Effect of alkaline pre-treatments on the synergistic enzymatic hydrolysis of sugarcane (Saccharum officinarum) bagasse by Clostridium cellulovorans XynA, ManA and ArfA
- Authors: Beukes, Natasha
- Date: 2011
- Subjects: Sugarcane -- Biotechnology Lignocellulose -- Biotechnology Renewable energy sources Hydrolysis Enzymes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3952 , http://hdl.handle.net/10962/d1004011
- Description: The continual increase in industrialization and global population has increased the dependency and demand on traditional fossil fuels for energy; however, there are limited amounts of fossil fuels available. The slow depletion of fossil fuels has sparked a fresh interest in renewable sources such as lignocellulose to produce a variety of biofuels, such as biogases (e.g. methane), bioethanol, biodiesel and a variety of other solvents and economically valuable by-products. Agricultural crop wastes produced in surplus are typically lignocellulosic in composition and thus partially recalcitrant to enzymatic degradation. The recalcitrant nature of plant biomass and the inability to obtain complete enzymatic hydrolysis has led to the establishment of various pre-treatment strategies. Alkaline pre-treatments increase the accessibility of the exposed surface to enzymatic hydrolysis through the removal of acetyl and uronic acid substituents on hemicellulose. Unlike the use of steam and acid pre-treatments, alkaline pre-treatments solubilize lignin and a small percentage of the hemicellulose, increasing enzyme accessibility and thus the hydrolysis of lignocellulose. The majority of Clostridium cellulovorans associated enzyme synergy studies have been devoted to an understanding of the cellulolytic and hemi-cellulolytic degradation of plant cell walls. However, little is known about the effect of various physical and chemical pre-treatments on the synergistic enzymatic degradation of plant biomass and possible depolymerization of plant cell walls. This study investigates the use of slake lime, sodium hydroxide and ammonium hydroxide to pre-treat sugarcane bagasse under mild conditions and elucidates potentially important synergistic associations between the C. cellulovorans enzymes for the enhanced degradation of lignocellulose. The primary aims of the study were addressed using of a variety of techniques. This included suitable vector constructs for the expression and purification of recombinant C. cellulovorans enzymes, identification of the effects of various pre-treatments on enzyme synergy, and identification of the resultant reducing sugars and phenolic compounds (released during the pre-treatment of the bagasse). This study also made use of physical and chemical pre-treatment methods, protein purification using affinity, high performance liquid and thin layer chromatography, mass spectrometry, sodium dodecyl sulphate and fluorophore-assisted polyacrylamide gel electrophoresis (FACE) , enzymatic degradation and synergy studies with various substrates indirectly using the 3, 4-dinitrosalicylic acid (DNS) reducing sugar assay. From this investigation, the following conclusions were made: alkaline pre-treatment successfully solublised, redistributed and removed lignin from the bagasse, increasing the digestibility of the substrates. In summary, the most effective pre-treatment employed 0.114 M ammonium hydroxide / gram bagasse at 70°C for 36 hours, followed by hydrolysis with an enzyme cocktail containing 25% ManA and 75% XynA. This increased the production of sugars approximately 13-fold. Analysis of the sugars produced by the synergistic hydrolysis of sugarcane bagasse (SCB) indicated the presence of xylose, indicating that the enzymes are potentially bifunctional under certain conditions. This study indicated that the use of mild pre-treatment conditions sufficiently removed a large portion of lignin without affecting the hemicellulose moiety of the SCB. This facilitated the potential use of the hemicellulose component for the production of valuable products (e.g. xylitol) in addition to the production of bioethanol. Thus, the potential use of additional components of holocellulose may generate an additional biotechnological benefit and allow a certain degree of flexibility in the biofuel industry, depending on consumer and industrial needs.
- Full Text:
- Date Issued: 2011
- Authors: Beukes, Natasha
- Date: 2011
- Subjects: Sugarcane -- Biotechnology Lignocellulose -- Biotechnology Renewable energy sources Hydrolysis Enzymes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3952 , http://hdl.handle.net/10962/d1004011
- Description: The continual increase in industrialization and global population has increased the dependency and demand on traditional fossil fuels for energy; however, there are limited amounts of fossil fuels available. The slow depletion of fossil fuels has sparked a fresh interest in renewable sources such as lignocellulose to produce a variety of biofuels, such as biogases (e.g. methane), bioethanol, biodiesel and a variety of other solvents and economically valuable by-products. Agricultural crop wastes produced in surplus are typically lignocellulosic in composition and thus partially recalcitrant to enzymatic degradation. The recalcitrant nature of plant biomass and the inability to obtain complete enzymatic hydrolysis has led to the establishment of various pre-treatment strategies. Alkaline pre-treatments increase the accessibility of the exposed surface to enzymatic hydrolysis through the removal of acetyl and uronic acid substituents on hemicellulose. Unlike the use of steam and acid pre-treatments, alkaline pre-treatments solubilize lignin and a small percentage of the hemicellulose, increasing enzyme accessibility and thus the hydrolysis of lignocellulose. The majority of Clostridium cellulovorans associated enzyme synergy studies have been devoted to an understanding of the cellulolytic and hemi-cellulolytic degradation of plant cell walls. However, little is known about the effect of various physical and chemical pre-treatments on the synergistic enzymatic degradation of plant biomass and possible depolymerization of plant cell walls. This study investigates the use of slake lime, sodium hydroxide and ammonium hydroxide to pre-treat sugarcane bagasse under mild conditions and elucidates potentially important synergistic associations between the C. cellulovorans enzymes for the enhanced degradation of lignocellulose. The primary aims of the study were addressed using of a variety of techniques. This included suitable vector constructs for the expression and purification of recombinant C. cellulovorans enzymes, identification of the effects of various pre-treatments on enzyme synergy, and identification of the resultant reducing sugars and phenolic compounds (released during the pre-treatment of the bagasse). This study also made use of physical and chemical pre-treatment methods, protein purification using affinity, high performance liquid and thin layer chromatography, mass spectrometry, sodium dodecyl sulphate and fluorophore-assisted polyacrylamide gel electrophoresis (FACE) , enzymatic degradation and synergy studies with various substrates indirectly using the 3, 4-dinitrosalicylic acid (DNS) reducing sugar assay. From this investigation, the following conclusions were made: alkaline pre-treatment successfully solublised, redistributed and removed lignin from the bagasse, increasing the digestibility of the substrates. In summary, the most effective pre-treatment employed 0.114 M ammonium hydroxide / gram bagasse at 70°C for 36 hours, followed by hydrolysis with an enzyme cocktail containing 25% ManA and 75% XynA. This increased the production of sugars approximately 13-fold. Analysis of the sugars produced by the synergistic hydrolysis of sugarcane bagasse (SCB) indicated the presence of xylose, indicating that the enzymes are potentially bifunctional under certain conditions. This study indicated that the use of mild pre-treatment conditions sufficiently removed a large portion of lignin without affecting the hemicellulose moiety of the SCB. This facilitated the potential use of the hemicellulose component for the production of valuable products (e.g. xylitol) in addition to the production of bioethanol. Thus, the potential use of additional components of holocellulose may generate an additional biotechnological benefit and allow a certain degree of flexibility in the biofuel industry, depending on consumer and industrial needs.
- Full Text:
- Date Issued: 2011
Effect of nanoparticles on the photophysicochemical behaviour of metallophthalocyanines
- Moeno, Sharon Keitumetse Gail Mpheletso
- Authors: Moeno, Sharon Keitumetse Gail Mpheletso
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Nanoparticles Photochemistry Quantum dots
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4310 , http://hdl.handle.net/10962/d1004968
- Description: The synthesis, spectroscopic characterization, and studies of the photophysicochemical behaviour of selective anionic, cationic and neutral metallophthallocyanine (MPc) complexes were carried out and the results are presented herein. Studies on the effect of the central metal ion, the solvent used and the presence of nanoparticles on the photophysicochemical properties were conducted. The findings showed that the photophysicochemical parameters were mostly enhanced in the presence of central metal ions of high atomic numbers and also in the presence of nanoparticles. It was also observed that solvents that encouraged the monomericity of the MPc complexes also lead to improved photophysical and photochemical behaviour. CdTe quantum dots (QDs) stabilized with mercaptocarbonic acids were also observed to cause stimulated emission of the MPcs through Förster resonance energy transfer (FRET) thus acting as energy donors while the respective MPc acted as energy acceptors in all the FRET studies. FRET was observed following the photoexcitation of QDs for all monomeric anionic MPcs but it was also shown to occur for some cationic MPcs in organic media. Both the substituent and solvent used were found to exert a strong influence on the occurrence of FRET. Other cationic MPcs however showed different behaviour in the presence of the meraptocarbonic stabilized CdTe QDs; with the cationic porphyrazine giving clear indications of Pc ring reduction. The rest of the cationic MPcs did not give clear evidence of Pc ring reduction, instead they showed signs of aggregate formation possibly from the assembly of electrostatic ion pair complexes which could result in reduction of the quaternized pyridinium ring of the substituent. Both the QDs and the MPc complex emission spectra were significantly quenched for each in the presence of the other. Stern-Volmer quenching studies indicated that both static and dynamic quenching of the QDs in the presence of MPcs took place. The fluorescence lifetimes of the mercaptopropionic acid (MPA) capped CdTe QDs in the presence of various MPc complexes showed quenching of mostly the longer lifetimes of the QDs in the presence of MPcs suggesting that the surface defects and states are involved in the interaction of the QDs and MPcs. An MPc complex terminating in thio tethers was employed in the conjugation to AuNPs. Spectroscopic and microscopic studies confirmed the formation of the MPc-AuNP conjugate which was also shown to exhibit improved photophysicochemical properties compared to the free MPc.
- Full Text:
- Date Issued: 2011
- Authors: Moeno, Sharon Keitumetse Gail Mpheletso
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Nanoparticles Photochemistry Quantum dots
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4310 , http://hdl.handle.net/10962/d1004968
- Description: The synthesis, spectroscopic characterization, and studies of the photophysicochemical behaviour of selective anionic, cationic and neutral metallophthallocyanine (MPc) complexes were carried out and the results are presented herein. Studies on the effect of the central metal ion, the solvent used and the presence of nanoparticles on the photophysicochemical properties were conducted. The findings showed that the photophysicochemical parameters were mostly enhanced in the presence of central metal ions of high atomic numbers and also in the presence of nanoparticles. It was also observed that solvents that encouraged the monomericity of the MPc complexes also lead to improved photophysical and photochemical behaviour. CdTe quantum dots (QDs) stabilized with mercaptocarbonic acids were also observed to cause stimulated emission of the MPcs through Förster resonance energy transfer (FRET) thus acting as energy donors while the respective MPc acted as energy acceptors in all the FRET studies. FRET was observed following the photoexcitation of QDs for all monomeric anionic MPcs but it was also shown to occur for some cationic MPcs in organic media. Both the substituent and solvent used were found to exert a strong influence on the occurrence of FRET. Other cationic MPcs however showed different behaviour in the presence of the meraptocarbonic stabilized CdTe QDs; with the cationic porphyrazine giving clear indications of Pc ring reduction. The rest of the cationic MPcs did not give clear evidence of Pc ring reduction, instead they showed signs of aggregate formation possibly from the assembly of electrostatic ion pair complexes which could result in reduction of the quaternized pyridinium ring of the substituent. Both the QDs and the MPc complex emission spectra were significantly quenched for each in the presence of the other. Stern-Volmer quenching studies indicated that both static and dynamic quenching of the QDs in the presence of MPcs took place. The fluorescence lifetimes of the mercaptopropionic acid (MPA) capped CdTe QDs in the presence of various MPc complexes showed quenching of mostly the longer lifetimes of the QDs in the presence of MPcs suggesting that the surface defects and states are involved in the interaction of the QDs and MPcs. An MPc complex terminating in thio tethers was employed in the conjugation to AuNPs. Spectroscopic and microscopic studies confirmed the formation of the MPc-AuNP conjugate which was also shown to exhibit improved photophysicochemical properties compared to the free MPc.
- Full Text:
- Date Issued: 2011
Effects of polarization in a distributed raman fibre amplifier
- Authors: Muguro, Kennedy Mwaura
- Date: 2011
- Subjects: Fiber optics , Polarization (Light) , Optical communications , Optical amplifiers , Raman effect
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10544 , http://hdl.handle.net/10948/d1014621
- Description: The need to exploit the large fibre bandwidth and increase the reach has seen the application of the Raman fibre amplifier (RFA) become indispensable in modern light wave systems. The success and resilience of RFAs in optical communication is deeply rooted in their unique optical properties and new technologies which have allowed the amplifier to come of age. However, the full potential of RFAs in optical communication and other applications are yet to be realized. More so are its polarization properties which still remain largely unexploited and have not been fully understood. In this work, fundamental issues regarding distributed RFA have been investigated with the aim of acquiring a better understanding of the amplifier polarization characteristics which have potential applications. In particular the effects of polarization mode dispersion (PMD) and polarization dependent loss (PDL) have been demonstrated both by simulation and experiment. The possibility of Raman polarization pulling in single mode fibres (SMFs) has also been addressed. Polarization sensitivity of RFA has been known for a long time but the clear manifestation of it has become evident in the advent of modern low PMD fibre. Unlike EDFAs which make use of special doped fibre, RFAs require no special fibre for operation. Besides, RFA uses a very long length of fibre and as such the fibre polarization characteristics come into play during amplification. In the demonstrations presented in this thesis a fibre of PMD coefficient < 0.05 pskm-1/2 was regarded as low PMD fibre while one having coefficient ≥ 0.05 pskm-1/2 was categorized to have high PMD unless otherwise stated. Several experiments were performed to evaluate the RFA gain characteristics with respect to fibre PMD and the system performance in the presence of noise emanating from amplified spontaneous emission (ASE). Analysis of Raman gain statistics was done for fibres of low and high PMD coefficients. The statistics of PDG and on-off gain were eventually used to demonstrate the extraction of PMD coefficients of fibres between 0.01- 0.1 pskm-1/2 using a forward pumping configuration. It was found that, at increasing pump power a linear relationship exists between forward and backward signal gain on a dB scale. The interaction of PDL and Raman PDG in the presence of PMD were observed at very fundamental level. It was found the presence of PDL serves to reduce the available on-off gain. It was also established that the presence of PMD mediates the interaction between PDG/PDL. When PMD is high it reduces PDG but the presence of PDL introduces a wavelength dependent gain tilting for WDM channels. Further analysis revealed that signal polarization is influenced by the pump SOP due to the pulling effect which is present even at moderate pump power.
