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)

The aim of this study is to determine the content of toxic and essentials elements in samples of nuts and seeds produced by ecologic agriculture and to compare results with nuts and seeds from conventional agriculture production. These nuts and seeds can be bought in the Czech market (except bio pine nuts, bio pecan nuts and bio pistachios). The amount of elements was analysed using inductively coupled plasma mass spectrometry after previous digestion of samples using microwaves. This study summarizes the main physiological functions of toxic and essentials elements. Results were also compared with another studies. It does not results from all measured amounts of all essential elements, that bio nuts and seeds have higher amounts of these elements; however, all amounts of toxic elements in bio nuts and seeds are lower than in the no-bio ones. For more precise results it would be necessary to measure more samples.

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.