D.Ing.

The rhodophytes or red seaweeds are an ancient group of organisms that are related to plants. Like terrestrial plants, they use secondary compounds to protect themselves from microbial infection and grazing by herbivores. However, unlike terrestrial plants, they produce mostly halogenated secondary compounds and rarely alkaloids. Osmundaria serrata (Rhodophyta) is found along the eastern South African coast and the Maldive Islands. Its descriptive common name is “red spirals” and the species is adapted to live in habitats with high wave action. Extracts from this seaweed had previously shown to have antimicrobial activity, but ecologically irrelevant microbes were used to test the extracts. In this study, ten bacteria were isolated from the surface of O. serrata and its habitat, and identified. Mostly aerobic and Gram-negative bacteria were isolated (Halomonas and Pseudomonas species) along with facultatively anaerobic forms (Vibrio spp.) and a Gram-positive (Marinococcus sp.). These were used in bioassays to compare the activity of extracts made from O. serrata and other seaweeds that occur in the same habitat. Marine bacteria are the initial colonizers in biofilm formation and subsequent fouling of surfaces in marine environments. The study of these bacteria in relation to their macroalgal hosts may help to control biofouling of surfaces that cause economic losses worldwide. A comparison was made between using agar dilution and microtitre methods for testing the antibacterial activity of an O. serrata extract. The microtitre method was found to be more sensitive than the agar dilution method. Possibly because e some of the bacteria on the petri plates (in the agar dilution method) were not in direct contact with the toxicant in the growth medium, but were in direct contact in the liquid medium of the wells in the microtitre plates. The extract from 0. serrata was the most active of the thirteen species of macroalgae collected from the same habitat and tested for antibacterial activity. Deformities in bacteria were observed in response to the 0. serrata extract. Increased capsule production and blebbing of the outer membranes were observed by transmission electron microscopy (negative staining). Lanosol diethyl ether was isolated from 0. serrata and tested for antibacterial activity. Lanosol is produced mainly by the rhodophytes, but it is also found in other macroalgae and fungi in lower concentrations. The compound inhibited the test bacteria with average MIC's of 0.27 ± 0.07 mg.mr1 (bacteriostatic) and 0.69 ± 0.15 mg.mr1 (bactericidal). Different forms of biofilm were observed by scanning electron microscopy on the thirteen species of macroalgae. These ranged from a very little biofilm covering on the calcified reds to complex communities on the other macroalgae. The treatment with OS04 vapour before fixation in glutaraldehyde preserved the biofilm structure better than no treatment and indicated that lipids are important in maintaining biofilm structure. Since a complex biofilm community was seen on the surface of 0. serrata, it is unlikely that lanosol functions as an antifouling agent. This chemical seems to multifunctional with antimicrobial and feeding deterrent activities. / Thesis (PhD (Botany))--University of Pretoria, 2006. / Plant Science / unrestricted

Electrostatic charge generation is unavoidable in gas-solid fluidized beds due to the repeated particle-particle and particle reactor wall contacts and separations. In industrial operations such as in polyethylene production this phenomenon results in the significant problem of reactor wall fouling, known as “sheeting”. To better understand the underlying charging mechanisms involved in gas-solid fluidized beds in an attempt to eliminate and/or reduce the effect a novel on-line electrostatic charge measurement technique was developed, which concurrently provided information on both the degree of fluidized bed electrification and reactor wall fouling. A Faraday cup replaced the windbox of the fluidized bed while another cup was placed at the top of the column. The distributor plate was uniquely designed for the systematic removal of bed particles and those adhered to the column wall for their charge measurement with the bottom Faraday cup, and the charge of the entrained particles was measured by the top Faraday cup. This is the first study which allowed the charge measurement of particles in the bulk of the bed, particles adhered to the column wall, and those entrained, simultaneously. In addition, this method uniquely permitted the evaluations of the degree of reactor wall fouling under different operating conditions. An experimental program was designed to investigate the influence of bed hydrodynamics (fluidizing gas velocity and particle size), fluidization column wall material, and the addition of different solid additives. Fluidizing particles were polyethylene resin from an industrial reactor. Bi-polar charging was observed where the elutriated particles were oppositely charged compared to those in the bulk of the bed and those adhered to the column wall. Particles within the wall coating were also found to be bi-polarly charged. With the resin tested as received, a certain sized particles (350-575 µm) adhered to the column wall. The specific charge of the particles near the column wall was found not to be a definite indication of the amount of wall fouling. Increasing the gas velocity promoted wall fouling and elevated the charge density of the particles within both bubbling and slugging flow regimes. The effect of solid additive injection was examined with two static drivers known to reduce wall fouling in industrial operations, a deactivated catalyst, and the catalyst support. It was found that the catalyst promoted, while one of the static drivers reduced wall fouling.