- Full Text:
- Date Issued: 2011
- Authors: Muguro, Kennedy Mwaura
- Date: 2011
- Subjects: Fiber optics , Polarization (Light) , Optical communications , Optical amplifiers , Raman effect
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10544 , http://hdl.handle.net/10948/d1014621
- Description: The need to exploit the large fibre bandwidth and increase the reach has seen the application of the Raman fibre amplifier (RFA) become indispensable in modern light wave systems. The success and resilience of RFAs in optical communication is deeply rooted in their unique optical properties and new technologies which have allowed the amplifier to come of age. However, the full potential of RFAs in optical communication and other applications are yet to be realized. More so are its polarization properties which still remain largely unexploited and have not been fully understood. In this work, fundamental issues regarding distributed RFA have been investigated with the aim of acquiring a better understanding of the amplifier polarization characteristics which have potential applications. In particular the effects of polarization mode dispersion (PMD) and polarization dependent loss (PDL) have been demonstrated both by simulation and experiment. The possibility of Raman polarization pulling in single mode fibres (SMFs) has also been addressed. Polarization sensitivity of RFA has been known for a long time but the clear manifestation of it has become evident in the advent of modern low PMD fibre. Unlike EDFAs which make use of special doped fibre, RFAs require no special fibre for operation. Besides, RFA uses a very long length of fibre and as such the fibre polarization characteristics come into play during amplification. In the demonstrations presented in this thesis a fibre of PMD coefficient < 0.05 pskm-1/2 was regarded as low PMD fibre while one having coefficient ≥ 0.05 pskm-1/2 was categorized to have high PMD unless otherwise stated. Several experiments were performed to evaluate the RFA gain characteristics with respect to fibre PMD and the system performance in the presence of noise emanating from amplified spontaneous emission (ASE). Analysis of Raman gain statistics was done for fibres of low and high PMD coefficients. The statistics of PDG and on-off gain were eventually used to demonstrate the extraction of PMD coefficients of fibres between 0.01- 0.1 pskm-1/2 using a forward pumping configuration. It was found that, at increasing pump power a linear relationship exists between forward and backward signal gain on a dB scale. The interaction of PDL and Raman PDG in the presence of PMD were observed at very fundamental level. It was found the presence of PDL serves to reduce the available on-off gain. It was also established that the presence of PMD mediates the interaction between PDG/PDL. When PMD is high it reduces PDG but the presence of PDL introduces a wavelength dependent gain tilting for WDM channels. Further analysis revealed that signal polarization is influenced by the pump SOP due to the pulling effect which is present even at moderate pump power.
- Full Text:
- Date Issued: 2011
Enhancing the role of the Kaizen suggestion tool in South African lean automotive companies of the Eastern Cape
- Authors: Adedeji, Adeyemi Charles
- Date: 2011
- Subjects: Lean manufacturing , Manufacturing processes , Production management -- Mathematical models
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:8644 , http://hdl.handle.net/10948/d1008157 , Lean manufacturing , Manufacturing processes , Production management -- Mathematical models
- Description: The Toyota manufacturing system, aptly referred to as Lean manufacturing, has received a reasonable appreciation and awareness over the past decade in South African industry. This production phenomenon constitutes an organizational culture that encourages world-class production success through the liberation of factory resources, while employees are empowered and encouraged to contribute ideas for the improvement of processes and products. However, despite lean awareness and the crucial role of employee participation in the suggestion of ideas in world-class organizations, the performance level of lean manufacturing in South African industry is largely devoid of the Kaizen suggestion tool, particularly in the automotive companies of the Eastern Cape. The aim of this research was to proffer appropriate recommendations, improved awareness, understanding and practice for the improvement of the Kaizen suggestion principle in the automotive companies of the Eastern Cape. The research primarily focused on the ‘management/employees’ paradigm within the organisational context. The methodology employed in the study included a thorough review of the relevant literature and a questionnaire, which was developed and administered to both the management and employees of the thirty automotive components suppliers in Eastern Cape. The target companies constituted the units of analyses and therefore provided the opportunity for a detailed investigation of the links between management and employees as well as a submission of ideas for operational and organisational processes as established in the literature review. Epistemologically, the research is objectivist and paradigmically, positivist. However, some qualitative aspects of the data were relevant to the study and, therefore, were used in a complementary manner. The case approach utilized mixed methods by applying a range of data collection techniques and evidence from multiple sources while the sampling technique was sequential, involving both purposive and stratified random sampling. The study reveals the apparent lack of a systematic mechanism for the practice and administration of the Kaizen suggestion tools in most Eastern Cape automotive companies. This demerit is found to have negatively affected maximum employee participation and involvement in organizational decision making within the Province. The study has established a basic level of awareness and understanding among employees / employers relations that the Kaizen suggestion scheme is a vital tool for delivering strategic objectives in the management of decision making and organizational growth. The study strongly advocates the inclusion of employee suggestion systems as part of the organizational process.
- Full Text:
- Date Issued: 2011
- Authors: Adedeji, Adeyemi Charles
- Date: 2011
- Subjects: Lean manufacturing , Manufacturing processes , Production management -- Mathematical models
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:8644 , http://hdl.handle.net/10948/d1008157 , Lean manufacturing , Manufacturing processes , Production management -- Mathematical models
- Description: The Toyota manufacturing system, aptly referred to as Lean manufacturing, has received a reasonable appreciation and awareness over the past decade in South African industry. This production phenomenon constitutes an organizational culture that encourages world-class production success through the liberation of factory resources, while employees are empowered and encouraged to contribute ideas for the improvement of processes and products. However, despite lean awareness and the crucial role of employee participation in the suggestion of ideas in world-class organizations, the performance level of lean manufacturing in South African industry is largely devoid of the Kaizen suggestion tool, particularly in the automotive companies of the Eastern Cape. The aim of this research was to proffer appropriate recommendations, improved awareness, understanding and practice for the improvement of the Kaizen suggestion principle in the automotive companies of the Eastern Cape. The research primarily focused on the ‘management/employees’ paradigm within the organisational context. The methodology employed in the study included a thorough review of the relevant literature and a questionnaire, which was developed and administered to both the management and employees of the thirty automotive components suppliers in Eastern Cape. The target companies constituted the units of analyses and therefore provided the opportunity for a detailed investigation of the links between management and employees as well as a submission of ideas for operational and organisational processes as established in the literature review. Epistemologically, the research is objectivist and paradigmically, positivist. However, some qualitative aspects of the data were relevant to the study and, therefore, were used in a complementary manner. The case approach utilized mixed methods by applying a range of data collection techniques and evidence from multiple sources while the sampling technique was sequential, involving both purposive and stratified random sampling. The study reveals the apparent lack of a systematic mechanism for the practice and administration of the Kaizen suggestion tools in most Eastern Cape automotive companies. This demerit is found to have negatively affected maximum employee participation and involvement in organizational decision making within the Province. The study has established a basic level of awareness and understanding among employees / employers relations that the Kaizen suggestion scheme is a vital tool for delivering strategic objectives in the management of decision making and organizational growth. The study strongly advocates the inclusion of employee suggestion systems as part of the organizational process.
- Full Text:
- Date Issued: 2011
Exploring opportunities for action competence development through learners' participation in waste management activities in selected primary schools in Botswana
- Authors: Silo, Nthalivi
- Date: 2011
- Subjects: Environmental education -- Botswana -- Case studies Environmental education -- Study and teaching (Primary) -- Botswana -- Case studies Environmental education -- Activity programs -- Botswana -- Case studies Student-centered learning -- Botswana -- Case studies Refuse and refuse disposal -- Environmental aspects -- Botswana -- Case studies Active learning -- Botswana -- Case studies Competency-based education -- Botswana -- Case studies Teacher-student relationships -- Botswana -- Case studies
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1541 , http://hdl.handle.net/10962/d1003423
- Description: The broader aim of this study is to probe participation of learners in waste management activities in selected primary schools in Botswana and through these activities, explore opportunities for action competence development. The study starts by tracing and outlining the socio-ecological challenges that confront children and the historical background of learner-centred education which gave rise to an emphasis on learner participation in Botswana education policy. It then maps out the development of children's participation in the global, regional and Botswana contexts by tracing the development of environmental education from early ecological and issue resolution goals of environmental education to sustainable development discourses. The focus is on policy issues and how learner participation has been represented and implemented in environmental education. The study then probes the rhetorical and normalised emphases on participation, and seeks further insight into how learners can be engaged in participatory learning processes that are meaningful, purposeful and that broaden their action competence and civic agency. The study uses the Cultural Historical Activity Theory (CHAT) methodology to build a picture of waste management activity systems in primary schools and to bring to the surface contradictions and tensions in learner participation in these activity systems. These contradictions are used to open up expansive learning participatory processes with learners using the Danish action competence framework. The expansive learning process uses action competence models that provide potential for transformative participation with learners, and new and different opportunities for learner participation. Case study research was used and conducted in the south eastern region of Botswana in three primary schools in three contexts, namely urban, peri-urban and rural. The data was largely generated through focus group interviews during workshops with children and observations of waste management activities. These two methods formed the main data generation methods. They were complemented by semi-structured interviews with teachers, and other actors in the waste management activities, learners' activities and work, learners' notes, photographs and children's drawings as well as show-and-tell explanations by learners. Content analysis and the abductive mode of inference were used to analyse data in all three case studies. Findings from the first phase of the study reveal that participation of learners in waste management activities was largely teacher-directed. This resulted in a mis-match between teachers views of what practices are necessary and important, and children's views of what practices are necessary and important in and for environmental education. Due to culturally and historically formed views of environmental education, the study reveals that teachers wanted children to pick up litter, and this was their primary environmental education concern. Learners on the other hand, identified sanitation management in the school toilets as their primary waste management concern. Teachers had not considered this an environmental education concern. Using the action competence expansive learning approach, the second phase of the study addressed this tension by opening up dialogue between teachers and learners and amongst the learners themselves through an expansive learning process supporting children's participation and action competence development. Through this teacher-learner dialogical engagement, a broader range of possibilities became available and ideas around participation were radically changed. The study further reveals that the achievement of this open dialogue provided for a better relationship within the school community. And with improved communication came better ideas to solve waste management issues that the community still face on a daily basis, such as too much litter. Newly devised solutions were practical and had a broader impact than the initial ones that teachers had always focussed on. They included mobilising the maintenance of toilets, landscaping the school premises and even re-contextualising the litter management that had always caused tensions between learners and teachers. Children seemed to be developing not only a better understanding of the environment, but also developing the ability to resolve conflict amongst themselves and with their elders. By engaging in dialogue with children, they became co-catalysts for change in the school community. This study shows that if children's participation is taken seriously, and if opportunities for dialogue exist between teachers and children, positive changes for a healthier environment can be created in schools. It reveals that children also appeared to be feeling more confident and more equipped to consider changes in their environment outside of the school community. The study further shows that participation in environmental education involves more than cognitive changes as proposed in earlier constructivist literature; it includes in-depth engagement with socio-cultural dynamics and histories in the school context, such as the cultural histories of teachers, schooling and authority structures in the cultural community of the school. The study recommends that there is need to strengthen Teacher Education programmes to develop teaching practices and support for teachers to identify ways of engaging learners' views on issues in the school in open, dialogical ways. Such Teacher Education programmes should deepen teachers' understandings of learners' zone of proximal development (ZPD), demonstrating how dialogue and scaffolding are part of a teacher's role in supporting learning. This is shown in the three case studies that form part of this study. Finally, the study also deepens insights of using the Cultural Historical Activity theory (CHAT) to shed light on issues surrounding learner participation within the socio-cultural and historical environmental education contexts of the schools. The action competence models used in the study provide a tool for revealing forms of learner participation. This tool can be used for critical reflections and monitoring of teaching practices in schools.
