Aplousobranch ascidians (Tunicata: Ascidiacea) from Southern Africa
- Authors: Parker-Nance, Shirley
- Date: 2003
- Subjects: Sea squirts -- South Africa -- Classification , Aplousobranchia -- South Africa -- Classification
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11078 , http://hdl.handle.net/10948/311 , Sea squirts -- South Africa -- Classification , Aplousobranchia -- South Africa -- Classification
- Description: The ascidian (subphylum Tunicata: class Ascidiacea) fauna along the southern African coast constitutes an important component of the sessile benthic reef fauna. Little is known of the species composition, biodiversity and distribution of ascidians on southern African intertidal and subtidal reefs. Past research on the ascidian fauna of South Africa was sporadic and limited, with only about one hundred and seventy species recorded during the last one hundred and twenty years. This is the first taxonomic study undertaken by a South African resident scientist. The study focused on six genera in four families (Euherdmaniidae, Polyclinidae, Pseudodistomidae and Didemnidae) belonging to the class Ascidiacea and suborder Aplousobranchia. Five species new to science, two Polyclinum, two Pseudodistoma and one Polysyncraton species are described. New additional information on the distribution of five species previously known to science, including one recorded for the first time along the South African coast, is presented. A literature review and comparison of the taxonomic important characteristics is made of all species known globally for the six genera. These six genera comprise twelve Euherdmania, fifteen Aplidiopsis, forty Polyclinum thirty-one Pseudodistoma, six Atriolum and sixty-eight Polysyncraton species.
- Full Text:
- Date Issued: 2003
- Authors: Parker-Nance, Shirley
- Date: 2003
- Subjects: Sea squirts -- South Africa -- Classification , Aplousobranchia -- South Africa -- Classification
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11078 , http://hdl.handle.net/10948/311 , Sea squirts -- South Africa -- Classification , Aplousobranchia -- South Africa -- Classification
- Description: The ascidian (subphylum Tunicata: class Ascidiacea) fauna along the southern African coast constitutes an important component of the sessile benthic reef fauna. Little is known of the species composition, biodiversity and distribution of ascidians on southern African intertidal and subtidal reefs. Past research on the ascidian fauna of South Africa was sporadic and limited, with only about one hundred and seventy species recorded during the last one hundred and twenty years. This is the first taxonomic study undertaken by a South African resident scientist. The study focused on six genera in four families (Euherdmaniidae, Polyclinidae, Pseudodistomidae and Didemnidae) belonging to the class Ascidiacea and suborder Aplousobranchia. Five species new to science, two Polyclinum, two Pseudodistoma and one Polysyncraton species are described. New additional information on the distribution of five species previously known to science, including one recorded for the first time along the South African coast, is presented. A literature review and comparison of the taxonomic important characteristics is made of all species known globally for the six genera. These six genera comprise twelve Euherdmania, fifteen Aplidiopsis, forty Polyclinum thirty-one Pseudodistoma, six Atriolum and sixty-eight Polysyncraton species.
- Full Text:
- Date Issued: 2003
Sandy beach morphodynamics and macrobenthic communities in temperate, subtropical and tropical regions : a macroecological approach
- Authors: Soares, Alexandre Goulart
- Date: 2003
- Subjects: Seashore ecology , Intertidal ecology , Benthos
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11077 , http://hdl.handle.net/10948/293 , Seashore ecology , Intertidal ecology , Benthos
- Description: A comprehensive study involving 52 microtidal beaches spanning from reflective to dissipative states and located in tropical, subtropical and temperate regions in the Atlantic, Pacific and Indian oceans was carried out to unravel the relative roles of latitude and beach morphodynamics in determining beach macrobenthic species richness, abundance, biomass and mean individual body sizes. Since beach slope is one of the most important factors controlling beach fauna, a model based on beach geometry was applied to the sub-aerial beach deposit to understand the role of physical factors in predicting equilibrium beach slopes. Additionally, it was tested if the occurrence of beach types is related to latitude, and how physical factors change with morphodynamics and latitude. The beach morphometric model makes three assumptions: 1) that the cross-section of a beach deposit is equivalent to a right-angled triangle, 2) that the physical hydrodynamic factors (wave height and spring tide amplitude) and the beach deposit characteristics (sand grain size, beach slope and width) are interchangeable with their geometric counterparts producing an equation to explain beach geometry, and 3) that the predicted beach slope is in equilibrium with the hydrodynamic and sedimentological forces. The equation for predicting beach slope was derived and then tested against field data collected over 52 beaches. The predicted slopes were not significantly different from the observed slopes of the studied natural beaches. However some estimated slopes were different than observed ones. Possible sources of deviation between calculated and observed slopes may be the systematic sampling errors associated with field data. Alternatively, observed slopes could be the result of past hydrodynamic conditions, explaining the differences with the slopes calculated by the beach morphometric model, which assumes a state of equilibrium between beach slope and hydrodynamic conditions. A higher correlation of beach faunal structure with observed slopes rather than with present hydrodynamic conditions could then be indicative of faunal responses to previous hydrodynamic conditions in the same way was the observed slopes. The beach morphometric model could therefore be also useful in predicting faunal responses to changing hydrodynamic conditions. Since the model does not consider wave period, it is concluded that further tests should be done using laboratory and time-series field data and incorporating the role of wave period and beach permeability to ascertain its predictive value. Tropical regions had significantly more beaches in a reflective state than temperate and subtropical regions. Some tropical beaches were fronted by coral reefs, which not only provided coarse carbonate particles, but also additionally dissipated the low wave energy present in these climatic areas. Only one dissipative beach with high energy was found in the tropics, in southeast Madagascar. Temperate and subtropical regions, on the other hand, were dominated by dissipative beaches with medium to fine sands. Open oceanic reflective beaches were non-existent in the subtropics and rare in temperate regions, only occurring in estuaries, enclosed bays or on islands facing the continent. Intermediate beaches were more common in the subtropics but also occurred frequently in the other two regions, having higher energy in temperate regions. Reflective beaches had significantly steeper slopes, coarser sands, smaller waves and shorter swash lengths when compared to dissipative beaches. Additionally, reflective beaches were narrower, had deeper water tables and in consequence shorter saturation zones. Wave periods and surfzone widths were on average larger on dissipative than on reflective beaches. The frequency of occurrence of beach types is therefore related to the climatic signature of each latitude. Mid latitudes would be predicted to have more dissipative beaches with large and long waves because of their proximity to the storm generating belt around 50-60° S - these beaches will have a predominantly finer sands because of the input by rivers in rainy areas. Lower latitudes will have more reflective beaches due to a modal low energy wave climate and also because of the presence of inshore and offshore biotic structures such as coral reefs that dissipate even more the energy from the waves. Tropical and subtropical regions had larger marine species pools than temperate regions. After controlling for biogeographical differences in total species pool, dissipative beaches were on average significantly richer than intermediate and reflective beaches. Crustaceans were also more diverse on dissipative beaches, this difference being not significant for either molluscs or polychaetes. Significant relationships were found between total beach species richness (with or without terrestrial species), crustacean and mollusc species richness with beach morphodynamics as represented by the Dean’s index. Indices incorporating the role of tide, such as BSI, were less important in predicting species richness on the microtidal beaches studied here. Several other physical factors were also significantly correlated with species richness, the most important being the Beach Deposit Index, i.e. BDI, a composite index of beach slope and grain size. The highest correlation was between BDI and relative species richness, i.e. local beach species richness / regional species richness. Total regional marine species richness was higher in Madagascar and North Brazil (tropical beaches) than in Southeast Brazil (subtropical), or the West Coast of South Africa and South-Central Chile (temperate beaches). Not only was the pool of species capable of colonizing beaches richer in tropical and subtropical regions, but also local diversity of each morphodynamic beach type was higher among tropical beaches than their temperate counterparts. Although the results of this study agree with the predictions of the swash exclusion hypotheses, several reflective and intermediate beaches had higher species richness than predicted before and this seems to be linked to the presence of finer sediments and a less turbulent flow for larvae to settle. It is concluded that beach species richness is not necessarily controlled by one major morphodynamic parameter; this control is complex and probably involves multiple interacting biotic (biological interactions) and abiotic (e.g. grain size, wave height, beach slope and width, water table) factors. Species richness seems to be controlled on two different scales: on an evolutionary one where tropical and subtropical regions have higher regional and local diversity due to higher speciation rates; and on an ecological scale, where fine grained sand beaches have their carrying capacity enhanced by higher larval settlement rates and survival of recruits towards adulthood. On average dissipative beaches had higher total densities and macrofaunal abundances than reflective ones. Crustaceans, terrestrial species and cirolanid isopods such as Excirolana spp. were also more abundant on dissipative beaches. The difference was not significant for molluscs and polychaetes. Significant relationships were found between total abundance, crustacean species richness and beach morphodynamics as represented by the Dean’s index. Again, BSI was less important than individual physical factors in determining faunal abundance on the studied microtidal beaches. Several other physical factors were also significantly correlated with abundance, the most important being the Beach Deposit Index (BDI). The highest correlation was between BDI and total macrofaunal abundance. Factors related to surf zone processes, and possibly productivity, were highly correlated with total community, crustaceans, Excirolana spp. and terrestrial species abundances. The abundances of polychaetes and molluscs were better correlated with factors related to the beach deposit (BDI, slope, grain size and water table depth). Significant differences were observed between latitudinal regions for the average beach and also for each beach type. In general temperate beaches harboured larger community densities and abundances, and also crustacean, Excirolana spp. and terrestrial abundances. Mollusc and polychaete abundances were larger on subtropical and tropical beaches. The control of abundance on a sandy beach is complex and involves multifactorial processes at evolutionary and ecological scales. At evolutionary scales animals seem to attain higher abundances in the region where they first evolved, e.g. amphipods and isopods in temperate regions. At ecological scales they attain higher abundances where productivity is higher (total macrofaunal, crustaceans, Excirolana spp., terrestrial spp.) or where the settlement environment is more benign (molluscs and polychaetes). Dissipative beaches supported larger average and total community biomass than reflective beaches. Crustaceans, terrestrial species and cirolanid isopods such as Excirolana spp. also had larger biomass on dissipative beaches. The difference was not significant for molluscs and polychaetes. Significant relationships were found between the biomass of community and taxonomic groups with beach morphodynamics as represented by the Dean’s morphodynamic index. On the microtidal beaches studied here, BSI was less important than other morphodynamic indices and single physical factors in determining faunal biomass and mean individual body size. Surf zone characteristics such as wave height, period and surf zone width had the highest correlations with community, crustacean.
