Waste-generating industrialisation is intrinsically associated with population and economic proliferation. This places considerable emphasis on South Africa's water shortage due to the integral relationship between population growth rate and infrastructure development. Of the various types of industry-generated effluents, those containing organic pollutants such as phenols are generally difficult to remediate. Much work has been reported in the literature on the use of enzymes for the removal of phenols from these waste-streams but little application of this bioremediation approach has reached practical fruition. This study focuses on integrating and synergistically combining the advantages of enzyme-mediated dephenolisation of synthetic and industrial effluent with that of membrane teclmology. The ability of the enzyme polyphenol oxidase to convert phenol and a number of its derivatives to chemically reactive o-quinones has been reported extensively in the literature. These o-quinones can then physically be removed from solution using various precipitation or adsorption techniques. The enzyme is, however, plagued by a product-induced phenomenon known as suicide inactivation, which renders it inactive and thus limits its application as a bioremediation tool. Integrating membrane technology with the enzyme's catalytic ability by immobilising polyphenol oxidase onto polysulphone and poly(ether sulphone) capillary membranes enabled the physical removal of these inhibitory products from the micro-environment of the immobilised enzyme which therefore increased the phenol conversion capability of the immobilised biocatalyst. Under non-immobilised conditions it was found that when exposed to a mixture of various phenols the substrate preference of the enzyme is a function of the R-group. Under immobilised conditions, however, the substrate preference of the enzyme becomes a function of certain transport constraints imposed by the capillary membrane itself. Furthermore, by integrating a quinone-removal process in the enzyme-immobilised bioreactor configuration, a 21-fold increase in the amount of substrate converted per Unit enzyme was observed when compared to the conversion capacity of the inunobilised enzyme without the product removal step. Comparisons were also made using different membrane bioreactor configurations (orientating the capillaries transverse as opposed to parallel to the module axis) and different immobilisation matrices (poly(ether sulphone) and polysulphone capillary membranes). Conversion efficiencies as high as 77% were maintained for several hours using the combination of transverse-flow modules and novel polysulphone capillary membranes. It was therefore concluded that immobilisation of polyphenol oxidase on capillary membranes does indeed show considerable potential for future development.

M.Sc. / The prevalence of natural organic matter (NOM) in water remains a huge challenge for water treatment companies and municipalities. NOM, however, is not a stand-alone problem as it affects water quality in many ways. NOM is largely responsible for the formation of disinfection by-products (DBPs) via its interaction with disinfectants during water disinfection. It is implicated for the undesirable colour, taste and odour of water and NOM even inhibits precipitation precursors which form the backbone of drinking water treatment. There is therefore no question that NOM, which is either a precursor to or direct cause of the problems highlighted above, should be considered as one of the critical design parameters to be considered for drinking water treatment. In our laboratories, research that involves the use of cyclodextrin (CD) polyurethanes for the removal of organic pollutants from water has been extensively investigated, and the CD polyurethanes have demonstrated the ability to effectively remove the organic species from water at low (ppb) concentrations. CDs, which are cyclic oligomers consisting of glucopyranosyl units linked together through α-1,4 glycosidic linkages, behave like molecular hosts. They are capable of forming inclusion complexes with guest molecules and hence can be utilised for the removal of organic contaminants from water. Their solubility in water, however, limits their application in the removal of organic contaminants from water. This limitation is easily resolved by polymerising the CDs into water-insoluble polymers with bifunctional linkers such as hexamethylene diisocyanate (HMDI). In this study, CD polyurethanes and ion exchange resins were used for the removal of NOM and possibly its DBPs from water. This study first investigated the local NOM source to establish its type and character, hence the study involved the characterization of the bulk water samples and fractionating the NOM using ion exchange resins for further characterization. The water samples were found to consist mainly of humic substances in the form of hydrophobic NOM, with the hydrophilic basic (HpiB) fraction being the most abundant NOM fraction in all samples. Trihalomethanes (THMs) were used as a representative of DBPs in this vii study. THMs formation studies of the individual NOM fractions indicated that all six NOM fractions were found to form THMs but in varying proportions. The HpiB fraction was found to be the most reactive precursor fraction for THMs formation. The ozonation process was also independently evaluated for its ability to remove the NOM fractions from water. Ozonation was found not to be very effective at NOM removal since it only resulted in a 12% overall decrease of the NOM in the water samples. The CD polyurethanes, when used alone, were also not very effective at removing the NOM fractions from water (maximum of 33% NOM removal). On the other hand, the combination method (i.e. the use of CD polyurethanes and ozonation for NOM removal) resulted in a good capability of the CD polyurethanes at decreasing some NOM fractions in water as evidenced by a 73% and 88% decrease of the HpiB and hydrophilic acid (HpiA) fractions, respectively. The 73% reduction of the HpiB fraction demonstrates a great success of the combination approach employed herein, as this study reports this fraction as the most reactive precursor fraction for THM formation.

