Radiation damage in GaAs and SiC
- Authors: Janse van Vuuren, Arno
- Date: 2011
- Subjects: Gallium arsenide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10515 , http://hdl.handle.net/10948/1477 , Gallium arsenide semiconductors
- Description: In this dissertation the microstructure and hardness of phosphorous implanted SiC and neutron irradiated SiC and GaAs have been investigated. SiC is important due to its application as a barrier coating layer in coated particle fuel used in high temperature gas cooled reactors. The characterisation of neutron irradiated GaAs has been included in this study in order to compare the radiation damage produced by protons and neutrons since proton bombardment of SiC could in principle be used for out-of-reactor simulations of the neutron irradiation damage created in SiC during reactor operation. The following SiC and GaAs compounds were investigated: As-implanted and annealed single crystal 6H-SiC wafers and polycrystalline 3C-SiC bulk material implanted with phosphorous ions. As-irradiated and annealed polycrystalline 3C-SiC bulk material irradiated with fast neutrons. As-irradiated and annealed single crystal GaAs wafers irradiated with fast neutrons. The main techniques used for the analyses were transmission electron microscopy (TEM) and nano-indentation hardness testing. The following results were obtained for the investigation of implanted and irradiated SiC and GaAs: Phosphorous Implanted 6H-SiC and 3C-SiC The depth of the P+ ion damage was found to be in good agreement with predictions by TRIM 2010. Micro-diffraction of the damage region in P+ implanted 6H-SiC (dose 5×1016 ions/cm2) indicates that amorphization occurred and that recrystallisation of this layer occurred during annealing at 1200°C. TEM analysis revealed that the layer recrystallised in the 3C phase of SiC and twin defects also formed within the layer. Micro-diffraction of the damage region in P+ implanted 3C-SiC (dose 1×1015 ions/cm2) indicates that amorphization also occurred for this sample and that recrystallisation of this layer occurred during annealing at 800°C. Nano-hardness testing of the P+ implanted 6H-SiC indicated that the hardness of the implanted SiC was initially much lower than unimplanted SiC due to the formation of an amorphous layer during ion implantation. After annealing the implanted SiC at 800°C and 1200°C, the hardness increased due to re-crystallisation and point defect hardening. Neutron Irradiated 3C-SiC TEM investigations of neutron irradiated 3C-SiC revealed the presence dark spot defects for SiC samples irradiated to a dose of 5.9×1021 n/cm2 and 9.6×1021 n/cm2. Neutron Irradiated GaAs TEM investigation revealed a high density of dislocation loops in the unannealed neutron irradiated GaAs. The loop diameters increased after post-irradiation annealing in the range 600 to 800 °C. The dislocation loops were found to be of interstitial type lying on the {110} cleavage planes of GaAs. This finding is in agreement with earlier studies on 300 keV proton bombarded and 1 MeV electron irradiated GaAs where interstitial loops on {110} planes became visible after annealing at temperatures exceeding 500 °C. The small dislocation loops on the {110} planes of the neutron irradiated GaAs transformed to large loops and dislocations after annealing at 1000 °C.
