Nano-gefunctionaliseerde membraandistillatiemembranen voor drinkwaterproductie uit zout of brak water

Abstract in English and GermanThe reported PhD research study was conceived from real water problems experienced by a rural community in South Africa (SA). Specifically, water quality in the Nandoni Dam situated in the Vhembe District, Limpopo Province, South Africa was assessed in order to determine its fitness for use, following complaints by community members using this water for drinking and domestic purposes. The dam supplies water to 55 villages with approximately 800 000 residents. At the inception of the study, there was little scientific information relating to the quality of the water in the dam. Water samples from various sites across the Nandoni Dam, a primary source of domestic water supply in the region, were collected through each season of the year over a period of 12 months to ascertain the concentrations of dissolved salts in the dam. Additionally, harmful polycyclic aromatic hydrocarbons (PAHs) and phenols were assessed. The concentrations of the ions contributing to water salinity were generally lower than the brackish water bracket (i.e. 500 – 30 000 mg/L) but too high for potable water. The concentration of the phenols was relatively higher than the threshold limit of drinking water. Therefore, the water sourced from the Nandoni Dam was found not suitable for human consumption and therefore required integrated water resource management, as well as robust and cost-effective water treatment especially since the salinity of the water was high even after treatment by a water treatment plant sourcing water from the dam. In an attempt to develop a suitable energy-efficient technology or system for complete removal of salts (desalination) from the salty water (including brackish water), electrospun polyvinylidene fluoride (PVDF) nanofibre membranes were synthesised and evaluated for removal of salts using the Direct Contact Membrane Distillation (DCMD) process. The nanofibre membranes were synthesised with combined high mechanical stability, porosity, and superhydrophobicity to prevent fouling and wetting while maintaining high salt rejection and water flux. Organically functionalised silica nanoparticles (f-SiO2NPs) were embedded on PVDF nanofibre membranes using an in-situ electrospinning technique for superhydrophobicity enhancement. These modified membranes displayed Young’s modulus of ~43 MPa and showed highly porous properties (~80% porosity, 1.24-1.41 μm pore sizes) with superhydrophobic surfaces (contact angle >150°). Membranes embedded with octadecyltrimethoxysilane (OTMS), and chlorodimethyl-octadecyl silane (Cl-DMOS), octadecyltrimethoxysilane (ODTS)-modified SiO2NPs were the most efficient; rejecting >99.9% of NaCl salt, with a water flux of approximately 30.7-34.2 LMH at 60°C, thus indicating their capacity to produce potable water. The superhydrophobic membranes were coated with a thin layer consisting of carboxylated multiwalled carbon nanotubes (f-MWCNTs) and silver nanoparticles (AgNPs) to reduce membrane fouling. The AgNPs and f-MWCNTs were uniformly distributed with size diameters of 28.24±1.15 nm and 6.7±2.1 nm respectively as evidenced by transmission electron microscopy (TEM) micrographs. The antibacterial AgNPs embedded in the PVDF nanofibre membranes inhibited the growth of Gram-positive Geobacillus stearothermophilus and Staphylococcus aureus as well as Gram-negative Pseudomonas aeruginosa and Klebsiella pneumoniae indicating their potential to prevent biofilm formation. Fouling tests were conducted using bovine serum albumin (BSA), sodium alginate, colloidal silica, and thermophilic bacteria effluent as model organic, inorganic, and bio-foulants, respectively, using DCMD. The uncoated membranes were characterised by a flux decays ranging from 30% to 90% and salt rejection decays ranging from 1.4% to 6.1%. Membrane coating reduced the flux and salt rejection decays to 10–24% and 0.07–0.75%, respectively. Although the initial flux decreased from 42 to 16 LMH when using coated membranes, the resistance of these coated membranes to water flux and salt rejection decays indicated that coating could be a suitable one-step solution