- Full Text:
- Date Issued: 2011
- Authors: Silo, Nthalivi
- Date: 2011
- Subjects: Environmental education -- Botswana -- Case studies Environmental education -- Study and teaching (Primary) -- Botswana -- Case studies Environmental education -- Activity programs -- Botswana -- Case studies Student-centered learning -- Botswana -- Case studies Refuse and refuse disposal -- Environmental aspects -- Botswana -- Case studies Active learning -- Botswana -- Case studies Competency-based education -- Botswana -- Case studies Teacher-student relationships -- Botswana -- Case studies
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1541 , http://hdl.handle.net/10962/d1003423
- Description: The broader aim of this study is to probe participation of learners in waste management activities in selected primary schools in Botswana and through these activities, explore opportunities for action competence development. The study starts by tracing and outlining the socio-ecological challenges that confront children and the historical background of learner-centred education which gave rise to an emphasis on learner participation in Botswana education policy. It then maps out the development of children's participation in the global, regional and Botswana contexts by tracing the development of environmental education from early ecological and issue resolution goals of environmental education to sustainable development discourses. The focus is on policy issues and how learner participation has been represented and implemented in environmental education. The study then probes the rhetorical and normalised emphases on participation, and seeks further insight into how learners can be engaged in participatory learning processes that are meaningful, purposeful and that broaden their action competence and civic agency. The study uses the Cultural Historical Activity Theory (CHAT) methodology to build a picture of waste management activity systems in primary schools and to bring to the surface contradictions and tensions in learner participation in these activity systems. These contradictions are used to open up expansive learning participatory processes with learners using the Danish action competence framework. The expansive learning process uses action competence models that provide potential for transformative participation with learners, and new and different opportunities for learner participation. Case study research was used and conducted in the south eastern region of Botswana in three primary schools in three contexts, namely urban, peri-urban and rural. The data was largely generated through focus group interviews during workshops with children and observations of waste management activities. These two methods formed the main data generation methods. They were complemented by semi-structured interviews with teachers, and other actors in the waste management activities, learners' activities and work, learners' notes, photographs and children's drawings as well as show-and-tell explanations by learners. Content analysis and the abductive mode of inference were used to analyse data in all three case studies. Findings from the first phase of the study reveal that participation of learners in waste management activities was largely teacher-directed. This resulted in a mis-match between teachers views of what practices are necessary and important, and children's views of what practices are necessary and important in and for environmental education. Due to culturally and historically formed views of environmental education, the study reveals that teachers wanted children to pick up litter, and this was their primary environmental education concern. Learners on the other hand, identified sanitation management in the school toilets as their primary waste management concern. Teachers had not considered this an environmental education concern. Using the action competence expansive learning approach, the second phase of the study addressed this tension by opening up dialogue between teachers and learners and amongst the learners themselves through an expansive learning process supporting children's participation and action competence development. Through this teacher-learner dialogical engagement, a broader range of possibilities became available and ideas around participation were radically changed. The study further reveals that the achievement of this open dialogue provided for a better relationship within the school community. And with improved communication came better ideas to solve waste management issues that the community still face on a daily basis, such as too much litter. Newly devised solutions were practical and had a broader impact than the initial ones that teachers had always focussed on. They included mobilising the maintenance of toilets, landscaping the school premises and even re-contextualising the litter management that had always caused tensions between learners and teachers. Children seemed to be developing not only a better understanding of the environment, but also developing the ability to resolve conflict amongst themselves and with their elders. By engaging in dialogue with children, they became co-catalysts for change in the school community. This study shows that if children's participation is taken seriously, and if opportunities for dialogue exist between teachers and children, positive changes for a healthier environment can be created in schools. It reveals that children also appeared to be feeling more confident and more equipped to consider changes in their environment outside of the school community. The study further shows that participation in environmental education involves more than cognitive changes as proposed in earlier constructivist literature; it includes in-depth engagement with socio-cultural dynamics and histories in the school context, such as the cultural histories of teachers, schooling and authority structures in the cultural community of the school. The study recommends that there is need to strengthen Teacher Education programmes to develop teaching practices and support for teachers to identify ways of engaging learners' views on issues in the school in open, dialogical ways. Such Teacher Education programmes should deepen teachers' understandings of learners' zone of proximal development (ZPD), demonstrating how dialogue and scaffolding are part of a teacher's role in supporting learning. This is shown in the three case studies that form part of this study. Finally, the study also deepens insights of using the Cultural Historical Activity theory (CHAT) to shed light on issues surrounding learner participation within the socio-cultural and historical environmental education contexts of the schools. The action competence models used in the study provide a tool for revealing forms of learner participation. This tool can be used for critical reflections and monitoring of teaching practices in schools.
- Full Text:
- Date Issued: 2011
Fundamental investigations into the factors affecting the response of laccase-based electrochemical biosensors
- Authors: Fogel, Ronen
- Date: 2011
- Subjects: Laccase Phenols Biosensors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4073 , http://hdl.handle.net/10962/d1007166
- Description: Given their widespread effects and distribution in both natural and industrial environments, the monitoring of phenolic compounds is of considerable analytical interest. Electrochemical biosensor technologies, in particular those comprising laccase enzymes, afford many potential benefits to address this analytical need. However, several key factors affecting sensor response currently limit their applicability. This Thesis reports on the fabrication and optimisation of an electrochemical laccase-based biosensor towards the application of the monitoring of phenolic compounds. Selected factors considered to affect sensor response were investigated using the optimised biosensor. These included: electrochemical, biochemical and substrate-dependent factors, which were found to intersect in modulating biosensor response signals. Through the application of transducer-dependent and substrate-dependent parameters, the selective and simultaneous detection of a mixture of different phenolic analytes is successfully demonstrated. This Thesis also investigates the use of Quartz-Crystal Microbalance with Dissipation (QCM-D) technology, an analytical technique that measures physical parameters of thin-film structures, towards the successful monitoring of enzyme immobilisation strategies. These strategies are fundamental to the successful fabrication of biosensors, and the real-time monitoring of immobilised film formations is of considerable research interest. In the studies reported on in this Thesis, QCM-D technology was demonstrated to be an effective complementary technology in the prediction of film immobilisation techniques on the resultant biochemical kinetics of immobilised enzymes.
- Full Text:
- Date Issued: 2011
- Authors: Fogel, Ronen
- Date: 2011
- Subjects: Laccase Phenols Biosensors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4073 , http://hdl.handle.net/10962/d1007166
- Description: Given their widespread effects and distribution in both natural and industrial environments, the monitoring of phenolic compounds is of considerable analytical interest. Electrochemical biosensor technologies, in particular those comprising laccase enzymes, afford many potential benefits to address this analytical need. However, several key factors affecting sensor response currently limit their applicability. This Thesis reports on the fabrication and optimisation of an electrochemical laccase-based biosensor towards the application of the monitoring of phenolic compounds. Selected factors considered to affect sensor response were investigated using the optimised biosensor. These included: electrochemical, biochemical and substrate-dependent factors, which were found to intersect in modulating biosensor response signals. Through the application of transducer-dependent and substrate-dependent parameters, the selective and simultaneous detection of a mixture of different phenolic analytes is successfully demonstrated. This Thesis also investigates the use of Quartz-Crystal Microbalance with Dissipation (QCM-D) technology, an analytical technique that measures physical parameters of thin-film structures, towards the successful monitoring of enzyme immobilisation strategies. These strategies are fundamental to the successful fabrication of biosensors, and the real-time monitoring of immobilised film formations is of considerable research interest. In the studies reported on in this Thesis, QCM-D technology was demonstrated to be an effective complementary technology in the prediction of film immobilisation techniques on the resultant biochemical kinetics of immobilised enzymes.
- Full Text:
- Date Issued: 2011
Identity, belonging and ecological crisis in South African speculative fiction
- Authors: Steenkamp, Elzette Lorna
- Date: 2011
- Subjects: South African fiction -- History and criticism Identity (Philosophical concept) in literature Group identity in literature Ecology in literature Science fiction, South African -- History and criticism Fantasy fiction, South African -- History and criticism Ecofiction -- History and criticism Ecocriticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2219 , http://hdl.handle.net/10962/d1002262
- Description: This study examines a range of South African speculative novels which situate their narratives in futuristic or ‘alternative’ milieus, exploring how these narratives not only address identity formation in a deeply divided and rapidly changing society, but also the ways in which human beings place themselves in relation to Nature and form notions of ‘ecological’ belonging. It offers close readings of these speculative narratives in order to investigate the ways in which they evince concerns which are rooted in the natural, social and political landscapes which inform them. Specific attention is paid to the texts’ treatment of the intertwined issues of identity, belonging and ecological crisis. This dissertation draws on the fields of Ecocriticism, Postcolonial Studies and Science Fiction Studies, and assumes a culturally specific approach to primary texts while investigating possible cross-cultural commonalities between Afrikaans and English speculative narratives, as well as the cross-fertilisation of global SF/speculative features. It is suggested that South African speculative fiction presents a socio-historically situated, rhizomatic approach to ecology – one that is attuned to the tension between humanistic- and ecological concerns.
- Full Text:
- Date Issued: 2011
- Authors: Steenkamp, Elzette Lorna
- Date: 2011
- Subjects: South African fiction -- History and criticism Identity (Philosophical concept) in literature Group identity in literature Ecology in literature Science fiction, South African -- History and criticism Fantasy fiction, South African -- History and criticism Ecofiction -- History and criticism Ecocriticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2219 , http://hdl.handle.net/10962/d1002262
- Description: This study examines a range of South African speculative novels which situate their narratives in futuristic or ‘alternative’ milieus, exploring how these narratives not only address identity formation in a deeply divided and rapidly changing society, but also the ways in which human beings place themselves in relation to Nature and form notions of ‘ecological’ belonging. It offers close readings of these speculative narratives in order to investigate the ways in which they evince concerns which are rooted in the natural, social and political landscapes which inform them. Specific attention is paid to the texts’ treatment of the intertwined issues of identity, belonging and ecological crisis. This dissertation draws on the fields of Ecocriticism, Postcolonial Studies and Science Fiction Studies, and assumes a culturally specific approach to primary texts while investigating possible cross-cultural commonalities between Afrikaans and English speculative narratives, as well as the cross-fertilisation of global SF/speculative features. It is suggested that South African speculative fiction presents a socio-historically situated, rhizomatic approach to ecology – one that is attuned to the tension between humanistic- and ecological concerns.
- Full Text:
- Date Issued: 2011
Information security service management : a service management approach to information security management
- Authors: Rastogi, Rahul
- Date: 2011
- Subjects: Information technology -- Security measures
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9755 , http://hdl.handle.net/10948/1389 , Information technology -- Security measures
- Description: In today’s world, information and the associated Information Technology are critical assets for many organizations. Any information security breach, or compromise of these assets, can lead to serious implications for organizations that are heavily dependent on these assets. For such organizations, information security becomes vital. Organizations deploy an information security infrastructure for protecting their information assets. This infrastructure consists of policies and controls. Organizations also create an information security management system for managing information security in the organization. While some of the policies and controls are of a purely technical nature, many depend upon the actions of end-users. However, end-users are known to exhibit both compliant and noncompliant behaviours in respect of these information security policies and controls in the organization. Non-compliant information security behaviours of end-users have the potential to lead to information security breaches. Non-compliance thus needs to be controlled. The discipline of information security and its management have evolved over the years. However, the discipline has retained the technology-driven nature of its origin. In this context, the discipline has failed to adequately appreciate the role played by the end-users and the complexities of their behaviour, as it relates to information security policies and controls. The pervasive information security management philosophy is that of treating end-users as the enemy. Compliance is sought to be achieved through awareness programs, rewards, punishments and evermore strict policies and controls. This has led to a bureaucratic information security management approach. The philosophy of treating end-users as the enemy has had an adverse impact on information security in the organization. It can be said that rather than curbing non-compliance by end-users, the present-day bureaucratic approach to information security management has contributed to non-compliance. This thesis calls this the end-user crisis. This research aims at resolving this crisis by identifying an improved approach to information security management in the organization. This research has applied the service management approach to information security management. The resultant Information Security Service Management (ISSM) views end-users as assets and resources, and not as enemies. The central idea of ISSM is that the end-user is to be treated as a customer, whose needs are to be satisfied. This research presents ISSM. This research also presents the various components of ISSM to aid in its implementation in an organization.
- Full Text:
- Date Issued: 2011
- Authors: Rastogi, Rahul
- Date: 2011
- Subjects: Information technology -- Security measures
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9755 , http://hdl.handle.net/10948/1389 , Information technology -- Security measures
- Description: In today’s world, information and the associated Information Technology are critical assets for many organizations. Any information security breach, or compromise of these assets, can lead to serious implications for organizations that are heavily dependent on these assets. For such organizations, information security becomes vital. Organizations deploy an information security infrastructure for protecting their information assets. This infrastructure consists of policies and controls. Organizations also create an information security management system for managing information security in the organization. While some of the policies and controls are of a purely technical nature, many depend upon the actions of end-users. However, end-users are known to exhibit both compliant and noncompliant behaviours in respect of these information security policies and controls in the organization. Non-compliant information security behaviours of end-users have the potential to lead to information security breaches. Non-compliance thus needs to be controlled. The discipline of information security and its management have evolved over the years. However, the discipline has retained the technology-driven nature of its origin. In this context, the discipline has failed to adequately appreciate the role played by the end-users and the complexities of their behaviour, as it relates to information security policies and controls. The pervasive information security management philosophy is that of treating end-users as the enemy. Compliance is sought to be achieved through awareness programs, rewards, punishments and evermore strict policies and controls. This has led to a bureaucratic information security management approach. The philosophy of treating end-users as the enemy has had an adverse impact on information security in the organization. It can be said that rather than curbing non-compliance by end-users, the present-day bureaucratic approach to information security management has contributed to non-compliance. This thesis calls this the end-user crisis. This research aims at resolving this crisis by identifying an improved approach to information security management in the organization. This research has applied the service management approach to information security management. The resultant Information Security Service Management (ISSM) views end-users as assets and resources, and not as enemies. The central idea of ISSM is that the end-user is to be treated as a customer, whose needs are to be satisfied. This research presents ISSM. This research also presents the various components of ISSM to aid in its implementation in an organization.