- Full Text:
- Date Issued: 2011
- Authors: Janse van Vuuren, Arno
- Date: 2011
- Subjects: Gallium arsenide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10515 , http://hdl.handle.net/10948/1477 , Gallium arsenide semiconductors
- Description: In this dissertation the microstructure and hardness of phosphorous implanted SiC and neutron irradiated SiC and GaAs have been investigated. SiC is important due to its application as a barrier coating layer in coated particle fuel used in high temperature gas cooled reactors. The characterisation of neutron irradiated GaAs has been included in this study in order to compare the radiation damage produced by protons and neutrons since proton bombardment of SiC could in principle be used for out-of-reactor simulations of the neutron irradiation damage created in SiC during reactor operation. The following SiC and GaAs compounds were investigated: As-implanted and annealed single crystal 6H-SiC wafers and polycrystalline 3C-SiC bulk material implanted with phosphorous ions. As-irradiated and annealed polycrystalline 3C-SiC bulk material irradiated with fast neutrons. As-irradiated and annealed single crystal GaAs wafers irradiated with fast neutrons. The main techniques used for the analyses were transmission electron microscopy (TEM) and nano-indentation hardness testing. The following results were obtained for the investigation of implanted and irradiated SiC and GaAs: Phosphorous Implanted 6H-SiC and 3C-SiC The depth of the P+ ion damage was found to be in good agreement with predictions by TRIM 2010. Micro-diffraction of the damage region in P+ implanted 6H-SiC (dose 5×1016 ions/cm2) indicates that amorphization occurred and that recrystallisation of this layer occurred during annealing at 1200°C. TEM analysis revealed that the layer recrystallised in the 3C phase of SiC and twin defects also formed within the layer. Micro-diffraction of the damage region in P+ implanted 3C-SiC (dose 1×1015 ions/cm2) indicates that amorphization also occurred for this sample and that recrystallisation of this layer occurred during annealing at 800°C. Nano-hardness testing of the P+ implanted 6H-SiC indicated that the hardness of the implanted SiC was initially much lower than unimplanted SiC due to the formation of an amorphous layer during ion implantation. After annealing the implanted SiC at 800°C and 1200°C, the hardness increased due to re-crystallisation and point defect hardening. Neutron Irradiated 3C-SiC TEM investigations of neutron irradiated 3C-SiC revealed the presence dark spot defects for SiC samples irradiated to a dose of 5.9×1021 n/cm2 and 9.6×1021 n/cm2. Neutron Irradiated GaAs TEM investigation revealed a high density of dislocation loops in the unannealed neutron irradiated GaAs. The loop diameters increased after post-irradiation annealing in the range 600 to 800 °C. The dislocation loops were found to be of interstitial type lying on the {110} cleavage planes of GaAs. This finding is in agreement with earlier studies on 300 keV proton bombarded and 1 MeV electron irradiated GaAs where interstitial loops on {110} planes became visible after annealing at temperatures exceeding 500 °C. The small dislocation loops on the {110} planes of the neutron irradiated GaAs transformed to large loops and dislocations after annealing at 1000 °C.
- Full Text:
- Date Issued: 2011
Responses of intertidal macroalgae and associated fauna to interactive processes acting over multiple spatial scales
- Authors: Mostert, Bruce Petrus
- Date: 2011 , 2010-12-01
- Subjects: Biodiversity -- South Africa , Spatial ecology , Marine algae -- South Africa , Marine organisms -- Effect of water pollution on
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5890 , http://hdl.handle.net/10962/d1013370
- Description: The decrease of biological diversity from low latitudes near the equator towards high latitudes is one of the most fundamental patterns noted in ecology. These trends have been the subject of numerous terrestrial and marine studies and have caused the proposal of several explanatory hypotheses. No single hypothesis has adequately accounted for these observed trends. Furthermore, large-scale patterns are frequently modified by processes acting at meso- to small-scales. It is imperative to understand the interaction of these processes to elucidate the mechanisms controlling the structure of intertidal assemblages. The main aim of this thesis was to test the influence of multiple processes at a range of spatial scales on biogenic engineers. Biogenic engineers, such as macroalgae, have been reported to be strongly influenced by processes such as grazing, biogeography and upwelling and subsequent effects are expected to be linked to their associated assemblages. I used infaunal assemblages associated with macroalgae as a model system to understand the interactive effects of meso-scale upwelling in conjunction with large-scale factors (regional and biogeographic). Three species of macroalgae, Hypnea spicifera, Champia lumbricalis and Bifurcaria brassicaeformis, inhabiting different but overlapping home ranges were used in this study. Smaller scale, physical attributes and the associated fauna of these algal species were compared. The effects of meso- to large-scale physical gradients on marine organisms have been investigated in many instances and resultant gradients in physical variables observed. This study was undertaken to investigate morphological trends exhibited by Hypnea spicifera and Champia lumbricalis to compare possible similarities between coastlines and to determine if inferred meso- to large-scale