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

Biotechnology of sulphate reducing bacteria has developed rapidly in recent years with the recognition of their extensive and diverse biocatalytic potential. However, their application in a number of areas has been constrained due to problems including poor cell retention within the continuous bioprocess reactor environment, and contamination of the treated stream with residual organic feed components and cell biomass. These problems have so far excluded the application of biological sulphate reduction in the treatment of ‘clean’ inorganic waste streams where components such as sulphate, acidity and heavy metal contamination require treatment. This study investigated the effective immobilisation of sulphate reducing bacterial cultures and proposed that the disarticulation of the electron donor and carbon source supply using such systems would create the basis for their application in the treatment of ‘clean’ inorganic waste streams. A functional and stable sulphate reducing culture was selected and following evaluation using a number of techniques, was immobilised by encapsulation within a calcium-alginate-xanthum gum membrane to give robust capsules with good sulphate reduction activity. The concept of disarticulation was investigated in a swing-back cycle where the carbon source was excluded and the electron donor supplied in the form of hydrogen gas in a continuous up-flow capsule-packed column reactor. Following a period of operation in this mode (4-12 days), the system was swung back to a carbon feed to supply requirements of cell maintenance (2-3 days). Three types of synthetic ‘clean’ inorganic waste stream treatments were investigated, including sulphate removal, neutralisation of acidity and heavy metal (copper and lead) removal. The results showed: • Sulphate removal at a rate of 50 mg SO₄²⁻L/day/g initial wet mass of capsules during three 4-day cycles of electron donor phase. This was comparable to the performance of free cell systems; • Neutralisation of acidity where influent pH values of 2.4 and 4.0 were elevated to above pH 7.5; • Copper removal of 99 and 85 % was achieved with initial copper concentrations of 2 and 60 mg/L respectively; • Percentage lead removal values of 49 and 78 % were achieved; This first report on the application of the concept of capsular immobilisation and disarticulation in the treatment of ‘clean’ inorganic waste streams will require future studies in order to extend the development of the full potential of the concept.

New approaches to the application of membranes for the production of potable water are constantly being sought after in anticipation of future demands for increasingly rigorous water quality standards and reduced environmental impact. A major limitation, however, is membrane fouling, which manifests itself as a continual reduction in flux over time and thus restricts the practical implementation to restore flux. Mechanical and chemical methods have been implemented to restore flux to ultrafiltration systems, but these either result in a break in the process operation or lead to membrane damage or additional pollution problems. This project was aimed to develop a 'defouling on demand' stategy for cleaning membranes used during brown water ultrafiltration. The process involves the use of activatable peroxidase enzymes, which were immobilised onto flat sheet polysulphone membranes. Following flux decline which reaches a critical level with the build-up of the foulant layer, the immobilised enzyme layer was activated by the addition of a chemical activator solution, in this case hydrogen peroxidase and manganous sulphate. Manganese peroxidase was found to be the most effective enzyme at alleviating fouling by degrading the foulant layer formed on the membrane surface and hence restored flux to the ultrafiltration system. A 93% flux improvement was observed when manganese peroxidase was activated when 800uM manganous sulphate, 100mM hydrogen peroxide were added in the presence of a manganese chelator, lactate. The concept and the potential benefits this system holds will be discussed in further detail.

One problem of intensive fish culture systems is the progressive build-up of toxic wastes such as ammonia. The possibility of improving aquaculture water quality using two kinds of zeolite is discussed. Zeolites are alumino-silicates whose framework allows them to exchange cations. Ion exchange has been demonstrated to be competitive with other methods of ammonia removal due to the high selectivity for ammonia exhibited by zeolite materials. In this study an unknown Zambian zeolite (identified as laumontite by X-ray diffraction techniques) and Pratley clinoptilolite (a South African zeolite) were tested under laboratory conditions and in a fresh water recirculating system. Ammonia cation exchange capacities (CEC) and suitable application rates for efficient water treatment were determined using the batch and column ion exchange procedures. Estimated ammonia uptake, the most important criterion used to assess performance of zeolite filters was strongly influenced by zeolite type, particle size, pre-treatment, regeneration and ion exchange method used. Statistical analysis showed significant differences in average ammonia CEC values between clinoptilolite (14.94 mg g⁻¹) and laumontite (2.77 mg g⁻¹), with the former displaying a higher Na⁺ ® NH₄⁺ exchange rate especially in the early reaction stages. This difference accords with the higher purity of clinoptilolite, 47% as opposed to 4.7% for laumontite, which makes it a better zeolite for ammonium removal. CEC increased linearly as particle size of the clinoptilolite was reduced resulting in a linear regression model (y = 18.29 – 3.704 x; r² = 74%). Pre-treatment of clinoptilolite using 1N NaCl significantly improved the ammonia CEC of clinoptilolite. Overall performance of both the batch and column methods achieved after regeneration (18.3 mg g⁻¹) was 25% higher than the estimated CEC values (13.0 mg g⁻¹) for the unregenerated samples of clinoptilolite. Comparison of CEC estimates using Pratley clinoptilolite, showed that average batch CEC estimates were significantly lower than the column method estimates. The average ammonia CEC values estimated in a fresh water recirculating system (5.80 mg g⁻¹ and 4.12 mg g⁻¹ for the 0.7-1.0 and 1.0-1.4 mm particle sizes, respectively) were significantly lower than the column and batch estimates for the same particle sizes (P < 0.05). Some nitrite (NO₂) and nitrate (NO3) build up was experienced probably due to the growth of autotrophs in the filters. Mass balance of nitrogen (N) for the three treatments of the fish trial (0.7-1.0 mm, 1.0-1.4 mm and the control treatment that had no zeolite in the filter) indicated that less that 10% of the N was retained for growth. It was found that 60% of the NH₄-N present associated with the soluble N was available for absorption by the zeolite filter or biological nitrification and that a total of approximately 22% of NH₄-N available was absorbed by clinoptilolite. The results indicate that the rate of nitrification can be deductively estimated by allowing a zeolite filter to become a biological filter. It is concluded that water treatment by ion exchange using natural zeolites, provides a reliable and efficient method for ammonia removal and appears to be a viable supplementary water treatment method for fresh water systems.

