This research report submitted to the Faculty of Health Sciences, University of the Witwatersrand, in partial fulfilment of the requirements for the degree of Master of Science in Dentistry. School of Oral Health Science, Faculty of Health Sciences, University of the Witwatersrand, South Africa Johannesburg, 2017 / Purpose: Resin restorative materials have improved over the years. A major obstacle to the acquisition of acceptable bond strength of bonding agents is the presence of contaminated dentine cavity preparations. The purpose of this study was to investigate the effects of oral contaminants such as blood, saliva and a disinfectant contamination on the shear bond strength of a nanocomposite on a self-etching adhesive system. Materials and Methods: Thirty-six caries free premolar teeth were extracted and placed in a disinfectant solution containing 0.5 % Chloramine T solution, and then randomly distributed into four groups. Each tooth was then placed into a stainless steel ring supported by clear self-curing acrylic. They were thereafter immersed into a saline solution of 37 ̊C - 37.5 ̊C in an incubator for 24 hours. The enamel surfaces of the premolars were then ground with a Pro-trim 1725 Hertz grinder using 600 grit silicon carbide fine grinding paper to expose the dentine surface of each tooth. The sample was then re-immersed in the saline solution and incubated at 37°C - 37.5°C. The teeth were then arranged into the four groups: Group 1 (control group); Group 2 (human blood contamination at 5 seconds); Group 3 (human saliva contamination at 5 seconds) and Group 4 (chlorine dioxide contamination at 5 seconds). A self-etching adhesive bonding system (Scotchbond universal™) and Filtek supreme XTE composite was applied to the exposed dentine surface. Samples were randomised and then sheared using an Instron testing machine to determine their bond strengths. The fractured components of each sample were measured, compared and further examined under a stereo microscope to determine the modes of failure. The data were analysed using a one-way analysis of variance (ANOVA) and the level of significance was set at a p-value of less than 0.05. Results: A significant difference was found in the shear bond strength between the control (group 1) and the blood contaminated group (group 2) (p-value of 0.00064). The chlorine dioxide group (group 4) that had no effect on shear bond strength to dentine (p-value of 0.55). Adhesive failures (between bonding agent and dentine) were predominant in group 2 and to a lesser extent in group 3. Most group 4 samples had cohesive fractures (within the dentine). Conclusion: The bond strength to dentine using a self-etching adhesive was reduced when contaminated with blood. Group 2 samples (blood) caused significantly greater bonding failure as compared to all the other groups. Chlorine dioxide solution is a powerful disinfectant and does not affect the bonding to dentine. The null hypothesis statement, which stated that there was no difference in the shear strength between any of the conditions, was thus rejected. Further studies on the application of chlorine dioxide as a disinfectant on cavity preparations need to be considered given the surprising positive results of chlorine dioxide group. / MT2018

Nickel-manganese-cobalt oxide (NMC) cathode materials have been applied in most Li-ion batteries, but there are nevertheless some concerns regarding the stability of this material. High voltage and high temperature during charging have been shown to accelerate the dissolution of NMC due to the release of more acidic components because of rapid electrolyte decomposition. Mn-contaminants (Mn2+) are hypothesized to diminish the diffusion coefficient of Li+ in the electrolyte attributed to the competitive interaction between Mn2+ ions and Li+ ions. With characterizations including 7Li and 1H pulsed field-gradient nuclear magnetic resonance (PFG-NMR) spectroscopy, we demonstrated the Mn (II)-contaminants effect on diffusion coefficient on Li+ dynamics. Under the influence of deliberate manganese salt-additive to the electrolyte, the coin cell shows a capacity fading and unstable charging behavior. The PFG-NMR measurements also validated our hypotheses, as the results showing that Mn-containment causes decrease ~15% in the diffusion coefficient on Li-self diffusion. The activation energy for lithium-ion transport over the temperature range of (273 K - 303 K), was not changed by the presence of the Mn-contaminant electrolyte, which indicates the Mn (II) does not affect the Li-ion transport mechanism. The relative test also includes comparisons with other contamination, such as iron contamination from stain-less steels spacers and copper contamination from the current collector. Additionally, the lithium self-diffusion coefficient was tested before and after charging using a full battery configuration. In electrolytes containing manganese contaminants, a more significant decrease in the diffusion coefficient was observed after charging. Ideally, operando experiments can be used to observe the impact of manganese ions on the SEI. By combining both types of experiments, a closer approximation to the actual application conditions of market-used batteries can be achieved. / Thesis / Master of Science (MSc) / The