processes influence physical trends in a similar manner despite the coastlines being affected by different hydrodynamic processes. The macroalgae were located in two distinctly different upwelling regimes, Hypnea spicifera on the east and south coasts and Champia lumbricalis on the west coast. Upwelling (delivery of nutrients and primary production) was not found to be an important factor in determining the physical characteristics of macroalgae but there were clear patterns linked to latitude. Mean percentage cover of Hypnea spicifera was positively correlated with distance along the east and south coasts. Mean mass and mean surface area of H. spicifera were, however, negatively correlated with distance from Port St Johns. Mean frond length showed a negative trend but this relationship was not statistically significant. On the west coast, there was a significant increase in mean frond length from north to south for Champia lumbricalis. Mean surface area and mean mass of C. lumbricalis exhibited non-significant negative trends from north to south while there was a non-significant positive trend for mean percentage cover. Following the “Productivity Hypothesis”, these patterns from north to south along the coastlines of South Africa could have important implications for biodiversity associated with these algae. Many previous studies have focussed on the effects of upwelling on species (i.e. effects of nutrients and temperature) but have failed to separate this effect from large scale effects such as biogeography and latitudinal gradients. I tested the influence meso-scale upwelling, large-scale biogeographic processes and latitudinal gradients with two different species of macroalgae one on the east and south coasts of South Africa and the other on the west coast. Hypnea spicifera inhabits the east and south coasts of South Africa spanning two biogeographic provinces and is generally affected by relatively weak upwelling, whereas Champia lumbricalis inhabits the west coast spanning one biogeographic province which is subjected to intense persistent upwelling year round. Within the east and west coast biogeographic provinces there are, however, regions with both upwelling and non-upwelling. On the east and south coasts, entire assemblages differed significantly among the three Regions (St Lucia, Port Alfred and Knysna, while assemblages between upwelling/non-upwelling areas were not different. Assemblages on the different shores differed significantly from each other. There were no significant effects of region or upwelling for the number of individuals of Crustacea or Polychaeta, while Mollusca showed a significant effect of region. The number of individuals of other taxa showed a significant interaction of region and upwelling. Region had a significant effect on number of species of molluscs and other taxa, while there was no effect for either region or upwelling for the Crustacea or Polychaeta. In general different factors were shown to be important (region and shore) while upwelling was rarely important. On the west coast assemblages associated with C. lumbricalis were not influenced by region or upwelling but there were significant differences between shores. Region, upwelling ad shore did not affect number of individuals. There was a significant interaction of region and upwelling for the number of species of crustaceans, while numbers of species of Mollusca, Polychaeta and other taxa showed no effects. In general, regional factors strongly influenced most organisms, while upwelling played a minor role. Hypotheses about differences between upwelling and non-upwelling regions in terms of species abundances and composition due to the input of cold nutrient rich water were not supported. A link between the effects of larger-scale biogeographic factors and their influence on habitat forming taxa and the resultant effects on associated infauna would be a likely explanation for the patterns observed in this study. Diversity of assemblages is known to be influenced by the structural complexity of a habitat, increasing complexity increases the amount of available niches therefore potentially increasing the number of species found within that habitat. Three species of macroalgae, Hypnea spicifera, Champia lumbricalis and Bifurcaria brassicaeformis were selected on the basis of being structurally similar and having their distributional ranges overlap in order to elucidate the effects of structure and macroalgal species on associated assemblages. Hypnea spicifera is different in terms of surface area and biomass from Champia lumbricalis and Bifurcaria brassicaeformis. Assemblages of species found on the three rhodophytes showed both shore and the species of alga had significant effects on composition. Only numbers of individuals of molluscs were affected by the species of alga. Crustacea and Polychaeta showed an interaction of the species of alga with shore. In the case of this study, it is likely that the three species of macroalgae mitigate biological stressors such as predation and physical stressors such as wave exposure and desiccation. In general, meso-scale upwelling is suggested to be marginalised when considering the structuring of assemblages associated with macroalgae, while large scale biogeography has more of an influence. Within shores, assemblages were also strongly influenced by smaller-scale factors such as differences in the structure and species of alga. This study indicates the importance of investigating patterns across a range of spatial scales to gain a comprehensive understanding of factors influencing intertidal organisms.