Cancer is the second leading cause of death in the world. It is therefore critically important to detect cancer in its early stage to significantly increase the survival rate of cancer patients. Circulating tumour cells (CTCs) are cancer cells that peel off from primary tumour and enter bloodstream in early stage of a cancer, and thus it has been established that these CTCs are reliable targets for early cancer diagnosis. However, background signal reduction and optimization of CTC capturing mechanisms are still significant challenges in CTC detections with high sensitivities and accuracies. To this end, we have developed an aptamers and dendrimers based ultra non-fouling microfluidic detection system for sensitive detections of circulating tumour cells. More specifically, we demonstrate a simple strategy to bind PDMS and SU-8 surfaces in order to prepare a hybrid microfluidic device and subsequently modify both surfaces simultaneously using poly(amidoamine) (PAMAM), a highly hydrophilic dendrimer to improve non-fouling properties of the hybrid microfluidic channel. The resulting hybrid microfluidic system shows a remarkable non-specific adsorption suppression of 99.7% when tested with hydrophobic microbead suspension, an ultra non-fouling performance that has not been reported before. This is significantly important for detections with high sensitivities. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle are used to characterize and confirm surface modifications. In addition, we investigate the combined effects of surface properties on surface non-fouling performance to both live and dead cells. (3-aminopropyl)-trimethoxysilane (APTMS), carboxyl functionalized PAMAM dendrimer (PAMAM-COOH) and amino functionalized PAMAM dendrimer (PAMAM-NH2) are used to provide different surfaces with various surface hydrophilicity, electric charge and roughness. We show that electric charge of a surface is the most important factor influencing non- specific adsorption of live cells to the surface while hydrophilicity/hydrophobicity of a surface is the most important factor for dead cells. Atomic force microscopy, water contact angle and microscopy are used to characterize and confirm surface modifications. To further exploit and improve capturing efficiency of target cancer cells, we investigate the effect of the length of spacers that tether capturing aptamer to the microfluidic surfaces on capturing performance of CCRF-CEM circulating tumour cells. Aptamers with different lengths of thymine base spacers are immobilized onto PAMAM dendrimer modified surfaces in microfluidic channels. We demonstrate that ten thymine bases spacer has the best length for sgc8 aptamer to form its secondary structure for CCRF-CEM cell capture. Water contact angle, and microscopy are used to characterize and confirm surface modifications. Taken together, the results of this study significantly highlight the importance of different considerations on surface modification and its optimizations when designing a microfluidic system for high sensitivity detection and biosensing applications.

