3. Electronic Theses and Dissertations (ETDs) - All submissions
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Item An assessment and evaluation of dissolved methane concentrations at a natural gas extraction site in the Free State Province, South Africa(2018) Patel, KhalidA worldwide concern associated with natural gas exploration and extraction is the potential for contamination of shallow groundwater. A natural gas extraction operation is underway near Virginia in the Free State Province of South Africa. The aim of this study is to determine whether ongoing gas extraction activity has affected the chemical composition of surrounding groundwater. This was achieved through resampling of boreholes (water wells) previously sampled in 2015 by the operator, prior to gas extraction. Dissolved methane (CH4) above the laboratory limit of detection was present in six out of seven re-sampled boreholes, at distances between 153 and 1538 m from the production well. Dissolved CH 4 concentrations ranged from < 0.007 to 3.16 mgCH4/l, with an average of 0.234 mg/l. Dissolved CH4 concentrations were positively correlated with manganese (r=0.347, n=55, p=0.010) and negatively correlated with bromide (r=-0.338, n=55, p=0.012), calcium (r=-0.303, n=55, p=0.024), sulfate (r=-363, n=55, p=0.006) and electrical conductivity (r=-0.266, n=55, p=0.049). No statistically significant correlation was observed between dissolved CH4 concentrations and proximity to the gas well (r = 0.221, n = 55, p = 0.105), elevation relative to the production well (r = 0.190, n = 55, p = 0.165) or sampling depth (r = .330, n = 55, p = 0.469). The small observed decrease in the mean concentration of dissolved CH 4 between 2015 and 2017 was not statistically significant (p = 0.812). Thus, no evidence was found that the gas extraction operation has contributed to increased concentrations of CH4 in groundwater by means by stray gas migration from the production well. The methane in the sampled wells is believed to be of biogenic origin, based on the positive correlation between dissolved CH4 and NH4 (p=0.045) and the non-detection of higher-chain hydrocarbons. Comparison of pre- and during-production analyses for 24 water quality variables identified several statistically-significant changes over time: increases in pH (0.195 units), arsenic (0.002 mg/l), lead (0.001 mg/l), potassium (0.875 mg/l) and dissolved organic carbon (7.647 mg/l). The South African drinking quality guidelines were exceeded, both before and during gas production, for electrical conductivity, chloride and manganese.Item Synthesis of magnetic sorbents modifie with moringa oleifera extracts for the removals of environmental orgamnic pollutants(2018) Kgatitsoe, Maureen MaletsatsiModern developments on nanoparticles (NPs) has led to new innovation in nanoparticles that can be used for the treatment of polluted water. Magnetic NPs are of great interest because of their unique properties and promising applications. Their stability is essential to prevent them from agglomeration, hence, modification with a specific coating layer can assist in the selectivity function and stability of the magnetic NPs. In this work, a magnetic organic nano-adsorbent was synthesized and investigated for the application in the extraction of nitroaromatic explosive compounds from aqueous solutions. The approach was to find a possible synergy between the adsorptive properties of Moringa oleifera and the high surface area of the NPs. The magnetic NPs were utilized for their ferromagnetic properties which assist in the extraction procedure. M. oleifera was used as a natural coating agent to functionalize the magnetic NPs and also to provide stability. There are numerous chemical procedures to synthesize magnetite and one of the simplest and convenient procedures, co-precipitation, was used in this study. Magnetite can be easily oxidized under ambient conditions, hence, in order to prevent oxidation, M. oleifera extracts were used as a coating agent. The synthesized uncoated magnetite NPs and M. oleifera coated magnetite NPs were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR), Brunauer, Emmett and Teller (BET) and thermogravimetric analysis (TGA). The M. oleifera leaf extract was obtained using pressurized hot water extraction (PHWE) at 80°C and the seed extract was purchased as a pure oil. Both the M. oleifera leaf and seed extracts were characterized by FTIR and gas chromatography–mass spectrometry (GC-MS) for possible organic