The presence of organic contaminants in water has caused great concern over their potential adverse health impact on humans and animals. Organic contaminants found in water are both naturally occurring and synthetic. Various chemical and physical water treatment processes are being used to remove organic contaminants. Conventional water treatment methods include the utilization of activated carbon for the removal of organic contaminants. It is generally conceded that activated carbon owes its adsorptive properties primarily to its large surface area, as well as to its pore size. Although activated carbon is nonselective against most of the water contaminants, it does not remove the concentration of organic contaminants to acceptable levels i.e. ppb. Moreover, activated carbon also absorbs moisture from the air and as a result loses its absorptive effectiveness. For this reason attention has been being given to alternative methods for water treatment especially for the removal of organic pollutants. In this study, cyclodextrin polymers that were water insoluble were synthesized and tested for their ability to remove organic species in water. Cyclodextrins (CDs) and their corresponding derivatives have been used in a wide range of applications including pharmaceutical and pesticide removal and catalysis. Cyclodextrins are cyclic oligosaccharides derived from enzyme degradation of starch. They are known as molecular hosts capable of including of forming inclusion complexes, with a degree of selectivity, with a range of guest molecules via a noncovalent interaction in their hydrophobic cavities. Although the interaction between cyclodextrin and an organic molecule is the basis for absorption or separation of various organic agents, the solubility of cyclodextrin in water and organic solvents impose limitations to the application of cyclodextrins in water treatment. Therefore, polymerizing a cyclodextrin monomer with an excess of a bifunctional linker produces an insoluble polymer which can form inclusion complexes with guest molecules. In this project, the synthesis of a number of cyclodextrin polymers was performed by reacting cyclodextrin with bifunctional linkers. / Dr. B. B. Mamba Dr. R. W. M. Krause Dr. T. J. Malefetse

Effects of several important source-related and operation-related factors on particle formation and growth as well as potential particle and dissolved organic matter removal by alum coagulation are described. Two representative natural water sources, with low turbidities and high concentrations of dissolved organic matter, and one commercially available crystalline silica, with defined characteristics, were employed to establish initial aquatic particle and dissolved organic matter conditions. Six experimental variables utilized for evaluation include initial pH, initial turbidity, applied pre-ozonation dose, alum dose, flocculation time and sedimentation time. A bench-scale experimental apparatus with capabilities of ozonation, coagulation, sedimentation and membrane filtration was employed to conduct a series of selected experiments. Each factor investigated in this research proves to be able to inpart, individually or collectively, statistically significant effects on particle formation and growth during alum coagulation. While the addition of model particles shows significant enhancement in particle growth, it fails to demonstrate significant improvement in the removal of dissolved organic matter. On the contrary, effects of pH and alum dose on particle formation and growth are accompanied by corresponding effects on the removal of dissolved organic matter. Pre-ozonation of dissolved organic matter renders the dissolved organic matter more hydrophilic by increasing the number of carboxylic acid functional groups. This phenomenon can significantly improve or impede particle growth as well as dissolved organic matter removal during alum coagulation, depending on raw water chemistry and other operational factors. Alum coagulation under all of the conditions investigated in this research is demonstrably more effective in removing aquatic humic susbtances with higher apparent molecular weights and fewer carboxylic acid functional groups, as opposed to those with lower apparent molecular weight and more carboxylic acid functional groups. The predominant removal mechanisms were found to occur at the beginning stage of the coagulation process; that is, the rapid mixing period. The remaining dissolved organic matter and humic substances can form significant amounts of trihalomethanes upon reaction with chlorine.

M.Sc. / The prevalence of toxic contaminants in water remains a huge challenge for water supplying companies and municipalities. Both organic and inorganic contaminants (especially heavy metals) pollutants are often present in water distribution networks. Organic and inorganic pollutants often co-occur in drinking water networks. However, at present there is no water treatment intervention that simultaneously removes organic and inorganic pollutants from water. Additionally, current water treatment technologies fail to remove these contaminants to parts per billion (ppb or µg.L-1) levels. Methods that can simultaneously remove organic and inorganic pollutants to desired levels need to be developed. In our laboratories, both functionalised and unfunctionalised cyclodextrin (CD) polymers have demonstrated the ability to effectively remove organic species from water at low (ppb) concentrations. Cyclodextrins (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 interacting with a range of guest molecules within their cylindrical hydrophobic cavities thereby forming the so-called inclusion complexes. Their solubility in water, however, precludes their application in the removal of organic pollutants from water. This limitation is easily dealt with by polymerizing the CDs into water insoluble polymers with suitable bifunctional linkers. On the other hand, ionic liquids (ILs) have been reported to “absorb” heavy metal ions from aqueous media. ILs are low melting point molten salts that are composed of organic cations (e.g. imidazolium and pyridinium ions) and mostly inorganic anions like Cl–, Br–, [PF6]– and [BF4]–. In this study, the two systems were combined by an initial attachment of the imidazolium or pyridinium rings to the cyclodextrin moiety. Polymerisation of the resulting cyclodextrin-ionic liquid (CD-IL) complexes with a suitable linker produced the corresponding water insoluble CD-IL polymers. This dual system has shown excellent capabilities for the removal of model pollutants such as p-nitrophenol (PNP) and 2,4,6-trichlorophenol (TCP) and chromium (Cr6+) from aqueous media. However, the CD-IL polymers showed very little affinity for the absorption of cadmium from water. TGA and DSC studies showed that these polymers are stable over a wide range of temperatures (100-400 C).