- Full Text:
- Date Issued: 2003
- Authors: Soares, Alexandre Goulart
- Date: 2003
- Subjects: Seashore ecology , Intertidal ecology , Benthos
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11077 , http://hdl.handle.net/10948/293 , Seashore ecology , Intertidal ecology , Benthos
- Description: A comprehensive study involving 52 microtidal beaches spanning from reflective to dissipative states and located in tropical, subtropical and temperate regions in the Atlantic, Pacific and Indian oceans was carried out to unravel the relative roles of latitude and beach morphodynamics in determining beach macrobenthic species richness, abundance, biomass and mean individual body sizes. Since beach slope is one of the most important factors controlling beach fauna, a model based on beach geometry was applied to the sub-aerial beach deposit to understand the role of physical factors in predicting equilibrium beach slopes. Additionally, it was tested if the occurrence of beach types is related to latitude, and how physical factors change with morphodynamics and latitude. The beach morphometric model makes three assumptions: 1) that the cross-section of a beach deposit is equivalent to a right-angled triangle, 2) that the physical hydrodynamic factors (wave height and spring tide amplitude) and the beach deposit characteristics (sand grain size, beach slope and width) are interchangeable with their geometric counterparts producing an equation to explain beach geometry, and 3) that the predicted beach slope is in equilibrium with the hydrodynamic and sedimentological forces. The equation for predicting beach slope was derived and then tested against field data collected over 52 beaches. The predicted slopes were not significantly different from the observed slopes of the studied natural beaches. However some estimated slopes were different than observed ones. Possible sources of deviation between calculated and observed slopes may be the systematic sampling errors associated with field data. Alternatively, observed slopes could be the result of past hydrodynamic conditions, explaining the differences with the slopes calculated by the beach morphometric model, which assumes a state of equilibrium between beach slope and hydrodynamic conditions. A higher correlation of beach faunal structure with observed slopes rather than with present hydrodynamic conditions could then be indicative of faunal responses to previous hydrodynamic conditions in the same way was the observed slopes. The beach morphometric model could therefore be also useful in predicting faunal responses to changing hydrodynamic conditions. Since the model does not consider wave period, it is concluded that further tests should be done using laboratory and time-series field data and incorporating the role of wave period and beach permeability to ascertain its predictive value. Tropical regions had significantly more beaches in a reflective state than temperate and subtropical regions. Some tropical beaches were fronted by coral reefs, which not only provided coarse carbonate particles, but also additionally dissipated the low wave energy present in these climatic areas. Only one dissipative beach with high energy was found in the tropics, in southeast Madagascar. Temperate and subtropical regions, on the other hand, were dominated by dissipative beaches with medium to fine sands. Open oceanic reflective beaches were non-existent in the subtropics and rare in temperate regions, only occurring in estuaries, enclosed bays or on islands facing the continent. Intermediate beaches were more common in the subtropics but also occurred frequently in the other two regions, having higher energy in temperate regions. Reflective beaches had significantly steeper slopes, coarser sands, smaller waves and shorter swash lengths when compared to dissipative beaches. Additionally, reflective beaches were narrower, had deeper water tables and in consequence shorter saturation zones. Wave periods and surfzone widths were on average larger on dissipative than on reflective beaches. The frequency of occurrence of beach types is therefore related to the climatic signature of each latitude. Mid latitudes would be predicted to have more dissipative beaches with large and long waves because of their proximity to the storm generating belt around 50-60° S - these beaches will have a predominantly finer sands because of the input by rivers in rainy areas. Lower latitudes will have more reflective beaches due to a modal low energy wave climate and also because of the presence of inshore and offshore biotic structures such as coral reefs that dissipate even more the energy from the waves. Tropical and subtropical regions had larger marine species pools than temperate regions. After controlling for biogeographical differences in total species pool, dissipative beaches were on average significantly richer than intermediate and reflective beaches. Crustaceans were also more diverse on dissipative beaches, this difference being not significant for either molluscs or polychaetes. Significant relationships were found between total beach species richness (with or without terrestrial species), crustacean and mollusc species richness with beach morphodynamics as represented by the Dean’s index. Indices incorporating the role of tide, such as BSI, were less important in predicting species richness on the microtidal beaches studied here. Several other physical factors were also significantly correlated with species richness, the most important being the Beach Deposit Index, i.e. BDI, a composite index of beach slope and grain size. The highest correlation was between BDI and relative species richness, i.e. local beach species richness / regional species richness. Total regional marine species richness was higher in Madagascar and North Brazil (tropical beaches) than in Southeast Brazil (subtropical), or the West Coast of South Africa and South-Central Chile (temperate beaches). Not only was the pool of species capable of colonizing beaches richer in tropical and subtropical regions, but also local diversity of each morphodynamic beach type was higher among tropical beaches than their temperate counterparts. Although the results of this study agree with the predictions of the swash exclusion hypotheses, several reflective and intermediate beaches had higher species richness than predicted before and this seems to be linked to the presence of finer sediments and a less turbulent flow for larvae to settle. It is concluded that beach species richness is not necessarily controlled by one major morphodynamic parameter; this control is complex and probably involves multiple interacting biotic (biological interactions) and abiotic (e.g. grain size, wave height, beach slope and width, water table) factors. Species richness seems to be controlled on two different scales: on an evolutionary one where tropical and subtropical regions have higher regional and local diversity due to higher speciation rates; and on an ecological scale, where fine grained sand beaches have their carrying capacity enhanced by higher larval settlement rates and survival of recruits towards adulthood. On average dissipative beaches had higher total densities and macrofaunal abundances than reflective ones. Crustaceans, terrestrial species and cirolanid isopods such as Excirolana spp. were also more abundant on dissipative beaches. The difference was not significant for molluscs and polychaetes. Significant relationships were found between total abundance, crustacean species richness and beach morphodynamics as represented by the Dean’s index. Again, BSI was less important than individual physical factors in determining faunal abundance on the studied microtidal beaches. Several other physical factors were also significantly correlated with abundance, the most important being the Beach Deposit Index (BDI). The highest correlation was between BDI and total macrofaunal abundance. Factors related to surf zone processes, and possibly productivity, were highly correlated with total community, crustaceans, Excirolana spp. and terrestrial species abundances. The abundances of polychaetes and molluscs were better correlated with factors related to the beach deposit (BDI, slope, grain size and water table depth). Significant differences were observed between latitudinal regions for the average beach and also for each beach type. In general temperate beaches harboured larger community densities and abundances, and also crustacean, Excirolana spp. and terrestrial abundances. Mollusc and polychaete abundances were larger on subtropical and tropical beaches. The control of abundance on a sandy beach is complex and involves multifactorial processes at evolutionary and ecological scales. At evolutionary scales animals seem to attain higher abundances in the region where they first evolved, e.g. amphipods and isopods in temperate regions. At ecological scales they attain higher abundances where productivity is higher (total macrofaunal, crustaceans, Excirolana spp., terrestrial spp.) or where the settlement environment is more benign (molluscs and polychaetes). Dissipative beaches supported larger average and total community biomass than reflective beaches. Crustaceans, terrestrial species and cirolanid isopods such as Excirolana spp. also had larger biomass on dissipative beaches. The difference was not significant for molluscs and polychaetes. Significant relationships were found between the biomass of community and taxonomic groups with beach morphodynamics as represented by the Dean’s morphodynamic index. On the microtidal beaches studied here, BSI was less important than other morphodynamic indices and single physical factors in determining faunal biomass and mean individual body size. Surf zone characteristics such as wave height, period and surf zone width had the highest correlations with community, crustacean.