M.Sc. / Improper disposal of industrial effluents that contain heavy metals such as mercury causes a threat to the environment due to the toxic effects of such matal even at low concentrations. It is also known that sewage waste in water contains bacteria that pose a health hazard to human beings, animals and micro-organisms. One major concern is the transmission of diseases through drinking this water; which destabilizes the water supply. Water for human consumption therefore needs to be of high quality. In this study copper-containing multiwalled carbon nanotubes (Cu/MWCNTs) were investigated for their ability to remove and kill mercury (Hg2+) and Escherichia coli (E. coli), a major species found in the coliform bacteria. These Cu/MWCNTs were synthesized “in situ” by using an electric arc-discharge apparatus and separately via one of two multi-step wet chemical techniques namely; an electroless plating and impregnation method respectively. MWCNTs used for the wet techniques were synthesized by a nebulized spray pyrolysis (NSP) process using ferrocene/toluene under argon flow. These MWCNTs were purified and functionalized to introduce functional groups that made provision for the nucleation of the copper metal on the surface of MWCNTs. Infrared spectroscopy confirmed the successful introduction of COOH and O-H groups on the surface of MWCNTs. Raman spectroscopy confirmed a relative increase in the intensity the ratio of the D-band after functionalization. Deposition of the copper nanoparticles by electroless plating method in different volumes of 100 ml, 80 ml and 60 ml produced copper nanoparticles of varying sizes and distribution on the surface of MWCNTs. SEM images revealed densely and homogeneously distributed small sized copper nanoparticles that followed the trend; 100 ml> 80 ml > 60 ml. The volume proved to be a critical factor of the electroless plating bath with an increase or decrease of the volume affecting the concentration of the Cu2+ ions and HCHO, which also affected the pH of the plating solution.

M.Sc. / Millions of inhabitants worldwide are exposed to arsenic contaminated drinking water as a result of natural and man-made processes. Arsenic especially its inorganic forms, arsenic (III) and arsenic (V) have negative effects on human health especially in developing countries. Therefore fabricating low cost and efficient adsorbents for arsenic (III) removal is of great importance. The aim of this study is to use magnetite (Fe3O4) as filler, incorporated into a polymer blend forming composites as adsorbents for arsenic (III) removal. This work presents the fabrication, characterization and application of Fe3O4-EVA/PCL composites for arsenic (III) removal from water. Fe3O4/Ethylene-vinyl acetate copolymer (EVA)/polyaniline (PANI) and Fe3O4/Ethylene-vinyl acetate copolymer (EVA)/polycaprolactone (PCL) nanocomposites have been successfully synthesized by melt blending technique using a laboratory mixer (Thermo Scientific Haake Rheomex OS). The composites were characterized using scanning electron microscopy (SEM) and x-ray diffraction (XRD) techniques. Thermal analysis was done by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mechanical properties using INSTRON 4443 mechanical Tester. Ability of [EVA (70%) PCL (15%) Fe3O4 (15%)] composites to adsorbed As(III) from water has been investigated through batch experiments. The maximum adsorption was 2.83 mg/g of As(III) ions at 26 ±1°C and pH 8.6. Adsorption data were fitted to Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The process fits well with the Langmuir isotherm. As(III) obeyed pseudo-second order kinetics. The nanocomposites investigated in this study showed good potential for As(III) removal from contaminated water may be due to the dispersion of the magnetite nanoparticles into the polymer blend composites which increases the surface area for the adsorption.

M.Tech. (Biotechnology) / Please refer to full text to view abstract

D.Ing.

M.Tech. (Extraction Metallurgy) / For many decades, carbon nanotubes (CNTs) have been used as adsorbents for the removal of pollutants from wastewaters because of their unique properties such as inert surface, resistance to acid and base environment, rigidity and strength. Herein is a report of application of functionalised CNTs on the adsorption of metal ions from aqueous solutions and mine leachates. The CNTs were first synthesised in-house, purified, functionalised and characterised with various characterisation techniques: FTIR (Fourier Transform Infrared), SEM (Scanning Electron Microscopy, TEM (Transmission Electron Microscopy), EDS (Energy Dispersive Spectroscopy), Raman Spectroscopy, TGA (Thermal Gravimetric Analysis) and BET (Brunauer-Emmet-Teller). Together, these techniques gave substantiation for structure, surface and chemical modification of the synthesised moieties. After characterisation, the functional groups were attached to the walls of the tubes and this implies successful functionalisation...

