This study aims to examine the throughput of nanoparticles through a Cladophora cellulose based virus removal filter. The effect of Brownian motion and flow velocity on the retention of 5 nm gold nanoparticles, 12.8 nm dextran nanoparticles and 28 nm ΦX174 bacteriophages was examined through MATLAB simulations and filtration experiments. Modeling of Brownian motion at different flow velocities was performed in MATLAB by solving the Langevin equation for particle position and velocity for all three types of particles. The motion of all three particle types was shown to be constrained at local flow velocities of 1∙10-2 m/s or greater. The constraint was greatest for ΦX174 bacteriophages, followed by dextran particles and then gold particles as a result of particle diameter. To verify the effect experimentally, virus removal filters were prepared with a peak pore width of 23 nm. Filtration experiments were performed at different flux values where gold and dextran particles did not exhibit any difference in retention between fluxes. However, a significant amount of gold and dextran particles were removed by the filter despite being smaller than the measured pore size. A decrease in retention with filtrated volume was observed for both particle types. Filtration of ΦX174 bacteriophages exhibited a difference in retention at different fluxes, where all bacteriophages where removed at a higher flux. The results from both simulations and experiments suggest that the retentive mechanism in filtering is more complex than what can be described only by size exclusion sieving, Brownian diffusion and hydrodynamic constraint of particles.

L’objectif de ce travail de thèse est de démontrer qu’il est possible d’utiliser des mesures en continu de turbidité pour suivre la pollution particulaire dans les réseaux d’assainissement et d’évaluer l’apport de ces mesures pour la gestion des réseaux en temps réel ou en temps différé. Dans une première partie, la mise en oeuvre de la mesure en continu de turbidité est décrite. Les éléments principaux contribuant à l’incertitude sont identifiés et des méthodes de calcul des incertitudes adaptées sont proposées. Les questions de fiabilité et de représentativité de la mesure de turbidité sont traitées et aboutissent à des solutions d’installation des sondes in situ et à des protocoles de suivi et de maintenance. Enfin, les perturbations affectant le signal sont quantifiées et des méthodes de filtrage sont comparées. La deuxième partie est consacrée à l’analyse du comportement de la turbidité à partir des données acquises sur deux sites du réseau unitaire parisien en 2006. 80 événements pluvieux sont décrits par leurs concentrations moyennes et maximales et par leurs courbes de distribution masse/volume. Ces critères ont été intégrés dans des typologies qui ont ensuite été mises en relation avec des paramètres de débit et de durée de temps sec ayant précédé l’événement. Cette analyse permet de caractériser la variabilité de façon détaillée. La variabilité de la décantabilité des particules a été également étudiée à partir de données provenant de bassins de décantation. Enfin, deux applications sont proposées. La première est une évaluation en temps différé de flux de polluants. Deux modes d’exploitation de prélèvements d’échantillons réalisés sur un nombre fixé d’événements pluvieux sont comparés. L’un n’utilise que les résultats d’analyses des échantillons au laboratoire pour établir une concentration moyenne. L’autre utilise les prélèvements pour établir des relations entre turbidité et paramètres polluants, ensuite appliquées à des mesures en continu de turbidité. Une seconde série d’applications porte sur l’utilisation de la turbidité pour la gestion en temps réel des flux. Deux configurations-types génériques ont été étudiées. Pour chacune, une stratégie utilisant seulement le débit est comparée à une stratégie utilisant turbidité et débit. Les simulations sont effectuées pour de larges gammes de paramétrage des configurations et avec des données réelles de débit et de turbidité en entrée du système. Pour les applications d’évaluation de flux comme de gestion en temps réel, le gain apporté par la turbidité est chiffré et s’avère significatif / The purpose of this thesis is to prove the usefulness of continuous turbidity measurements for the monitoring of particulate pollution in combined sewer systems, and assess the contribution of these measurements to real-time and lagged control of sewer systems. In the first part, the implementation of continuous turbidity measurements is described. The main uncertainties components are identified and appropriate calculation methods for the uncertainties are proposed. The issues of reliability and representativeness of turbidity measurements are treated and lead to solutions for the in situ installation of turbidimeters and the definition of proper monitoring and maintenance protocols. Finally, the noise which disturbs turbidity measurements is quantified, and filtering methods are compared. The second part is devoted to the analysis of turbidity behaviour, drawing from data monitored on two sites in the combined