- Full Text:
- Date Issued: 2003
The effects of goat browsing on ecosystem patterns and processes in succulent thicket, South Africa
- Lechmere-Oertel, Richard Geoffrey
- Authors: Lechmere-Oertel, Richard Geoffrey
- Date: 2003
- Subjects: Succulent plants -- South Africa -- Eastern Cape , Landscape ecology -- South Africa -- Eastern Cape , Goats -- Feeding and feeds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11074 , http://hdl.handle.net/10948/309 , Succulent plants -- South Africa -- Eastern Cape , Landscape ecology -- South Africa -- Eastern Cape , Goats -- Feeding and feeds
- Description: Transformation in the arid succulent thicket of the Eastern Cape of South Africa in response to unsustainable livestock production has been widespread, with less than 10 percent remaining intact. Transformation in succulent thicket has resulted in large areas of dense thicket (comprising a two-phase mosaic of perennial-vegetated patches separated by animal paths and bare patches) being replaced with a ‘pseudo-savanna’ of remnant canopy trees with a structurally simple field layer of ephemeral and short- lived perennial grasses and forbs. There is an extensive literature describing the transformation of succulent thicket, with many speculative statements about the underlying mechanisms of transformation. The central focus of this study was to improve our mechanistic understanding of transformation in succulent thicket using field experiments. Hopefully these results will set another foundation upon which future management of succulent thicket can be improved and large-scale restoration initiated. This study comprises four themes that are linked to the concept of landscape function. The central premise of landscape function is that functional landscapes have mechanisms that capture and retain scarce resources. Conversely, as landscapes become increasingly dysfunctional, so these mechanisms become disrupted. In succulent thicket, dysfunctio n appears to be linked to the reduced ability to harvest water, cycle carbon and a loss of organic carbon. In this thesis I examined some of the key processes that influence water and organic carbon fluxes: perennial vegetation cover, soil fertility, litter fall and decomposition, and runoff and soil erosion. The experimental design that was used for all this work was a factorial ANOVA based on replicated fenceline contrasts that reflect differences in long-term management history. The main objectives of this thesis were to: quantify the patterns of transformation in an arid form of succulent thicket, including changes in the biomass, cover and structure of the dominant vegetation guilds; test the stability of the transformed succulent thicket ecosystem to show whether it is a new stable state or an intermediate stage in a trajectory towards a highly desertified state where only the ephemeral grasses and forbs persist; describe and compare soil fertility across transformation contrasts, concentrating on changes in the spatial patterns of soil resources and the ability of the soil to harvest precipitation; to compare litter fall and decomposition of leaf material from the dominant plants in intact and transformed succulent thicket; to quantify and compare run-off and erosion from run-off plots in intact and transformed succulent thicket. Transformation and stability I quantified the changes in plant diversity, physiognomy and biomass that occur across transformation contrasts. Thicket transformation results in a significant loss of plant diversity and functional types. There is also a significant reduction in the biomass (c. 80 t.ha-1) and structural complexity of the vegetation, both vertically and horizontally. These results were interpreted in terms of their implications for ecosystem functioning and stability. To test the stability of the transformed succulent thicket I used aerial photographs and ground-truthing to track the survivorship of canopy trees over 60 years in pseudo-savanna landscapes. I also measured seedling establishment in different habitats. I show that the pseudo-savanna is not a stable state owing to ongoing adult mortality and no recruitment of canopy trees. Soil fertility and water status I hypothesised that the above-ground changes in ve getation would be accompanied by similar trends in the pattern and levels of soil nutrient resources and the ability of the landscape to harvest precipitation. I compared soil fertility (organic carbon, available nitrogen and phosphorus), texture, matric potential, and surface micro-topography in the two main micro- habitats on either side of the replicated fenceline contrasts. The results show that intact spekboom thicket has a distinct spatial pattern of soil fertility where nutrients and organic carbon are concentrated under the patches of perennial shrubs, compared to under canopy trees and open spaces. Transformation results in a significant homogenisation out of this pattern and an overall reduction in the fertility of the landscape. The proportion of the landscape surface that would promote infiltration of water decreases from 60 – 0.6 percent. Soil moisture retention (matric potential) also decreases with transformation. I interpreted these patterns in terms of the ability of the landscape to harvest and release water after rainfall events. Litter fall and decomposition Surface litter and soil organic matter are critical components to wooded ecosystems; contributing to several ecosystem functions. The rates of litter fall and decomposition are ratelimiting steps in nutrient cycling and incorporation of organic matter into the soil. The ecological mechanisms behind the collapse of succulent thicket in the face of domestic herbivory are not fully understood, but are believed to include the breakdown of several ecosystem processes, including litter fall and decomposition. I quantified the changes in litter fall and litter decomposition of four of the dominant perennial woody plants (Euclea undulata, Pappea capensis, Portulacaria afra and Rhus longispina) across the replicated fenceline. Litter fall was measured over 14 months using mesh traps. Decomposition was measured over 15 months using a combination of litterbags and unprotected leaf packs. I also quantified soil microclimate during the experimental period; hypothesising that transformation would lead to soil conditions less amenable for biotic activity. Litter fall in succulent thicket was very high for a semi-arid system, comparing more to temperate forests. The leaf-succulent P. afra contributed the largest single component of the total litter production at a landscape scale. The effect of transformation on litter fall was species specific. Deep-rooted or drought-adapted species showed no change in litter yield with transformation; shallow-rooted species showed a significant decrease. There were few significant differences in decomposition rates across the transformation gradient and between litter types. Portulacaria afra litter had the steepest rate of mass loss, and was most affected by transformation. The more recalcitrant (high C:N ratio) leaves of P. capensis remained largely unaffected by transformation. These results indicate the critical role of the perennial vegetation in incorporating organic carbon into the soil. Transformation of succulent thicket leads to a disruption of the flow of carbon into the soil, reinforcing the cycle of transformation through reduced fertility. Rehabilitation of this ecosystem will require the active establishment of species, such as P. afra, that will restart the flow of carbon into the soil. Run-off & Erosion The landscape function model predicts that functional semi-arid shrublands efficiently conserve limiting resources such as water and water-bourn sediments (soil and organic matter). As these rangelands become transformed through unsustainable livestock production, so their ability to conserve resources decreases. The primary determinant of landscape function and conservation of resources appears to be the proportional cover of perennial vegetation. I hypothesised that the switch from a two-phase mosaic dominated by perennial succulent and woody shrubs to a single phase system dominated by an ephemeral field layer would be accompanied by disruption of the mechanisms that conserve resources. Specifically, I tested the hypothesis that transformation of succulent thicket increases runoff volume, sediment concentration of runoff, soil erosion and loss of organic matter at a patch scale (c. 100 m2). Runoff and water-borne sediment were measured from runoff plots established across replicated fenceline contrasts. Data were collected from eight extreme weather events over two years. There were no significant differences between runoff and erosion across the transformation contrast, as each extreme weather event was unique in terms of its runoff response. The transformed runoff plots alone also gave inconsistent results, largely due to differences in the cover of ephemeral forbs and weakly perennial grasses. Runoff and erosion were not predictable from the data across the transformation gradient due to complex interactions between the nature of the above-ground vegetation, soil micro-topography and land use history. The results highlighted the need for longer-term catchment experiments to generate a predictive understanding of the effect of transformation on runoff and erosion in succulent thicket.
- Full Text:
- Date Issued: 2003
- Authors: Lechmere-Oertel, Richard Geoffrey
- Date: 2003
- Subjects: Succulent plants -- South Africa -- Eastern Cape , Landscape ecology -- South Africa -- Eastern Cape , Goats -- Feeding and feeds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11074 , http://hdl.handle.net/10948/309 , Succulent plants -- South Africa -- Eastern Cape , Landscape ecology -- South Africa -- Eastern Cape , Goats -- Feeding and feeds
- Description: Transformation in the arid succulent thicket of the Eastern Cape of South Africa in response to unsustainable livestock production has been widespread, with less than 10 percent remaining intact. Transformation in succulent thicket has resulted in large areas of dense thicket (comprising a two-phase mosaic of perennial-vegetated patches separated by animal paths and bare patches) being replaced with a ‘pseudo-savanna’ of remnant canopy trees with a structurally simple field layer of ephemeral and short- lived perennial grasses and forbs. There is an extensive literature describing the transformation of succulent thicket, with many speculative statements about the underlying mechanisms of transformation. The central focus of this study was to improve our mechanistic understanding of transformation in succulent thicket using field experiments. Hopefully these results will set another foundation upon which future management of succulent thicket can be improved and large-scale restoration initiated. This study comprises four themes that are linked to the concept of landscape function. The central premise of landscape function is that functional landscapes have mechanisms that capture and retain scarce resources. Conversely, as landscapes become increasingly dysfunctional, so these mechanisms become disrupted. In succulent thicket, dysfunctio n appears to be linked to the reduced ability to harvest water, cycle carbon and a loss of organic carbon. In this thesis I examined some of the key processes that influence water and organic carbon fluxes: perennial vegetation cover, soil fertility, litter fall and decomposition, and runoff and soil erosion. The experimental design that was used for all this work was a factorial ANOVA based on replicated fenceline contrasts that reflect differences in long-term management history. The main objectives of this thesis were to: quantify the patterns of transformation in an arid form of succulent thicket, including changes in the biomass, cover and structure of the dominant vegetation guilds; test the stability of the transformed succulent thicket ecosystem to show whether it is a new stable state or an intermediate stage in a trajectory towards a highly desertified state where only the ephemeral grasses and forbs persist; describe and compare soil fertility across transformation contrasts, concentrating on changes in the spatial patterns of soil resources and the ability of the soil to harvest precipitation; to compare litter fall and decomposition of leaf material from the dominant plants in intact and transformed succulent thicket; to quantify and compare run-off and erosion from run-off plots in intact and transformed succulent thicket. Transformation and stability I quantified the changes in plant diversity, physiognomy and biomass that occur across transformation contrasts. Thicket transformation results in a significant loss of plant diversity and functional types. There is also a significant reduction in the biomass (c. 80 t.ha-1) and structural complexity of the vegetation, both vertically and horizontally. These results were interpreted in terms of their implications for ecosystem functioning and stability. To test the stability of the transformed succulent thicket I used aerial photographs and ground-truthing to track the survivorship of canopy trees over 60 years in pseudo-savanna landscapes. I also measured seedling establishment in different habitats. I show that the pseudo-savanna is not a stable state owing to ongoing adult mortality and no recruitment of canopy trees. Soil fertility and water status I hypothesised that the above-ground changes in ve getation would be accompanied by similar trends in the pattern and levels of soil nutrient resources and the ability of the landscape to harvest precipitation. I compared soil fertility (organic carbon, available nitrogen and phosphorus), texture, matric potential, and surface micro-topography in the two main micro- habitats on either side of the replicated fenceline contrasts. The results