- Full Text:
- Date Issued: 2011
Intellectualisation of African languages with particular reference to isiXhosa
- Authors: Maseko, Pamela
- Date: 2011
- Subjects: Xhosa language -- Study and teaching -- South Africa , Language and education -- South Africa , African languages
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/58035 , vital:27035
- Description: The research explores the relationship between language and education, and motivates for the intellectualisation of African languages, isiXhosa in particular, and for their use in education. The main rationale behind this is that access to, and success in education can largely be realised if that education is mediated in one’s first language. The thesis discusses works of prominent scholars who have written on the subject - relating cognitive abilities and achievement in education to language in which that education is offered. The lack of terminology in new domains in African languages as barrier to mother tongue education is laid bare by looking specifically at the history of intellectualisation of isiXhosa, from the missionaries in the 1820s up to the new endeavours as recently as 2008. Terminologies that were developed during the Bantu Education era, where development of isiXhosa and other indigenous African languages was accelerated in order to respond to the demands of moedertaal-onderwys (mother tongue education) are surveyed, and the process of their development analysed. Three main terminology lists developed during this period are analysed against terminology development principles, approaches and methods that are seen as a measure to ensure quality terminology development. The efforts of the development of isiXhosa during the post-apartheid South Africa, especially the government-driven initiatives, are also critiqued even though these are not as effective and as extensive, especially in education. The result of this analysis is that African languages and isiXhosa in particular, can be used in scientific disciplines and at the highest levels of education. Its grammar is advanced, and its lexicon is extensive such that new concepts that need to be named can be named, using appropriate term creation strategies. There are also technological tools such as WordSmith tools that can be used that can advance its development, ensuring that the concept represented in the newly-created term is precise, concise and appropriate in terms of its discipline. Therefore it is argued that, in the interim, terminologies should be developed, in various subjects, to support learning, which at this stage is mediated in English, for those students who have other languages as mother tongue. Those terminologies that have been developed in the various historical periods should be collated, revised and brought into the classrooms. The thesis argues that real intellectualisation of isiXhosa and other African languages rests on the use of these languages in classrooms and lecture halls, and in the value that all role players place on these languages.
- Full Text:
- Date Issued: 2011
- Authors: Maseko, Pamela
- Date: 2011
- Subjects: Xhosa language -- Study and teaching -- South Africa , Language and education -- South Africa , African languages
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/58035 , vital:27035
- Description: The research explores the relationship between language and education, and motivates for the intellectualisation of African languages, isiXhosa in particular, and for their use in education. The main rationale behind this is that access to, and success in education can largely be realised if that education is mediated in one’s first language. The thesis discusses works of prominent scholars who have written on the subject - relating cognitive abilities and achievement in education to language in which that education is offered. The lack of terminology in new domains in African languages as barrier to mother tongue education is laid bare by looking specifically at the history of intellectualisation of isiXhosa, from the missionaries in the 1820s up to the new endeavours as recently as 2008. Terminologies that were developed during the Bantu Education era, where development of isiXhosa and other indigenous African languages was accelerated in order to respond to the demands of moedertaal-onderwys (mother tongue education) are surveyed, and the process of their development analysed. Three main terminology lists developed during this period are analysed against terminology development principles, approaches and methods that are seen as a measure to ensure quality terminology development. The efforts of the development of isiXhosa during the post-apartheid South Africa, especially the government-driven initiatives, are also critiqued even though these are not as effective and as extensive, especially in education. The result of this analysis is that African languages and isiXhosa in particular, can be used in scientific disciplines and at the highest levels of education. Its grammar is advanced, and its lexicon is extensive such that new concepts that need to be named can be named, using appropriate term creation strategies. There are also technological tools such as WordSmith tools that can be used that can advance its development, ensuring that the concept represented in the newly-created term is precise, concise and appropriate in terms of its discipline. Therefore it is argued that, in the interim, terminologies should be developed, in various subjects, to support learning, which at this stage is mediated in English, for those students who have other languages as mother tongue. Those terminologies that have been developed in the various historical periods should be collated, revised and brought into the classrooms. The thesis argues that real intellectualisation of isiXhosa and other African languages rests on the use of these languages in classrooms and lecture halls, and in the value that all role players place on these languages.
- Full Text:
- Date Issued: 2011
Intelligent automotive thermal comfort control
- Authors: Kranz, Jürgen
- Date: 2011
- Subjects: Automobiles -- Heating and ventilation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9645 , http://hdl.handle.net/10948/1435 , Automobiles -- Heating and ventilation
- Description: Mobility has become a substantial part in our society. Since we spend a lot of our available time on the road, we expect the automotive environment to provide similar comfort levels than residential buildings. Within this context, this research thesis especially focuses on automotive thermal comfort control. The automotive cabin is a very special environment, which is characterized by extreme inhomogeneity and overall transient behavior. Thermal comfort is a very vague and a very subjective term, which depends on physiological and psychological variables. Theories for thermal comfort in transient environments have not been fully established yet and researchers are still busy with its investigation. At present, automotive industry relies on extensive thermal comfort models, manikins and powerful simulation tools to assess and control thermal comfort. This thesis studies the application of artificial intelligence and proposes a blackbox approach which aims for extracting thermal comfort knowledge directly from human's interaction with the HVAC controls. This methodology avoids the use of human physiological and psychological thermal comfort models and does not require any a-priori knowledge. A novel comfort acquisition tool has been developed and has been integrated into a research vehicle in order to gather the required data for system learning. Data has been collected during spring, autumn and summer conditions in Southern Africa. Methods of data mining have been applied and an intelligent implementation using artificial neural networks has been proposed. The achieved results are promising and allow for about 87 perecent correct classification. It is concluded that methods of artificial intelligence perform well and are far superior compared to conventional approaches. These methods can be used as a powerful tool for the development process of vehicle air-conditioning controls and have great potential for time and cost reduction.
- Full Text:
- Date Issued: 2011
- Authors: Kranz, Jürgen
- Date: 2011
- Subjects: Automobiles -- Heating and ventilation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9645 , http://hdl.handle.net/10948/1435 , Automobiles -- Heating and ventilation
- Description: Mobility has become a substantial part in our society. Since we spend a lot of our available time on the road, we expect the automotive environment to provide similar comfort levels than residential buildings. Within this context, this research thesis especially focuses on automotive thermal comfort control. The automotive cabin is a very special environment, which is characterized by extreme inhomogeneity and overall transient behavior. Thermal comfort is a very vague and a very subjective term, which depends on physiological and psychological variables. Theories for thermal comfort in transient environments have not been fully established yet and researchers are still busy with its investigation. At present, automotive industry relies on extensive thermal comfort models, manikins and powerful simulation tools to assess and control thermal comfort. This thesis studies the application of artificial intelligence and proposes a blackbox approach which aims for extracting thermal comfort knowledge directly from human's interaction with the HVAC controls. This methodology avoids the use of human physiological and psychological thermal comfort models and does not require any a-priori knowledge. A novel comfort acquisition tool has been developed and has been integrated into a research vehicle in order to gather the required data for system learning. Data has been collected during spring, autumn and summer conditions in Southern Africa. Methods of data mining have been applied and an intelligent implementation using artificial neural networks has been proposed. The achieved results are promising and allow for about 87 perecent correct classification. It is concluded that methods of artificial intelligence perform well and are far superior compared to conventional approaches. These methods can be used as a powerful tool for the development process of vehicle air-conditioning controls and have great potential for time and cost reduction.
- Full Text:
- Date Issued: 2011
Investigation of photosensitising behaviour of Ni, Pd and Pt phthalocyanines towards phenolic pollutants
- Authors: Ogunbayo, Taofeek Babatunde
- Date: 2011
- Subjects: Phthalocyanines Pollutants Photochemistry Photosensitizing compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4321 , http://hdl.handle.net/10962/d1004979
- Description: Syntheses of various octasubstituted open-shell (Ni(II), Pd(II) and Pt(II)) metallophthalocyanines and their metal-free analogues have been carried out. Spectroscopic characterizations, photophysical and photochemical studies were carried out to determine the effects of these metals on the molecules using the metal-free phthalocyanine analogues as benchmark. Metal-binding studies of few thio-derivatised phthalocyanines were done to increase the number of palladium metal on the phthalocyanine ligands and determine the effect of increasing number of this metal on phthalocyanine properties. Palladium (PdPc) and platinum phthalocyanines (PtPc) gave good triplet and singlet oxygen quantum yields making them suitable for further investigation in application as photosensitisers. Using 4-nitrophenol as model pollutant, photosensitization reactions were carried out under homogenous and heterogeneous conditions. The reactions were monitored using UV-vis spectroscopy. The MPcs were adsorbed on functionalized single wall carbon nanotube (SWCNT-COOH) to form heterogeneous photosensitizers with PtPc failing to adsorb on the SWCNT-COOH. Under the heterogeneous condition, all the PdPcs photosensitization kinetics was consistent with Langmuir-Hinshelwood reaction model. The best photosenstiser, β-palladium dodecylthio phthalocyanine was also deployed in sensitization of oxidation of 4-chlorophenol and pentachlorophenol under homogenous and heterogeneous conditions to establish the ability of the molecules to sensitize oxidation of wide range of phenolic pollutants. Identifications of the products of the reactions were conducted using gas chromatography and high pressure liquid chromatography (HPLC) hyphenated with mass analyzer (LC-MS). Mechanisms of all the reactions were investigated and all the complexes, in spite of reduced lifetime resulting from open-shell nature of the metals, sensitized the reactions through singlet oxygen mediated pathway. All the heterogeneous sensitisers were recyclable in the 4- nitrophenol oxidation but β-palladium dodecylthio phthalocyanine proved unrecyclable in the oxidation of pentachlorophenol.
- Full Text:
- Date Issued: 2011
- Authors: Ogunbayo, Taofeek Babatunde
- Date: 2011
- Subjects: Phthalocyanines Pollutants Photochemistry Photosensitizing compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4321 , http://hdl.handle.net/10962/d1004979
- Description: Syntheses of various octasubstituted open-shell (Ni(II), Pd(II) and Pt(II)) metallophthalocyanines and their metal-free analogues have been carried out. Spectroscopic characterizations, photophysical and photochemical studies were carried out to determine the effects of these metals on the molecules using the metal-free phthalocyanine analogues as benchmark. Metal-binding studies of few thio-derivatised phthalocyanines were done to increase the number of palladium metal on the phthalocyanine ligands and determine the effect of increasing number of this metal on phthalocyanine properties. Palladium (PdPc) and platinum phthalocyanines (PtPc) gave good triplet and singlet oxygen quantum yields making them suitable for further investigation in application as photosensitisers. Using 4-nitrophenol as model pollutant, photosensitization reactions were carried out under homogenous and heterogeneous conditions. The reactions were monitored using UV-vis spectroscopy. The MPcs were adsorbed on functionalized single wall carbon nanotube (SWCNT-COOH) to form heterogeneous photosensitizers with PtPc failing to adsorb on the SWCNT-COOH. Under the heterogeneous condition, all the PdPcs photosensitization kinetics was consistent with Langmuir-Hinshelwood reaction model. The best photosenstiser, β-palladium dodecylthio phthalocyanine was also deployed in sensitization of oxidation of 4-chlorophenol and pentachlorophenol under homogenous and heterogeneous conditions to establish the ability of the molecules to sensitize oxidation of wide range of phenolic pollutants. Identifications of the products of the reactions were conducted using gas chromatography and high pressure liquid chromatography (HPLC) hyphenated with mass analyzer (LC-MS). Mechanisms of all the reactions were investigated and all the complexes, in spite of reduced lifetime resulting from open-shell nature of the metals, sensitized the reactions through singlet oxygen mediated pathway. All the heterogeneous sensitisers were recyclable in the 4- nitrophenol oxidation but β-palladium dodecylthio phthalocyanine proved unrecyclable in the oxidation of pentachlorophenol.
- Full Text:
- Date Issued: 2011
Land use change, landslide occurrence and livelihood strategies on Mount Elgon Slopes, Eastern Uganda
- Authors: Mugagga, Frank
- Date: 2011
- Subjects: Land use -- Uganda -- Mount Elgon National Park , Landslides -- Uganda -- Mount Elgon National Park , Land degradation -- Uganda -- Mount Elgon National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10646 , http://hdl.handle.net/10948/1468 , Land use -- Uganda -- Mount Elgon National Park , Landslides -- Uganda -- Mount Elgon National Park , Land degradation -- Uganda -- Mount Elgon National Park
- Description: An investigation of the relationship between the physical, pedological and anthropogenic influences on landslide occurrence on the midslopes within and outside Mt Elgon National Park was carried out. One of the landslides occurred in a protected pristine forest environment within the Park while the other two were located at sites deforested for cultivation within and outside the National Park. Field based surveys, GIS techniques and laboratory tests were used to collect and analyze the data. A household survey was undertaken to establish the main community livelihood strategies, the drivers of land use change and implications for land degradation on the mid slopes of Mt Elgon. Aerial photographs taken in 1960 and orthophoto maps formed the benchmark for the analysis of the respective land use changes between 1995 and 2006, using 30m Landsat TM and 20m SPOT MS images in IDRISI Andes GIS environment. Landslide sites were mapped using a Magellan Professional MobileMapperTMCX and terrain parameters were derived using a 15M Digital Elevation Model. A hybrid supervised/unsupervised classification approach was employed to generate land cover maps from which the areal extent of three land cover classes (agricultural fields, woodlands and forests) was calculated. Particle size distribution and atterberg limits were used to test the hypothesis that soils at the landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention. Shear strength parameters (internal of friction and cohesion) were used calculate the slope factor of safety to ascertain slope stability at pristine and disturbed landslide sites. Results from the socio-economic survey revealed that smallholder subsistence agriculture and encroachment on the National Park resources are the main sources of livelihoods for the communities surrounding the Park. The communities also have a strong socio-cultural attachment to the National Park, as it is the source of items used during traditional rituals like circumcision. Encroachment is driven by the high population pressure and the prevalent political climate. Farmers mainly use slash and burn technique to prepare land for cultivation and those close to the National Park are reluctant to adopt appropriate farming and soil conservation practices due to the uncertainties surrounding their future on such plots. Slash and burn iii techniques were observed to accelerate various forms of erosion including rills, gullies and sheet. Soil and water conservation techniques were mainly practiced on privately owned farms. The period 1960 and 1995 was characterized by minimal land use changes and no encroachment into the designated Mount Elgon National Park. Conversely, the period 1995 – 2006 marked a significant loss of woodlands and forest cover particularly on steep concave slopes (36º – 58º) within the National Park. The land use change trends were attributed to the prevalent land politics and exponential population growth in the region. The encroachment onto the critical slopes was noted to have induced a series of shallow and deep landslides in the area. Deforestation on Mt Elgon was reported to have both onsite and offsite climate variability and implications in the form of drought, heat waves, flash floods, economic dislocation, crop failure and associated malnutrition in surrounding low lying areas. The soils on pristine and disturbed slopes contain high amount of clay (>10 percent), are fine textured (>50 percent of the material passing the 0.075mm sieve) and highly plastic. These soil attributes imply low permeability, excessive water retention and high susceptibility to expansion and sliding. The vertic nature of soils at Nametsi was confirmed by the extremely high plasticity indices (averaging 33percent), while, high liquid limits at Buwabwala (53 percent) and Kitati (59 percent) qualified the soils as vertisols which are associated with landslides. The results point to the fact that soils at landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention. Therefore, the hypothesis that soils at three landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention is accepted. Notwithstanding the fact that the study was focussed on mid-altitude slopes of Mt Elgon, the results are in tandem with investigations carried out earlier on the lower densely populated slopes, thus confirming the widespread nature of problem soils on Mt Elgon. There is an urgent need to control human population growth and restore forest cover on the heavily deforested steep slopes particularly within the National Park, and restrain communities from encroaching on the pristine slopes of Mt Elgon. This will be achieved if the politicians, Park Authorities and local communities jointly participate in the design and implementation of CFMs. Future research could focus on climate change implications of deforestation of Mt Elgon environments and quantification of carbon loss related to deforestation and soil degradation in the mountain environments.