sewer of Paris in 2006. Eighty rain events are described by their mean and maximum concentrations and by their mass/volume distribution curves. These criteria are used to define typologies, which are then linked to flow parameters and to the antecedent dry weather period of the event. This analysis leads to a detailed description of variability. The variability of the settling characteristics of the particles was also studied using data coming from sedimentation tank. Finally two applications are developed. The first is an assessment of lagged pollutant loads. Two methods for exploiting samples taken during a fixed number of rain events are compared. The first method only uses the results of sample analysis to establish an average concentration. The second method uses samples to calibrate relationships between turbidity and pollutant parameters, which are then applied to continuous turbidity measurements. Another group of applications deals with the use of turbidity for real time control of pollutants flows. Two kinds of configuration were studied. For each one, a strategy only using flow data is compared with a strategy using turbidity and flow data. Simulations are performed for a wide range of configuration parameters with real flow and turbidity data at the entrance of the system. For the application of assessment of pollutants flow as well as for real time control applications, the improvement brought by turbidity was assessed and proved to be significant

Abstract Interactions between the components of papermaking suspensions (e.g. fibres, fillers, fines and polymers) have a remarkable effect on various unit processes in papermaking. The filterability of fibre suspensions, which is a crucial property for example in paper sheet forming and solid recovery, is also known to be depended on particle interactions. However, due to the complex nature of the interactions, the role of these phenomena in fibre suspension filtration is still not fully understood. The focus of this thesis was to find out how phenomena associated to fibre flocculation, fibre deflocculation and filler particle deposition affect the filterability of fibre suspensions in terms of their dewaterability and retention. It was shown that the influence of fibre flocculation on dewatering is closely related to the structure of fibre flocs. More importantly, the internal density of flocs and factors that impacted the packing structure of filter cakes, such as floc size, played a crucial role in fibre suspension dewaterability. Dense flocs with a low internal porosity particularly induces fast water flow by a mechanism termed as the “easiest path mechanism” through the large voids around the flocs. The effect of fibre suspension dispersing on dewaterability and particularly fines retention was found to be associated to the mechanism of action of the deflocculation agent. Carboxymethylcellulose (CMC), the deflocculant used in this study, had detrimental effects on the dewatering of a pulp suspension both when being adsorbed on fibre surfaces and when remained in the liquid phase. However, adsorbed CMC causes more plugging of the filter cake because it disperses the fines more profoundly. Thus the adsorbed CMC also reduces fines retention considerably more than CMC did in the liquid phase. Filler deposition and retention was found to be significantly higher on pulp fines fractions of mechanical and chemical pulp than on fibre fractions due to the higher external surface area of fines. The surface charge densities of pulp fractions also affected their ability to adsorb fillers. Cationic charges of filler particles was in turn observed to induce deposition of fillers on fibre surfaces which increased retention but also the dewaterability of a fibre suspension due to a decrease in total surface area of a suspension.

Extracellular vesicles (exosomes) are the subject of current nephrology proteomics research as they are considered as a promising source of potential biomarkers of kidney disease. This work is focused on discovery of the most appropriate procedure for the urinary exosomes isolation. We have compared already described methods, based on different physicochemical principles of isolation: hydrostatic filtration dialysis (HFD), differential ultracentrifugation, ultrafiltration through a 100 kDa filter, or sample precipitation with Total Exosome Isolation (from urine) kit. Characterization of individual isolated exosomal fractions was performed using SDS-PAGE method (presence of contaminating proteins), western blot analysis (detection of exosomal markers TSG101, alix), nanoparticle tracking analysis (NTA, vesicle size and concentration) or transmission electron microscopy (TEM, vesicles morphology). Due to the presence of contaminating proteins in urine samples, which could distort the results of subsequent proteomic assays, the conditions for the cleavage of undesirable proteins by proteinase K prior to their own isolation were optimized. It has been found that the best yield and purity of the isolated exosomal fractions were provided by a process combining HFD with differential ultracentrifugation...