for fouling mitigation in DCMD. The major challenge would be to design the MD membranes with architectures that allow a high-water flux to be maintained i.e., a highly porous layer. Furthermore, the volatile compounds bearing hydrophobic groups were pretreated to reduce their fouling capacity on PVDF nanofibre membranes. In this study, polyacrylonitrile (PAN) and polyethylene-imine (PEI) functionalised-PAN nanofibre membranes were synthesised and evaluated as a pretreatment for the removal of chlorophenol and nitrophenol from solutions. Under optimised experimental conditions, adsorption capacities ranging from 27.3 – 38.4 mg/g for PAN and PEI-modified nanofibres, respectively, were recorded. The PEI-functionalised nanofibres showed a high potential as a pretreatment step to be integrated to MD process. Ultimately an integrated water desalination system was developed. This involved a pretreatment filter (pore size ~100 μm) containing PEI-functionalised PAN nanofibre materials to reduce particulates and large molecules of dissolved organic/inorganic compounds from the water to be treated. In this research, it was observed that the pre-treatment step was not sufficient in removing all traces of compounds causing fouling of the superhydrophobic PDVF nanofibre membranes. As such, coating of the membranes with a thin hydrophilic layer and coupled with the filtration pretreatment step was found to provide fouling-resistance properties, high salt rejection, and low flux decays on brackish water collected at an estuary in Belgium and the Nandoni Dam in South Africa, demonstrating the potential of the MD separation process towards potable water recovery from brackish water.Het onderzoek in dit proefschrift was gebaseerd op concrete waterproblemen die een landelijke gemeenschap in Zuid-Afrika (SA) ervaart. In het bijzonder werd de waterkwaliteit in het Nandoni-reservoir in het Vhembe-district in de provincie Limpopo in Zuid-Afrika onderzocht, om te bepalen of dit water geschikt is voor gebruik, na klachten van leden van de gemeenschap die dit water gebruiken als drinkwater en voor huishoudelijk gebruik. Het reservoir levert water aan 55 dorpen met ongeveer 800.000 inwoners. Bij het begin van het onderzoek was er weinig wetenschappelijke informatie over de kwaliteit van het water in het reservoir. Watermonsters van verschillende locaties in het reservoir, dat een primaire bron van drinkwater is in de regio, werden gedurende verschillende seizoenen van het jaar verzameld over een periode van 12 maanden, om de concentraties van de meest voorkomende ionen in het reservoir te bepalen. Bovendien werden de concentraties van schadelijke polycyclische aromatische koolwaterstoffen (PAK's) en fenolen gemeten. De concentraties van de ionen die bijdroegen aan het zoutgehalte van het water waren in het algemeen lager dan de drempel om het water als brak water te bestempelen (dat wil zeggen 500 – 30 000 mg/l), maar waren te hoog voor drinkwater. De concentratie van de fenolen was hoger dan de limiet voor drinkwater. Daarom bleek het water afkomstig van het Nandoni reservoir niet geschikt voor menselijke consumptie. Een beter geïntegreerd waterbeheer is dus nodig om deze bron voor drinkwater te beschermen, naast een robuuste en kosteneffectieve waterbehandeling. Deze waterbehandeling moet vooral het zoutgehalte van het water naar beneden halen, maar ook de concentraties van fenolen. In een poging om een geschikte energie-efficiënte technologie of een systeem voor de volledige verwijdering van zouten (~ontzilting) uit brak water te ontwikkelen, werden elektrisch gesponnen polyvinylideenfluoride (PVDF) nanovezelmembranen gesynthetiseerd en beoordeeld op verwijdering van zouten met behulp van Direct Contact Membraandestillatie (DCMD). De nanovezelmembranen hadden een gecombineerde hoge mechanische stabiliteit, porositeit en superhydrofobiciteit, die hielp om vervuiling (fouling) en vloeistofintrede in de poriën (wetting) te voorkomen, terwijl een hoge zoutverwijdering en hoge waterflux doorheen de membranen gehandhaafd bleven. Organische gefunctionaliseerde silica-nanodeeltjes (f-SiO2NP's) werden nadien geïncorporeerd in de PVDF nanovezelmembranen met behulp van een in-situ elektrospinning