The waste water from the industrial production of the herbicide monosodium methyl arsenate was treated using coagulation. The coagulation process as developed in this research proved to be suitable for arsenic removal in aqueous media using chromium (III), calcium (II), and combination of calcium (II) and chromium (III), and magnesium (II). The results obtained suggest that the coagulation process can be used for the treatment of the waste water from the monosodium methyl arsenate production. Response surface methodology was used to study the effects of the various parameters, namely pH, mole ratios (Cr:As, Ca:As, and Mg:As), concentration of flocculent and initial arsenic concentration. To optimize the process conditions for the maximum removal of arsenic. Central composite and factorial designs were used to study the effects of these variables and to predict the effect of each. ANOVA was used to identify those factors which had significant effects on model quality and performance. The initial arsenic concentration appeared to be the only significant factor. These models were statistically tested and verified by confirmation experiments.

Laboratory lysimeters were used to investigate the behaviour, over time, of a humid west coast forest soil under intermittent primary municipal waste water irrigation. Mineral soil packed to a depth of 69 cm and to a uniform density of about 0.9 gm per cm³ was covered with a forest floor 9 cm thick. Sintered glass bead tensiometers were used to gauge the water potential distributions in the soil lysimeters. Irrigation and drainage systems were designed to maintain constant rates of waste water application and facilitate measurement of drainage rates. Two groups of soil lysimeters each with triplicate samples, were loaded with waste water at the rates of 0.23 cm per day ( 37 cm³ per day ) and 0.47 cm per day ( 75 cm³ per day ) for a period of 9 months. The soil lysimeters were incubated at a temperature of about 15.5 degrees Centigrade. The total amounts of nitrogen added to both groups of soil lysimeters were 223.7 gm and 436.9 gm or equivalent to 1.4 % and 2.7 % of the total nitrogen of the original soil, respectively. Renovations of wastewater in terms of nitrogen were 75 % and 43 % with respect to the two groups of soil lysimeters. Renovations in terms of phosphorus were more than 99 % in both groups of soil lysimeters. Retention of nutrients by the soil was increased with time under favourable aerobic conditions. Uptake of nutrients by vegetation in the field would minimize leaching losses. Results from this experiment indicated no significant changes in the physical and chemical behaviour of the soils. Proper design of the waste water irrigation system in terms of loading would maximize the efficiency of renovation without deteriorating the behaviour of the soils. / Land and Food Systems, Faculty of / Graduate

A laboratory investigation into foam separation processes, as applied to kraft pulping and bleaching effluents is described. Two methods, foam fractionation and ion flotation were tested in the laboratory. The procedures developed concentrated primarily on the removal of effluent colour because this property lent itself most readily to the available analytical methods, and because effluent colour removal presents one of the greatest waste water treatment problems facing the industry today. The foam fractionation technique was not successful. Substantial colour removals were obtained, but it was subsequently shown that the mechanism of removal was really an ion flotation. Positive results were obtained with the use of the ion flotation process for removal of effluent colour. At optimum conditions, the recovery of flotable material and the corresponding removal of effluent colour were in excess of 95 per cent. Variation of surfactant dosage showed that below a critical level no colour was removed. As concentrations increased above this value the amount of colour removed increased rapidly, reaching a high removal level beyond which increases in surfactant concentration were of little value. The rate of flotation recovery was found to be significantly affected by the air sparge rate and the sparger pore size, both parameters which would determine the area available for adsorption. The pH of the flotation cell solution had a marked effect on the system. Optimum pH was clearly defined as 5.1. Removal of material other than just the chromophoric fraction was apparent. Biological oxygen demand data, while not extensive, demonstrate a significant reduction in the bio-degradable portion of the effluent. The possible future development of the process into a viable candidate for industrial application is discussed. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