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Exposure to arsenic (As) in water, the ubiquitous toxin that poses adverse health risks to tens of millions, is the result of both anthropogenic and geochemical mobilization. Despite recent publicity and an increased public awareness, the dangers associated with arsenic exposure rank among the top priorities of public health agencies globally. Existing sequestration applications mainly include reductions and adsorption with zero-valent metals and their oxides. The performance of adsorption media is known to preferentially favor aqueous As(V) over As(III) due to the charge of the dissolved oxyanion. Magnetic nanoparticles (MNP) have been the focus of multidisciplinary research efforts for the removal of aqueous toxic metals and metalloids since they can be magnetically separated from the treated water. This improves isolation and allows for regeneration of the MNP, reducing cost and resource consumption. This research is focused on As(III & V) sequestration through the use of synthetic ligands N,N’bis(2-mercaptoethyl)isophthalamide (abbreviated BDTH2) and 2,2’- (isophthaloybis(azanaediyl))bis-3-mercaptopropanoic acid (abbreviated ABDTH2). Additionally, As(III) sequestration with ABDTH2 functionalized on silica core-shell MNP (ABDTH2 MNP), magnetite MNP (ABDTH2@MNP), and commercial silica beads (ABDTH2 Si60) is demonstrated. Both BDTH2 and ABDTH2are effective precipitation agents for the removal of As(III) through the formation of S-As covalent bonds. ABDTH2MNP reduced a 200 ppb As(III) batch solution to below 10 ppb at pH 5,7, and 9. Additionally, complete removal was achieved in the presence of anions at concentrations of 200, 500, and 1000 ppb. This system was evaluated for the removal of total arsenic from industrial solutions accumulated during the production of renewable biogas in landfills. Direct precipitation with BDTH2 and ABDTH2 was inhibited by the complex matrix. However, batch removal with ABDTH2@MNP was effective in removing 82% of the inorganic arsenic. Sequestration of arsenic and speciation from these industrial solutions remains a challenge.

MSc. (Applied Chemistry) / Remediation of POPs particularly the chlorinated compounds in water is therefore crucial. This research work describes the modification of polyethersulfone (PES) thin-film membrane composite (TFC) with functionalised carbon nanotubes (f-CNTs) using the phase invasion method. The oxidised CNTs were successfully decorated with Zero-Valent (ZV) Fe/Ni nanoparticles for the adsorption and degradation studies of polychlorinated organic pollutants (in this case the dichlorodiphenyltrichloroethanes (DDTs)). The in situ modification procedure was carried out using different quantities (0.04 wt%, 0.1 wt% and 0.2 wt%) of Fe/Ni-f-CNTs nanohybrids dispersed in a DMAc solution and dipping the polyethersulfone powder into a suspension containing the Fe/Ni-f-CNTs to form a nano-composite membrane. The formed composite membrane characteristics were investigated with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle (CA) and X-ray diffraction spectroscopy (XRD). The incorporation of nanohybrid in the PES membrane was found to increase the surface smoothness and the hydrophilicity of the composites. In addition, there was an increase in the adsorption of DDTs with increase in the nano-hybrid loading as indicated by the adsorption studies using the Langmuir isotherm and Freundlich isotherm studies. The data obtained from the batch studies closely fitted with the Langmuir isotherm based on the characteristic parameter RL found to lie within the standard range 0 < RL < 1 .