compounds assisting in the stability of the magnetite. From the BET results of the coated magnetic NPs at different times, it was observed that with increasing coating time, the surface area decreased while the pore size increased. To optimize the extraction of nitroaromatic explosive compounds (NAECs), the parameters that were investigated were sample pH, contact time, mass of adsorbent and initial concentration. The optimum value for pH of the sample was found at pH8 and for the contact time an optimum of 120 min was found. The mass of M. oleifera coated magnetic NPs for the maximum removal of explosives were found to be 100 mg. The adsorption capacity of the NAECs was obtained in the range of 0.45 and 0.76 mg g-1 at optimum conditions. During kinetic studies it was observed that the pseudo second order model explained the extent of the adsorption mechanism. It was observed that the Langmuir model was favourable as compared to the Freundlich model. The order of selectivity for the NAECs studied was observed as follows: 2-NT ≈ 3-NT > 4NT > NB > 2,6-DNT > 1,3-DNB. The limit of detection (LOD) found was 0.37 – 4.47 and 0.45 – 5.66 ng.mL-1 for extraction using magnetic NPs coated with M. oleifera leaf and seed extract, respectively. The percentage recovery for the extraction of NAECs at optimum conditions was obtained in the range 14 – 46%.Item Metabolomic exploration of pharmacologically relevant metabolites in Moringa oleifera and Moringa ovalifolia through the use of UPLC-qTOF-MS and multivariate models(2017) Makita, Charlene SampuPlant metabolomics is considered a holistic qualitative and quantitative analysis of primary and secondary metabolites under specific conditions. Metabolomics provides functional information that is important in the biological studies of plants. Moreover, chromatographic techniques in combination with mass spectrometry are presently commonly utilized analytical technologies that are used in metabolomics studies. Moringa oleifera (M. oleifera) is an acclaimed medicinal herb and is considered one of the most superior plants based on its nutritional and medicinal attributes. Signature compounds such as chlorogenic acids and flavonoids found in Moringa plants are considered beneficial as they are responsible for the health properties found in these plants. Out of the 13 species belonging to the Moringaceae family, M. oleifera is the most widely studied. Furthermore, plants are known to produce compounds, such as flavonoids, as a response to biotic stresses (pest resistance) and abiotic stresses (harsh environmental conditions such as drought or cold). Other species belonging to the Moringaceae family such as Moringa ovalifolia (M. ovalifolia), located in the dry desert and semi-desert areas of Namibia, has not been reported much in literature. Moreover, there is very little work done on other classes of compounds that are possibly present in M. ovalifolia. Therefore, the significant correlation between desert plants and their possible increased flavonoid content is of interest in this study and is worth investigating. Moreover, in an effort to compare Moringa species in that regard, a holistic approach to metabolite fingerprinting using UPLC-qTOF-MS was thus employed for the characterization of possible metabolite markers and taxonomical differences in M. ovalifolia and M. oleifera plant species (Paper I). From the results, 17 flavonoid compounds were identified. Interestingly, M. oleifera and M. ovalifolia had a similar aglycone profile, however, they had a different sugar moiety. Rutinoside sugar moieties were only found to be present in M. ovalifolia indicating that it is only capable of attaching the rutinoside sugar moiety to its flavonoid skeleton. M. oleifera, however, is capable of attaching many sugar moieties to its flavonoid skeleton. The outcomes of this research additionally demonstrated for the first time the significance of sugar attachment for taxonomical classification of related species and that the contrasts between the grouped species are likely because of genetic variations as opposed to environmental influences. This study further provided potential chemotaxonomic biomarkers and a classification model was generated to classify and differentiate between closely related Moringa species utilizing multivariate analysis (Paper III). Moreover, chlorogenic acids which are esters formed between derivatives such as cinnamic acid and quinic acid molecules, were identified in M. ovalifolia plants