M = modified) nanocomposites possess high thermal stability. Raw N-MWCNTs showed higher stability as compared to oxidised N-MWCNTs, which decomposes at lower temperatures of 200 °C. No weight loss was observed below 800 °C for the hydrazine functionalised nanocomposites as compared to the triethylenetetramine (TETA)- substituted nanocomposites, which showed weight loss at 300 °C. Toxic elements in solutions before and after treatment were quantified using flame atomic absorption spectrometry (F-AAS). The adsorption isotherms of the as-prepared nanocomposites for chromium, nickel and lead removal fitted both the Langmuir and Freundlich model depending on the adsorbent used, which suggest that the adsorption process met both monolayer and heterogeneous adsorption. Thermodynamic analysis showed that the adsorption of Cr(III), Cr(VI), Ni(II) and Pb(II) ions are spontaneous and endothermic. The as-prepared nanocomposites showed an outstanding regeneration performance retaining over 50% toxic elements removal. Thus, the as prepared nanocomposites are promising for practical application in toxic element treatment. Analysis of the collected river and borehole water in Sekhukhune indicated that the concentration of total chromium, nickel and lead before treatment varied from (0.207 to 0.286 mg/L), (0.226 to 0.380 mg/L) and (3.301 to 8.017 mg/L), respectively which were above acceptable levels recommended by the South African National Standards (SANS), United States Environmental Protection Agency (USEPA) and World Health Organisation (WHO), i.e., 0.05 mg/L, 0.07 mg/L and 0.01 mg/L. After treatment, the nanocomposites were able to remove 100% of the metal ions from the water. TETA-functionalised nanocomposites showed greater removal efficiencies in comparison to the hydrazine-functionalised nanocomposites for all the studies done. / Water Research Commission (WRC)

PhDENV / Department of Ecology and Resource Management / See the attached abstract below