Background-Heart failure is common in patients with chronic kidney disease. We studied risk factors for incident heart failure among 3557 participants in the CRIC (Chronic Renal Insufficiency Cohort) Study. Methods and Results-Kidney function was assessed by estimated glomerular filtration rate (eGFR) using serum creatinine, cystatin C, or both, and 24-hour urine albumin excretion. During an average of 6.3 years of follow-up, 452 participants developed incident heart failure. After adjustment for age, sex, race, and clinical site, hazard ratio (95% CI) for heart failure associated with 1 SD lower creatinine-based eGFR was 1.67 (1.49, 1.89), 1 SD lower cystatin C-based-eGFR was 2.43 (2.10, 2.80), and 1 SD higher log-albuminuria was 1.65 (1.53, 1.78), all P< 0.001. When all 3 kidney function measures were simultaneously included in the model, lower cystatin C-based eGFR and higher log-albuminuria remained significantly and directly associated with incidence of heart failure. After adjusting for eGFR, albuminuria, and other traditional cardiovascular risk factors, anemia (1.37, 95% CI 1.09, 1.72, P= 0.006), insulin resistance (1.16, 95% CI 1.04, 1.28, P= 0.006), hemoglobin A1c (1.27, 95% CI 1.14, 1.41, P< 0.001), interleukin-6 (1.15, 95% CI 1.05, 1.25, P= 0.002), and tumor necrosis factor-a (1.10, 95% CI 1.00, 1.21, P= 0.05) were all significantly and directly associated with incidence of heart failure. Conclusions-Our study indicates that cystatin C-based eGFR and albuminuria are better predictors for risk of heart failure compared to creatinine-based eGFR. Furthermore, anemia, insulin resistance, inflammation, and poor glycemic control are independent risk factors for the development of heart failure among patients with chronic kidney disease.

Maintenance of membrane performance requires inevitable cleaning or defouling of fouled membranes. Membrane cleaning using enzymes such as proteases, lipases, α-glucosidases from a sulphidogenic bioreactor was investigated. At first, dilute and concentrated enzyme extract were prepared form the sulphidogenic pellet. Enzyme assays on 0.5 % azocaisen, 1 % triacetin and 1 mg/ml ρ-nitrophenyl-α-D-glucopyranoside were performed using the concentrated enzyme extract (0 – 200 mg/ml). For membrane fouling, an abattoir effluent was obtained from Ostritech Pty (Ltd), Grahamstown, South Africa. The effluent was characterised for presence of potential foulants such as lipids, proteins, amino acids and carbohydrates. Static fouling of polysulphone membranes (0.22 μm, 47 mm) was then performed using the abattoir effluent. Cleaning of the fouled membranes was also performed using at first the dilute and then the concentrated form (200 mg/ml) of enzyme extracts. Qualitative and quantitative biochemical analysis for proteins, lipids and carbohydrates was performed to ascertain the presence of foulants on polysulphone membranes and their removal by dilute or concentrated enzyme extracts. The ability of dilute enzyme extracts to remove proteins lipids, and carbohydrates fouling capillary UF membrane module; their ability to restore permeate fluxes and transmembrane pressure after cleaning/defouling was also investigated. Permeate volumes from this UF membrane module were analysed for protein, amino acids, lipids, and carbohydrates concentrations after fouling and defouling. Fouling was further characterized by standard blocking, cake filtration and pore blocking models using stirred UF cell and polyethersulphone membranes with MWCO of 30 000, 100 000 and 300 000. After characterization of fouling, polyethersulphone membranes with MWCO of 30 000 and 300 000 were defouled using the concentrated enzyme extract (100 mg ml). Enzyme activities at 200 mg/ml of enzyme concentration were 8.071 IU, 86.71 IU and 789.02 IU for proteases, lipases and α-glucosidases. The abattoir effluent contained 553 μg/ml of lipid, 301 μg/ml of protein, 141 μg/ml of total carbohydrate, and 0.63 μg/ml of total reducing sugars. Proteins, lipids and carbohydrates fouling polysulphone membranes after a day were removed by 23.4 %, when a dilute enzyme was used. A concentrated enzyme extract of 200 mg/ml was able to remove proteins, lipids and carbohydrates up to 5 days of fouling by 100 %, 82 %, 71 %, 68 % and 76 % respectively. Defouling of dynamically fouled capillary ultrafiltration membranes using sulphidogenic proteases was successful at pH 10, 37°C, within 1 hour. Sulphidogenic proteases activity was 2.1 U/ml and flux Recovery (FR %) was 64. Characterization of fouling revealed that proteins and lipids were major foulants while low concentration of carbohydrates fouled polyethersulphone membranes. Fouling followed standard blocking for 10 minutes in all the membranes; afterwards fouling adopted cake filtration model for membranes with 30 000 MWCO and pore