- Full Text:
- Date Issued: 2011
- Authors: Mostert, Bruce Petrus
- Date: 2011 , 2010-12-01
- Subjects: Biodiversity -- South Africa , Spatial ecology , Marine algae -- South Africa , Marine organisms -- Effect of water pollution on
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5890 , http://hdl.handle.net/10962/d1013370
- Description: The decrease of biological diversity from low latitudes near the equator towards high latitudes is one of the most fundamental patterns noted in ecology. These trends have been the subject of numerous terrestrial and marine studies and have caused the proposal of several explanatory hypotheses. No single hypothesis has adequately accounted for these observed trends. Furthermore, large-scale patterns are frequently modified by processes acting at meso- to small-scales. It is imperative to understand the interaction of these processes to elucidate the mechanisms controlling the structure of intertidal assemblages. The main aim of this thesis was to test the influence of multiple processes at a range of spatial scales on biogenic engineers. Biogenic engineers, such as macroalgae, have been reported to be strongly influenced by processes such as grazing, biogeography and upwelling and subsequent effects are expected to be linked to their associated assemblages. I used infaunal assemblages associated with macroalgae as a model system to understand the interactive effects of meso-scale upwelling in conjunction with large-scale factors (regional and biogeographic). Three species of macroalgae, Hypnea spicifera, Champia lumbricalis and Bifurcaria brassicaeformis, inhabiting different but overlapping home ranges were used in this study. Smaller scale, physical attributes and the associated fauna of these algal species were compared. The effects of meso- to large-scale physical gradients on marine organisms have been investigated in many instances and resultant gradients in physical variables observed. This study was undertaken to investigate morphological trends exhibited by Hypnea spicifera and Champia lumbricalis to compare possible similarities between coastlines and to determine if inferred meso- to large-scale processes influence physical trends in a similar manner despite the coastlines being affected by different hydrodynamic processes. The macroalgae were located in two distinctly different upwelling regimes, Hypnea spicifera on the east and south coasts and Champia lumbricalis on the west coast. Upwelling (delivery of nutrients and primary production) was not found to be an important factor in determining the physical characteristics of macroalgae but there were clear patterns linked to latitude. Mean percentage cover of Hypnea spicifera was positively correlated with distance along the east and south coasts. Mean mass and mean surface area of H. spicifera were, however, negatively correlated with distance from Port St Johns. Mean frond length showed a negative trend but this relationship was not statistically significant. On the west coast, there was a significant increase in mean frond length from north to south for Champia lumbricalis. Mean surface area and mean mass of C. lumbricalis exhibited non-significant negative trends from north to south while there was a non-significant positive trend for mean percentage cover. Following the “Productivity Hypothesis”, these patterns from north to south along the coastlines of South Africa could have important implications for biodiversity associated with these algae. Many previous studies have focussed on the effects of upwelling on species (i.e. effects of nutrients and temperature) but have failed to separate this effect from large scale effects such as biogeography and latitudinal gradients. I tested the influence meso-scale upwelling, large-scale biogeographic processes and latitudinal gradients with two different species of macroalgae one on the east and south coasts of South Africa and the other on the west coast. Hypnea spicifera inhabits the east and south coasts of South Africa spanning two biogeographic provinces and is generally affected by relatively weak upwelling, whereas Champia lumbricalis inhabits the west coast spanning one biogeographic province which is subjected to intense persistent upwelling year round. Within the east and west coast biogeographic provinces there are, however, regions with both upwelling and non-upwelling. On the east and south coasts, entire assemblages differed significantly among the three Regions (St Lucia, Port Alfred and Knysna, while assemblages between upwelling/non-upwelling areas were not different. Assemblages on the different shores differed significantly from each other. There were no significant effects of region or upwelling for the number of individuals of Crustacea or Polychaeta, while Mollusca showed a significant effect of region. The number of individuals of other taxa showed a significant interaction of region and upwelling. Region had a significant effect on number of species of molluscs and other taxa, while there was no effect for either region or