techniek om zo een nog grotere superhydrofobiciteit te bekomen. Deze gemodificeerde membranen hadden een degelijke treksterkte (Young's modulus van ~ 43 MPa) en waren zeer poreus (~ 80% porositeit, 1.24-1.41 μm poriegrootte). Het oppervlak van de membranen vertoonde inderdaad superhydrofobe eigenschappen (contacthoek met water > 150 °). De membranen ingebed met octadecyltrimethoxysilaan (ODTS) SiO2NP's waren het meest efficiënt: ze toonden een zoutretentie van> 99.9% voor NaCl, bij een waterflux van ongeveer 30.7-34.2 l/(m².h) bij 60 ° C (ten opzichte van 20°C in het permeaat), wat aangeeft dat ze in staat zijn om drinkbaar water te produceren. De superhydrofobe membranen werden nadien ook gecoat met een dunne laag bestaande uit gecarboxyleerde multiwall-carbon nanotubes (f-MWCNT's) en zilver nanodeeltjes (AgNP's), in een poging om membraanvervuiling te verminderen. De AgNP's en f-MWCNT’s hadden uniforme diameters van respectievelijk 28,24 ± 1,15 nm en 6,7 ± 2,1 nm (zoals bleek uit transmissie-elektronenmicroscopie (TEM)). De antibacteriële AgNP's ingebed in de PVDF-nanovezelmembranen remden de groei van Gram-positieve Geobacillus stearothermophilus en Staphylococcus aureus bacteriën, evenals Gram-negatieve Pseudomonas aeruginosa en Klebsiella pneumoniae bacteriën. Dit toont het potentieel van deze membranen om biofilmvorming te voorkomen. Vervuilingsproeven (in DCMD) werden uitgevoerd met behulp van runderserumalbumine (BSA), natriumalginaat, colloïdaal silica, en thermofiele bacteriën - als respectievelijk organische, anorganische en biologische vervuiling. De niet-gemodificeerde membranen werden gekenmerkt door een fluxverval, met een daling van de flux met 30% tot 90%, naast een daling van de zoutretentie met 1.4% tot 6.1%. Bij de gecoate membranen daalde de flux slechts met 10-24% en de zoutverwijdering slechts met 0.07-0.75% respectievelijk. Hoewel de initiële flux ook afnam (van 42 naar ± 16 l/(m².h)) bij het gebruik van gecoate membranen, toonde de hogere weerstand tegen vervuiling van deze gecoate membranen aan dat deze coating een geschikte oplossing zou kunnen zijn tegen vervuiling in DCMD. Bovendien kan de synthese in één stap verlopen. De grootste uitdaging zal echter zijn om MD-membranen te ontwerpen waarbij de coating de oorspronkelijke waterflux/de porositeit van de membranen niet teveel verlaagt. Daarnaast werden gemodificeerde PVDF nanovezels geproduceerd om de verwijdering van vluchtige, hydrofobe stoffen (zoals fenolen) door adsorptie aan deze vezels te verhogen. Er werden polyacrylonitril (PAN) en polyethyleen-imine (PEI) gefunctionaliseerde PAN nanovezels gesynthetiseerd, waarna deze geëvalueerd werden als adsorbens (en dus voorbehandeling voor de membraanstap) voor chloorfenol en nitrofenol. Onder geoptimaliseerde experimentele omstandigheden werden adsorptiecapaciteiten tussen respectievelijk 27.3 en 38.4 mg / g voor PAN- en PEI-gemodificeerde nanovezels gemeten. De PEI-gefunctionaliseerde nanovezels vertoonden een hoog potentieel als een voorbehandelingsstap voor de hierboven beschreven DCMD. Tenslotte werd ook een geïntegreerd waterontziltingssysteem ontwikkeld. Dit systeem bestond uit een voorbehandelingsstap met PEI-gefunctionaliseerde PAN-nanovezels (in de vorm van een membraan met poriegrootte ~100 μm), gevolgd door een gemodificeerde DCMD stap. De voorbehandeling diende om deeltjes en grote opgeloste organische verbindingen uit het te behandelen water te verwijderen voor de DCMD-stap. In dit onderzoek werd waargenomen dat de voorbehandelingsstap niet voldoende was om alle organische contaminanten te verwijderen die vervuiling veroorzaakten op de superhydrofobe PDVF nanovezelmembranen in de DCMD-stap. Toch bleek coating van de DCMD membranen met een dunne hydrofiele laag (gekoppeld aan de voorbehandelingsstap) een voldoende bescherming tegen vervuiling te bieden zodat de zoutretentie en waterflux van deze membranen hoog bleef. De combinatie van voorbehandeling – gemodificeerde DCMD werd succesvol getest op water uit de Schelde en uit het Nandoni reservoir, waarmee het potentieel van de technologie om drinkwater uit brak water te produceren werd aangetoond.School of SciencePh.D. (Applied Biological Science : Environmental Technology