- Full Text:
- Date Issued: 2011
- Authors: Mugagga, Frank
- Date: 2011
- Subjects: Land use -- Uganda -- Mount Elgon National Park , Landslides -- Uganda -- Mount Elgon National Park , Land degradation -- Uganda -- Mount Elgon National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10646 , http://hdl.handle.net/10948/1468 , Land use -- Uganda -- Mount Elgon National Park , Landslides -- Uganda -- Mount Elgon National Park , Land degradation -- Uganda -- Mount Elgon National Park
- Description: An investigation of the relationship between the physical, pedological and anthropogenic influences on landslide occurrence on the midslopes within and outside Mt Elgon National Park was carried out. One of the landslides occurred in a protected pristine forest environment within the Park while the other two were located at sites deforested for cultivation within and outside the National Park. Field based surveys, GIS techniques and laboratory tests were used to collect and analyze the data. A household survey was undertaken to establish the main community livelihood strategies, the drivers of land use change and implications for land degradation on the mid slopes of Mt Elgon. Aerial photographs taken in 1960 and orthophoto maps formed the benchmark for the analysis of the respective land use changes between 1995 and 2006, using 30m Landsat TM and 20m SPOT MS images in IDRISI Andes GIS environment. Landslide sites were mapped using a Magellan Professional MobileMapperTMCX and terrain parameters were derived using a 15M Digital Elevation Model. A hybrid supervised/unsupervised classification approach was employed to generate land cover maps from which the areal extent of three land cover classes (agricultural fields, woodlands and forests) was calculated. Particle size distribution and atterberg limits were used to test the hypothesis that soils at the landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention. Shear strength parameters (internal of friction and cohesion) were used calculate the slope factor of safety to ascertain slope stability at pristine and disturbed landslide sites. Results from the socio-economic survey revealed that smallholder subsistence agriculture and encroachment on the National Park resources are the main sources of livelihoods for the communities surrounding the Park. The communities also have a strong socio-cultural attachment to the National Park, as it is the source of items used during traditional rituals like circumcision. Encroachment is driven by the high population pressure and the prevalent political climate. Farmers mainly use slash and burn technique to prepare land for cultivation and those close to the National Park are reluctant to adopt appropriate farming and soil conservation practices due to the uncertainties surrounding their future on such plots. Slash and burn iii techniques were observed to accelerate various forms of erosion including rills, gullies and sheet. Soil and water conservation techniques were mainly practiced on privately owned farms. The period 1960 and 1995 was characterized by minimal land use changes and no encroachment into the designated Mount Elgon National Park. Conversely, the period 1995 – 2006 marked a significant loss of woodlands and forest cover particularly on steep concave slopes (36º – 58º) within the National Park. The land use change trends were attributed to the prevalent land politics and exponential population growth in the region. The encroachment onto the critical slopes was noted to have induced a series of shallow and deep landslides in the area. Deforestation on Mt Elgon was reported to have both onsite and offsite climate variability and implications in the form of drought, heat waves, flash floods, economic dislocation, crop failure and associated malnutrition in surrounding low lying areas. The soils on pristine and disturbed slopes contain high amount of clay (>10 percent), are fine textured (>50 percent of the material passing the 0.075mm sieve) and highly plastic. These soil attributes imply low permeability, excessive water retention and high susceptibility to expansion and sliding. The vertic nature of soils at Nametsi was confirmed by the extremely high plasticity indices (averaging 33percent), while, high liquid limits at Buwabwala (53 percent) and Kitati (59 percent) qualified the soils as vertisols which are associated with landslides. The results point to the fact that soils at landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention. Therefore, the hypothesis that soils at three landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention is accepted. Notwithstanding the fact that the study was focussed on mid-altitude slopes of Mt Elgon, the results are in tandem with investigations carried out earlier on the lower densely populated slopes, thus confirming the widespread nature of problem soils on Mt Elgon. There is an urgent need to control human population growth and restore forest cover on the heavily deforested steep slopes particularly within the National Park, and restrain communities from encroaching on the pristine slopes of Mt Elgon. This will be achieved if the politicians, Park Authorities and local communities jointly participate in the design and implementation of CFMs. Future research could focus on climate change implications of deforestation of Mt Elgon environments and quantification of carbon loss related to deforestation and soil degradation in the mountain environments.
- Full Text:
- Date Issued: 2011
Land use/cover change modelling and land degradation assessment in the Keiskamma catchment using remote sensing and GIS
- Authors: Mhangara, Paidamwoyo
- Date: 2011
- Subjects: Land use -- South Africa -- Eastern Cape , Land degradation -- South Africa -- Eastern Cape , Keiskamma River (South Africa)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10647 , http://hdl.handle.net/10948/1467 , Land use -- South Africa -- Eastern Cape , Land degradation -- South Africa -- Eastern Cape , Keiskamma River (South Africa)
- Description: Land degradation in most communal parts of the Keiskamma catchment has reached alarming proportions. The Keiskamma catchment is particularly predisposed to severe land degradation associated with soil erosion, thicket degradation and deteriorating riparian vegetation. There is a close coupling between land use/cover dynamics and degradation trends witnessed in the catchment. Soil erosion is prevalent in most of the communal areas in the catchment. The principal aim of this study was to investigate land use/cover trends, model the spatial patterns of soil loss and predict future land use/cover scenarios as a means of assessing land degradation in the Keiskamma catchment. Multi-temporal Landsat satellite imagery from 1972 to 2006 was used for land use/cover change analyses using object-oriented post-classification comparison. Fragmentation analysis was performed by computing and analyzing landscape metrics in the riparian and adjacent hillslope areas to determine the land cover structural changes that have occurred since 1972. The landscape function analysis was used to validate the current rangeland conditions in the communal areas and the former commercial farms. The current condition of the riparian zones and proximal hillslopes was assessed using the Rapid Appraisal of Riparian Condition and future land use/cover scenarios were simulated using the Markovcellular automata model. Spatial patterns of soil loss in the Keiskamma catchment were determined using the Sediment Assessment Tool for Effective Erosion Control (SATEEC), which is a GIS based RUSLE model that integrates sediment delivery ratios. Object oriented classification was used to map soil erosion surfaces and valley infill in ephemeral stream channels as a means of demonstrating the major sediment transfer processes operating in the Keiskamma catchment. The Mahalanobis distance method was used to compute the topographic thresholds for gully erosion. To understand the effect of soil characteristics in severe forms of erosion, laboratory analyses were undertaken to determine the physico-chemical soil properties. iv The temporal land use/cover analysis done using the post-classification change detection indicated that intact vegetation has undergone a significant decline from 1972 to 2006. The temporal changes within the intermediate years are characterized by cyclic transitions of decline and recovery of intact vegetation. An overall decline in intact vegetation cover, an increase in degraded vegetation and bare eroded soil was noted. Fragmentation analyses done in the communal villages of the central Keiskamma catchment indicated increasing vegetation fragmentation manifested by an increase in smaller and less connected vegetation patches, and a subsequent increase of bare and degraded soil patches which are much bigger and more connected. The Landscape Organisation Index revealed very low vegetation connectivity in the communal rangelands that have weak local traditional institutions. Fragmentation analyses in the riparian and proximal hillslopes revealed evidence of increasing vegetation fragmentation from 1972 to 2006. The Markov Cellular Automata simulation predicted a decline in intact vegetation and an increase in bare and degraded soil in 2019. The Keiskamma catchment was noted as experiencing high rates of soil loss that are above provincial and national averages. The classification of erosion features and valley infill showcased the vegetation enrichment in the ephemeral streams which is occurring at the expense of high soil losses from severe gully erosion on the hillslopes. This in turn has led to an inversion of grazing patterns within the catchment, such that grazing is now concentrated within the ephemeral stream channels. Soil chemical analyses revealed a high sodium content and low soluble salt concentration, which promote soil dispersion, piping and gully erosion. The presence of high amounts of illite-smectite in the catchment also accounts for the highly dispersive nature of the soil even at low SAR values. Significant amounts of swelling 2:1 silicate clays such as smectites cause cracking and contribute to the development of piping and gullying in the catchment. Given the worsening degradation trends in the communal areas, a systematic re-allocation of state land in sections of the catchment that belonged to the former commercial farms is recommended to alleviate anthropogenic pressure. Strengthening local institutions that effectively monitor and manage natural resources will be required in order to maintain v optimum flow regimes in rivers and curb thicket degradation. Measures to curb environmental degradation in the Keiskamma catchment should encompass suitable ecological interventions that are sensitive to the socio-economic challenges facing the people in communal areas.
- Full Text:
- Date Issued: 2011
- Authors: Mhangara, Paidamwoyo
- Date: 2011
- Subjects: Land use -- South Africa -- Eastern Cape , Land degradation -- South Africa -- Eastern Cape , Keiskamma River (South Africa)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10647 , http://hdl.handle.net/10948/1467 , Land use -- South Africa -- Eastern Cape , Land degradation -- South Africa -- Eastern Cape , Keiskamma River (South Africa)
- Description: Land degradation in most communal parts of the Keiskamma catchment has reached alarming proportions. The Keiskamma catchment is particularly predisposed to severe land degradation associated with soil erosion, thicket degradation and deteriorating riparian vegetation. There is a close coupling between land use/cover dynamics and degradation trends witnessed in the catchment. Soil erosion is prevalent in most of the communal areas in the catchment. The principal aim of this study was to investigate land use/cover trends, model the spatial patterns of soil loss and predict future land use/cover scenarios as a means of assessing land degradation in the Keiskamma catchment. Multi-temporal Landsat satellite imagery from 1972 to 2006 was used for land use/cover change analyses using object-oriented post-classification comparison. Fragmentation analysis was performed by computing and analyzing landscape metrics in the riparian and adjacent hillslope areas to determine the land cover structural changes that have occurred since 1972. The landscape function analysis was used to validate the current rangeland conditions in the communal areas and the former commercial farms. The current condition of the riparian zones and proximal hillslopes was assessed using the Rapid Appraisal of Riparian Condition and future land use/cover scenarios were simulated using the Markovcellular automata model. Spatial patterns of soil loss in the Keiskamma catchment were determined using the Sediment Assessment Tool for Effective Erosion Control (SATEEC), which is a GIS based RUSLE model that integrates sediment delivery ratios. Object oriented classification was used to map soil erosion surfaces and valley infill in ephemeral stream channels as a means of demonstrating the major sediment transfer processes operating in the Keiskamma catchment. The Mahalanobis distance method was used to compute the topographic thresholds for gully erosion. To understand the effect of soil characteristics in severe forms of erosion, laboratory analyses were undertaken to determine the physico-chemical soil properties. iv The temporal land use/cover analysis done using the post-classification change detection indicated that intact vegetation has undergone a significant decline from 1972 to 2006. The temporal changes within the intermediate years are characterized by cyclic transitions of decline and recovery of intact vegetation. An overall decline in intact vegetation cover, an increase in degraded vegetation and bare eroded soil was noted. Fragmentation analyses done in the communal villages of the central Keiskamma catchment indicated increasing vegetation fragmentation manifested by an increase in smaller and less connected vegetation patches, and a subsequent increase of bare and degraded soil patches which are much bigger and more connected. The Landscape Organisation Index revealed very low vegetation connectivity in the communal rangelands that have weak local traditional institutions. Fragmentation analyses in the riparian and proximal hillslopes revealed evidence of increasing vegetation fragmentation from 1972 to 2006. The Markov Cellular Automata simulation predicted a decline in intact vegetation and an increase in bare and degraded soil in 2019. The Keiskamma catchment was noted as experiencing high rates of soil loss that are above provincial and national averages. The classification of erosion features and valley infill showcased the vegetation enrichment in the ephemeral streams which is occurring at the expense of high soil losses from severe gully erosion on the hillslopes. This in turn has led to an inversion of grazing patterns within the catchment, such that grazing is now concentrated within the ephemeral stream channels. Soil chemical analyses revealed a high sodium content and low soluble salt concentration, which promote soil dispersion, piping and gully erosion. The presence of high amounts of illite-smectite in the catchment also accounts for the highly dispersive nature of the soil even at low SAR values. Significant amounts of swelling 2:1 silicate clays such as smectites cause cracking and contribute to the development of piping and gullying in the catchment. Given the worsening degradation trends in the communal areas, a systematic re-allocation of state land in sections of the catchment that belonged to the former commercial farms is recommended to alleviate anthropogenic pressure. Strengthening local institutions that effectively monitor and manage natural resources will be required in order to maintain v optimum flow regimes in rivers and curb thicket degradation. Measures to curb environmental degradation in the Keiskamma catchment should encompass suitable ecological interventions that are sensitive to the socio-economic challenges facing the people in communal areas.