Produced water (PW), or water associated with crude oil extraction, is the largest oily wastewater stream generated worldwide. The reuse and reclamation of these important water volumes are critical for more sustainable operation in the oilfield. Ceramic membrane filtration is a promising technology for PW treatment; however, fouling is the major drawback for a broader application. Fouling leads to higher resistance to flow, reducing membrane lifetime, and ultimately leading to higher capital expenditures and operating expenses. Further understanding of the interactions between PW foulants and the ceramic materials is needed for designing fouling control strategies and cleaning protocols for ceramic membranes. This work explored different techniques to characterize, visualize, and quantify the submicron PW contaminants content and its adsorption interactions with metal oxides. We visualized and characterized submicron oil droplets in oilfield PW samples by applying suitable advanced microscopy techniques. For the first time, crude oil droplets as small as 20 nm were found in oilfield PW together with other submicron contaminants. The adsorption studies performed by quartz crystal microbalance with dissipation (QCM-D) showed that the interactions of organic surface-active compounds with the metal oxides are driven by the nature of the surfactant and not by the surface properties. This has implications in the selection of the ceramic membrane material, wherein electrostatic interactions should not be taken as the only predicting factor of adsorption and fouling during PW treatment. Furthermore, our results suggested that the more fluid or viscoelastic-like the contaminant layer, the more difficult the cleaning process from the metal oxide. It demonstrates that the mechanical property of the attached films is a crucial factor in designing appropriate cleaning protocols for ceramic membranes. Finally, QCM-D and advanced microscopy techniques were applied to analyze adsorption and cleaning of contaminants in a complex Bahraini PW into alumina as a case study. Bacteria were found to attach irreversibly on the alumina surface, promoting nucleation points for calcium precipitates. The protocols developed in this work are suitable for understanding membrane fouling phenomena in the micron scale and could be implemented before filtration pilot testing to save time and expenses at larger scales.

Low-pressure membrane systems such as Microfiltration (MF) and Ultrafiltration (UF) have been presented as viable option to pre-treatment systems in potable water applications. UF membranes are sporadically backwashed with ultra-filtered water to remove deposited matter from the membrane and restore it. Several factors that may cause permeability and selectivity decrease are involved and numerous procedures are applicable to achieve this objective. Membrane cleaning is the most important step required to maintain the characteristics of the membrane. This research was made with the purpose of investigating the effects of acid cleaning during chemically enhanced backwashing (CEB) on the performance of ultrafiltration (UF) membranes in seawater reverse osmosis (SWRO) pretreatment. To accomplish this, the questions made were: Does the acid addition (before or after the alkali CEB) influence the overall CEB cleaning effectiveness on Dow UF membrane? Does the CEB order of alkali (NaOCl) and acid (H2SO4) affect the overall CEB cleaning effectiveness? If yes, which order is better/worse? What is the optimal acid CEB frequency that will ensure the most reliable performance of the UF?. To answer this queries, a series of sequences were carried out with different types of chemical treatments: Only NaOCl, daily NaOCl plus weekly acid, daily NaOCl plus daily acid, and weekly acid plus daily NaOCl. To investigate the consequence of acid by studying the effect of operational data like the trans-pressure membrane, resistance or permeability and support that by the analytical experiments (organic, inorganic and microbial characterization). Microorganisms were removed almost completely at hydraulic cleaning and showed no difference with addition of acid. As a conclusion of the operational data the organic and inorganic chatacterization resulted in the elimination of the first sequence due to the acummulation of fouling over time, which produces that the cleaning increases downtime, productivity diminishes, Increases water cost, shortens membrane lifespan and the frequency of cleaning in place (CIP). The elimination of the third sequence, NaOCl followed by daily acid, resulted in excessive dosing of acid which affects fibers and increases the water cost. The removal of organic carbon and inorganic fractions for the second and third sequence were investigated. The better removal of Iron was in the last sequence with value of 11.52 mg/l due to acid was dose first which target inorganic foulants. The better removal of bio polymers was obtained at the second sequence with a value of 0.95 mg/l owed to the influence of chorine CEB to acid which oxidized biopolymers with higher molecular weight to smaller, then when the acid CEB removed it in a larger amount. While the last sequence was 0.57 mg/l. It can be concluded that second sequence provided a better removal that the last sequence. To support this conclusion, the operational data was compared to the second sequence is operationally sustainable, therefore in this revision the best sequence was the second.