show that intact spekboom thicket has a distinct spatial pattern of soil fertility where nutrients and organic carbon are concentrated under the patches of perennial shrubs, compared to under canopy trees and open spaces. Transformation results in a significant homogenisation out of this pattern and an overall reduction in the fertility of the landscape. The proportion of the landscape surface that would promote infiltration of water decreases from 60 – 0.6 percent. Soil moisture retention (matric potential) also decreases with transformation. I interpreted these patterns in terms of the ability of the landscape to harvest and release water after rainfall events. Litter fall and decomposition Surface litter and soil organic matter are critical components to wooded ecosystems; contributing to several ecosystem functions. The rates of litter fall and decomposition are ratelimiting steps in nutrient cycling and incorporation of organic matter into the soil. The ecological mechanisms behind the collapse of succulent thicket in the face of domestic herbivory are not fully understood, but are believed to include the breakdown of several ecosystem processes, including litter fall and decomposition. I quantified the changes in litter fall and litter decomposition of four of the dominant perennial woody plants (Euclea undulata, Pappea capensis, Portulacaria afra and Rhus longispina) across the replicated fenceline. Litter fall was measured over 14 months using mesh traps. Decomposition was measured over 15 months using a combination of litterbags and unprotected leaf packs. I also quantified soil microclimate during the experimental period; hypothesising that transformation would lead to soil conditions less amenable for biotic activity. Litter fall in succulent thicket was very high for a semi-arid system, comparing more to temperate forests. The leaf-succulent P. afra contributed the largest single component of the total litter production at a landscape scale. The effect of transformation on litter fall was species specific. Deep-rooted or drought-adapted species showed no change in litter yield with transformation; shallow-rooted species showed a significant decrease. There were few significant differences in decomposition rates across the transformation gradient and between litter types. Portulacaria afra litter had the steepest rate of mass loss, and was most affected by transformation. The more recalcitrant (high C:N ratio) leaves of P. capensis remained largely unaffected by transformation. These results indicate the critical role of the perennial vegetation in incorporating organic carbon into the soil. Transformation of succulent thicket leads to a disruption of the flow of carbon into the soil, reinforcing the cycle of transformation through reduced fertility. Rehabilitation of this ecosystem will require the active establishment of species, such as P. afra, that will restart the flow of carbon into the soil. Run-off & Erosion The landscape function model predicts that functional semi-arid shrublands efficiently conserve limiting resources such as water and water-bourn sediments (soil and organic matter). As these rangelands become transformed through unsustainable livestock production, so their ability to conserve resources decreases. The primary determinant of landscape function and conservation of resources appears to be the proportional cover of perennial vegetation. I hypothesised that the switch from a two-phase mosaic dominated by perennial succulent and woody shrubs to a single phase system dominated by an ephemeral field layer would be accompanied by disruption of the mechanisms that conserve resources. Specifically, I tested the hypothesis that transformation of succulent thicket increases runoff volume, sediment concentration of runoff, soil erosion and loss of organic matter at a patch scale (c. 100 m2). Runoff and water-borne sediment were measured from runoff plots established across replicated fenceline contrasts. Data were collected from eight extreme weather events over two years. There were no significant differences between runoff and erosion across the transformation contrast, as each extreme weather event was unique in terms of its runoff response. The transformed runoff plots alone also gave inconsistent results, largely due to differences in the cover of ephemeral forbs and weakly perennial grasses. Runoff and erosion were not predictable from the data across the transformation gradient due to complex interactions between the nature of the above-ground vegetation, soil micro-topography and land use history. The results highlighted the need for longer-term catchment experiments to generate a predictive understanding of the effect of transformation on runoff and erosion in succulent thicket.
- Full Text:
- Date Issued: 2003
A comparison of programming notations for a tertiary level introductory programming course
- Authors: Cilliers, Charmain Barbara
- Date: 2004
- Subjects: Computer programming -- Study and teaching (Higher) -- South Africa , Computer programmers -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11093 , http://hdl.handle.net/10948/d1019679
- Description: Increasing pressure from national government to improve throughput at South African tertiary education institutions presents challenges to educators of introductory programming courses. In response, educators must adopt effective methods and strategies that encourage novice programmers to be successful in such courses. An approach that seeks to increase and maintain satisfactory throughput is the modification of the teaching model in these courses by adjusting presentation techniques. This thesis investigates the effect of integrating an experimental iconic programming notation and associated development environment with existing conventional textual technological support in the teaching model of a tertiary level introductory programming course. The investigation compares the performance achievement of novice programmers using only conventional textual technological support with that of novice programmers using the integrated iconic and conventional textual technological support. In preparation for the investigation, interpretation of existing knowledge on the behaviour of novice programmers while learning to program results in a novel framework of eight novice programmer requirements for technological support in an introductory programming course. This framework is applied in the examination of existing categories of technological support as well as in the design of new technological support for novice programmers learning to program. It thus provides information for the selection of existing and the design of new introductory programming technological support. The findings of the investigation suggest strong evidence that performance achievement of novice programmers in a tertiary level introductory programming course improves significantly with the inclusion of iconic technological support in the teaching model. The benefits are particularly evident in the portion of the novice programmer population who have been identified as being at risk of being successful in the course. Novice programmers identified as being at risk perform substantially better when using iconic technological support concurrently with conventional textual technological support than their equals who use only the latter form. Considerably more at risk novice programmers using the integrated form of technological support are in fact successful in the introductory programming course when compared with their counterparts who use conventional textual technological support only. The contributions of this thesis address deficiencies existing in current documented research. These contributions are primarily apparent in a number of distinct areas, namely: • formalisation of a novel framework of novice programmer requirements for technological support in an introductory programming course; • application of the framework as a formal evaluation technique; • application of the framework in the design of a visual iconic programming notation and development environment; • enhancement of existing empirical evidence and experimental research methodology typically applied to studies in programming; as well as • a proposal for a modified introductory programming course teaching model. The thesis has effectively applied substantial existing research on the cognitive model of the novice programmer as well as that on experimental technological support. The increase of throughput to a recommended rate of 75 percent in the tertiary level introductory programming course at the University of Port Elizabeth is attributed solely to the incorporation of iconic technological support in the teaching model of the course.
- Full Text:
- Date Issued: 2004
- Authors: Cilliers, Charmain Barbara
- Date: 2004
- Subjects: Computer programming -- Study and teaching (Higher) -- South Africa , Computer programmers -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11093 , http://hdl.handle.net/10948/d1019679
- Description: Increasing pressure from national government to improve throughput at South African tertiary education institutions presents challenges to educators of introductory programming courses. In response, educators must adopt effective methods and strategies that encourage novice programmers to be successful in such courses. An approach that seeks to increase and maintain satisfactory throughput is the modification of the teaching model in these courses by adjusting presentation techniques. This thesis investigates the effect of integrating an experimental iconic programming notation and associated development environment with existing conventional textual technological support in the teaching model of a tertiary level introductory programming course. The investigation compares the performance achievement of novice programmers using only conventional textual technological support with that of novice programmers using the integrated iconic and conventional textual technological support. In preparation for the investigation, interpretation of existing knowledge on the behaviour of novice programmers while learning to program results in a novel framework of eight novice programmer requirements for technological support in an introductory programming course. This framework is applied in the examination of existing categories of technological support as well as in the design of new technological support for novice programmers learning to program. It thus provides information for the selection of existing and the design of new introductory programming technological support. The findings of the investigation suggest strong evidence that performance achievement of novice programmers in a tertiary level introductory programming course improves significantly with the inclusion of iconic technological support in the teaching model. The benefits are particularly evident in the portion of the novice programmer population who have been identified as being at risk of being successful in the course. Novice programmers identified as being at risk perform substantially better when using iconic technological support concurrently with conventional textual technological support than their equals who use only the latter form. Considerably more at risk novice programmers using the integrated form of technological support are in fact successful in the introductory programming course when compared with their counterparts who use conventional textual technological support only. The contributions of this thesis address deficiencies existing in current documented research. These contributions are primarily apparent in a number of distinct areas, namely: • formalisation of a novel framework of novice programmer requirements for technological support in an introductory programming course; • application of the framework as a formal evaluation technique; • application of the framework in the design of a visual iconic programming notation and development environment; • enhancement of existing empirical evidence and experimental research methodology typically applied to studies in programming; as well as • a proposal for a modified introductory programming course teaching model. The thesis has effectively applied substantial existing research on the cognitive model of the novice programmer as well as that on experimental technological support. The increase of throughput to a recommended rate of 75 percent in the tertiary level introductory programming course at the University of Port Elizabeth is attributed solely to the incorporation of iconic technological support in the teaching model of the course.
- Full Text:
- Date Issued: 2004
On the mocvd growth of ZnO
- Authors: Pagni, Olivier Demeno
- Date: 2004
- Subjects: Zinc oxide thin films , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11075 , http://hdl.handle.net/10948/382 , Zinc oxide thin films , Metal organic chemical vapor deposition
- Description: Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.
- Full Text:
- Date Issued: 2004
- Authors: Pagni, Olivier Demeno
- Date: 2004
- Subjects: Zinc oxide thin films , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11075 , http://hdl.handle.net/10948/382 , Zinc oxide thin films , Metal organic chemical vapor deposition
- Description: Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.
- Full Text:
- Date Issued: 2004
The concentration of ten metals in the tissues of shark species Squalus megalops and Mustelus mustelus (Chondrichthyes) occuring along the Southeastern coast of South Africa
- Erasmus, Christina Petronella
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on. , Marine pollutio -- South Africa.
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11095 , http://hdl.handle.net/10948/d1019683
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on. , Marine pollutio -- South Africa.