- Full Text:
- Date Issued: 2011
Macrophytes as indicators of physico-chemical factors in South African Estuaries
- Authors: Bezuidenhout, Chantel
- Date: 2011
- Subjects: Estuarine ecology -- South Africa , Aquatic plants -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10597 , http://hdl.handle.net/10948/1387 , Estuarine ecology -- South Africa , Aquatic plants -- South Africa
- Description: This study investigated the response of macrophytes to physico-chemical factors in seven South African estuaries and showed that dominant salt marsh species that occur in different estuaries respond to the same environmental factors. The most important variables influencing distribution were elevation, water level, sediment- and groundwater electrical conductivity and depth to the water table. In permanently open estuaries (Kromme and Olifants) transect surveys identified three distinct vegetation zones i.e. submerged macrophytes, intertidal salt marsh and supratidal salt marsh. In the Kromme Estuary intertidal salt marsh (81.2 ha) covered extensive areas, whereas supratidal (143 ha) and floodplain (797.1 ha) salt marsh were dominant in the Olifants Estuary. Transect surveys identified four distinct vegetation zones (submerged macrophytes, intertidal salt marsh, supratidal salt marsh and reeds and sedges) in the temporarily open/closed estuaries (Mngazi, Great Brak, East Kleinemonde and Seekoei estuaries), although all zones did not occur in all of the estuaries sampled. In the Mngazi Estuary reeds and sedges (1.09 ha) covered extensive areas (no submerged or salt marsh vegetation was present), whereas salt marsh (Great Brak 24.45 ha, East Kleinemonde 17.44 ha and Seekoei 12.9 ha) vegetation was dominant in the other estuaries. Despite the geographic differences, environmental factors influencing macrophyte distribution were similar in all estuaries. Canonical Correspondence Analysis showed that vegetation distribution was significantly affected by elevation, groundwater and sediment electrical conductivity and depth to groundwater. Supratidal species were associated with a greater depth to groundwater (1.2 ± 0.04 m; n = 153) compared to intertidal species (0.5 ± 0.01 m; n = 361). Correlation analysis showed that water level and rainfall were correlated with groundwater electrical conductivity in the lower and upper intertidal zones for all the estuaries sampled. These data indicate the influence of the estuary channel on the physico-chemical conditions of the salt marsh. Low rainfall (16 ± 3.3 mm per annum) in the Olifants Estuary (30-100 mS cm-1) and lack of freshwater flooding in the Kromme Estuary (42-115 mS cm-1) have resulted in high sediment electrical conductivity by comparison with the other estuaries sampled. In the Orange River Estuary approximately 70 ha of salt marsh have been lost through the building of a causeway and flood control levees. Even though salt marsh vegetation can tolerate hypersaline sediments by using the less saline water table, the groundwater at the Orange River Estuary was too saline (avg. of 90.3 ± 6.55 mS cm-1, n = 38) to be of use to the dominant floodplain species, Sarcocornia pillansii. Freshwater inflow to estuaries is important in maintaining longitudinal salinity gradients and reducing hypersaline conditions. In the Olifants Estuary and the Orange River Estuary where supratidal salt marsh is dominant, freshwater inflow is important in raising the water level and maintaining the depth to groundwater and salinity. Lack of freshwater inflow to the Kromme Estuary has highlighted the importance of rainfall in maintaining sediment salinity within acceptable ranges for the salt marsh. Macrophytes are relatively good indicators of physico-chemical factors in estuaries. From an understanding of the response of specific species to environmental variables, ecological water requirements can be set and sensitive areas can be rehabilitated.
- Full Text:
- Date Issued: 2011
- Authors: Bezuidenhout, Chantel
- Date: 2011
- Subjects: Estuarine ecology -- South Africa , Aquatic plants -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10597 , http://hdl.handle.net/10948/1387 , Estuarine ecology -- South Africa , Aquatic plants -- South Africa
- Description: This study investigated the response of macrophytes to physico-chemical factors in seven South African estuaries and showed that dominant salt marsh species that occur in different estuaries respond to the same environmental factors. The most important variables influencing distribution were elevation, water level, sediment- and groundwater electrical conductivity and depth to the water table. In permanently open estuaries (Kromme and Olifants) transect surveys identified three distinct vegetation zones i.e. submerged macrophytes, intertidal salt marsh and supratidal salt marsh. In the Kromme Estuary intertidal salt marsh (81.2 ha) covered extensive areas, whereas supratidal (143 ha) and floodplain (797.1 ha) salt marsh were dominant in the Olifants Estuary. Transect surveys identified four distinct vegetation zones (submerged macrophytes, intertidal salt marsh, supratidal salt marsh and reeds and sedges) in the temporarily open/closed estuaries (Mngazi, Great Brak, East Kleinemonde and Seekoei estuaries), although all zones did not occur in all of the estuaries sampled. In the Mngazi Estuary reeds and sedges (1.09 ha) covered extensive areas (no submerged or salt marsh vegetation was present), whereas salt marsh (Great Brak 24.45 ha, East Kleinemonde 17.44 ha and Seekoei 12.9 ha) vegetation was dominant in the other estuaries. Despite the geographic differences, environmental factors influencing macrophyte distribution were similar in all estuaries. Canonical Correspondence Analysis showed that vegetation distribution was significantly affected by elevation, groundwater and sediment electrical conductivity and depth to groundwater. Supratidal species were associated with a greater depth to groundwater (1.2 ± 0.04 m; n = 153) compared to intertidal species (0.5 ± 0.01 m; n = 361). Correlation analysis showed that water level and rainfall were correlated with groundwater electrical conductivity in the lower and upper intertidal zones for all the estuaries sampled. These data indicate the influence of the estuary channel on the physico-chemical conditions of the salt marsh. Low rainfall (16 ± 3.3 mm per annum) in the Olifants Estuary (30-100 mS cm-1) and lack of freshwater flooding in the Kromme Estuary (42-115 mS cm-1) have resulted in high sediment electrical conductivity by comparison with the other estuaries sampled. In the Orange River Estuary approximately 70 ha of salt marsh have been lost through the building of a causeway and flood control levees. Even though salt marsh vegetation can tolerate hypersaline sediments by using the less saline water table, the groundwater at the Orange River Estuary was too saline (avg. of 90.3 ± 6.55 mS cm-1, n = 38) to be of use to the dominant floodplain species, Sarcocornia pillansii. Freshwater inflow to estuaries is important in maintaining longitudinal salinity gradients and reducing hypersaline conditions. In the Olifants Estuary and the Orange River Estuary where supratidal salt marsh is dominant, freshwater inflow is important in raising the water level and maintaining the depth to groundwater and salinity. Lack of freshwater inflow to the Kromme Estuary has highlighted the importance of rainfall in maintaining sediment salinity within acceptable ranges for the salt marsh. Macrophytes are relatively good indicators of physico-chemical factors in estuaries. From an understanding of the response of specific species to environmental variables, ecological water requirements can be set and sensitive areas can be rehabilitated.
- Full Text:
- Date Issued: 2011
Management and the dynamics of labour process: study of workplace relations in an oil refinery, Nigeria
- Oladeinde, Olusegun Olurotimi
- Authors: Oladeinde, Olusegun Olurotimi
- Date: 2011
- Subjects: Nigerian National Petroleum Corporation Personnel management -- Nigeria Petroleum industry and trade -- Personnel management -- Nigeria Performance -- Management -- Nigeria Industrial relations -- Nigeria Organizational behavior -- Nigeria Total quality management -- Nigeria Labor unions -- Nigeria Petroleum workers -- Nigeria -- Attitudes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3299 , http://hdl.handle.net/10962/d1003087
- Description: The focus of this thesis is on labour-management relations in the Nigerian National Petroleum Corporation (NNPC), Nigeria. The study explores current managerial practices in the corporation and their effects on the intensification of work, and how the management sought to control workers and the labour process. The study explores the experiences of workers and their perception of managerial practices. Evidence suggests that managerial practices and their impacts on workplace relations in NNPC have become more subtle, with wider implications for workers’ experience and the labour process. Using primary data obtained through interviews, participant observation, and documentary sources, the thesis assesses how managerial practices are varieties of controls of labour in which workers’ consent is also embedded. This embeddedness of the labour process generates new types of worker subjectivity and identity, with significant implications for labour relations. The study suggests that multiple dimensions of workers’ sense-making reflect the structural and subjective dimensions of the labour process. In NNPC, the consequence of managerial practices has been an emergence of a new type of subjectivity; one that has closely identified with the corporate values and is not overtly disposed towards resistance or dissent. While workers consent at NNPC continues to be an outcome of managerial practices, the thesis examined its implications. The thesis seeks to explain the effects of managerial control mechanisms in shaping workers’ experience and identity. However, the thesis shows that while workers remain susceptible to these forms of managerial influence, an erasure or closure of oppositions or recalcitrance will not adequately account for workers’ identity-formation. The thesis shows that while managerial control remains significant, workers inhabit domains that are ‘unmanaged’ and ‘unmanageable’ where ‘resistance’ and ‘misbehaviour’ reside. Without a conceptual and empirical interrogation, evidence of normative and mutual benefits of managerial practices or a submissive image of workers will produce images of workers that obscure their covert opposition and resistance. Workers ‘collude’ with the ‘hubris’ of management in order to invert and subvert managerial practices and intentions. Through theoretical reconceptualization, the thesis demonstrates the specific dimensions of these inversions and subversions. The thesis therefore seeks to re-insert “worker-agency” back into the analysis of power-relations in the workplace; agency that is not overtly under the absolute grip of managerial control, but with a multiplicity of identities and multilevel manifestations.
- Full Text:
- Date Issued: 2011
- Authors: Oladeinde, Olusegun Olurotimi
- Date: 2011
- Subjects: Nigerian National Petroleum Corporation Personnel management -- Nigeria Petroleum industry and trade -- Personnel management -- Nigeria Performance -- Management -- Nigeria Industrial relations -- Nigeria Organizational behavior -- Nigeria Total quality management -- Nigeria Labor unions -- Nigeria Petroleum workers -- Nigeria -- Attitudes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3299 , http://hdl.handle.net/10962/d1003087
- Description: The focus of this thesis is on labour-management relations in the Nigerian National Petroleum Corporation (NNPC), Nigeria. The study explores current managerial practices in the corporation and their effects on the intensification of work, and how the management sought to control workers and the labour process. The study explores the experiences of workers and their perception of managerial practices. Evidence suggests that managerial practices and their impacts on workplace relations in NNPC have become more subtle, with wider implications for workers’ experience and the labour process. Using primary data obtained through interviews, participant observation, and documentary sources, the thesis assesses how managerial practices are varieties of controls of labour in which workers’ consent is also embedded. This embeddedness of the labour process generates new types of worker subjectivity and identity, with significant implications for labour relations. The study suggests that multiple dimensions of workers’ sense-making reflect the structural and subjective dimensions of the labour process. In NNPC, the consequence of managerial practices has been an emergence of a new type of subjectivity; one that has closely identified with the corporate values and is not overtly disposed towards resistance or dissent. While workers consent at NNPC continues to be an outcome of managerial practices, the thesis examined its implications. The thesis seeks to explain the effects of managerial control mechanisms in shaping workers’ experience and identity. However, the thesis shows that while workers remain susceptible to these forms of managerial influence, an erasure or closure of oppositions or recalcitrance will not adequately account for workers’ identity-formation. The thesis shows that while managerial control remains significant, workers inhabit domains that are ‘unmanaged’ and ‘unmanageable’ where ‘resistance’ and ‘misbehaviour’ reside. Without a conceptual and empirical interrogation, evidence of normative and mutual benefits of managerial practices or a submissive image of workers will produce images of workers that obscure their covert opposition and resistance. Workers ‘collude’ with the ‘hubris’ of management in order to invert and subvert managerial practices and intentions. Through theoretical reconceptualization, the thesis demonstrates the specific dimensions of these inversions and subversions. The thesis therefore seeks to re-insert “worker-agency” back into the analysis of power-relations in the workplace; agency that is not overtly under the absolute grip of managerial control, but with a multiplicity of identities and multilevel manifestations.
