In recent years an emphasis has been placed on the development of alternative and clean energy sources to reduce the global use of fossil fuels. One of these alternatives entails the use of H2 as an energy carrier, which can be obtained amongst others using thermochemical processes, for example the hybrid sulphur process (HyS). The HyS process is based on the thermal decomposition of sulphuric acid into water, sulphur dioxide and oxygen. The subsequent chemical conversion of the sulphur dioxide saturated water back to sulphuric acid and hydrogen is achieved in an electrolyser using a platinum coated proton exchange membrane. This depolarised electrolysis requires a theoretical voltage of only 0.158 V compared to water electrolysis requiring approximately 1.23 V. One of the steps in the development of this technology at the North-West University, entailed the establishment of the platinum coating technology which entailed two steps; firstly using newly obtained equipment to manufacture the membrane electro catalyst assemblies (MEA’s) and gas diffusion electrodes (GDE’s) and secondly to test these MEA’s and GDE’s using sulphur dioxide depolarized electrolysis by comparing the manufactured MEA’s and GDE’s to commercially available MEA’s and GDE’s. Different MEA’s and GDE’s were manufactured using both a screen printing (for the microporous layer deposition) and a spraying technique. The catalyst loadings were varied as well as the type and thickness of the proton exchange membranes used. The proton exchange membranes that were included in this study were Nafion 117®, sPSU-PBIOO and SfS-PBIOO membranes whereas the gas diffusion layer consisted of carbon paper with varying thicknesses (EC-TP01-030 – 0.11 mm and EC-TP01-060 – 0.19mm). MEA and GDE were prepared by first preparing an ink that was used both for MEA and GDE spraying. The MEA’s were prepared by spraying various catalyst coatings onto the proton exchange membranes containing 0.3, 0.6 and 0.9 mg/cm2 platinum respectively. The GDE’s were first coated by a micro porous carbon layer using the screen printing technique in order to attain a suitable surface for catalyst deposition. Using the spraying technique GDE’s containing 0.3, 0.6, 0.9 mg/cm2 platinum were prepared. After SEM analysis, the MEA’s and GDE’s performance was measured using SO2 depolarized electrolysis. From the electrolysis experiments, the voltage vs. current density generated during operation, the hydrogen production, the sulphuric acid generation and the hydrogen production efficiency was obtained. From the results it became clear that while the catalyst loading had little effect on performance there were a number of factors that did have a significant influence. These included the type of proton exchange membrane, the membrane thickness and whether the catalyst coating was applied to the proton exchange membrane (MEA) or to the gas diffusion layer (GDE). During SO2 depolarized electrolysis VI curves were generated which gave an indication of the performance of the GDE’s and MEA’s. The best preforming GDE was GDE-3 (0.46V @ 320 mA/cm2), which included a GDE EC-TP01-060, while the best preforming MEA’s were NAF-4 (0.69V @ 320mA/cm2) consisting of a Nafion117 based MEA and PBI-1 (0.43V @ 320mA/cm2) made from a sPSU-PBIOO blended membrane. During hydrogen production it became clear that the GDE’s produced the most hydrogen (best was GDE-02 a in house manufactured GDE yielding 67.3 mL/min @ 0.8V), followed by the Nafion® MEA’s (best was NAF-4 a commercial MEA yielding 57.61 mL/min @ 0.74V) and the PBI based MEA’s. , (best was PBI-2 with 67.11 mL/min @ 0.88V). Due to the small amounts of acid produced and the SO2 crossover, a significant error margin was observed when measuring the amount of sulphuric acid produced. Nonetheless, a direct correlation could still be seen between the acid and the hydrogen production as had been expected from literature. The highest sulphuric acid concentrations produced using the tested GDE’s and MEA’s from this study were the in-house manufactured GDE-01 (3.572mol/L @ 0.8V), the commercial NAF-4 (4.456mol/L @ 0.64V) and the in-house manufactured PBI-2 (3.344mol/L @ 0.8V). The overall efficiency of the GDE’s were similar, ranging from less than 10% at low voltages (± 0.6V) increasing to approximately 60% at ± 0.8V. For the MEA’s larger variation was observed with NAF-4 reaching efficiencies of nearly 80% at 0.7V. In terms of consistency of performance it was shown that the Nafion MEA’s preformed most consistently followed by the GDE’s and lastly the PBI based MEA’s which for the PBI based membranes can probably be ascribed to the significant difference in thickness of the thin PBI vs. the Nafion based membranes. In summary the study has shown the results between the commercially obtained and the in-house manufactured GDE’s and MEA’s were comparable confirming the suitability of the coating techniques evaluated in this study. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The ever increasing demand for a clean and renewable energy source has stimulated research for alternatives for the use of fossil fuels, which contribute significantly to global warming. The SO2 oxidation reaction was studied for production of hydrogen as a clean and renewable energy carrier. This reaction occurs at a lower standard electrode potential (0.158 V vs. SHE) than normal water electrolysis (1.23 V vs. SHE). This is a theoretical indication that the SO2 oxidation reaction has possible potential when compared to normal water electrolysis, since hydrogen production may occur at lower potentials and therefore lower cost. Rh was compared with Pt for the SO2 oxidation reaction since little research has been done on this catalyst and many studies exist in which Pt was used as catalyst. The oxygen reduction reaction and ethanol oxidation reaction were also included in this study to create a foundation for the catalysts studied, since the SO2 oxidation reaction is complicated by different adsorbed species that can form according to various mechanisms. The electrochemical techniques employed in this study to characterize the catalysts included cyclic voltammetry from which onset potentials and limiting current densities were determined, as well as from which some qualitative analysis was done. Linear polarization experiments were used during rotating disk electrode studies from which Levich and Koutecky-Levich analyses were done and the number of electrons transferred calculated and compared between the two catalysts. From the Koutecky-Levich analysis the kinetic current density was also obtained for use in Tafel analysis for further comparison between catalysts. It was found that Rh showed good behaviour for the oxygen reduction reaction when compared to Pt with similar onset potentials and limiting current densities. From Levich analysis it was concluded that both catalysts achieved diffusion limitation at high overpotentials. However, from the calculated number of electrons transferred it was evident that a difference in mechanism existed between catalysts and that the mechanism for both changed in the potential range studied, which is confirmed by the Tafel slopes. For the ethanol oxidation reaction it was shown that Rh exhibited very low catalytic activity in comparison with Pt. However, it was concluded from cyclic voltammetry and rotating disk electrode studies that more adsorbed species were present on the surface of Rh than on Pt. These results confirmed the possibility of using Rh as a co-catalyst together with Pt since it was shown from rotating disk electrode studies that low adsorption of ethanol and its oxidation products caused species to be transported away from the surface of the electrode during rotation. For the SO2 oxidation reaction it was found that Rh exhibited very poor catalytic activity together with being very susceptible to poisoning by adsorbed species. Pt showed very good behaviour, which corresponded well with what had been observed in literature. Levich analysis revealed that Pt did not exhibit diffusion limitation and Koutecky-Levich analysis revealed that a 2 electron reaction occurred on Pt, which corresponds with the SO2 oxidation reaction during which 2 electrons are transferred. It was, therefore, shown that Rh could exhibit good behaviour and act as a suitable catalyst in certain circumstances. However, for the SO2 oxidation reaction, which was the main focus of this study it was shown that Rh is not a suitable catalyst, either alone or as co-catalyst. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The sulfite pulping process is today practised in only a small number of pulp mills around the globe and the number of sulfite mills that use sodium as the base (cation) is less than five. However, due to the increasing interest in the wood based biorefinery concept, the benefits of sulfite pulping and especially the sodium based variety, has recently gained a lot of interest. It was therefore considered to be of high importance to further study the sodium based sulfite process to investigate if its benefits could be better utilized in the future in the production of dissolving pulps. Of specific interest was to investigate how the pulping conditions in the initial part of the cook (≥ 60 % pulp yield) should be performed in the best way. Thus, this thesis is focused on the initial phase of single stage sodium bisulfite cooking of either 100 % spruce or 100 % pine wood chips. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and cooking time were varied. Activation energies for different wood components were investigated as well as side reactions concerning the formation of thiosulfate and sulfate. / Single stage sodium bisulfite cooking was carried out on either spruce or pine wood chips to investigate the influence of several process parameters in the initial phase of such a cook i.e. between 100 % and 60 % pulp yield. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and time in the initial stage were varied. The influence of dissolved organics and inorganics components in the cooking liquor on the final pulp properties and side reactions were investigated. The impact of temperature and time on the pulp components were analyzed with respect to carbohydrates, lignin, extractives and thiosulfate. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. It was found that if using a mill prepared cooking acid, this had a beneficial effect with respect to side reactions, better extractives removal and higher pH stability during the cook, compared to a corresponding cook with a lab prepared cooking acid. Cooking with mill prepared and lab prepared cooking acids showed the same behaviour with respect to delignification and carbohydrate degradation, but the lab acid experiments resulted in a higher thiosulfate formation during the cook. The cellulose yield was not affected at all during the initial phase of the sulfite cook verifying earlier results by other researchers. The temperature had an influence on both the delignification rate and the rate of hemicelluloses removal.  The corresponding activation energies were found to increase in the following order; cellulose, xylan, glucomannan and lignin. / <p>Artikel 1: "The Initial Phase of Sodium Bisulfite Pulping of Spruce: Part 1" ingick i avhandlingen som manuskript. Nu publicerad.</p>

Traffic population in the UK has grown by 27% in 2002 and predicted to continue to an estimated 38% in 2016 and up to 60% by 2031. This means vehicular emissions from road transport may account for higher proportion of total emissions of pollutants resulting in air pollution with its attendant consequences. Although poor air quality concerns has often been linked to urban areas, many rural areas apparently have locations where air quality objectives may be threatened especially in the wake of increasing vehicular population. Thus, this elicits the necessity to investigate the relationship between vehicular emissions and air quality. This study investigated the influence of vehicular traffic on a major trunk road on rural air quality through continuous measurements of nitrogen dioxide, sulphur dioxide and hydrocarbon between June 2008 and April 2010 along a major trunk road in a catalogued rural environment in the UK. Collection and analysis of pollutants was by Dräger short-term tubes and Dräger passive diffusion tube techniques. Throughout the sampling period, concentrations of sulphur dioxide were not detected using the short-term tube technique but were detected by the passive diffusion tubes. The study found that variations in mean concentrations of the pollutants were synonymous with traffic frequency and were influenced by meteorological conditions especially wind speed, temperature and relative humidity. Results observed concentration decline trend with increasing distance and showed maximum concentrations during winter, mainly in areas of close proximity to anthropogenic source, and minimum in summer. Values between winter year 1 and winter year 2 monitoring campaigns showed significant difference (P<0.05 and R=0.91) as was in summer year 1 and year 2 (P<0.05 and R=0.94), spring year 1 and year 2 (P<0.05 and R=0.84) and autumn year 1 and year 2 (P<0.05 and R=0.79). When compared with the guidance limits, NO2 Page ii showed exceededance at roadside and 50 m, and at some sample sites, up to 100 m from the road. Conversely, SO2 did not show any exceedance but statistical analyses was mostly significant between concentrations and distance at p≤0.05, suggesting the variability of pollutants, as well as the influence of distance on their temporal and spatial distribution. Results also show that pollutants correlated very well with daily traffic population with strong positive r2 and R-values. Similarly, the study considered the application of hazel leave (Corylus avellana) and ryegrass (Lolium perenne) vegetation samples in monitoring rural air quality. Both samples were collected in different seasons and distances (5m, 50m, and 100m) from the A49 trunk road at four rural sites characterised with diverse traffic densities and anthropogenic activities. The aim was to determine the elemental content and trends within the samples and to investigate the influence of distance from the road, height from ground level, and sampling season on the elemental levels. The levels of Al, As, Ba, Ca, Si, Mg, S, Cd, Cr, Na, Ni, Sb, Se, Sn, Mo, Mn, C, K, P, Cl, Ti, Fe, Zn, and Pb were determined using X-ray fluorescence (XRF), inductively coupled plasma-mass spectrometer (ICP-MS), and Scanning Electron Microscopy-Energy Dispersive X-ray spectrometer (SEM-EDX). Results show that despite the traffic