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11095 , http://hdl.handle.net/10948/d1019683
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
The concentration of ten metals in the tissues of shark species Squalus megalops and Mustelus mustelus (chondrichthyes) occuring along the Southeastern coast of South Africa
- Erasmus, Christina Petronella
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on , Marine pollution -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11085 , http://hdl.handle.net/10948/328 , Sharks -- South Africa -- Effect of metals on , Marine pollution -- South Africa
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on , Marine pollution -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11085 , http://hdl.handle.net/10948/328 , Sharks -- South Africa -- Effect of metals on , Marine pollution -- South Africa
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
The effects of selected proline-based cyclic dipeptides on growth and induction of apoptosis in cancer cells
- Authors: Brauns, Seth Clint Aron
- Date: 2004
- Subjects: Cyclic peptides , Antineoplastic agents -- Testing , Apoptosis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11088 , http://hdl.handle.net/10948/396 , Cyclic peptides , Antineoplastic agents -- Testing , Apoptosis
- Description: An increasing number of cyclic dipeptides (CDPs) have been shown to exhibit important biological activity including antifungal, antibacterial, anticonvulsant and immunomodulatory activity. Furthermore, some CDP derivatives have been shown to exhibit antitumour activity in vitro and in vivo. Several proline-based CDPs that exhibit biological activity have been detected in various processed foods and beverages. In the present study, the potential of seven proline-based CDPs to inhibit cancer cell growth was investigated in HT-29 (colon), HeLa (cervical), MCF-7 (breast) and WHCO3 (oesophageal) cancer cell lines. The CDPs used in this study were cyclo(Phe-Pro), cyclo(Tyr-Pro), cyclo(Gly-Pro), cyclo(Pro- Pro), cyclo(His-Pro), cyclo(Leu-Pro) and cyclo(Thr-Pro). The sulforhodamine B (SRB) cell growth assay was used in an initial screening phase to investigate the effects of the CDPs in HT-29, HeLa and MCF-7 cells. After exposing the cells to 10mM of the respective CDPs for 48 hours, the SRB assay results showed that only cyclo(Phe-Pro) exhibited more than 50% growth inhibition (p<0.01) in the three cell lines. The other CDPs showed comparatively marginal growth-inhibitory effects, except for cyclo(Tyr-Pro), which exhibited a pronounced effect in MCF-7 cells compared to HT-29 and HeLa cells. The MTT assay was used to confirm the SRB assay results for cyclo(Phe-Pro) and cyclo(Tyr-Pro), extending the investigation to the use of the fourth cell line WHCO3 and using a longer exposure time of 72 hours. The MTT assay demonstrated a dosedependent (0.008-10 mM) growth inhibition by cyclo(Phe-Pro) with an IC50 value of 4.04 ± 1.15 mM for HT-29 cells. Cyclo(Phe-Pro) was subsequently used to investigate whether the growth-inhibitory effects of this CDP were related to the induction of apoptosis in HT-29 cells. Hoechst 33342 staining showed that 5mM cyclo(Phe-Pro) induced characteristic chromatin condensation and nuclear fragmentation in 18.3 ± 2.8% (p<0.01) of HT-29 cells after 72 hours. Furthermore, annexin V binding revealed that HT-29 cells treated with 5 mM cyclo(Phe-Pro) displayed phosphatidylserine externalization after 48 hours. In addition, it was shown that 10 mM cyclo(Phe-Pro) induced poly(ADP-ribose)polymerase PARP cleavage, one of the hallmark events of apoptosis. The use of the broad-range caspase inhibitor Z-VAD-FMK, showed that this PARP cleavage was caspase-dependent, which in turn was confirmed by demonstrating an increase in caspase-3 activity (p<0.01) in cyclo(Phe- Pro)-treated HT-29 cells. In conclusion, these findings demonstrate that cyclo(Phe-Pro) inhibited the growth of HT- 29, MCF-7, HeLa and WHCO3 cells, and induced apoptosis in HT-29 colon cancer cells, suggesting the potential antitumour activity of cyclo(Phe-Pro)-related CDPs.
- Full Text:
- Date Issued: 2004
- Authors: Brauns, Seth Clint Aron
- Date: 2004
- Subjects: Cyclic peptides , Antineoplastic agents -- Testing , Apoptosis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11088 , http://hdl.handle.net/10948/396 , Cyclic peptides , Antineoplastic agents -- Testing , Apoptosis
- Description: An increasing number of cyclic dipeptides (CDPs) have been shown to exhibit important biological activity including antifungal, antibacterial, anticonvulsant and immunomodulatory activity. Furthermore, some CDP derivatives have been shown to exhibit antitumour activity in vitro and in vivo. Several proline-based CDPs that exhibit biological activity have been detected in various processed foods and beverages. In the present study, the potential of seven proline-based CDPs to inhibit cancer cell growth was investigated in HT-29 (colon), HeLa (cervical), MCF-7 (breast) and WHCO3 (oesophageal) cancer cell lines. The CDPs used in this study were cyclo(Phe-Pro), cyclo(Tyr-Pro), cyclo(Gly-Pro), cyclo(Pro- Pro), cyclo(His-Pro), cyclo(Leu-Pro) and cyclo(Thr-Pro). The sulforhodamine B (SRB) cell growth assay was used in an initial screening phase to investigate the effects of the CDPs in HT-29, HeLa and MCF-7 cells. After exposing the cells to 10mM of the respective CDPs for 48 hours, the SRB assay results showed that only cyclo(Phe-Pro) exhibited more than 50% growth inhibition (p<0.01) in the three cell lines. The other CDPs showed comparatively marginal growth-inhibitory effects, except for cyclo(Tyr-Pro), which exhibited a pronounced effect in MCF-7 cells compared to HT-29 and HeLa cells. The MTT assay was used to confirm the SRB assay results for cyclo(Phe-Pro) and cyclo(Tyr-Pro), extending the investigation to the use of the fourth cell line WHCO3 and using a longer exposure time of 72 hours. The MTT assay demonstrated a dosedependent (0.008-10 mM) growth inhibition by cyclo(Phe-Pro) with an IC50 value of 4.04 ± 1.15 mM for HT-29 cells. Cyclo(Phe-Pro) was subsequently used to investigate whether the growth-inhibitory effects of this CDP were related to the induction of apoptosis in HT-29 cells. Hoechst 33342 staining showed that 5mM cyclo(Phe-Pro) induced characteristic chromatin condensation and nuclear fragmentation in 18.3 ± 2.8% (p<0.01) of HT-29 cells after 72 hours. Furthermore, annexin V binding revealed that HT-29 cells treated with 5 mM cyclo(Phe-Pro) displayed phosphatidylserine externalization after 48 hours. In addition, it was shown that 10 mM cyclo(Phe-Pro) induced poly(ADP-ribose)polymerase PARP cleavage, one of the hallmark events of apoptosis. The use of the broad-range caspase inhibitor Z-VAD-FMK, showed that this PARP cleavage was caspase-dependent, which in turn was confirmed by demonstrating an increase in caspase-3 activity (p<0.01) in cyclo(Phe- Pro)-treated HT-29 cells. In conclusion, these findings demonstrate that cyclo(Phe-Pro) inhibited the growth of HT- 29, MCF-7, HeLa and WHCO3 cells, and induced apoptosis in HT-29 colon cancer cells, suggesting the potential antitumour activity of cyclo(Phe-Pro)-related CDPs.
- Full Text:
- Date Issued: 2004
Metalorganic vapour phase epitaxial growth and characterisation of Sb-based semiconductors
- Authors: Vankova, Viera
- Date: 2005
- Subjects: Compound semiconductors , Epitaxy , Organometallic compounds , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10548 , http://hdl.handle.net/10948/d1019678
- Description: This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.
- Full Text:
- Date Issued: 2005
- Authors: Vankova, Viera
- Date: 2005
- Subjects: Compound semiconductors , Epitaxy , Organometallic compounds , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10548 , http://hdl.handle.net/10948/d1019678
- Description: This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.
- Full Text:
- Date Issued: 2005
On the growth and characterisation of AIGaN alloys for optoelectronic applications
- Authors: James, Grant Robert
- Date: 2005
- Subjects: Gallium nitride -- Electric properties , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8824 , vital:26433
- Description: In this study the growth and characterisation of undoped and Si-doped AlxGa1-xN has been performed. The layers were grown using low-pressure metalorganic vapour phase deposition (MOCVD) on sapphire substrates. The optical and electrical properties of the AlxGa1-xN layers were studied using variable temperature Hall effect and photoluminescence measurements. AlxGa1-xN layers were grown over the entire composition range. Room temperature ultraviolet (UV) transmission measurements showed that the material quality was very good for layers with an Al content, x, of 0 _ x _ 0.5. However, the quality of layers of higher composition was seen to rapidly decrease with increasing x. The electrical and optical properties of AlxGa1-xN with x < 0.5 were also good, comparable to those reported on in literature. The study of the Si-doping of AlxGa1-xN was performed in two parts; firstly a series of Al0.23Ga0.77N samples was grown in which the doping level was increased from zero to n _ 3 × 1018 cm-3. A similar, albeit a less rigorous, study was performed for Al0.41Ga0.59N and Al0.5Ga0.5N. A second series of samples was then grown in which the doping level was kept constant, while the Al content was incrementally increased. Room temperature Hall effect measurements performed on Si-doped Al0.23Ga0.77N showed that the electron concentration did not scale linearly with the silane flow, as was the case in GaN. It was also seen that the electron mobility of the layers increased with slight Si-doping, possibly due to an improvement in the crystalline quality and/or a change in the conduction mechanism. It was also found that at higher compositions (x = 0.41 and 0.50) an increase in the doping level resulted in an increase in the mobility. Variable temperature Hall effect and photoluminescence measurements, performed on the Al0.23Ga0.77N samples, revealed a good correlation between the first PL activation energy E1 and the donor activation energy ED, prompting the conclusion that the first PL recombination channel in AlxGa1-xN is due to the delocalisation of excitons bound at neutral Si donors. Furthermore, E1 and ED were seen to decrease with n1/3, as is the case for GaN and other semiconductor materials. It was also observed that strong exciton localisation occurs in slightly Si-doped material, with the amount of localization becoming less at higher doping levels. Possible mechanisms responsible for the second PL recombination channel of activation energy E2 were also proposed. The electrical and optical properties of the second set of AlxGa1-xN samples was then studied. The PL properties of undoped AlxGa1-xN were typical of a homogeneous alloy system, with the increase in the PL FWHM and exciton localisation energies with x following the trend predicted by alloy disorder theory. The variation of the band gap energy with the Al content could not, however, be fitted over the entire composition range using a single bowing parameter. It was proposed that this was due either to an effect of the 9 7 valence band crossover, or due to exciton localisation at alloy disorder and/or impurities. As was the case for GaN and Al0.23Ga0.77N, all undoped material was highly resistive. As was mentioned earlier, the exciton localisation energies increased according to alloy disorder theory in undoped AlxGa1-xN. In the doped samples, however, a large increase in the donor localisation energy was measured for x > 0.3. The possibility that Si could become a DX-centre in AlxGa1-xN was then investigated. However, Hall effect measurements showed that the Si activation energy increased in good agreement with the model of a shallow effective mass state donor, with no sudden increase in ED being observed up to x = 0.4. It was then suggested that the increase in the E1 and E2 activation energies, as well as the exciton localisation energies, could be due to the 9 7 valence band crossover, which occurs at roughly the same composition. However, due to the scarcity of reports on the valence band structure in AlxGa1-xN no conclusions could be made at this stage as to the effect of the 9 7 valence band crossover on the PL properties of AlxGa1-xN.