species for the first time (Paper II ). Chlorogenic acids are difficult to identify and differentiate since they are structurally complex. This study demonstrated the effectiveness of an UPLC-ISCID-MS/MS based platform to aid in the profiling of isomers and derivatives of chlorogenic acids present in M. ovalifolia. This approach further showed M. ovalifolia as a valuable source of molecules with therapeutic potential. Based on the classification model generated in Paper II, the biomarkers identified were utilized in order to differentiate between 12 M. oleifera cultivars (Paper III). Three sought after flavonoid compounds, namely, quercetin rutinoside (rutin), kaempferol rutinoside and isorhamnetin rutinoside were identified as potential chemotaxonomic markers amongst the 12 Moringa cultivars. Metabolite distribution patterns of the 12 cultivars were analyzed using a metabolomics approach with the aid of UHPLC-qTOF-MS in combination with multivariate data models such as principal component analysis (PCA), hierarchical clustering analysis (HCA) and box-whiskers plot. According to the results, three main cultivars, namely: TOT4977, CHM and TOT5330 were identified as potential cultivars for pharmacological and nutritional purposes according to the presence and abundance of the three studied rutinoside bearing flavonoid molecules.Item Development of a high pressure hydrometallurgical process for the extraction of iron from iron oxide bearing materials(2016) Rolfe, WesleyThe feasibility of extracting iron from iron(III) oxide bearing materials with acetylacetone has been under investigation for many years. This is an alternate, environmentally friendly process for the recovery of iron compared to conventional processes that are energy intensive, have numerous costly process steps and produce large quantities of greenhouse gases. Iron(III) oxide bearing waste materials can be used in this process which reduces its environmental impact as it would not require waste storage. This study investigated the feasibility of reducing the reaction time of the liquid phase extraction of iron from iron ore fines by performing the extraction at elevated pressures and temperatures. It was found that that the extraction under pressure was dependent on temperature, pressure, particle size and solid to liquid ratio. It was found that at high temperatures and long extraction times, an unknown secondary reaction occurs that consumes the desired product, iron(III) acetylacetonate, and inhibits the recovery of these crystals. This results in lower extraction yields. It was found that the side reaction was largely dependent on the temperature of the system and the amount of iron(III) acetylacetonate present. The effects of the side reaction could be limited by lower operating temperatures and reducing the total reaction times. An optimum conversion of iron(III) oxide to iron(III) acetylacetonate of 47.2% was achieved for synthetic iron (III) oxide (> 95 wt% Fe2O3) at a total extraction time of 4 h, 160 °C, 0.025 g:1 mL, operating pressure of 1700 kPa, initial N2 feed pressure of 1010 kPa and 375 rpm stirrer speed. The optimum extraction of iron from iron ore fines (> 93 wt% Fe2O3) to iron(III) acetylacetonate was found to be 20.7% at 4 h, 180 °C, 0.025 g:1 mL and operating pressure of 1900 kPa, initial N2 feed pressure of 1010 kPa and 375 rpm stirrer speed. These are the optimum conditions where the side reaction is limited to improve the recovery and desired reaction conversion capabilities of the process. The operation under pressure yielded lower conversions than that of the atmospheric leaching process developed by Tshofu (acetylacetone water system under reflux). It was also found that it was not possible to reduce the extraction time and achieve comparable extractions when operating at higher temperatures and pressures. The formation of an additional unwanted product would also lead to unnecessary treatment costs in an industrial process. Hence, it was found that pressure leaching as an alternative is not currently viable due to the lower yields and associated high costs. Atmospheric leaching seems to be the most economically feasible option until a better alternative is found.Item Purification of coal fly ash leach solution by solvent extraction(2016) Rushwaya, Mutumwa JepsonThe solvent extraction of iron and titanium from solution generated by the two-step sulphuric acid leaching of coal fly ash by Primene JMT was investigated. The influence of hydrogen ion