upwelling for the Crustacea or Polychaeta. In general different factors were shown to be important (region and shore) while upwelling was rarely important. On the west coast assemblages associated with C. lumbricalis were not influenced by region or upwelling but there were significant differences between shores. Region, upwelling ad shore did not affect number of individuals. There was a significant interaction of region and upwelling for the number of species of crustaceans, while numbers of species of Mollusca, Polychaeta and other taxa showed no effects. In general, regional factors strongly influenced most organisms, while upwelling played a minor role. Hypotheses about differences between upwelling and non-upwelling regions in terms of species abundances and composition due to the input of cold nutrient rich water were not supported. A link between the effects of larger-scale biogeographic factors and their influence on habitat forming taxa and the resultant effects on associated infauna would be a likely explanation for the patterns observed in this study. Diversity of assemblages is known to be influenced by the structural complexity of a habitat, increasing complexity increases the amount of available niches therefore potentially increasing the number of species found within that habitat. Three species of macroalgae, Hypnea spicifera, Champia lumbricalis and Bifurcaria brassicaeformis were selected on the basis of being structurally similar and having their distributional ranges overlap in order to elucidate the effects of structure and macroalgal species on associated assemblages. Hypnea spicifera is different in terms of surface area and biomass from Champia lumbricalis and Bifurcaria brassicaeformis. Assemblages of species found on the three rhodophytes showed both shore and the species of alga had significant effects on composition. Only numbers of individuals of molluscs were affected by the species of alga. Crustacea and Polychaeta showed an interaction of the species of alga with shore. In the case of this study, it is likely that the three species of macroalgae mitigate biological stressors such as predation and physical stressors such as wave exposure and desiccation. In general, meso-scale upwelling is suggested to be marginalised when considering the structuring of assemblages associated with macroalgae, while large scale biogeography has more of an influence. Within shores, assemblages were also strongly influenced by smaller-scale factors such as differences in the structure and species of alga. This study indicates the importance of investigating patterns across a range of spatial scales to gain a comprehensive understanding of factors influencing intertidal organisms.
- Full Text:
- Date Issued: 2011
Restoring the biodiversity of canopy species within degraded spekboom thicket
- Van der Vyver, Marius Lodewyk
- Authors: Van der Vyver, Marius Lodewyk
- Date: 2011
- Subjects: Plant diversity , Biodiversity
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10602 , http://hdl.handle.net/10948/1564 , Plant diversity , Biodiversity
- Description: I investigated the return of plant canopy diversity to degraded spekboom thicket landscapes under restoration treatment. I attempted the reintroduction of five nursery propagated and naturally-occurring plant species in severely degraded Portulacaria afra Jacq. (spekboom) dominated thickets that have been subjected to a restoration method involving the planting of dense rows of P. afra truncheons for various time periods and also in degraded and intact thickets. I also planted nursery propagated P. afra cuttings. An average of 30 propagules of each species, were planted in each of the chosen areas in two distinct seasons that exhibited distinct rainfall peaks. Sixteen propagules of P. afra were also planted in each treatment only once. Propagules of the two thicket woody canopy species (S. longispina and P. capensis) showed a total survival of 1% and 9%, respectively. Survival of L. ferocissimum and R. obovatum was 19% and 70% and all propagules of P. afra survived. Analyses showed that survival is primarily tied to a species effect, with R. obovatum and P. afra showing significantly better survival than the other species. Within the other surviving few species a significant preference for overhanging canopy cover was observed. The results show little significance of restoration treatment for propagule survival, suggesting that a range of conditions is needed for the successful establishment of canopy species that likely involves a microclimate and suitable substrate created by canopy cover and litter fall, combined with an exceptional series of rainfall events. I found that the high costs involved with a biodiversity planting endeavour, and the low survival of propagules of thicket canopy plant species (P. afra excepted), renders the proposed biodiversity planting restoration protocol both ecologically and economically inefficient. Restoration success involves the autogenic regeneration of key species or functional groups within the