The contamination of water by organic compounds has resulted in an escalation in research efforts to combat this problem. These organics can be harmful to human health and the environment in general, and they pose unique challenges to several industrial applications. Even when present at very low concentrations, they tend to bioaccumulate and interact with endocrine systems. However, due to the chemical nature of these compounds, current technologies are still challenged to effect their removal from water. Of currently used technologies, activated carbon and reverse osmosis can remove most of the organic pollutants but fail to remove them to very low concentrations (ng/L levels). Recent studies have explored the capabilities of nanoporous cyclodextrin (CD) polymers, a class of nanomaterials that show great potential to absorb organic contaminants from water. The project reported in this dissertation was undertaken to further explore the efficacy of these polymers in order to assist industries and municipalities in their quest to solve the problem of water contamination by organic species. The ability of these polymers to remove selected organic contaminants from water at varying concentrations was studied. The investigated pollutants were chlorinated disinfection by-products (DBPs), taste and odour causing compounds (geosmin and 2-methylisoborneol) and humic acid, which was used to mimic natural organic matter (NOM). Water samples were pre-concentrated using solid phase extraction (SPE) and subsequently quantified by Gas Chromatography-Mass Spectrometry (GC/MS). The CD polymers demonstrated absolute efficiency at quenching organics at very low concentrations compared to granular activated carbon (GAC). The recyclability efficiency of the CD polymers was also investigated. Most of the work was carried out using rapid small scale column tests (RSSCTs) that were designed in our laboratories. The general design of the study and pathway that was followed while conducting these experiments is shown in the flow diagram on the next page. / Dr. B.B. Mamba

Persistent organic pollutants (POPs) fall under a group of synthetic chemicals known for their persistence in environmental matrices such as soil and water, and are used in industrial, domestic and agricultural applications. Because of their volatility and lipophilicity, POPs can be transported far away from their point sources and bio-accumulate in food and in fatty tissues of humans and animals. In view of their toxicity and carcinogenicity some organic pollutants such as polychlorinated biphenyl (PCBs), organochlorine pesticides (OCPs) and phenolic derivatives (chlorophenol and nitrophenol) have been classified by United State Environmental Protection Agency (USEPA) and World Health Organization (WHO) as priority pollutants. The present work evaluated the distribution patterns of 19 polychlorinated biphenyls congeners, 17 organochlorine pesticides and selected phenolic derivatives (USEPA 11-priority pollutants) in the Buffalo River, in the Eastern Cape Province, South Africa between December 2015 and May 2016. The Liquid-liquid extraction technique was used for PCBs, OCPs and phenolic derivatives in the river water samples. Silica gel and florisil clean up were carried out for PCBs and OCPs samples respectively and analyzed with gas chromatography electron capture detector (GC/ECD). Phenolic compounds were derivatized and analyzed by gas chromatography mass spectrometer (GC/MS). Limits of detection (LOD), limit of quantitation (LOQ) and relative standard deviation (RSD) for the PCBs were 10 to 330 ng/L, 20 to 1,060 ng/L and 1.18 to 14.1 percent respectively. The LOD, LOQ and RSD for the OCPs were from 20 - 60 ng/L, 110 - 530 ng/L and 0.02 - 0.06 percent, while the corresponding values for the phenolic derivatives were 10 to 70 ng/L, 33 to 222 ng/L and 1.99 - 10.86 percent. In summer, the concentrations of PCBs, OCPs and phenolic derivatives ranged from <LOD to 482 ng/L, <LOD to 4,403 ng/L and <LOD to 1,546 ng/L respectively, while in autumn they were from <LOD to 2,383 ng/L, <LOD to 858 ng/L and <LOD to 713 ng/L in that order. Also, in summer, the level of occurrence of total PCB congeners detected at the various sampling sites were Buffalo River Estuary (BRE) 11 percent, Mdantsane (MSN) 16 percent, Zwelitsha (ZW) 26 percent, King William’s Town (KWT) 47 percent, Izele (IZ) 32 percent, and Maden (MD) 21 percent. The level of occurrence of total OCPs at BRE was 65 percent, at MSN 65 percent, at ZW 82 percent, at KWT 47 percent, at IZ 29 percent, and at MD 18 percent. The level of occurrence of total phenolic derivatives at BRE was 63 percent, at MSN 63 percent, at ZW 54 percent, at KWT 63 percent, at IZ 63 percent, and at MD 54 percent. In autumn, the level of occurrence of total PCBs at BRE was 68 percent, at MSN 16 percent, at ZW 42 percent, at KWT 26 percent, at IZ 47 percent, and at MD 0 percent. The level of occurrence of total OCPs at BRE was 65 percent, at MSN 53 percent, at ZW 41 percent, at KWT 35 percent, at IZ 53 percent, and at MD 18 percent. The level of occurrence of total phenolic derivatives at BRE was 63 percent, at MSN 63 percent, at ZW 54 percent, at KWT 18 percent, at IZ 18 percent, and at MD 45 percent. In summer, the levels of PCBs in all sampling sites were below WHO recommended maximum permissible levels (500 ng/L) for humans but in autumn the levels were above the recommended values in all the sites except MD. The cancer risk assessment values were above permissible 10-6 while hazard quotients were above the USEPA maximum limits of unity. OCPs levels were above the USEPA limits (100 ng/L) in all sampling locations in both seasons. The cancer risk assessment values were below permissible 10-6 but hazard quotients were above the USEPA maximum limits. Phenolic derivatives were also above the USEPA maximum permissible limit (500 ng/L) in most of the sampling locations in summer whereas during autumn the values were notably below the permissible limit at ZW, KWT, IZ and MD. The cancer risk assessment values and hazard quotients were above USEPA maximum limits of 10-6 and unity respectively. Conclusively, the results of this study reveal that the pollutants were present in the river at concentrations higher than the tolerable limit for human and wildlife and thereby may constitute a serious risk to public health. Therefore, it is recommended that proper regulation of the use of the compounds and their safe disposal be ensured to protect aquatic resources and the well-being of humans.