concentration, Primene JMT concentration, aqueous to organic volume phase ratio and temperature on the extraction of iron and titanium was determined by the use of Design of Experiments. Hydrogen ion concentration and the interaction between the aqueous to organic volume phase ratio with Primene JMT concentration had a significant effect on the extraction of iron while temperature did not. Hydrogen ion concentration and temperature did not have a significant effect on the extraction of titanium, while the interaction between Primene JMT concentration and aqueous to organic volume phase ratio had a significant effect. Extraction improvement tests showed that at a hydrogen ion concentration of 0.28M, 88% iron and 99% extraction of titanium from coal-fly ash leach solution could be achieved. Construction of a McCabe-Thiele diagram showed that a four-stage solvent extraction system with Primene JMT could reduce the iron and titanium concentration in the coal fly ash leach solutions to below 0.05g/LItem Development of pressurised hot water extraction (PHWE) for essential components from Moringa Oleifera and Ovalifolia leaves(2015-02-06) Matshediso, Phatsimo GimamahUnable to load abstract.Item A study of the elemental analysis and the effect of the pressurised hot water extraction method (PHWE) on the antibacterial activity of Moringa oleifera and Moringa ovalifolia plant parts(2015-01-30) Makita, Charlene SampuHeavy metal pollution is an increasing phenomenon and contamination of these heavy metals has detrimental effects on the environment and humans. The concentrations of metals in the soil, leaves, stem bark and flowers of Moringa ovalifolia sampled from Okahandja, Okaukuejo, Halali and Tsumeb in Namibia were investigated. Acid digestion of all samples was performed utilising the microwave technique. Determination of elements from the extracts were analysed by inductively coupled plasma - optical emission spectroscopy (ICP-OES). No lethal amounts of heavy metals were found in the soil, leaves, stem bark and flowers of Moringa ovalifolia. The results from Moringa ovalifolia was compared to spinach from another similar study. On average, Moringa leaves contained more or less similar amounts of Zn (29.4 mg kg-1) and Cr (13.2 mg kg-1) but higher higher amounts of Fe (263.8 mg kg-1) concentrations than spinach, with values of Zn (30.0 mg kg-1), Cr (20.0 mg kg-1) and Fe (190 mg kg-1) from a previous study. In this study, selected statistical methods such as correlation analysis and principal component analysis were used to identify the origin of these metals in the soil, leaves and stem bark collected from the Moringa farm, national parks and the road side in Namibia. From the correlation analysis, it was found that Co, Mg, Cr and Mg pairs were highly significant to each other. The principal component analysis revealed that heavy metals gave 53.41% of the total variance in factor 1. Sources of Mg and Ni could be from vehicle emissions. Factor 2 revealed As, Co, Al, and Si contributing to a total variance of 25.15% Co suggesting that the metals present could be as a result of geologic sources. This iii study proves that statistical analysis may provide a scientific foundation for the observation of heavy metal accumulation in samples. Pressurised hot water extraction (PHWE) was used for the extraction of bioactive compounds from the leaves and stem bark of Moringa ovalifolia and Moringa oleifera samples. The aim of the study was to assess the effect of temperature and extraction process of the Moringa extracts on Staphylococcus aureus (S. areus), Enterococcus faecalis (E. faecelis) and Pseudomonas aeruginosa (P. aeruginosa). The antibacterial activities of the extracts at varying temperatures were evaluated using the disk diffusion method where the zones of inhibition were recorded. ANOVA, which was calculated at a significance level of 0.05, was used to analyse the data. Antimicrobial activity of the stem bark extracts and leaf extracts from different sites extracted at 25˚C and 80˚C showed significant difference. As temperature increased, a decrease in inhibition was observed for stem bark extracts from different sites tested again S. areus, E. faecelis and P. aeruginosa. When the PHWE stem bark extracts collected in Tsumeb, were compared with ethanol and cold water extractions, the PHWE had more activity than other two methods. This proves that PHWE may be used as a novel extraction to get essential compounds from indigenous plant materials.