Membrane processes are considered energy-efficient for water desalination and treatment. However most membranes are based on polymers prepared from fossil petrochemical sources. The development of multilayer membranes for nanofiltration and ultrafiltration, with thin selective layers of naturally available cellulose, has been hampered by the availability of non-aggressive solvents. We propose the manufacture of cellulose membranes based on two approaches: (i) silylation, coating from solutions in tetrahydrofuran, followed by solvent evaporation and cellulose regeneration by acid treatment; (ii) casting from solution in 1-ethyl-3-methylimidazolum acetate ([C2mim]OAc), an ionic liquid, followed by phase inversion in water. In the search for less harsh, greener membrane manufacture, the combination of cellulose and ionic liquid is of high interest. Due to the abundance of OH groups and hydrophilicity, cellulose-based membranes have high permeability and low fouling tendency. Membrane fouling is one of the biggest challenges in membrane industry and technology. Accumulation and deposition of foulants onto the surface reduce membrane efficiency and requires harsh chemical cleaning, therefore increasing the cost of maintenance and replacement. In this work the resistance of cellulose 5 membranes towards model organic foulants such as Suwanee River Humic Acid (SRHA) and crude oil have been investigated. Cellulose membrane was tested in this work for oil-water (o/w) separation and exhibited practically 100 % oil rejection with good flux recovery ratio and membrane resistivity. The influence of anionic, cationic and ionic surfactant as well as pH and crude oil concentration on oil separation was investigated, giving a valuable insight in experimental and operational planning.

Cette thèse porte sur l’élaboration et l’étude des performances de membranes d’ultrafiltration PVDF-TiO2 possédant des propriétés anti-colmatantes et photo-induites. La membrane est obtenue par application de la méthode de séparation de phases induite par un non-solvant sur un collodion de polyfuorure de vinylidène au sein duquel ont été incorporées des nanoparticules de TiO2. Il est montré : i) que la presence des nanoparticules de TiO2 les propriétés membranaires, et notamment le flux de perméat, par rapport à la membrane PVDF ; ii) que l’augmentation de la température de préparation de la membrane permettait de modifier la structure membranaire, en passant d’une morphologie constituée principalement de macrovides (dite en “doigts de gants”) à des températures basses à une morphologie spongieuse, contenant des pores de plus petite taille, à température élevée. Au-delà de la structure membranaire, des propriétés telles que la perméabilité, la porosité, la résistance mécanique, la cristallinité et les propriétés thermiques sont également influences par les changements de température de formation. Lorsque les membranes PVDF-TiO2 sont mises en oeuvre en mode photo-filtration (c.-à-d. filtration avec irradiation ultraviolette (UV) continue sur la membrane), le flux à l’eau pure de la membrane PVDF-TiO2 est encore augmenté, du fait du phénomène d’hydrophilicité photo-induite des nanoparticules de TiO2. Des premières estimations suggèrent que la photo-filtration par les membranes PVDF-TiO2 serait une économiquement rentable, car le gain en termes de filtration et qualité d’eau l’emporterait sur le cout énergétique induit par l’irradiation UV. En outre, l’efficacité de la photo-filtration a été évaluée avec des solutions d’alimentation synthétiques contenant des composés inorganiques et organiques représentatifs des eaux de surface. Il a été montré que si la plupart des ions inorganiques communément rencontrés dans l’eau potable n’ont aucun effet sur l’efficacité de la photo-filtration, la coexistence de Cu2+ et HCO3- dans l’eau d’alimentation entraîne un colmatage inorganique sévère qui inhibe le phénomène hydrophilicité photoinduite. En outre, la membrane PVDF-TiO2 présente également des flux plus élevés et une activité photocatalytique lors de la photo-filtration de solutions contenant des matières colmatantes organiques comme les acides humiques ou l’alginate de sodium. En conclusion, la membrane composite PVDF-TiO2 a démontré des propriétés et des performances significativement améliorées par rapport à la membrane PVDF, a fortioti lorsqu’elle est mise en oeuvre dans un système de photo-filtration sous irradiation UV. Ainsi, ce sont des matériaux prometteurs pour des applications membranaires en traitement de l’eau. / This thesis deals with the elaboration and performance of a specific type of ultrafiltration membrane with anti-fouling and photo-induced properties, the PVDF-TiO2 composite membrane. The membrane was fabricated via the nonsolvent-induced phase separation method by incorporating titanium dioxide (TiO2) nanoparticles into the polyvinylidene fluoride (PVDF) polymer matrix. The TiO2 nanoparticles played a significant role in facilitating the membrane formation process and improving the composite membrane properties compared to the neat PVDF membrane. It was demonstrated that, by changing the membrane preparation temperature, the membrane structure could be affected dramatically, notably the morphological dominance of finger-like macrovoids at lower temperatures and their diminution in both size and number when temperature increased. Other membrane properties also saw systematic transitions with changes in formation temperature, as characterized by permeability, porosity, mechanical strength, crystallinity, and thermal properties. In terms of performance, the PVDF-TiO2 membrane exhibited superior permeate flux compared to the neat PVDF membrane. More importantly, when being operated in photo-filtration mode (i.e. filtration with continuous ultraviolet (UV) irradiation on the membrane), the pure water flux of PVDF-TiO2 membrane could be further increased, thanks to the enhanced hydrophilicity of the membrane, which comes from the photo-induced hydrophilicity phenomenon of TiO2. Preliminary estimations suggest that photo-filtration is a cost-effective method, as the benefit from enhanced water output outweighs the extra energy demand for UV irradiation. Furthermore, the efficiency of photo-filtration was evaluated with synthetic feed solutions containing inorganic and organic contents representative in surface water. It was identified that, while most of the common inorganic ions in drinking water had no effects on photo-filtration efficiency, the coexistence of Cu2+ and HCO3- in the feed led to severe inorganic fouling and inhibited the photo-induced hydrophilicity phenomenon. Besides, the PVDF-TiO2 membrane also showed its stronger flux performance and photocatalytic activity during photo-filtration of solutions containing organic foulants like humic acids or sodium alginate. In conclusion, the PVDF-TiO2 composite membrane exhibited much improved properties and performance compared to the neat PVDF membrane, and even stronger performance when operated in photo-filtration mode. Thus, it is a promising candidate to be used in membrane-based applications for water treatment.