Water is an important resource. It is used for domestic, industrial, agricultural and recreational purposes. The quality of water is, however, significantly deteriorating due to the accumulation of organic species in aqueous system. Domestic, industrial and commercial activities comprise the biggest source of organic pollutants in municipal water. The increase of water pollution by these organics has led to the development of several water purification measures. Among others, water treatment technologies that are in place consist of ion exchange, activated carbon adsorption, reverse osmosis, molecular sieves and zeolites. However, none of these techniques have been reported to remove organic pollutants to parts-per-billion (ppb) or microgram-per-litre (ìg/L) levels. Recently, it has been reported that cyclodextrin nanoporous polymers are capable of absorbing these pollutants from water to such desirable levels. Cyclodextrins (CDs), basically starch derivatives, are cyclic oligomers consisting of glucopyranosyl units linked together through á-1,4-glycosidic linkages. They behave as molecular hosts capable of interacting with a range of guest molecules in a noncovalent manner within their cylindrical hydrophobic cavities. These interactions are a basis for the inclusion of various organic species. However, the high solubility of cyclodextrins in aqueous medium limits their application in the removal of organic pollutants from water. To make them insoluble, they are converted into highly cross-linked polymers. This is achieved by polymerizing the cyclodextrins with suitable difunctional linkers. In this project, a wide variety of monofunctionalized CDs have been effectively prepared using efficient modification strategies and successfully characterized by Infra-red (IR) and Nuclear Magnetic Resonance (NMR) spectroscopy. From these monofunctionalized CDs and corresponding linkers, insoluble nanoporous polymers with different physical properties were synthesized (Scheme 1). / Dr. B.B. Mamba

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.

D.Phil. (Chemistry) / Please refer to full text to view abstract

This research was conducted to study the use of radiation in water treatment as an alternative to chlorination which has caused health concerns due to the formation of harmful disinfection by-products. Groundwater solutions from the Biscayne aquifer were radiated with Cobalt-60 gamma radiation and studied for changes in dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), fluorescence and trihalomethane formation potential (THMFP). Molecular fractionations were conducted by ultrafiltration. Effect of the combination of radiation/peroxide was studied for DOC and UV254. Radiation showed significant removal in DOC and THMFP. Similar results were seen in the fluorescence and UV absorbance experiments. Radiation/peroxide did not improve the DOC removal. Radiation of the groundwater samples broke the larger molecular weight fractions in to smaller fractions.

Use of dye sensitized photooxidation is potentially a low cost means of degrading many of the hazardous compounds found in wastewaters. This study investigated the use of methylene blue as a sensitizer to degrade ortho-, meta-, and para-cresol, carbofuran and acrylonitrile. Significant reductions were found when aqueous solutions of the cresol isomers and carbofuran were illuminated and aerated in the presence of methylene blue. An average of 78% reduction of cresol was observed in seven hours. Carbofuran showed an average percent reduction of 56% in two hours. No loss was observed when the dye was absent. Acrylonitrile was found to be volatile and was stripped from solution by aeration. / M.S.