differentials between the sampling sites, the pollution level of heavy metals were generally low in all sampling site and concentrations of Cr, Cu, Ni, Pb, and Ti exhibited inverse relationship with distance, decreasing in levels with increasing distance from the trunk road. Although root uptake from the soil is a potential source of heavy metals, geochemistry research of the study area did not show any evidence that proves any major heavy metals deposit concerns in the soil. It is therefore possible that heavy metal emissions were deposited in a form that was not readily available for root uptake, thereby narrowing the presence of heavy metal pollutants to other potential Page iii sources. However, this study found high level of heavy metals at the roadside measurements in the order of Zn (0.703 ppm) > Ti (0.346 ppm) > Cr (0.111 ppm) > Cu (0.106 ppm) > Pb (0.026 ppm) > Ni (0.025 ppm). They were found in different magnitudes higher than their respective levels at 50 and 100 m from the trunk road and therefore tend to support traffic origin. Findings from this study show that heavy metals exhibited different degree of correlation between individual elements, ranging from very strong positive to weak, as well as negative correlations. Statistical analyses show that the elements predominantly exhibited statistically significant differences between elements and between distances from the road. Overall, findings from this study demonstrate that both vegetation species prove to be successfully useful in determining the pollution status and trends of traffic-related heavy metals.

South Africa has the largest economy in Africa, with significant mining and metallurgical activities. A large fraction of the mineral assets is concentrated in the Bushveld Igneous Complex (BIC), with the western limb being the most exploited. Although the western BIC is considered to be an air pollution hotspot, inadequate air quality data currently exists for this area. To partially address this knowledge gap, a comprehensive air quality monitoring station was operated for more than two years at Marikana in the western BIC. Basic meteorological parameters, precipitation, Photosynthetic Photon Flux Density (PPFD), trace gas concentrations (SO2, NO, NOx, O3, and CO), physical aerosol parameters (particle number and air ion size distributions, as well as aerosol light absorption) and total PM10 mass concentration were measured. Compared with South African and European ambient air quality standards, SO2, NO2 and CO concentrations were generally below the air quality standards, with average concentrations for the sampling period of 3.8ppb (9.9μg/m³), 8.5ppb (15.9μg/m³) and 230ppb (270μg/m³), respectively. The major source of SO2 was identified as high-stack industry emissions, while household combustion was identified as the predominant source of NO2 and CO. In contrast, O3 exceeded the eight-hour moving average standard (61ppb / 120μg/m³) 322 times per year. The main contributing factor was identified to be the influx of regional air masses, with high O3 precursor concentrations. PM10 exceeded the current South African 24-hour standard (120μg/m³) on average 6.6 times per year, the future 2015 standard (75μg/m³) 42.3 times per year and the European standard (50μg/m³) 120.2 times per year. The PM10 average concentration for the sampling period was 44μg/m³, which exceeded the current European and future (2015) South African annual average standard (40μg/m³), emphasising the PM pollution problem in the western BIC. The main source of PM10 was identified as household combustion. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012

Student Number :8701745W - MSc research report - Faculty of Science / An air chemistry study over the United Arab Emirates revealed a high concentration of sulphur dioxide. SO2 and its resultant aerosols can have a significant effect on the atmospheric processes. These aerosols could both directly and indirectly affect the climate by scattering solar radiation and increasing the albedo of the atmosphere or by altering the cloud formation processes and characteristics. Sulphur dioxide and the resultant aerosols also have a damaging effect on the environment and on human health. Previous studies reviewed suggest that pollution can be transported for hundreds of kilometres from the source of the emission and affect the air chemistry of the receptor regions. The possibility that long-range transport of pollution to the UAE may have contributed to these high concentrations was also investigated. The possibility that the UAE is a receptor region of pollution transported over long distances is investigated with the intention of identifying the possible source regions of this pollution. In order to examine the import of pollution to the UAE it was important to analyse the background sulphur concentrations of the atmosphere over the UAE.