<p>The clogging of filtration membrane by particles otherwise known as fouling is a major concern in membrane filtration technology due reduction of flux, membrane lifespan and system performance, with an associated increase in process and operating costs in industries that utilize membrane in their production process. Cleaning or replacement of a fouled membrane requires production to be interrupted or the entire system to be shut down. This is because the cleaning or replacement of the fouled membrane requires production to be interrupted for the cleaning process or the entire system to be shut down for the replacement process to take place, leading to great losses to the industries involved. Many approaches have been devised over the years to tackle this problem, of which not only undermine the performance of the filtration membrane but also contribute to great losses to industries that apply them. Cheaper and more efficient means of fouling control remains the key to solving this problem. </p> <p> </p> <p>A water filtration system is proposed that uses piezoelectric crystals attached on a tubular polyvinylidene fluoride (PVDF) membrane to increase flux and delay the clogging of the pores of the filtration membrane (by particles). Filtration tests with mud solution showed that the membrane vibrated with piezoelectrics reduced the clogging of the pores and increased permeate flux of the filtration process as compared to the non-vibrated membrane. To optimize the permeate flux production of the system and fouling reduction, the effects of voltage, concentration and location of piezoelectric crystals<a> were investigated. An equation to best fit the experimental data was developed which can help in the optimization of the variables.</a></p> <p> </p> <p> </p> <p> </p> <p> </p> <p> </p>

The construction and operation of central wastewater treatment plants started around the 20th century. With the advent of rigorous membrane research and development in the middle of the 20th century, more and more wastewater plants started incorporating a Membrane BioReactor, MBR, in their design. The MBR system however is far from perfect. Membrane systems continuously foul, and if fouling is incurred for a long period of time, maintenance and cleaning costs will rise in proportion. A Fouling monitoring and prediction tool has been designed in MATLAB\Simulink. The model takes states related to membrane fouling, and calculates the membrane total resistance based on deterministic and stochastic models. The tool is capable of predicting future TMP cycles based on older TMP performance via an artificial neural network algorithm. TMP data have been synthetically generated from a validated mathematical model. Finally, an artificial neural network controller is implemented to control temperature and MLSS around their desired setpoints. The controller is able to minimize disturbances in both states in a narrow band around their desired setpoints.