- Full Text:
- Date Issued: 2005
- Authors: James, Grant Robert
- Date: 2005
- Subjects: Gallium nitride -- Electric properties , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8824 , vital:26433
- Description: In this study the growth and characterisation of undoped and Si-doped AlxGa1-xN has been performed. The layers were grown using low-pressure metalorganic vapour phase deposition (MOCVD) on sapphire substrates. The optical and electrical properties of the AlxGa1-xN layers were studied using variable temperature Hall effect and photoluminescence measurements. AlxGa1-xN layers were grown over the entire composition range. Room temperature ultraviolet (UV) transmission measurements showed that the material quality was very good for layers with an Al content, x, of 0 _ x _ 0.5. However, the quality of layers of higher composition was seen to rapidly decrease with increasing x. The electrical and optical properties of AlxGa1-xN with x < 0.5 were also good, comparable to those reported on in literature. The study of the Si-doping of AlxGa1-xN was performed in two parts; firstly a series of Al0.23Ga0.77N samples was grown in which the doping level was increased from zero to n _ 3 × 1018 cm-3. A similar, albeit a less rigorous, study was performed for Al0.41Ga0.59N and Al0.5Ga0.5N. A second series of samples was then grown in which the doping level was kept constant, while the Al content was incrementally increased. Room temperature Hall effect measurements performed on Si-doped Al0.23Ga0.77N showed that the electron concentration did not scale linearly with the silane flow, as was the case in GaN. It was also seen that the electron mobility of the layers increased with slight Si-doping, possibly due to an improvement in the crystalline quality and/or a change in the conduction mechanism. It was also found that at higher compositions (x = 0.41 and 0.50) an increase in the doping level resulted in an increase in the mobility. Variable temperature Hall effect and photoluminescence measurements, performed on the Al0.23Ga0.77N samples, revealed a good correlation between the first PL activation energy E1 and the donor activation energy ED, prompting the conclusion that the first PL recombination channel in AlxGa1-xN is due to the delocalisation of excitons bound at neutral Si donors. Furthermore, E1 and ED were seen to decrease with n1/3, as is the case for GaN and other semiconductor materials. It was also observed that strong exciton localisation occurs in slightly Si-doped material, with the amount of localization becoming less at higher doping levels. Possible mechanisms responsible for the second PL recombination channel of activation energy E2 were also proposed. The electrical and optical properties of the second set of AlxGa1-xN samples was then studied. The PL properties of undoped AlxGa1-xN were typical of a homogeneous alloy system, with the increase in the PL FWHM and exciton localisation energies with x following the trend predicted by alloy disorder theory. The variation of the band gap energy with the Al content could not, however, be fitted over the entire composition range using a single bowing parameter. It was proposed that this was due either to an effect of the 9 7 valence band crossover, or due to exciton localisation at alloy disorder and/or impurities. As was the case for GaN and Al0.23Ga0.77N, all undoped material was highly resistive. As was mentioned earlier, the exciton localisation energies increased according to alloy disorder theory in undoped AlxGa1-xN. In the doped samples, however, a large increase in the donor localisation energy was measured for x > 0.3. The possibility that Si could become a DX-centre in AlxGa1-xN was then investigated. However, Hall effect measurements showed that the Si activation energy increased in good agreement with the model of a shallow effective mass state donor, with no sudden increase in ED being observed up to x = 0.4. It was then suggested that the increase in the E1 and E2 activation energies, as well as the exciton localisation energies, could be due to the 9 7 valence band crossover, which occurs at roughly the same composition. However, due to the scarcity of reports on the valence band structure in AlxGa1-xN no conclusions could be made at this stage as to the effect of the 9 7 valence band crossover on the PL properties of AlxGa1-xN.
- Full Text:
- Date Issued: 2005
An investigation of the binding capacities of recombinant domain mutants of the human Polymeric Immunoglobulin Receptor (pIgR)
- Authors: Prinsloo, Earl Adin Gerard
- Date: 2006
- Subjects: Immunoglobulins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10307 , http://hdl.handle.net/10948/403 , Immunoglobulins
- Description: The membrane bound glycoprotein, polymeric immunoglobulin receptor (pIgR) is the primary transport molecule of the polymeric immunoglobulins, dimeric IgA and pentameric IgM, across epithelial cells. This process, known as transcytosis, is essential in order to establish immunity at mucosal surfaces. Typically, pIgR binds to the polymeric immunoglobulin at the basolateral surface of the epithelial cell, via five homologous immunoglobulin-like domains of the ectodomain. Binding is covalent to IgA and non-covalent to IgM; the IgM binding varying among species. The pIgR-bound complex is released at the apical surface of the cell after cleavage of pIgR at Arg585, thereafter referred to as secretory component (SC). SC confers protective and immunologic functions to the polymeric immunoglobulin. Free SC, i.e. not complexed with polymeric immunoglobulins, is also known to be released into mucosal secretions; and binds to pathogenic bacteria and bacterial products. It is known that domain I of the ectodomain is the primary domain in the interaction with polymeric immunoglobulins, while domain V is involved in a covalent linkage with IgA. However, little is known of domains II-IV and their role in immunoglobulin binding, particularly to IgM. This study aimed to characterize the binding of recombinant human pIgR domain mutants to polymeric IgM using immunological, biophysical and cell based techniques; thereby allowing greater insight into the contribution of each of the five domains. The unique domain structure allowed for selective amplification of single and multiple domain mutants from cloned human PIGR ectodomain cDNA. Mutants were cloned and expressed in Esherichia coli BL21 (DE3) as inclusion bodies. Recombinant mutant proteins were refolded in vitro by equilibrium gradient dialysis and purified to homogeneity. Equilibrium binding data show significant contributions to specific binding as a factor of domain presence. Binding kinetics determined by biophysical surface plasmon resonance measurements show the interplay between association and dissociation rates as defined by individual domains. In vitro competitive binding studies using the human intestinal carcinoma, HT29, known to constitutively express pIgR, show that the constructed recombinant domain mutants outcompete native pIgR. The level of competition is shown to be dependant on the domains downstream of domain I. The data also confirm the biological activity of the first in vitro refolded recombinant human SC.
- Full Text:
- Date Issued: 2006
- Authors: Prinsloo, Earl Adin Gerard
- Date: 2006
- Subjects: Immunoglobulins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10307 , http://hdl.handle.net/10948/403 , Immunoglobulins
- Description: The membrane bound glycoprotein, polymeric immunoglobulin receptor (pIgR) is the primary transport molecule of the polymeric immunoglobulins, dimeric IgA and pentameric IgM, across epithelial cells. This process, known as transcytosis, is essential in order to establish immunity at mucosal surfaces. Typically, pIgR binds to the polymeric immunoglobulin at the basolateral surface of the epithelial cell, via five homologous immunoglobulin-like domains of the ectodomain. Binding is covalent to IgA and non-covalent to IgM; the IgM binding varying among species. The pIgR-bound complex is released at the apical surface of the cell after cleavage of pIgR at Arg585, thereafter referred to as secretory component (SC). SC confers protective and immunologic functions to the polymeric immunoglobulin. Free SC, i.e. not complexed with polymeric immunoglobulins, is also known to be released into mucosal secretions; and binds to pathogenic bacteria and bacterial products. It is known that domain I of the ectodomain is the primary domain in the interaction with polymeric immunoglobulins, while domain V is involved in a covalent linkage with IgA. However, little is known of domains II-IV and their role in immunoglobulin binding, particularly to IgM. This study aimed to characterize the binding of recombinant human pIgR domain mutants to polymeric IgM using immunological, biophysical and cell based techniques; thereby allowing greater insight into the contribution of each of the five domains. The unique domain structure allowed for selective amplification of single and multiple domain mutants from cloned human PIGR ectodomain cDNA. Mutants were cloned and expressed in Esherichia coli BL21 (DE3) as inclusion bodies. Recombinant mutant proteins were refolded in vitro by equilibrium gradient dialysis and purified to homogeneity. Equilibrium binding data show significant contributions to specific binding as a factor of domain presence. Binding kinetics determined by biophysical surface plasmon resonance measurements show the interplay between association and dissociation rates as defined by individual domains. In vitro competitive binding studies using the human intestinal carcinoma, HT29, known to constitutively express pIgR, show that the constructed recombinant domain mutants outcompete native pIgR. The level of competition is shown to be dependant on the domains downstream of domain I. The data also confirm the biological activity of the first in vitro refolded recombinant human SC.