La pollution atmosphérique malodorante provient essentiellement de quatre gaz SO2, H2S, NO2 et NH3. Afin de réduire au mieux ces effets néfastes sur la santé et l'environnement, il faut contrôler en continu les émanations de gaz le plus près possible de la source. Ce qui nécessite un appareil capable de détecter ces gaz polluants, simple d'utilisation, de taille et poids réduits. C'est dans cette optique que nous avons réalisé un nez électronique portable, servant à détecter les quatre gaz cibles déjà cités. La partie sensible de ce prototype est constituée d'une matrice de six capteurs à oxydes métalliques semi-conducteurs, dont nous utilisons la sensibilité croisée. Le nez électronique fonctionne sur le même principe que le nez humain, il doit apprendre à reconnaître une odeur. Cette phase d'apprentissage se déroule au laboratoire où nous envoyons sur les capteurs des mélanges gazeux connus et contrôlés. La réponse des capteurs varie en fonction de la nature du gaz (réducteur ou oxydant) et de leur sensibilité à celui-ci. Puis l'utilisation de méthodes d'analyse de données a prouvé que notre nez électronique peut discriminer un mélange gazeux complexe et le quantifier. Ensuite nous avons placé le nez électronique en situation réelle, en étudiant l'odeur dégagée par des fientes de canards dans une ferme expérimentale. Les résultats obtenus ont montré que cet appareil pouvait détecter de manière fiable les variations d'odeur en fonction des paramètres influents. Ainsi, nous avons réalisé la validation de notre prototype en laboratoire puis sur site. Mais les capteurs utilisés présentent un inconvénient, ils doivent conserver sans interruption leur température de fonctionnement (~ 350°C). Afin de prévenir cette forte consommation d'énergie, nous avons développé des capteurs polymères qui fonctionnent à température ambiante. La caractérisation en laboratoire a montré qu'ils sont sensibles aux gaz cibles étudiés. Leurs réponses à H2S laisse apparaître une bonne stabilité à court et moyen terme, qui permettra de les intégrer dans la matrice après complet développement / The malodorous atmospheric pollution results essentially from four gases SO2, H2S, No2 and NH3. To reduce at best these fatal effects on the health and the environment, it is necessary to control continuously the gas emanations closer to the source, That requires adevice enable to detect these polluant gases, easy to use, with reduced size and weight. In this way, we have realized a portable electronic nose, to detect of the four target gases already mentioned. The sensitive part of this prototype is composed of a matrix of six semi conducting metal oxide sensors, offering a good cross sensivity. The electronic nose mimics the human nose, he has to learn to recognize an odour. This learning phase is realised in the laboratoy by introducing in the sensor cell gas mixtures with controlled composition, The sensor response varies with the nature of the gas (reducing or oxidizing) and their own gas sensitivity. The use of analysis and data methods proves that our electronic nose can well discriminate a complex gas mixture and quantify it. Then, we have placed the electronic nose in a real situation, by studying the odour coming from a duck experimental farm. The obtained results showed that this prototype could well detect the variations of the odour level in accordance with the influent parameters. So, we have realized the laboratory and the real site validation of our electronic nose. But the metal oxide sensors present an inconvenient : they have to keep continuously their working temperature (~ 350°C). To prevent this strong energy consumption, we have developed polymer sensors which work at room temperature. The characterization in laboratory showed that they are sensitive to studied target gases. Their responses to H2S have a good stability in short and middle term, allowing to integrate them into the matrix after complete development

<p>The aim was to study the prevalence of asthma, eczema, allergy and respiratory symptoms among pupils in Shanxi province, China, in relation to home and school environment and outdoor air pollution. In one study there was a low prevalence of self-reported asthma, eczema and pollen or pet allergy among pupils (9-20y). Rural childhood and consumption of fruit and fish were negatively associated with asthma or allergy, while current urban residency and consumption of hamburgers tended to be risk factors. In another study in junior high school pupils, similar low prevalence of asthma and allergy was found. Compared with pupils at the same age in Uppsala, Sweden, asthma and allergy were less common while daytime attacks of breathlessness were more common in Chinese pupils. Parental asthma or allergy was a predictor of asthma symptoms. Factors in the home environment such as new floor, new furniture and ETS exposure were risk factors for asthma symptoms. Crowdedness, dust amount, CO₂, temperature and air humidity were