degraded ecosystem. Heavily degraded spekboom-dominated thicket does not spontaneously regenerate its former canopy species composition and this state of affairs was interpreted in terms of a state-and-transition conceptual model. Floristic analyses of degraded, intact and a range of stands under restoration treatment for varying time periods at two locations in Sundays Spekboomveld revealed that the stands under restoration are progressively regenerating canopy species biodiversity with increasing restoration age, and that intact sites are still the most diverse. The high total carbon content (TCC) measured within the older restored stands Rhinosterhoek (241 t C ha-1 after 50 years at a depth of 50 cm) rivals that recorded for intact spekboom thickets, and the number of recruits found within older restored sites rivals intact sites sampled. 2 The changes recorded in the above- and belowground environments potentially identify P. afra as an ecosystem engineer within spekboom dominated thickets that facillitates the build-up of carbon above- and belowground and the accompanying changes in soil quality and the unique microclimate aboveground, which enables the hypothetical threshold of the degraded state to be transcended. This restoration methodology is accordingly considered efficient and autogenic canopy species return was found to be prominent after a period of 35-50 years of restoration treatment.
- Full Text:
- Date Issued: 2011
- Authors: Van der Vyver, Marius Lodewyk
- Date: 2011
- Subjects: Plant diversity , Biodiversity
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10602 , http://hdl.handle.net/10948/1564 , Plant diversity , Biodiversity
- Description: I investigated the return of plant canopy diversity to degraded spekboom thicket landscapes under restoration treatment. I attempted the reintroduction of five nursery propagated and naturally-occurring plant species in severely degraded Portulacaria afra Jacq. (spekboom) dominated thickets that have been subjected to a restoration method involving the planting of dense rows of P. afra truncheons for various time periods and also in degraded and intact thickets. I also planted nursery propagated P. afra cuttings. An average of 30 propagules of each species, were planted in each of the chosen areas in two distinct seasons that exhibited distinct rainfall peaks. Sixteen propagules of P. afra were also planted in each treatment only once. Propagules of the two thicket woody canopy species (S. longispina and P. capensis) showed a total survival of 1% and 9%, respectively. Survival of L. ferocissimum and R. obovatum was 19% and 70% and all propagules of P. afra survived. Analyses showed that survival is primarily tied to a species effect, with R. obovatum and P. afra showing significantly better survival than the other species. Within the other surviving few species a significant preference for overhanging canopy cover was observed. The results show little significance of restoration treatment for propagule survival, suggesting that a range of conditions is needed for the successful establishment of canopy species that likely involves a microclimate and suitable substrate created by canopy cover and litter fall, combined with an exceptional series of rainfall events. I found that the high costs involved with a biodiversity planting endeavour, and the low survival of propagules of thicket canopy plant species (P. afra excepted), renders the proposed biodiversity planting restoration protocol both ecologically and economically inefficient. Restoration success involves the autogenic regeneration of key species or functional groups within the degraded ecosystem. Heavily degraded spekboom-dominated thicket does not spontaneously regenerate its former canopy species composition and this state of affairs was interpreted in terms of a state-and-transition conceptual model. Floristic analyses of degraded, intact and a range of stands under restoration treatment for varying time periods at two locations in Sundays Spekboomveld revealed that the stands under restoration are progressively regenerating canopy species biodiversity with increasing restoration age, and that intact sites are still the most diverse. The high total carbon content (TCC) measured within the older restored stands Rhinosterhoek (241 t C ha-1 after 50 years at a depth of 50 cm) rivals that recorded for intact spekboom thickets, and the number of recruits found within older restored sites rivals intact sites sampled. 2 The changes recorded in the above- and belowground environments potentially identify P. afra as an ecosystem engineer within spekboom dominated thickets that facillitates the build-up of carbon above- and belowground and the accompanying changes in soil quality and the unique microclimate aboveground, which enables the hypothetical threshold of the degraded state to be transcended. This restoration methodology is accordingly considered efficient and autogenic canopy species return was found to be prominent after a period of 35-50 years of restoration treatment.