- Full Text:
- Date Issued: 2011
Modelling the relationship between flow and water quality in South African rivers
- Authors: Slaughter, Andrew Robert
- Date: 2011
- Subjects: Water quality -- Measurement -- South Africa Water quality -- Mathematical models -- South Africa Streamflow -- South Africa Stream measurements -- Mathematical models -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6039 , http://hdl.handle.net/10962/d1006196
- Description: The National Water Act (Act 36 of 1998) provides for an ecological Reserve as the quantity (flow) and quality of water needed to protect aquatic ecosystems. While there are methods available to quantify the ecological Reserve in terms of flow, methods of linking flow to water quality are lacking. Therefore, the research presented in this thesis investigated various modelling techniques to estimate the effect of flow on water quality. The aims of the research presented in this thesis were: Aim 1: Can the relationship between flow and water quality be accurately represented by simple statistical models? Aim 2: Can relatively simple models accurately represent the relationship between flow and water quality? Aim 3: Can the effect of diffuse sources be omitted from a water quality model and still obtain realistic simulations, and if so under what conditions? Aim 4: Can models that solely use historical monitoring data, accurately represent the relationships between flow and water quality? In Chapter 3, simple Q-C regressions of flow and water quality were investigated using Department of Water Affairs (DWA) historical monitoring data. It was found that while flow versus salinity regressions gave good regression fits in many cases, the Q-C regression approach is limited. A mechanistic/statistical model that attempted to estimate the point and diffuse signatures of nutrients in response to flow was developed in Chapter 4 using DWA historical monitoring data. The model was verified as accurate in certain case studies using observed point loading information. In Chapter 5, statistical models that link land cover information to diffuse nutrient signatures in response to flow using DWA historical data were developed. While the model estimations are uncertain due to a lack of data, they do provide an estimation of the diffuse signature within catchments where there is flow and land cover information available. Chapter 6 investigates the extension of an existing mass-balance salinity model to estimate the effect of saline irrigation return flow on in-stream salinity. The model gave accurate salinity estimates for a low order stream with little or no irrigation within its catchment, and for a permanently flowing river within a catchment used extensively for irrigation. Chapter 7 investigated a modelling method to estimate the reaction coefficients involved in nitrification using only DWA historical monitoring data. Here, the model used flow information to estimate the residence time of nutrients within the studied river reaches. While the model obtained good estimations of nitrification for the data it was applied to, very few DWA data sets were suitable for the model. Chapter 8 investigated the ability of the in-stream model QUAL2K to estimate nutrient concentrations downstream of point and diffuse inputs of nutrients. It was found that the QUAL2K model can give accurate results in cases where point sources dominate the total nutrient inputs into a river. However, the QUAL2K simulations are too uncertain in cases where there are large diffuse source inputs of nutrients as the load of the diffuse inputs is difficult to measure in the field. This research highlights the problem of data scarcity in terms of temporal resolution as well as the range of constituents measured within DWA historical monitoring data for water quality. This thesis in addition argues that the approach of applying a number of models is preferable to applying one model to investigate the research aims, as particular models would be suited to particular circumstances, and the development of new models allowed the research aims of this thesis to be explored more thoroughly. It is also argued that simpler models that simulate a few key processes that explain the variation in observed data, are more suitable for implementing Integrated Water Resource Management (IWRM) than large comprehensive water quality models. From this research, it is clear that simple statistical models are not adequate for modelling the relationship between flow and water quality, however, relatively simple mechanistic models that simulate a limited number of processes and water quality variables, can provide accurate representations of this relationship. Under conditions where diffuse sources are not a major factor within a catchment, models that omit diffuse sources can obtain realistic simulations of the relationship between flow and water quality. Most of the models investigated in this thesis demonstrate that accurate simulations of the relationships between flow and water quality can be obtained using solely historical monitoring data.
- Full Text:
- Date Issued: 2011
- Authors: Slaughter, Andrew Robert
- Date: 2011
- Subjects: Water quality -- Measurement -- South Africa Water quality -- Mathematical models -- South Africa Streamflow -- South Africa Stream measurements -- Mathematical models -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6039 , http://hdl.handle.net/10962/d1006196
- Description: The National Water Act (Act 36 of 1998) provides for an ecological Reserve as the quantity (flow) and quality of water needed to protect aquatic ecosystems. While there are methods available to quantify the ecological Reserve in terms of flow, methods of linking flow to water quality are lacking. Therefore, the research presented in this thesis investigated various modelling techniques to estimate the effect of flow on water quality. The aims of the research presented in this thesis were: Aim 1: Can the relationship between flow and water quality be accurately represented by simple statistical models? Aim 2: Can relatively simple models accurately represent the relationship between flow and water quality? Aim 3: Can the effect of diffuse sources be omitted from a water quality model and still obtain realistic simulations, and if so under what conditions? Aim 4: Can models that solely use historical monitoring data, accurately represent the relationships between flow and water quality? In Chapter 3, simple Q-C regressions of flow and water quality were investigated using Department of Water Affairs (DWA) historical monitoring data. It was found that while flow versus salinity regressions gave good regression fits in many cases, the Q-C regression approach is limited. A mechanistic/statistical model that attempted to estimate the point and diffuse signatures of nutrients in response to flow was developed in Chapter 4 using DWA historical monitoring data. The model was verified as accurate in certain case studies using observed point loading information. In Chapter 5, statistical models that link land cover information to diffuse nutrient signatures in response to flow using DWA historical data were developed. While the model estimations are uncertain due to a lack of data, they do provide an estimation of the diffuse signature within catchments where there is flow and land cover information available. Chapter 6 investigates the extension of an existing mass-balance salinity model to estimate the effect of saline irrigation return flow on in-stream salinity. The model gave accurate salinity estimates for a low order stream with little or no irrigation within its catchment, and for a permanently flowing river within a catchment used extensively for irrigation. Chapter 7 investigated a modelling method to estimate the reaction coefficients involved in nitrification using only DWA historical monitoring data. Here, the model used flow information to estimate the residence time of nutrients within the studied river reaches. While the model obtained good estimations of nitrification for the data it was applied to, very few DWA data sets were suitable for the model. Chapter 8 investigated the ability of the in-stream model QUAL2K to estimate nutrient concentrations downstream of point and diffuse inputs of nutrients. It was found that the QUAL2K model can give accurate results in cases where point sources dominate the total nutrient inputs into a river. However, the QUAL2K simulations are too uncertain in cases where there are large diffuse source inputs of nutrients as the load of the diffuse inputs is difficult to measure in the field. This research highlights the problem of data scarcity in terms of temporal resolution as well as the range of constituents measured within DWA historical monitoring data for water quality. This thesis in addition argues that the approach of applying a number of models is preferable to applying one model to investigate the research aims, as particular models would be suited to particular circumstances, and the development of new models allowed the research aims of this thesis to be explored more thoroughly. It is also argued that simpler models that simulate a few key processes that explain the variation in observed data, are more suitable for implementing Integrated Water Resource Management (IWRM) than large comprehensive water quality models. From this research, it is clear that simple statistical models are not adequate for modelling the relationship between flow and water quality, however, relatively simple mechanistic models that simulate a limited number of processes and water quality variables, can provide accurate representations of this relationship. Under conditions where diffuse sources are not a major factor within a catchment, models that omit diffuse sources can obtain realistic simulations of the relationship between flow and water quality. Most of the models investigated in this thesis demonstrate that accurate simulations of the relationships between flow and water quality can be obtained using solely historical monitoring data.
- Full Text:
- Date Issued: 2011
Molecular analysis of genetic diversity in dometicated pigeonpea (Cajanus cajan (L.) Millsp.) and wild relatives
- Authors: Kassa, Mulualem Tamiru
- Date: 2011
- Subjects: Pigeon pea -- Variation Cajanus -- Variation Pigeon pea -- Genetics Cajanus -- Genetics Biodiversity Pigeon pea -- Phylogeny Cajanus -- Phylogeny Plant hybridization Plant diversity Transgenic plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4204 , http://hdl.handle.net/10962/d1003773
- Description: Cajanus cajan (L.) Millsp. (Pigeonpea) belongs to the Leguminosae genus Cajanus which is composed of 34 species. Pigeonpea is the only cultivated member of the genus, while the remaining species are wild relatives belonging mainly to the secondary gene pool. DNA sequence data from the nuclear ITS region and the chloroplast trnL-F spacer were utilized to investigate the phylogenetic relationships between Cajanus and five other allied genera in the subtribe Cajaninae. This study revealed the non-monophyly of Cajanus and Rhynchosia and supported the monophyly of Eriosema and Flemingia, but more sampling ,especially from the large genera of Rhynchosia and Eriosema, is recommend to adequately test the hypothesis of generic monophyly. The phylogenetic relationships within the genus Cajanus resolved Cajanus scarabaeoides (L.) Thouars as the most basal species in the Cajanus clade. The study also utilized Single Nucleotide Polymorphism (SNP) markers derived from low copy orthologous genes and genotyped using the high throughput SNP-OPA Illumina golden gate assay. The aim was to understand phylogenetic and domestication history, genetic structure, patterns of genetic diversity, gene flow and historical hybridization between Cajanus cajan (pigeonpea) and wild relatives. The neighbor-joining tree resolved well-supported clusters, which reflect the distinctiveness of species and congruence with their geographical origin. It supported the ITS based phylogeny and resolved C. scarabaeoides as basal to the Cajanus clade. The phylogenetic signal and genetic signatures revealed insights into the domestication history of pigeonpea. Our results supported Cajanus cajanifolius as the presumed progenitor of pigeonpea and we speculate that for pigeonpea there was a single major domestication event in India. Genetic admixture and historical hybridization were evident between pigeonpea and wild relatives. Abundant allelic variation and genetic diversity was found in the wild relatives, with the exception of wild species from Australia, as compared to the domesticated pigeonpea. There was a reduction of about 75% in genetic polymorphism in domesticated pigeonpea as compared to the wild relatives, indicating a severe “domestication bottleneck” during pigeonpea domestication. We discovered SNP markers associated with disease resistance (NBS-LRR) loci. The SNPs were mined in a comparison of BAC-end sequences (BES) of C. cajan and amplicons of the wild species, C. scarabaeoides. A total of ~3000 SNPs were identified from 304 BES. These SNPs could potentially be used in constructing a genetic map and for marker assisted breeding.
- Full Text:
- Date Issued: 2011
- Authors: Kassa, Mulualem Tamiru
- Date: 2011
- Subjects: Pigeon pea -- Variation Cajanus -- Variation Pigeon pea -- Genetics Cajanus -- Genetics Biodiversity Pigeon pea -- Phylogeny Cajanus -- Phylogeny Plant hybridization Plant diversity Transgenic plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4204 , http://hdl.handle.net/10962/d1003773
- Description: Cajanus cajan (L.) Millsp. (Pigeonpea) belongs to the Leguminosae genus Cajanus which is composed of 34 species. Pigeonpea is the only cultivated member of the genus, while the remaining species are wild relatives belonging mainly to the secondary gene pool. DNA sequence data from the nuclear ITS region and the chloroplast trnL-F spacer were utilized to investigate the phylogenetic relationships between Cajanus and five other allied genera in the subtribe Cajaninae. This study revealed the non-monophyly of Cajanus and Rhynchosia and supported the monophyly of Eriosema and Flemingia, but more sampling ,especially from the large genera of Rhynchosia and Eriosema, is recommend to adequately test the hypothesis of generic monophyly. The phylogenetic relationships within the genus Cajanus resolved Cajanus scarabaeoides (L.) Thouars as the most basal species in the Cajanus clade. The study also utilized Single Nucleotide Polymorphism (SNP) markers derived from low copy orthologous genes and genotyped using the high throughput SNP-OPA Illumina golden gate assay. The aim was to understand phylogenetic and domestication history, genetic structure, patterns of genetic diversity, gene flow and historical hybridization between Cajanus cajan (pigeonpea) and wild relatives. The neighbor-joining tree resolved well-supported clusters, which reflect the distinctiveness of species and congruence with their geographical origin. It supported the ITS based phylogeny and resolved C. scarabaeoides as basal to the Cajanus clade. The phylogenetic signal and genetic signatures revealed insights into the domestication history of pigeonpea. Our results supported Cajanus cajanifolius as the presumed progenitor of pigeonpea and we speculate that for pigeonpea there was a single major domestication event in India. Genetic admixture and historical hybridization were evident between pigeonpea and wild relatives. Abundant allelic variation and genetic diversity was found in the wild relatives, with the exception of wild species from Australia, as compared to the domesticated pigeonpea. There was a reduction of about 75% in genetic polymorphism in domesticated pigeonpea as compared to the wild relatives, indicating a severe “domestication bottleneck” during pigeonpea domestication. We discovered SNP markers associated with disease resistance (NBS-LRR) loci. The SNPs were mined in a comparison of BAC-end sequences (BES) of C. cajan and amplicons of the wild species, C. scarabaeoides. A total of ~3000 SNPs were identified from 304 BES. These SNPs could potentially be used in constructing a genetic map and for marker assisted breeding.