negatively associated with respiratory symptoms. Microbial chemical components like muramic acid and ergosterol, markers for bacteria and fungi, were negatively associated with wheeze or daytime attacks of breathlessness. The associations with endotoxin varied depending on the length of 3-hydroxy fatty acids of the lippopolysaccharides (LPS). Among outdoor air pollutants, SO₂ and formaldehyde were positively associated with asthma symptoms or respiratory infections. In addition, indoor SO₂, NO₂ and formaldehyde were positively associated with asthma symptoms and respiratory infections. In conclusion, rural childhood and dietary factors can be protective for asthma and allergy. ETS and chemical emissions from new material at home can be risk factors for asthmatic symptoms. In the school environment, factors of indoor origin seemed to be generally protective for respirator symptoms while factors of outdoor origin seemed to be risk factors.</p>

The aim was to study the prevalence of asthma, eczema, allergy and respiratory symptoms among pupils in Shanxi province, China, in relation to home and school environment and outdoor air pollution. In one study there was a low prevalence of self-reported asthma, eczema and pollen or pet allergy among pupils (9-20y). Rural childhood and consumption of fruit and fish were negatively associated with asthma or allergy, while current urban residency and consumption of hamburgers tended to be risk factors. In another study in junior high school pupils, similar low prevalence of asthma and allergy was found. Compared with pupils at the same age in Uppsala, Sweden, asthma and allergy were less common while daytime attacks of breathlessness were more common in Chinese pupils. Parental asthma or allergy was a predictor of asthma symptoms. Factors in the home environment such as new floor, new furniture and ETS exposure were risk factors for asthma symptoms. Crowdedness, dust amount, CO2, temperature and air humidity were negatively associated with respiratory symptoms. Microbial chemical components like muramic acid and ergosterol, markers for bacteria and fungi, were negatively associated with wheeze or daytime attacks of breathlessness. The associations with endotoxin varied depending on the length of 3-hydroxy fatty acids of the lippopolysaccharides (LPS). Among outdoor air pollutants, SO2 and formaldehyde were positively associated with asthma symptoms or respiratory infections. In addition, indoor SO2, NO2 and formaldehyde were positively associated with asthma symptoms and respiratory infections. In conclusion, rural childhood and dietary factors can be protective for asthma and allergy. ETS and chemical emissions from new material at home can be risk factors for asthmatic symptoms. In the school environment, factors of indoor origin seemed to be generally protective for respirator symptoms while factors of outdoor origin seemed to be risk factors.

South Africa has the largest economy in Africa, with significant mining and metallurgical activities. A large fraction of the mineral assets is concentrated in the Bushveld Igneous Complex (BIC), with the western limb being the most exploited. Although the western BIC is considered to be an air pollution hotspot, inadequate air quality data currently exists for this area. To partially address this knowledge gap, a comprehensive air quality monitoring station was operated for more than two years at Marikana in the western BIC. Basic meteorological parameters, precipitation, Photosynthetic Photon Flux Density (PPFD), trace gas concentrations (SO2, NO, NOx, O3, and CO), physical aerosol parameters (particle number and air ion size distributions, as well as aerosol light absorption) and total PM10 mass concentration were measured. Compared with South African and European ambient air quality standards, SO2, NO2 and CO concentrations were generally below the air quality standards, with average concentrations for the sampling period of 3.8ppb (9.9μg/m³), 8.5ppb (15.9μg/m³) and 230ppb (270μg/m³), respectively. The major source of SO2 was identified as high-stack industry emissions, while household combustion was identified as the predominant source of NO2 and CO. In contrast, O3 exceeded the eight-hour moving average standard (61ppb / 120μg/m³) 322 times per year. The main contributing factor was identified to be the influx of regional air masses, with high O3 precursor concentrations. PM10 exceeded the current South African 24-hour standard (120μg/m³) on average 6.6 times per year, the future 2015 standard (75μg/m³) 42.3 times per year and the European standard (50μg/m³) 120.2 times per year. The PM10 average concentration for the sampling period was 44μg/m³, which exceeded the current European and future (2015) South African annual average standard (40μg/m³), emphasising the PM pollution problem in the western BIC. The main source of PM10 was identified as household combustion. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012