Spectroscopic determination of water salinity in brackish surface water in Nandoni Dam, at Vhembe District, Limpopo Province, South Africa

The problem of limited water supply in the Vhembe District (Limpopo Province, South Africa) is exacerbated by a preponderance of dissolved salts, which cause disagreeable taste and odour in the water as reported by the communities using this water for drinking. The water treatment plant that supplies the treated water to the communities in the District sources this raw water from the Nandoni Dam at the Luvuvhu river catchment. There are no scientific studies that have been reported in the literature that focused on determining the levels of water salinity from various water sources in the municipalities of the District. Water samples from various sites across the Nandoni Dam, a primary source of domestic water supply in the region, were collected through each season over a period of twelve months in order to ascertain the concentrations of dissolved salts in the dam. Onsite analyses of the water samples were conducted using the YSI ProDSS multimeter, while the laboratory water analyses were conducted using the spectroquant and atomic absorption spectrometers. Although salinity tests seem to indicate that the water sampled across most of the Nandoni Dam is brackish during all seasons of the year with the highest being 750 mg/L, water samples from the dam mid-outlet and the treatment plant are slightly below the World Health Organization (WHO) brackish water bracket of 500 mg/L with unfavourable taste for drinking. Results from this study indicate that the water sourced from the Nandoni Dam is not suitable for human consumption and therefore requires integrated water resource management, as well as robust and cost-effective water desalination treatment

Removal of Fe and Mn from polluted water sources in Lesotho 3 using modified clays

Abstract: This paper reports the use of unfunctionalized and phenylalanine functionalized clays as an alternative cost effective, environmental friendly and efficient sorbent for the removal of Mn and Fe from polluted drinking water sources in Lesotho. Mn and Fe were found to be the most prevalent metal pollutants in rivers supplying three drinking water treatment plants situated in Maseru, Roma and Quthing. The Mn and Fe metals were adsorbed on two different clays (clay A – a black clay and clay B – a yellow clay) collected from Ha-Teko in Maseru (clay A) and Phoqoane in Mafeteng district (clay B) in Lesotho. As a common assessment for adsorption materials, comprehensive batch test studies were performed to assess the effect of pH, stirring time, initial concentration and 26 kinetic studies of the adsorption of these metals. The adsorption of the metals was greater at higher pH and equilibrium was reached at pH 8.0 after 30 min of stirring. The phenylalanine functionalized clays displayed improved adsorption efficiency of up 100 % (Fe adsorption using modified clay A in 30 min) while the unfunctionalized clays gave relatively low adsorption of up to 70 % (Fe and Mn adsorption using modified clay A). This was observed on real and simulated water samples. The findings of this work suggest that the clays, which are 31 present in abundance in Lesotho, can be effectively used for the removal of Fe and Mn from drinking water sources in Lesotho

The past in the present: race, gender and transnationalism in Zoë Wicomb’s October and Chimamanda Ngozi Adichie’s Americanah

This thesis will interrogate the ways in which the most recent novels of Zoë Wicomb and Chimamanda Ngozi Adichie (namely October and Americanah) explore race, gender and transnational issues. Wicomb and Adichie share an interest in representing the lives of people who have been historically marginalised by racial and gender classifications. This thesis will argue that historical and stereotypical ways of looking at people, particularly African people, are still prevalent in the twenty-first century. Wicomb’s interest is in the coloured community and the impact that apartheid ideology has had on it. She shows, as this thesis will argue, that notions of shame and respectability still influence the coloured community, post-1994, in the same ways they did under apartheid. Furthermore, the thesis will show that religion, which was used to justify apartheid, has been instrumental in maintaining racist and sexist norms in the coloured community in post-apartheid South Africa. Adichie’s novel, on the other hand, shows the impact of gender norms in Nigeria on her female characters. Unlike characters in Wicomb’s novel, Adichie’s mostly experience racial bias when they move to Western countries. This thesis will argue that many Western countries, which were the main beneficiaries of colonialism, continue to ‘other’ Africans, in spite of their claims to respect all human beings. Wicomb’s and Adichie’s novels depict characters that are moving between different continents, along with the impact that this has on them. In the twenty-first century, more people are moving between different spaces and, as a result, interacting with different cultures. These migrations, as this thesis will show, give rise to paradoxical circumstances: people are still being judged according to their race and gender, in spite of the freedom that these moves are supposed to lead to. Of central importance to both novels then is the question of home and belonging. Since people are moving between different continents, is it still possible to belong to one place? Is it in fact possible to belong at all? These are some of the questions that will be raised and answered in this thesis. Lastly, the thesis will look at the thematic representations of reading and writing in the novels under consideration. This is most evident in Adichie’s novel where her main character starts blogging as a way to express her dissatisfaction with the racist and sexist environment she encounters in the United States of America. The thesis will explore how Adichie examines blogging as a mode of communication that is unique to the twenty-first century. It will argue that it is perhaps through new media that historically subjugated subjects, such as African people and women, will be able to express themselves. Less hackneyed modes of communication might provide the necessary channels for those who have historically been denied voice to finally find it