- Full Text:
- Date Issued: 2011
Mutational analysis of the PacC binding sites within the aflR promoter in Aspergillus flavus
- Authors: Suleman, Essa
- Date: 2011
- Subjects: Mutation (Biology) , Genetic regulation , Proteins -- Synthesis , Microbiological synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10336 , http://hdl.handle.net/10948/d1012683 , Mutation (Biology) , Genetic regulation , Proteins -- Synthesis , Microbiological synthesis
- Description: It is generally known that media containing simple sugars (sucrose, glucose) and organic nitrogen sources (ammonium) when buffered to acidic pH stimulates aflatoxin production in Aspergillus flavus & A. parasiticus while lactose, nitrate and an alkaline pH inhibit aflatoxin biosynthesis. It has been shown that pH of the growth medium is the most important regulatory factor for aflatoxin biosynthesis since media containing stimulatory carbon and/or nitrogen sources (sucrose and ammonia) do not enhance aflatoxin (or sterigmatocystin) production at alkaline pH. RNA interference (in A. flavus) of the pH regulatory transcription factor, PacC, resulted in aflatoxin production under acidic and alkaline pH conditions whilst wildtype Aspergillus flavus produced aflatoxins only under acidic conditions. This conclusively proved that PacC negatively regulates aflatoxin production at alkaline pH in A. flavus. However the exact mechanism involved in PacC repression of aflatoxin biosynthesis at alkaline pH still remains unknown. The AflR protein is essential for expression of several genes in the aflatoxin biosynthetic cluster. In the current study, sequence analysis of the aflR promoter indicated the presence of two putative PacC binding sites within the aflR promoter of A. flavus 3357WT located at positions -162 and -487 bp from the start codon. The presence of the PacC binding sites in the aflR promoter indicated a possible link between aflR expression and PacC regulation under alkaline conditions. Thus, in this study, it was hypothesized that at alkaline pH, PacC inhibits aflR expression by binding to one or both of the PacC binding sites within the aflR promoter. This in turn, would result in inhibition of aflatoxin biosynthesis since expression of several aflatoxin biosynthetic pathway genes is dependent on activation by AflR. The aim and objective of this study was to test the validity of this hypothesis i.e. that at alkaline pH PacC binds to one or both of its recognition sites within the aflR promoter thereby inhibiting aflR expression which subsequently would result in inhibition of aflatoxin biosynthesis. This was done by first mutating each individual and then both PacC binding sites in the A. flavus 3357 aflR promoter via Single-Joint PCR (SJ-PCR) and fusing the wildtype and each mutated aflR promoter to the Green Fluorescent Protein (gfp) gene and the trpC terminator to yield a functional expression vector. These constructs were then transformed into A. flavus 3357.5. Positive transformants were confirmed to express GFP by fluorescence microscopy and spectrofluorometry. Quantification of GFP protein levels of the various transformants in this study indicated that PacC negatively regulated aflR promoter activity at alkaline pH. RT-qPCR was performed on positive transformants after growth on SLS medium at acidic and alkaline pH to determine if PacC negatively regulated aflR promoter activity at alkaline pH and to determine whether PacC binds preferentially to one or both recognition sites within the aflR promoter. RT-qPCR analysis suggest that PacC binds non-preferentially to both recognition sites within the aflR promoter on sucrose and lactose media at alkaline pH, although mutation of PacC binding site 2 results in a slightly higher expression compared to mutation of PacC binding site 1. Increasing the concentration of an aflatoxin conducive nitrogen source stimulated aflR promoter activity but this was not sufficient to overcome negative regulation by PacC. It is generally known that repression of aflR expression results in repression of aflatoxin biosynthesis irrespective of pH. The results of this study strongly suggest that PacC negatively regulates aflR promoter activity at alkaline pH by binding to one or both PacC recognition sites within the aflR promoter. Since aflR promoter activity is repressed by PacC at alkaline pH, this substantiates the hypothesis that PacC represses aflatoxin biosynthesis by inhibiting expression of aflR. Furthermore, the results of this study indicated that there may be some PacC protein present in the active form at acidic pH irrespective of the carbon source and nitrogen source used in the growth medium. RT-qPCR analysis indicated that any active PacC present at acidic pH may cause repression of the aflR promoter based on the position of the PacC binding site relative to the aflR start codon, although it appears that PacC may have a higher affinity for PacC binding site 2 (which is closer to the aflR start codon).
- Full Text:
- Date Issued: 2011
- Authors: Suleman, Essa
- Date: 2011
- Subjects: Mutation (Biology) , Genetic regulation , Proteins -- Synthesis , Microbiological synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10336 , http://hdl.handle.net/10948/d1012683 , Mutation (Biology) , Genetic regulation , Proteins -- Synthesis , Microbiological synthesis
- Description: It is generally known that media containing simple sugars (sucrose, glucose) and organic nitrogen sources (ammonium) when buffered to acidic pH stimulates aflatoxin production in Aspergillus flavus & A. parasiticus while lactose, nitrate and an alkaline pH inhibit aflatoxin biosynthesis. It has been shown that pH of the growth medium is the most important regulatory factor for aflatoxin biosynthesis since media containing stimulatory carbon and/or nitrogen sources (sucrose and ammonia) do not enhance aflatoxin (or sterigmatocystin) production at alkaline pH. RNA interference (in A. flavus) of the pH regulatory transcription factor, PacC, resulted in aflatoxin production under acidic and alkaline pH conditions whilst wildtype Aspergillus flavus produced aflatoxins only under acidic conditions. This conclusively proved that PacC negatively regulates aflatoxin production at alkaline pH in A. flavus. However the exact mechanism involved in PacC repression of aflatoxin biosynthesis at alkaline pH still remains unknown. The AflR protein is essential for expression of several genes in the aflatoxin biosynthetic cluster. In the current study, sequence analysis of the aflR promoter indicated the presence of two putative PacC binding sites within the aflR promoter of A. flavus 3357WT located at positions -162 and -487 bp from the start codon. The presence of the PacC binding sites in the aflR promoter indicated a possible link between aflR expression and PacC regulation under alkaline conditions. Thus, in this study, it was hypothesized that at alkaline pH, PacC inhibits aflR expression by binding to one or both of the PacC binding sites within the aflR promoter. This in turn, would result in inhibition of aflatoxin biosynthesis since expression of several aflatoxin biosynthetic pathway genes is dependent on activation by AflR. The aim and objective of this study was to test the validity of this hypothesis i.e. that at alkaline pH PacC binds to one or both of its recognition sites within the aflR promoter thereby inhibiting aflR expression which subsequently would result in inhibition of aflatoxin biosynthesis. This was done by first mutating each individual and then both PacC binding sites in the A. flavus 3357 aflR promoter via Single-Joint PCR (SJ-PCR) and fusing the wildtype and each mutated aflR promoter to the Green Fluorescent Protein (gfp) gene and the trpC terminator to yield a functional expression vector. These constructs were then transformed into A. flavus 3357.5. Positive transformants were confirmed to express GFP by fluorescence microscopy and spectrofluorometry. Quantification of GFP protein levels of the various transformants in this study indicated that PacC negatively regulated aflR promoter activity at alkaline pH. RT-qPCR was performed on positive transformants after growth on SLS medium at acidic and alkaline pH to determine if PacC negatively regulated aflR promoter activity at alkaline pH and to determine whether PacC binds preferentially to one or both recognition sites within the aflR promoter. RT-qPCR analysis suggest that PacC binds non-preferentially to both recognition sites within the aflR promoter on sucrose and lactose media at alkaline pH, although mutation of PacC binding site 2 results in a slightly higher expression compared to mutation of PacC binding site 1. Increasing the concentration of an aflatoxin conducive nitrogen source stimulated aflR promoter activity but this was not sufficient to overcome negative regulation by PacC. It is generally known that repression of aflR expression results in repression of aflatoxin biosynthesis irrespective of pH. The results of this study strongly suggest that PacC negatively regulates aflR promoter activity at alkaline pH by binding to one or both PacC recognition sites within the aflR promoter. Since aflR promoter activity is repressed by PacC at alkaline pH, this substantiates the hypothesis that PacC represses aflatoxin biosynthesis by inhibiting expression of aflR. Furthermore, the results of this study indicated that there may be some PacC protein present in the active form at acidic pH irrespective of the carbon source and nitrogen source used in the growth medium. RT-qPCR analysis indicated that any active PacC present at acidic pH may cause repression of the aflR promoter based on the position of the PacC binding site relative to the aflR start codon, although it appears that PacC may have a higher affinity for PacC binding site 2 (which is closer to the aflR start codon).
- Full Text:
- Date Issued: 2011
My other - my self: post-Cartesian ontological possibilities in the fiction of J M Coetzee
- Authors: Mfune, Damazio Laston
- Date: 2011
- Subjects: Coetzee, J. M., 1940- -- Criticism and interpretation Self in literature Identity (Psychology) in literature Consciousness in literature Intersubjectivity in literature Ontology in literature Metaphysics in literature South African fiction (English) -- 20th century -- History and criticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2246 , http://hdl.handle.net/10962/d1002289
- Description: The central argument of my study is that, among other matters, in his works, J.M. Coetzee could be said to demonstrate that the known Self is an embodied being and is not autonomous. With regard to the latter contention, Coetzee intimates that any two Subjects are implicated in each other’s subjectivities in a reciprocal process that involves what Derek Attridge has called “irruptions of otherness” (2005: xii) into the Subject’s subjectivity. These irruptions, which happen during the encounter, lead to a double loss of autonomy for each Subject and this phenomenon renders the relationship between Subjects non-dichotomus or non-binaric. In other words, the Subject does not produce the contents of his or her consciousness in a sui generis and ex nihilo fashion, and his or her ontological indebtedness to the Other constitutes his or her first loss of autonomy. As for those Others that do possess consciousness, the Subject is implicated in their consciousness and this constitutes the Subject’s second loss of autonomy. These losses counter the near solipsistic Nagelian neo-Cartesianism and paves the way for imagining both intra- and inter-species “intersubjectivity”. It is my view that this double loss of autonomy accounts for the sympathetic and empathetic imagination that we encounter in Coetzee’s fiction. Following Coetzee’s intimations of intersubjectivity through irruptions of otherness, what I see as my contribution to studies on this author’s work through this study is the link I have established between the physicalist strain within the philosophy of mind (whose central thesis is that consciousness is an embodied phenomenon) and a modified Kantian “metaphysics”, especially Immanuel Kant’s conception of concepts as comprising form and content. I have deployed this conception in demonstrating the Subject’s ontological indebtedness to external sources of the content part of consciousness. And, through the Husserlian concept of intentionality, and Kant’s (1929: 27) observation that we cannot have appearances without something that appears, I have linked the Subject to the sources of his or her content and thereby also demonstrated that the Subject is not eternally separated or alienated from those sources. Instead, the Subject is not simply contiguous but coterminous and co-extensive, albeit in a mediated way, with the external sources of the content part of his or her consciousness. Thus, while accepting the thesis of the Other’s radical otherness, I modify the thesis of the Other’s radical exteriority. Ultimately, then, ontologically speaking, the Coetzeean project could be described as one of embodying and grounding the supposedly autonomous, solipsistic and freefloating/disembodied Cartesian Subject. This he does by alerting this Subject, first and foremost, to its embodiedness and, further to that, pointing out its ontological indebtedness to its Others and its implication in the Others’s consciousnesses and so prevent it from continuing with its imperialistic and ecological barbarities. However, ethically speaking, beyond the reciprocal ethics that arises from mutual ontological indebtedness and implication, it is the selflessness that characterises a cruciform logic that comes across as the epitome of Coetzeean ethics.
- Full Text:
- Date Issued: 2011
- Authors: Mfune, Damazio Laston
- Date: 2011
- Subjects: Coetzee, J. M., 1940- -- Criticism and interpretation Self in literature Identity (Psychology) in literature Consciousness in literature Intersubjectivity in literature Ontology in literature Metaphysics in literature South African fiction (English) -- 20th century -- History and criticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2246 , http://hdl.handle.net/10962/d1002289
- Description: The central argument of my study is that, among other matters, in his works, J.M. Coetzee could be said to demonstrate that the known Self is an embodied being and is not autonomous. With regard to the latter contention, Coetzee intimates that any two Subjects are implicated in each other’s subjectivities in a reciprocal process that involves what Derek Attridge has called “irruptions of otherness” (2005: xii) into the Subject’s subjectivity. These irruptions, which happen during the encounter, lead to a double loss of autonomy for each Subject and this phenomenon renders the relationship between Subjects non-dichotomus or non-binaric. In other words, the Subject does not produce the contents of his or her consciousness in a sui generis and ex nihilo fashion, and his or her ontological indebtedness to the Other constitutes his or her first loss of autonomy. As for those Others that do possess consciousness, the Subject is implicated in their consciousness and this constitutes the Subject’s second loss of autonomy. These losses counter the near solipsistic Nagelian neo-Cartesianism and paves the way for imagining both intra- and inter-species “intersubjectivity”. It is my view that this double loss of autonomy accounts for the sympathetic and empathetic imagination that we encounter in Coetzee’s fiction. Following Coetzee’s intimations of intersubjectivity through irruptions of otherness, what I see as my contribution to studies on this author’s work through this study is the link I have established between the physicalist strain within the philosophy of mind (whose central thesis is that consciousness is an embodied phenomenon) and a modified Kantian “metaphysics”, especially Immanuel Kant’s conception of concepts as comprising form and content. I have deployed this conception in demonstrating the Subject’s ontological indebtedness to external sources of the content part of consciousness. And, through the Husserlian concept of intentionality, and Kant’s (1929: 27) observation that we cannot have appearances without something that appears, I have linked the Subject to the sources of his or her content and thereby also demonstrated that the Subject is not eternally separated or alienated from those sources. Instead, the Subject is not simply contiguous but coterminous and co-extensive, albeit in a mediated way, with the external sources of the content part of his or her consciousness. Thus, while accepting the thesis of the Other’s radical otherness, I modify the thesis of the Other’s radical exteriority. Ultimately, then, ontologically speaking, the Coetzeean project could be described as one of embodying and grounding the supposedly autonomous, solipsistic and freefloating/disembodied Cartesian Subject. This he does by alerting this Subject, first and foremost, to its embodiedness and, further to that, pointing out its ontological indebtedness to its Others and its implication in the Others’s consciousnesses and so prevent it from continuing with its imperialistic and ecological barbarities. However, ethically speaking, beyond the reciprocal ethics that arises from mutual ontological indebtedness and implication, it is the selflessness that characterises a cruciform logic that comes across as the epitome of Coetzeean ethics.
- Full Text:
- Date Issued: 2011
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011