increasing maturity of lithium battery technology has also promoted the advancement of the electric vehicle manufacturing industry. As an excellent new energy material, the application and development of lithium batteries will be the main trend in the future. However, while improving battery capacity and energy density, lithium batteries also face many challenges. The entire thesis work discusses how electrolyte degradation at high temperatures and high voltages accelerates the dissolution of transition metal manganese ions in NMC materials. The dissolution of manganese ions into the electrolyte creates a competitive effect with lithium ions, thereby reducing the performance of lithium batteries. Here, NMR technology was used to measure the negative effect of manganese ions on the self-diffusion coefficient of lithium ions in the electrolyte. Additionally, a set of operando experiments conducted at different discharge rates demonstrated the changes in mossy lithium and the solid electrolyte interface during the charge and discharge phases caused by pulse discharge. This also proved that such experimental designs can track the impact of manganese ions on the solid electrolyte interface and test the dissolution behavior and impact of manganese ions under different charge and discharge rates.

Ce travail de recherche porte sur l'étude de trois familles de contaminants organiques hydrophobes persistants : hydrocarbures aromatiques polycycliques (HAP), polychlorobiphényles (PCB) et pesticides organochlorés (OCP) dans les sédiments d'une lagune méditerranéenne : l'étang de Thau. Les niveaux et les distributions géographiques ont été déterminés pour chaque famille de contaminants étudiés. De même, leurs stocks et leurs flux ont été estimés dans le sédiment de surface. L'étude des carottes sédimentaires a permis de reconstituer l'historique de la contamination des sédiments de l'étang de Thau. Cet historique s'avère représentatif de l'évolution de la contamination au niveau national et concorde avec les tendances européennes et mondiales. L'étude des carottes sédimentaires a également fourni des renseignements sur la dynamique de la contamination des sédiments dans l'étang de Thau. Les grandes tendances temporelles, les inventaires et les flux ont été quantifiés pour les trois familles des contaminants étudiés. Enfin, une étude expérimentale plus restreinte sur la disponibilité des contaminants associés aux sédiments de l'étang a également été réalisée. Ce travail a permis d'aborder la disponibilité des contaminants sur différents niveaux d'une carotte sédimentaire en fonction de la nature : l'origine et l'âge de la matière organique et des propriétés physico-chimiques des contaminants. L'approche expérimentale de cette étude a été basée sur l'utilisation d'un échantillonneur passif. Les premiers résultats ouvrent des perspectives de travail visant à une meilleure compréhension de la disponibilité des contaminants sédimentaires.

The extensive use of pharmaceuticals and their poor removal by wastewater treatment plants has led to the emergence of pharmaceutical compounds as global aquatic contaminants. Progestins, the synthetic analogues to progesterone (P4), are receiving increasing attention as contaminants and have been shown to impair reproduction in fish and amphibians at low ng L-1 concentrations. Certain progestins have androgenic properties and are several orders of magnitude more potent in terms of reproductive impairment in fish than non-androgenic progestins. To characterize the androgenic effects of progestins in fish, adult three-spined sticklebacks (Gasterosteus aculeatus) and zebrafish (Danio rerio) larvae were exposed to progestins via the ambient water. In female sticklebacks, the androgenic progestins levonorgestrel (LNG) and norethindrone (NET) induced production of the androgenic biomarker protein spiggin and reduced production of the egg yolk protein vitellogenin. Comparison with well-known environmental androgens showed that LNG and NET, with regard to spiggin induction and vitellogenin induction, are among the most potent environmental androgens known. In male sticklebacks, LNG inhibited the post-breeding regression of secondary sex characters and spiggin production, as well as the resumption of spermatogenesis, functionally inhibiting the natural transition from breeding into non-breeding condition. Exposure of zebrafish larvae to LNG caused all fish to develop into males, whose sexual development was also significantly accelerated. P4 had no effect on the sex ratio, while slightly accelerating sexual development at high concentrations. Suppression of vitellogenesis in females, disruption of the male reproductive cycle, male-biased sex ratios and precious male puberty could all entail severe fitness costs and severely affect fish populations. Most of the effects of androgenic progestins in this thesis occurred at levels within the range of reported environmental levels, and may therefore occur in progestin-contaminated waters. In conclusion, the present results establish LNG and NET as highly potent androgenic pollutants of environmental concern, and provide strong support to the contention that the reproductive impairment in fish caused by progestins is chiefly mediated by their androgenic properties.