- Full Text:
- Date Issued: 2011
Solid-phase extraction based sample preparation for the determination of drug and organic pollutant residue
- Authors: Pule, Bellah Oreeditse
- Date: 2011 , 2011-02-08
- Subjects: Food contamination , Drugs -- Analysis , Pharmaceutical chemistry , Extraction (Chemistry) , Sorbents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4406 , http://hdl.handle.net/10962/d1006711 , Food contamination , Drugs -- Analysis , Pharmaceutical chemistry , Extraction (Chemistry) , Sorbents
- Description: This thesis presents solid phase extraction (SPE) methodologies based on mixed-mode polymeric sorbents; a mixed mode strong anion exchanger (Agilent SampliQ SAX) and a mixed mode strong cation exchanger (Agilent SampliQ SCX). Furthermore, dispersive-SPE based on a quick, easy, cheap, effective, rugged and safe (QuEChERS) method was assessed for applicability in the determination of drug residues. The mixed-mode polymeric sorbents were evaluated for the simultaneous fractionation of drugs that exhibit diverse polarities with acidic, basic and neutral functionalities in biological matrices (plasma and urine). The polymeric skeleton of these sorbents entails an exchanger group and therefore provides two retention mechanisms, strong cation or anion exchange retention mechanisms with hydrophobic interactions. It was demonstrated that with a sequential elution protocol for sample clean-up analytes were fractionated into acidic, basic and neutral classes. The SAX was employed for analysis of ketoprofen, naproxen (acidic drugs), nortriptyline (basic) and secobarbital (neutral) from urine sample. The SCX was used for fractionating phenobarbital, p-toluamide (acidic), amphetamine, m-toluidine (basic) and acetaminophen (neutral drug) from plasma sample. QuEChERS method was employed for quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) from fish fillets and soil; 9 sulfonamides (SAs) from chicken muscles and acrylamide (AA) in cooking oil. The analyte recoveries ranged from 79.6 - 109% with RSDs ranging from 0.06 - 1.9% at three different fortification levels. Good linearity (r2 > 0.9990) was attained for most analytes. The limits of detection and quantification ranged from 0.03 - 0.84 μg/ml and 0.81 - 1.89 μg/ml respectively for analytes in biological samples. LODs and LOQs for analytes in food and environmental samples ranged from 0.02 to 0.39 and 0.25 to 1.30 ng/g respectively.