Water as the Pore Former in the Synthesis of Hydrophobic PVDF Flat Sheet Membranes for Use in Membrane Distillation

Although PVDF flat sheet membranes have been widely tested in MD, their synthesis and modifications currently require increased use of green and inexpensive materials. In this study, flat sheet PVDF membranes were synthesized using phase inversion and water as the pore former. Remarkably, the water added in the casting solution improved the membrane pore sizes; where the maximum pore size was 0.58 µm. Also, the incorporation of f-SiO2NPs in the membrane matrix considerably enhanced the membrane hydrophobicity. Specifically, the membrane contact angles increased from 96° to 153°. Additionally, other parameters investigated were mechanical strength and liquid entry pressure (LEP). The maximum recorded values were 2.26 MPa and 239 kPa, respectively. The modified membranes (i.e., using water as the pore former and f-SiO2NPs) were the most efficient, showing maximum salt rejection of 99.9% and water flux of 11.6 LMH; thus, indicating their capability to be used as efficient materials for the recovery of high purity water in MD

Record-Making, Research, and Removal: Mitigating Impacts on Rock Art in a CRM Context in Southern Africa—the Case of the Metolong Dam, Lesotho

This paper reports on the steps taken to mitigate the impact of the Metolong Dam (Lesotho) on the rock art present within the catchment of its associated reservoir. Mitigation took four major forms: comprehensive survey and documentation, including both photography and tracing; pigment characterization and radiocarbon dating; exploration of the ongoing significance of rock art as a form of living heritage for people living in the vicinity; and removal of selected panels for permanent safekeeping. These steps are placed within the wider context of other cultural heritage management projects in Africa and their success evaluated. Recommendations are made for how similar work should be undertaken in future

Investigations of the effect of pore size of ceramic membranes on the pilot-scale removal of oil from oil-water emulsion

Oil-water emulsions are one of the most serious pollutants because of the large quantities produced by various industries, such as the petrochemical, oil and gas industries. One of the major methods to remove oil from wastewater is filtration using ceramic tubular microfiltration membranes. However, such membranes are vulnerable to fouling, which causes operational impairment. The aims of this work are to study the influence of membrane pore size on permeate flux and oil removal efficiency at different operating parameters and the reduction in fouling when used in combination with hybrid Coagulation/sand filter-MF pre-treatment process. The droplet size of the oil-water emulsion has an interaction with the pore size of the ceramic membrane. Therefore, each pore size may be optimal, depending upon the concentration of oil in the emulsion, and hence droplet size. Steady-state flux and oil removal efficiency were found to b highest for hybrid coagulation/sand filter –MF due to a reduction of membrane fouling by reducing the oil concentration in the inlet emulsion to the ceramic membrane

Combining Cellulose and Cyclodextrins: Fascinating Designs for Materials and Pharmaceutics

Cellulose and cyclodextrins possess unique properties that can be tailored, combined, and used in a considerable number of applications, including textiles, coatings, sensors, and drug delivery systems. Successfully structuring and applying cellulose and cyclodextrins conjugates requires a deep understanding of the relation between structural, and soft matter behavior, materials, energy, and function. This review focuses on the key advances in developing materials based on these conjugates. Relevant aspects regarding structural variations, methods of synthesis, processing and functionalization, and corresponding supramolecular properties are presented. The use of cellulose/cyclodextrin conjugates as intelligent platforms for applications in materials science and pharmaceutical technology is also outlined, focusing on drug delivery, textiles, and sensors