<p>It is estimated that 22 000 contaminated areas exist in Sweden today. In order to classify the risk of contaminant migration from these areas and to prioritize which of these contaminated areas should first be treated, the Swedish Environmental Protection Agency (EPA) has designed a method, for the investigation of contaminated areas (MIFO). One of these contaminated areas is the landfill Gräsötippen outside Köping. The landfill has been used by both Yara AB and the Köping municipality between the years 1945 and 1975, and both industrial and household waste have been deposited there. The aim of this report is to survey which contaminants that can be found in the soil and water in the landfill Gräsötippen and to evaluate the migration of these contaminants. With help of this information, the landfill will then be risk classified according to MIFO. The goal is that this report will provide a basis for future studies and remedial measures at the landfill.</p><p>To get a picture of what has been deposited at the landfill Gräsötippen, employees and former employees at Yara and others with connection to the landfill have been interviewed. Piezometers have been installed in and around the landfill so as to provide information on groundwater levels and movement, and for the collection of groundwater samples. Soils samples were collected as well. The water and soil samples were analyzed with regard to metals, organic compounds and nutrients. Furthermore, groundwater flow has been modeled using VS2DI, in order to get a picture of the groundwater’s flow direction and velocity under the landfill.</p><p>In the water samples, only lead was detected with levels over the Maximum Contaminant Level (MCL) from the EPA. Relatively high levels of nutrients were also detected. In the soil, carcinogenic PAH, PCB, aliphatic hydrocarbons, aromatic hydrocarbons, arsenic, lead, cadmium, mercury and zinc were detected over the EPA MCL. The landfill Gräsötippen has a good location in an area with deep clay, which prevents rapid spreading of contaminants. No high levels of contaminants are leaching out today. The spreading of the contaminants is minor; most of the contaminants are fixed in the soil and do not spread to the surroundings. The water flow’s primary direction from the landfill is south but there are also flows to the west and east. Today, there are a number of proposals with regard to decreasing the risk for future contaminant dispersal from the landfill and to keep control of the water that is used in the area. A few of these proposals are to finally cover the landfill, to analyze the grass and plants in the enclosed pasture on the landfill, and to continuously analyze the water in the installed piezometers and drinking water wells on and around the landfill. The landfill Gräsötippen is classified to risk class 3, moderate risk, according to MIFO.</p> / <p>Det uppskattas idag finnas 22 000 förorenade områden i Sverige. För att kunna riskklassa dessa förorenade områden och prioritera vilka som först bör efterbehandlas har Naturvårdsverket utarbetat en Metodik för Inventering av Förorenade Områden (MIFO). Gräsötippen utanför Köping är ett av dessa förorenade områden. Deponin har använts av både Yara AB och Köpings kommun mellan åren 1945-1975 och fungerat som deponi för både industri- och hushållsavfall. Syftet med denna rapport är att kartlägga vilka föroreningar som finns i mark och vatten i Gräsötippen och tolka föroreningarnas spridning. Utifrån den informationen ska deponin sedan riskklassas enligt MIFO. Målet är att rapporten ska kunna fungera som underlag för framtida åtgärdsplaner för Gräsötippen.</p><p>För att få en bild över vad som har deponerats på Gräsötippen har anställda och före detta anställda vid Yara samt andra som har haft anknytning till Gräsötippen intervjuats. Grundvattenrör har installerats i och runtom deponin för att det skulle kunna tolkas hur grundvattnet rör sig under deponin och för att det skulle kunna tas prover på grundvattnet och jorden. De vatten- och jordprover som togs, analyserades med avseende på metaller, organiska föreningar och närsalter. Dessutom har en modellering utförts i VS2DI för att få en bild över grundvattnets flödesriktning och hastighet under deponin.