- Full Text:
- Date Issued: 2006
Epitaxial growth and characterisation of CuGaS2
- Authors: Branch, Matthew Stewart
- Date: 2006
- Subjects: Epitaxy , Chalcopyrite , Semiconductors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10541 , http://hdl.handle.net/10948/438 , http://hdl.handle.net/10948/d1012893 , Epitaxy , Chalcopyrite , Semiconductors
- Description: In this work, the growth and characterisation of the chalcopyrite semiconductor CuGaS2 is presented. The purpose of this study is to gain a better understanding of the defect chemistry of this class of materials through a systematic study relating the structural and optical properties to the composition of thin films grown by metalorganic vapour phase epitaxy. Details associated with the optimisation of the growth process are presented in a format relating the changes in the composition and morphology to variations in the growth process. The structural properties of thin films grown on GaAs(001) substrates are described. A dominance of polycrystalline growth is found to occur for Cu-rich material, whereas near-stoichiometric to Ga-rich material is typified by epitaxial growth. Secondary phases are identified by X-ray diffractometry and Raman spectroscopy for severely non-stoichiometric material. In some cases, the formation of the cubic zincblende and CuPt polytype of CuGaS2 are identified by transmission electron microscopy. It will be shown that changes in the Cu/Ga ratio of the solid strongly influence the photoluminescence response of the layers. Weak excitonic luminescence is observed for both slightly Ga-rich and Cu-rich material. Near stoichiometric layers exhibit luminescence centered at ~2.4 eV. Cu-rich layers are dominated by a line occurring at ~2.1 eV, whereas a different line at ~2.25 eV dominates for Ga-rich layers. A clear picture emerges of the radiative mechanisms dominating for Cu-rich and Ga-rich layers.
- Full Text:
- Date Issued: 2006
- Authors: Branch, Matthew Stewart
- Date: 2006
- Subjects: Epitaxy , Chalcopyrite , Semiconductors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10541 , http://hdl.handle.net/10948/438 , http://hdl.handle.net/10948/d1012893 , Epitaxy , Chalcopyrite , Semiconductors
- Description: In this work, the growth and characterisation of the chalcopyrite semiconductor CuGaS2 is presented. The purpose of this study is to gain a better understanding of the defect chemistry of this class of materials through a systematic study relating the structural and optical properties to the composition of thin films grown by metalorganic vapour phase epitaxy. Details associated with the optimisation of the growth process are presented in a format relating the changes in the composition and morphology to variations in the growth process. The structural properties of thin films grown on GaAs(001) substrates are described. A dominance of polycrystalline growth is found to occur for Cu-rich material, whereas near-stoichiometric to Ga-rich material is typified by epitaxial growth. Secondary phases are identified by X-ray diffractometry and Raman spectroscopy for severely non-stoichiometric material. In some cases, the formation of the cubic zincblende and CuPt polytype of CuGaS2 are identified by transmission electron microscopy. It will be shown that changes in the Cu/Ga ratio of the solid strongly influence the photoluminescence response of the layers. Weak excitonic luminescence is observed for both slightly Ga-rich and Cu-rich material. Near stoichiometric layers exhibit luminescence centered at ~2.4 eV. Cu-rich layers are dominated by a line occurring at ~2.1 eV, whereas a different line at ~2.25 eV dominates for Ga-rich layers. A clear picture emerges of the radiative mechanisms dominating for Cu-rich and Ga-rich layers.
- Full Text:
- Date Issued: 2006
Metabolic effects brought about by tricyclic antidepressants and the contribution of a medicinal plant in alleviating high fat diet induced insulin resistance in male wistar rats
- Authors: Chadwick, Wayne
- Date: 2006
- Subjects: Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10329 , http://hdl.handle.net/10948/461 , Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Description: Type II diabetes is becoming a growing problem in developed countries worldwide. The median age for diagnosis was around sixty, but recent surveys have shown that the entire age distribution curve shifting left. The incidence of type II diabetes is thought to be parallel with the growing rate of obesity associated with an unhealthy western diet. Type II diabetes is an expensive disease to manage, it is for this reason that cheaper medication needs to be investigated in the form of traditional plants, such as Sutherlandia frutescens. Prescription medication, such as tricyclic antidepressants, may also increase body weight thereby playing a role in obesity. The cause of weight gain in such cases may go unrecognized or lead to cessation of the medication with or without the practitioner’s knowledge or approval. It is therefore necessary to investigate the causative agents responsible for the excessive weight gain. Drinking water containing extracts of S. frutescens or metformin was administered to two groups of eleven insulin resistant male Wistar rats. The insulin resistant control group received water without any medication. Rats were sacrificed after 8 weeks allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. The effect of the medication and the diet on muscle post receptor insulin signaling proteins was determined through Western blots. Liver proteomics was also performed using 2-D electrophoresis. In a separate experiment 26 male Wistar rats were exposed to strepotozotocin toxin, 7 of these rats received intravenous insulin treatment, 7 rats received S. frutescens extract and 7 rats received a combination of both medications, the remaining 5 received no treatment and served as the control. Rats were sacrificed after 6 days allowing for fasting blood glucose, insulin and tissue glycogen content determination. Two groups of 14 male Wistar rats received amitriptyline or trimipramine (common tricyclic antidepressants) in their drinking water, the control group (30 rats) received water without any medication. The rats’ weight and food consumption was monitored throughout the trial and their oxygen consumption was also determined. Rats were sacrificed after 6 weeks or 14 weeks of medicinal compliance allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. S. frutescens treatment normalized circulating serum insulin levels and significantly increased the rate of glucose clearance. Certain post receptor insulin signaling proteins were also significantly increased relative to the insulin resistant control group. 2-D electrophoresis identified the normalization of protein levels associated with the urea cycle. S. frutescens was also able to, independently; maintain normoglycaemic levels in the strepotozotocin treated group. The tricyclic antidepressants significantly increased blood glucose levels while significantly reducing tissue glycogen levels for both sacrifice periods. Serum insulin remained unchanged while a significant increase in insulin degradation and insulin degrading enzyme levels were found for both antidepressants. S. frutescens shows promise as a low cost antidiabetic medication for future use. Although the antidepressants did not promote weight gain, the increase in blood glucose levels may be cause for concern in patients with a pre-disposition toward developing diabetes.
- Full Text:
- Date Issued: 2006
- Authors: Chadwick, Wayne
- Date: 2006
- Subjects: Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10329 , http://hdl.handle.net/10948/461 , Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Description: Type II diabetes is becoming a growing problem in developed countries worldwide. The median age for diagnosis was around sixty, but recent surveys have shown that the entire age distribution curve shifting left. The incidence of type II diabetes is thought to be parallel with the growing rate of obesity associated with an unhealthy western diet. Type II diabetes is an expensive disease to manage, it is for this reason that cheaper medication needs to be investigated in the form of traditional plants, such as Sutherlandia frutescens. Prescription medication, such as tricyclic antidepressants, may also increase body weight thereby playing a role in obesity. The cause of weight gain in such cases may go unrecognized or lead to cessation of the medication with or without the practitioner’s knowledge or approval. It is therefore necessary to investigate the causative agents responsible for the excessive weight gain. Drinking water containing extracts of S. frutescens or metformin was administered to two groups of eleven insulin resistant male Wistar rats. The insulin resistant control group received water without any medication. Rats were sacrificed after 8 weeks allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. The effect of the medication and the diet on muscle post receptor insulin signaling proteins was determined through Western blots. Liver proteomics was also performed using 2-D electrophoresis. In a separate experiment 26 male Wistar rats were exposed to strepotozotocin toxin, 7 of these rats received intravenous insulin treatment, 7 rats received S. frutescens extract and 7 rats received a combination of both medications, the remaining 5 received no treatment and served as the control. Rats were sacrificed after 6 days allowing for fasting blood glucose, insulin and tissue glycogen content determination. Two groups of 14 male Wistar rats received amitriptyline or trimipramine (common tricyclic antidepressants) in their drinking water, the control group (30 rats) received water without any medication. The rats’ weight and food consumption was monitored throughout the trial and their oxygen consumption was also determined. Rats were sacrificed after 6 weeks or 14 weeks of medicinal compliance allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. S. frutescens treatment normalized circulating serum insulin levels and significantly increased the rate of glucose clearance. Certain post receptor insulin signaling proteins were also significantly increased relative to the insulin resistant control group. 2-D electrophoresis identified the normalization of protein levels associated with the urea cycle. S. frutescens was also able to, independently; maintain normoglycaemic levels in the strepotozotocin treated group. The tricyclic antidepressants significantly increased blood glucose levels while significantly reducing tissue glycogen levels for both sacrifice periods. Serum insulin remained unchanged while a significant increase in insulin degradation and insulin degrading enzyme levels were found for both antidepressants. S. frutescens shows promise as a low cost antidiabetic medication for future use. Although the antidepressants did not promote weight gain, the increase in blood glucose levels may be cause for concern in patients with a pre-disposition toward developing diabetes.