M.Sc. (Chemistry) / Polymer nanocomposites are a new class of composites in which at least one dimension of the particles dispersed in the polymer matrix is in the nanometer range. Recently, different types of zeolite minerals, either natural (Clinoptilolite, chabazite, modernite) or synthetic (A-type, X-type, Y-type) are being employed as particulate fillers into the polymer matrix. Owing to their unique ion exchange phenomenon, zeolites have been widely studied as heavy metal adsorbents, but very few researchers have focused on the sorption of heavy metal ions on zeolite-filled polymer nanocomposites...

M.Sc. (Chemistry) / The quality of fresh water is deteriorating due to pollution by a wide range of substances as a result of industrial, agricultural, domestic, mining and other anthropogenic activities. Even at trace levels in water, some pollutants are toxic to organisms through acute or chronic effects or through bioaccumulation. Conventional water treatment is often ineffective at removing pollutants to the ultra-low levels required by water quality standards and other technologies employed to remove toxic compounds from water have high capital and operating costs and other disadvantages. There is therefore an ongoing need to develop low-cost technologies that are effective for the removal of toxic pollutants from water. In our laboratories, iron and nickel (Fe/Ni) decorated carbon nanotube (CNT)/cyclodextrin polymers (β-CDs) showed promising results in previous studies carried out for the degradation and removal of toxic organic pollutants in water. However, the powder form of the polymer makes its direct application in water treatment difficult. The leaching of metal nanoparticles and carbon nanotubes from the polymer into the water being treated is also of concern due to their potential toxicity. In this study, alginate beads were investigated as supports for two kinds of nanocomposites, Fe/Ni decorated carbon nanotubes and Fe/Ni decorated carbon nanotube/cyclodextrin polymers. Alginate beads were selected as supports to render the nanocomposites more conducive towards water treatment applications since they are easy to handle and recover from water and are also stable supports that can prevent the leaching of nanomaterials into treated water.

M.Sc. / Inorganic pollutants like heavy metals are some of the major water pollutants worldwide. They are toxic and in some cases carcinogenic even at low concentrations. Their removal from industrial aqueous solutions, wastewater and hydrometallurgical process solutions prior to their release to the environment is necessary for a healthy biosphere which includes human beings, aquatic life and plants. There are several technologies used to remove metals such as Cu, Co, Zn, Hg from water. These include among others, ion exchange, membrane filtration, activated carbon, electrochemical treatment, chemical precipitation, reverse osmosis, coagulation and flocculation. Although they have been used in the removal of metal pollutants from water, these technologies produce high quantities of sludge. They are also expensive to operate and need well trained personnel to operate large chemical plants. Since current metal removal techniques have limitations, a need exists for the development of environmentally friendly and cost effective techniques for the removal of metal ions from aqueous media. The focus of this research project is on the use of micro-organisms as biosorbents for copper and cobalt pollutants in aqueous solutions. The experimental work was carried out on a laboratory scale and a summary of our findings is presented as follows: Synthetic sulphate solutions of copper and cobalt were prepared using CuSO4. 7H2O and CoSO4. 5H2O powders. Concentrations of 0.002 M, 0.07 M and 0.2 M copper and cobalt ions in solution were used as test synthetic solutions for our experiments. Mixed strains of bioleaching bacteria were sourced from Mintek (Randburg, South Africa) to test the viability of this research project. This consortium contained Acidithiobacillus caldus, Leptospirillum spp, Ferroplasma spp and Sulphobacillus spp. These bacteria were able to remove up to 55% copper and 25% cobalt from low concentrated copper and cobalt sulphate solutions with 69% and 58% removal demonstrated in the case of mine effluents emanating from metallurgical operations. Different strains of micro-organisms (bacteria) were isolated from mine dumps and mine operation effluents and soil from the Palabora Mining Company in Limpopo, a northern province in South Africa and Nigel Town in the Gauteng Province. The isolated bacterial strains were then identified using PCR analysis and strains from the Bacillus genre were found to be predominant. Shewanella spp was also present. Pseudomonas spp was isolated using Pseudomonas agar base. These bacteria were then cultured at different species-specific culture conditions and their capabilities to remove copper and cobalt ions first from synthetic solutions and subsequently from mine effluents emanating from metallurgical operations were tested. In the first stage of biosorption experiments, factors that affect biosorption mechanisms which include, solution concentration, biomass concentration, pH, contact time and the presence of other metal co-ions were investigated. A decrease in the amount of metal sorbed as solution concentrations increased was observed with all the bacterial strains. An increase in metal sorption was also observed when biomass concentration was increased. The pH was found to be a species dependant parameter.