</p><p>I vattenproven detekterades endast bly över Naturvårdsverkets riktvärde samt relativt höga halter av närsalter. I jorden detekterades cancerogena PAHer, PCB, alifater, aromater, arsenik, bly, kadmium, kvicksilver och zink över Naturvårdsverkets riktvärden. Gräsötippen är bra placerad i ett område med tjock lera som förhindrar snabb spridning och idag lakas inga höga halter av föroreningar ut. Spridningen av föroreningar är liten, istället ligger de flesta föroreningarna fast i marken och sprids därmed inte till omgivningen. Vattenflödets huvudriktning från deponin är söderut, men det sker även flöden åt både väster och öster. Det finns i dagens läge en del förslag på åtgärder som bör utföras på Gräsötippen för att minska risken för framtida spridning och upprätthålla kontroll på det vatten som används i närområdet. Några av dessa åtgärder är att sluttäcka deponin, att analysera gräs och växter i hagen på deponin samt att kontinuerligt analysera vattnet i grundvattenrören och brunnarna på och runt Gräsötippen. Vid riskklassningen av Gräsötippen enligt MIFO, klassas den till riskklass 3, måttlig risk.</p>

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During military operations, a small fraction of propellant mass is not consumed during firing and is deposited onto the ground surface. Soluble propellant constituents can be released from particulate residues into the environment. The release of uncombusted propellant residues and transformation products results in soil, surface water, and ultimately groundwater contamination. It is important to study the potential for off-site migration of munitions and to provide qualitative data that helps better understand transit of these propellant constituents. Propellant constituents of interest for this study were nitroglycerine (NG), 2,4-dinitrotoluine (2,4-DNT), 2,6-dinitrotoluine (2,6-DNT), and nitroguanidine (NQ). The goal of this work is to determine fate and transport parameters, partition/distribution coefficients and transformation rates for these compounds in three soils that represent a range of geographic locations and soil properties. This supports a companion study that looks at dissolution of constituents from fired and unfired solid propellant formulations and their transport in soil.

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Student Number : 0316126G - MSc dissertation - School of Animal, Plant and Environmental Sciences - Faculty of Science / I investigated whether inorganic contaminants associated with gold mining waste discharges in the Free State Province, South Africa, were accumulated by a threatened species of lizard, Cordylus giganteus; if the route of exposure could be dietary, and whether accumulation of contaminants could be associated with potential physiological costs. I compared elemental concentrations in tissue and blood samples between populations of this species, from four sites around the province. Inorganic contaminants were known to be elevated in soils, water, sediments and vegetation of the first mining site, and to a lesser extent at the second mining site. The third site was not known to be contaminated by mining discharges, but was selected because of its potential to be contaminated by wind-blown contaminants. This site was also heavily overgrazed. The fourth site was both uncontaminated by mining and relatively undisturbed. Lizards from the most contaminated site had significantly higher blood concentrations of Li, Na, Al, S, Ca, P, Si, Cr, Mn, Fe, Ni, W and Bi when compared with all the other sites investigated. Based upon a comparison of elemental concentrations in selected lizard prey items found at these sites (Coleoptera, Tenebrionidae) I did not find conclusive evidence for a dietary route of exposure to contaminants. I tested for significant differences in body condition among populations. Lizards from the heavily grazed site were in similar condition to lizards from the most contaminated site, and all these lizards were in significantly poorer condition than lizards from the undisturbed site. The adult sex ratio of the population inhabiting the most contaminated site also deviated significantly from an expected 1:1 ratio in favour of females. The reason for this deviation is not understood, but may be a consequence of sexes being differentially affected by inorganic contaminants. My research demonstrates that the disposal of gold and uranium mine waste has resulted in the accumulation of contaminants by a representative resident vertebrate, and that this accumulation is potentially associated with poorer body condition which might affect fitness. It highlights the potential threat of mining-waste discharges to lizards, shows the need for site remediation measures, and also highlights the need for further investigation into the potential effects of environmental contaminants from gold and uranium mine waste on exposed vertebrates in South Africa.