- Full Text:
- Date Issued: 2006
Characterization of WC-VC-Co and WC-VC-TiC-Co hardmetals
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
Contributions to the use of microalgae in estuarine freshwater reserve determinations
- Authors: Snow, Gavin Charles
- Date: 2007
- Subjects: Microalgae -- South Africa , Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10620 , http://hdl.handle.net/10948/709 , Microalgae -- South Africa , Estuarine ecology -- South Africa
- Description: The ecologist Garrett Hardin (1968) introduced a useful concept called the tragedy of the commons, which describes how ecological resources become threatened or lost. The term “commons” is based on the commons of old English villages and is symbolic of a resource that is shared by a group of people. If every person were to use each resource in a sustainable fashion it would be available in perpetuity. However, if people use more than their share they would only increase their personal wealth to the detriment of others. In addition, an increase in the population would mean that the size of each share would have to decrease to accommodate the larger number of people. As a result, resources are threatened by personal greed and uncontrolled population growth. Freshwater is an example of a common resource that is under threat in South Africa where the average annual rainfall is less than 60 percent of the global average (Mukheibir & Sparks 2006). The increasing demands for freshwater as well as its eutrophication are major concerns with regards to estuarine health, environmental resource management and human health. The correct management of water is necessary to ensure that it is utilised in a sustainable manner. The National Water Act (No. 36 of 1998) has provided the rights to water for basic human needs and for sustainable ecological function; the Basic Human Needs Reserve and Ecological Reserve are both provided as a right in law. The amount of water necessary for an estuary to retain an acceptable ecological status, known as the Estuarine Ecological Reserve, is determined through the implementation of procedures (rapid, intermediate or comprehensive) compiled by the Department of Water Affairs and Forestry (1999) in its Resource Directed Measures (RDM) for the Protection of Water Resources. The impact of restricted flow on estuaries can be reduced by manipulating the water released from impoundments, the regulation of water abstractions within the river catchment or both (Hirji et al. 2002). The reserve assessment method is designed to evaluate ecosystem requirements by employing groups of specialists from different disciplines. In South Africa, this includes hydrologists, sedimentologists, water chemists and biologists (including microalgae specialists). The use of microalgae in ecological assessments has largely been based on research that was initiated at the Nelson Mandela Metropolitan University (formerly University of Port Elizabeth) and subsequently at Rhodes University (Grahamstown) and the University of KwaZulu Natal (Durban). The microalgal research can be divided into two main focus areas; phytoplankton and benthic microalgae
- Full Text:
- Date Issued: 2007
- Authors: Snow, Gavin Charles
- Date: 2007
- Subjects: Microalgae -- South Africa , Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10620 , http://hdl.handle.net/10948/709 , Microalgae -- South Africa , Estuarine ecology -- South Africa
- Description: The ecologist Garrett Hardin (1968) introduced a useful concept called the tragedy of the commons, which describes how ecological resources become threatened or lost. The term “commons” is based on the commons of old English villages and is symbolic of a resource that is shared by a group of people. If every person were to use each resource in a sustainable fashion it would be available in perpetuity. However, if people use more than their share they would only increase their personal wealth to the detriment of others. In addition, an increase in the population would mean that the size of each share would have to decrease to accommodate the larger number of people. As a result, resources are threatened by personal greed and uncontrolled population growth. Freshwater is an example of a common resource that is under threat in South Africa where the average annual rainfall is less than 60 percent of the global average (Mukheibir & Sparks 2006). The increasing demands for freshwater as well as its eutrophication are major concerns with regards to estuarine health, environmental resource management and human health. The correct management of water is necessary to ensure that it is utilised in a sustainable manner. The National Water Act (No. 36 of 1998) has provided the rights to water for basic human needs and for sustainable ecological function; the Basic Human Needs Reserve and Ecological Reserve are both provided as a right in law. The amount of water necessary for an estuary to retain an acceptable ecological status, known as the Estuarine Ecological Reserve, is determined through the implementation of procedures (rapid, intermediate or comprehensive) compiled by the Department of Water Affairs and Forestry (1999) in its Resource Directed Measures (RDM) for the Protection of Water Resources. The impact of restricted flow on estuaries can be reduced by manipulating the water released from impoundments, the regulation of water abstractions within the river catchment or both (Hirji et al. 2002). The reserve assessment method is designed to evaluate ecosystem requirements by employing groups of specialists from different disciplines. In South Africa, this includes hydrologists, sedimentologists, water chemists and biologists (including microalgae specialists). The use of microalgae in ecological assessments has largely been based on research that was initiated at the Nelson Mandela Metropolitan University (formerly University of Port Elizabeth) and subsequently at Rhodes University (Grahamstown) and the University of KwaZulu Natal (Durban). The microalgal research can be divided into two main focus areas; phytoplankton and benthic microalgae
- Full Text:
- Date Issued: 2007
On the characterization of photovoltaic devices for concentrator purposes
- Authors: Vorster, Frederick Jacobus
- Date: 2007
- Subjects: Photovoltaic cells , Image processing , Solar cells
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10530 , http://hdl.handle.net/10948/639 , Photovoltaic cells , Image processing , Solar cells
- Description: This study originated from an evaluation of the performance of a commercially available high concentration point focus concentrator PV system. The effect of module design flaws was studied by using current-voltage (I-V) curves obtained from each module in the array. The position of reverse bias steps revealed the severity of mismatch in a string of series-connected cells. By understanding the effects of the various types of mismatch, power losses and damage to the solar cells resulting from hot spot formation can be minimized and several recommendations for improving the basic performance of similar systems were made. Concern over the extent and type of defect failure of the concentrator photovoltaic (CPV) cells prompted an investigation into the use of a light beam induced current (LBIC) technique to investigate the spatial distribution of defects. An overview of current and developing LBIC techniques revealed that the original standard LBIC techniques have found widespread application, and that far-reaching and important developments of the technique have taken place over the years. These developments are driven by natural progression as well as the availability of newly developed advanced measurement equipment. Several techniques such as Lock-in hermography and the use of infrared cameras have developed as complementary techniques to advanced LBIC techniques. As an accurate contactless evaluation tool that is able to image spatially distributed defects in cell material, the basis of this method seemed promising for the evaluation of concentrator cells.
- Full Text:
- Date Issued: 2007
- Authors: Vorster, Frederick Jacobus
- Date: 2007
- Subjects: Photovoltaic cells , Image processing , Solar cells
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10530 , http://hdl.handle.net/10948/639 , Photovoltaic cells , Image processing , Solar cells
- Description: This study originated from an evaluation of the performance of a commercially available high concentration point focus concentrator PV system. The effect of module design flaws was studied by using current-voltage (I-V) curves obtained from each module in the array. The position of reverse bias steps revealed the severity of mismatch in a string of series-connected cells. By understanding the effects of the various types of mismatch, power losses and damage to the solar cells resulting from hot spot formation can be minimized and several recommendations for improving the basic performance of similar systems were made. Concern over the extent and type of defect failure of the concentrator photovoltaic (CPV) cells prompted an investigation into the use of a light beam induced current (LBIC) technique to investigate the spatial distribution of defects. An overview of current and developing LBIC techniques revealed that the original standard LBIC techniques have found widespread application, and that far-reaching and important developments of the technique have taken place over the years. These developments are driven by natural progression as well as the availability of newly developed advanced measurement equipment. Several techniques such as Lock-in hermography and the use of infrared cameras have developed as complementary techniques to advanced LBIC techniques. As an accurate contactless evaluation tool that is able to image spatially distributed defects in cell material, the basis of this method seemed promising for the evaluation of concentrator cells.
- Full Text:
- Date Issued: 2007
On the microstructure and physical properties of hot pressed (Hf, Ti) C
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
- Full Text:
- Date Issued: 2007
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
- Full Text:
- Date Issued: 2007
Prime near-ring modules and their links with the generalised group near-ring
- Authors: Juglal, Shaanraj
- Date: 2007
- Subjects: Near-rings
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10507 , http://hdl.handle.net/10948/714 , Near-rings
- Description: In view of the facts that the definition of a ring led to the definition of a near- ring, the definition of a ring module led to the definition of a near-ring module, prime rings resulted in investigations with respect to primeness in near-rings, one is naturally inclined to attempt to define the notion of a group near-ring seeing that the group ring had already been defined and investigated into by, interalia, Groenewald in [7] . However, in trying to define the group near-ring along the same lines as the group ring was defined, it was found that the resulting multiplication was, in general, not associative in the near-ring case due to the lack of one distributive property. In 1976, Meldrum [19] achieved success in defining the group near-ring. How- ever, in his definition, only distributively generated near-rings were considered and the distributive generators played a vital role in the construction. In 1989, Le Riche, Meldrum and van der Walt [17], adopted a similar approach to that which led to a successful and fruitful definition of matrix near-rings, and defined the group near-ring in a more general sense. In particular, they defined R[G], the group near-ring of a group G over a near-ring R, as a subnear-ring of M(RG), the near-ring of all mappings of the group RG into itself. More recently, Groenewald and Lee [14], further generalised the definition of R[G] to R[S : M], the generalised semigroup near-ring of a semigroup S over any faithful R-module M. Again, the natural thing to do would be to extend the results obtained for R[G] to R[S : M], and this they achieved with much success.
- Full Text:
- Date Issued: 2007
- Authors: Juglal, Shaanraj
- Date: 2007
- Subjects: Near-rings
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10507 , http://hdl.handle.net/10948/714 , Near-rings
- Description: In view of the facts that the definition of a ring led to the definition of a near- ring, the definition of a ring module led to the definition of a near-ring module, prime rings resulted in investigations with respect to primeness in near-rings, one is naturally inclined to attempt to define the notion of a group near-ring seeing that the group ring had already been defined and investigated into by, interalia, Groenewald in [7] . However, in trying to define the group near-ring along the same lines as the group ring was defined, it was found that the resulting multiplication was, in general, not associative in the near-ring case due to the lack of one distributive property. In 1976, Meldrum [19] achieved success in defining the group near-ring. How- ever, in his definition, only distributively generated near-rings were considered and the distributive generators played a vital role in the construction. In 1989, Le Riche, Meldrum and van der Walt [17], adopted a similar approach to that which led to a successful and fruitful definition of matrix near-rings, and defined the group near-ring in a more general sense. In particular, they defined R[G], the group near-ring of a group G over a near-ring R, as a subnear-ring of M(RG), the near-ring of all mappings of the group RG into itself. More recently, Groenewald and Lee [14], further generalised the definition of R[G] to R[S : M], the generalised semigroup near-ring of a semigroup S over any faithful R-module M. Again, the natural thing to do would be to extend the results obtained for R[G] to R[S : M], and this they achieved with much success.
- Full Text:
- Date Issued: 2007
Synthesis, properties and reactions of Novel Quinone Methides
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
The kinetics and associated equilibria of high oxidation state osmium complexes
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007