blocking model for membranes with 300 000 MWCO. A concentration of 100 mg/ml of enzyme extract was able to remove fouling from membranes with MWCO of 30 000. Defouling membranes that followed pore blocking model i.e. 300 000 MWCO was not successful due to a mass transfer problem. From the results of defouling of 30 000 and 300 000 MWCO it was concluded that defouling of cake layer fouling (30 000 MWCO) was successful while defouling of pore blocking fouling was unsuccessful due to a mass transfer problem. The ratio of enzymes present in the enzyme extract when calculated based on enzymatic activity for proteases, lipases and α-glucosidases was 1.1 %, 11 % and 87.9 %. It was hypothesized that apart from proteases, lipases, α and β-glucosidases; phosphatases, sulphatases, amonipeptidases etc. from a sulphidogenic bioreactor clean or defoul cake layer fouling by organic foulants and pore blocking fouling provided the mass transfer problem is solved. However, concentration of enzymes from a sulphidogenic bioreactor has not been optimized yet. Other methods of concentrating the enzyme extract can be investigated for example use of organic solvents.

The Refcoal process is being developed to produce graphite from coal. Coal is dissolved in dimethylformamide (DMF) and sodium hydroxide (NaOH) is used as additive. After separation, the extracted coal (Refcoal) is precipitated with water and dried. The extraction process and subsequent solid-liquid separation processes have to be as efficient and cost-effective as possible. The purpose of the study was therefore to complete research on various unresolved aspects of the processes as identified by the candidate and supervisor. Extraction at 95 °C (DMF:coal:NaOH = 100:10:1), has an induction period of approximately 60 minutes observed, after which the reaction rate increases considerably. The reaction reaches completion after 360 minutes. An increase in stirring rate decreases extraction time due to the elimination of external mass-transfer limitations. The progress curves obtained for extraction at 135 °C with lower solvent-to-coal ratios differ dramatically from those obtained in previous studies, which indicates that changes in the raw materials and the experimental set-up have a great influence on the extraction at higher temperatures and concentrations. These extractions at higher temperatures using DMF:coal:NaOH ratios between 100:30:3 and 100:30:2 take approximately 360 minutes to complete and do not have an induction period as is the case with the extractions at 95 °C. It was found that the optimum DMF:coal ratio for an operating temperature of 135 °C, is 10:3. The high-temperature extractions reach completion in different time periods, depending on the amount of NaOH added to the reaction mixture. When very low concentrations of NaOH are added, the extraction will take much longer to complete and vice versa. The amount of NaOH used influences various aspects of the process. The cost analysis of the process falls beyond the scope of this investigation, but it is recommended that a thorough financial study is done to determine the optimum balance between raw materials, heat load and plant availability. The relationships between the concentration of Refcoal in the Refcoal solution and the absorbance values measured are polynomial expressions ending in downward concaves. The kinetics for the low-concentration (DMF:coal:NaOH = 100:10:1) extraction are best described by an autocatalytic reaction rate equation which is a function of coal, coal complex and NaOH concentration. A good fit was also obtained for the high temperature extractions. The rate expression is a function of both the coal and NaOH concentrations, but not of the coal complex. The sedimentation test showed promising results. The use of a thickener instead of a centrifuge to separate the insoluble material from the Refcoal solution would be a feasible cost-saving method. Filtration of the Refcoal solution (after centrifugation) using suitable filter media decreases the amount of impurities in the Refcoal. Filtration constants were determined for the best filter medium. The use of a hydrocyclone to separate the insoluble material from the extract is not recommended as it did not give the required efficiency to make the process viable. It is recommended that more tests be done under different conditions. Useful expressions were obtained for the change in viscosity with temperature for three different concentrations of Refcoal solution. It was determined that the viscosity of the Refcoal solution increases with time and it is therefore recommended that this be taken into account when equipment is being designed and plant scheduling is being done. / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2007. / Chemical Engineering / MEng / unrestricted