The objective of the research program was to demonstrate the technical feasibility of removing phosphorus, by the enhanced biological phosphorus removal mechanism, from domestic wastewater using a laboratory scale Sequencing Batch Rotating Biological Contactor (SBRBC). The rotating discs of the RBC were subjected to alternating anaerobic/aerobic conditions by varying the water level in the reaction vessel. At the start of the treatment cycle, the RBC reactor would be filled submerging the rotating discs and ensuring anaerobic conditions in the RBC biofilm. Acetate would be added to the reaction vessel at this time. Following the batch anaerobic react period part of the reactor contents were decanted to either the sewage feed tank or a separate holding vessel to later become part of the influent for the next treatment cycle. With the rotating: discs of the-RBC partially submerged oxygen was available to the bacteria, in the RBC biofilm. Three operating schedules were tried with the above process. Each operating schedule differed in the way the decanted wastewater from the anaerobic phase was handled. Batch tests were conducted weekly to determine the nature of the biological reactions taking place in each of the batch anaerobic and aerobic phases. The SBRBC process showed promise for enhanced biological phosphorus removal from domestic wastewater. Carbon removal and nitrification of the wastewater were secondary benefits to this process. The success of the process was found to be dependent on the attainment of proper anaerobic conditions at the start of each treatment cycle. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate

M.Ing. / Scaling problems in a heating or cooling system can be recognised by one or more of the following symptoms. Reduction in heat transfer rate, in which the formation of an insulating deposit on a heat transfer surface significantly reduces the cooling or heating efficiency of the equipment. Reduced water flow, which results from a partial or complete blockage of pipelines, condenser tubes, or other openings. Even a small build-up of scale on a heat exchange surface reduces water flow. Scale may continue to build up in boilers until heat transfer is so low that the metal overheats, permitting the tubes to rapture under the operating pressure. Scale is usually found in water-handling equipment in which water is heated, i.e. hot-water storage tanks, boilers, etc. The magnitude of this problem may be appreciated by considering that scaling can cause degradation, or complete failure in thermal and hydraulic performance which increases initial and operating costs (Chan and Ghassemi, 1991). A fairly low-pressure boiler, with only 0.6 mm of calcium sulphate scale on the tubes results in a 180°C temperature drop. The cost involved due to heat transfer inefficiency and the removal of scale, in Britain alone, is estimated at £1 billion per annum (Darvill, 1993). Poor conductivity of a 25 mm thick CaC03 scale layer can decrease the heat transfer by 95% (Glater eta/., 1980), whereas a Si02 scale layer 0.5 mm thick results in a 90% decrease in heat transfer (Grutsch and McClintock, 1984).

M.Tech. / This project aimed to develop the Potpaz ceramic water filter into an improved filter design optimally suited to South African rural conditions, to provide potable water rather than contaminated water to households. Communities that do not have access to in-house treated water often end up with a contaminated water supply, as the water to be consumed is usually sourced from communal water collection points and stored in containers. There is evidence that the water consumed at point-of-use in rural areas is not always of a potable quality due to possible contamination between collection and consumption. The existing Potpaz home water treatment device has been scientifically proven to return contaminated water to a potable state. A limited number have been imported to South Africa for use in a project that studied the effect of household point-of-use treatment on the health of the consumer. It was not at all certain whether the households would use these devices effectively because this filter was not part of their everyday water system. Part of investigating whether or not they would effectively use this filter was the inclusion of industrial design within the filter assessment section of a larger research project conducted in the Vhembe region to understand the requirements of the user. Industrial design concerns itself with the requirements of the user, as well as knowledge regarding product design, development and manufacturing. Households that took part in the point-of-use project used the Potpaz home water treatment device for more than two months and were approached to provide feedback regarding its use. From the feedback, it became evident that there were aspects of the Potpaz design that needed modification towards an improved water filter more suited for its intended use in rural households. An Action Researchinfluenced methodology and User Centred Design approach informed the collection of original data and feedback on areas of improvement. This, together with visits to local shops and community potters, provided sufficient background to understand the needs and preferences of the intended rural users regarding the use of the device. This informed the design process and increased the chances of developing a readily accepted, more suitable product to the intended users and the domestic environment in which they live. To achieve this, this project focused on the following aspects regarding Potpaz filters: placement, use and design aspects of usability and ergonomics. Development of the improved filter design culminated in rapid prototyping of a scale model and the fabrication of a full-size working model allowing for physical interface to evaluate the success of the design solution.