- Full Text:
- Date Issued: 2011
- Authors: Pule, Bellah Oreeditse
- Date: 2011 , 2011-02-08
- Subjects: Food contamination , Drugs -- Analysis , Pharmaceutical chemistry , Extraction (Chemistry) , Sorbents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4406 , http://hdl.handle.net/10962/d1006711 , Food contamination , Drugs -- Analysis , Pharmaceutical chemistry , Extraction (Chemistry) , Sorbents
- Description: This thesis presents solid phase extraction (SPE) methodologies based on mixed-mode polymeric sorbents; a mixed mode strong anion exchanger (Agilent SampliQ SAX) and a mixed mode strong cation exchanger (Agilent SampliQ SCX). Furthermore, dispersive-SPE based on a quick, easy, cheap, effective, rugged and safe (QuEChERS) method was assessed for applicability in the determination of drug residues. The mixed-mode polymeric sorbents were evaluated for the simultaneous fractionation of drugs that exhibit diverse polarities with acidic, basic and neutral functionalities in biological matrices (plasma and urine). The polymeric skeleton of these sorbents entails an exchanger group and therefore provides two retention mechanisms, strong cation or anion exchange retention mechanisms with hydrophobic interactions. It was demonstrated that with a sequential elution protocol for sample clean-up analytes were fractionated into acidic, basic and neutral classes. The SAX was employed for analysis of ketoprofen, naproxen (acidic drugs), nortriptyline (basic) and secobarbital (neutral) from urine sample. The SCX was used for fractionating phenobarbital, p-toluamide (acidic), amphetamine, m-toluidine (basic) and acetaminophen (neutral drug) from plasma sample. QuEChERS method was employed for quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) from fish fillets and soil; 9 sulfonamides (SAs) from chicken muscles and acrylamide (AA) in cooking oil. The analyte recoveries ranged from 79.6 - 109% with RSDs ranging from 0.06 - 1.9% at three different fortification levels. Good linearity (r2 > 0.9990) was attained for most analytes. The limits of detection and quantification ranged from 0.03 - 0.84 μg/ml and 0.81 - 1.89 μg/ml respectively for analytes in biological samples. LODs and LOQs for analytes in food and environmental samples ranged from 0.02 to 0.39 and 0.25 to 1.30 ng/g respectively.
- Full Text:
- Date Issued: 2011
SphereZyme (TM) technology for enhanced enzyme immobilisation application in biosensors
- Authors: Molawa, Letshego Gloria
- Date: 2011
- Subjects: Immobilized enzymes , Hydrolases , Hydrolysis , SphereZyme , Biosensors , Proteolytic enzymes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3989 , http://hdl.handle.net/10962/d1004048 , Immobilized enzymes , Hydrolases , Hydrolysis , SphereZyme , Biosensors , Proteolytic enzymes
- Description: Self-immobilisation enzyme technologies, such as SphereZyme™, suffer from the lack of applicability to hydrolyse large substrates. Solid support immobilisation is usually a method of choice, to produce a stable biocatalyst for large substrates hydrolysis in the industry. In order to investigate this limitation, a commercial protease called Alcalase® was chosen as a model enzyme due to its natural activity (hydrolysis of large substrates-proteins). Prior to immobilising through the SphereZyme™ technology, Alcalase® was partially purified through dialysis followed by CM Sepharose™ FF cation exchanger. Sample contaminants, such as salts and stabilisers can inhibit protein crosslinking by reacting with glutaraldehyde. Alcalase® was successfully separated into 3 proteases with the major peak correlating to a positive control run on native PAGE, indicating that it was likely subtilisin Carlsberg. A 16% alkaline protease activity for azo-casein hydrolysis was retained when 5% v/v PEI: 25% v/v glutaraldehyde solution was used as a crosslinking agent in Alcalase® SphereZyme™ production. An increase in activity was also observed for monomeric substrates (PNPA) where the highest was 55%. The highest % activities maintained when 0.33 M EDA: 25% v/v glutaraldehyde solution was initially used as crosslinking agent were 4.5% and 1.6% for monomeric and polymeric substrates, respectively. PEI is a hydrophilic branched polymer with an abundance of amine groups compared to EDA. A comparison study of immobilisation efficiencies of SphereZyme™, Eupergit® and Dendrispheres was also performed for large substrate biocatalysis. The two latter technologies are solid-support immobilisation methods. Dendrispheres reached its maximum loading capacity in the first 5 minute of the one hour binding time. Twenty minutes was chosen as a maximum binding time since there was constant protein maintained on the solid support and no enzyme loss was observed during the 1 hour binding time. PEI at pH 11.5, its native pH, gave the highest immobilisation yield and specific activity over the PEI pH range of 11.5 to 7. SphereZyme™ had the highest ratio for azocasein hydrolysis followed by Dendrispheres and Eupergit®. The SphereZyme™ was also shown to be applicable to biosensors for phenol detection. Different modifications of glassy carbon electrode (GCE) were evaluated as a benchmark for the fabrication of SphereZyme™ modified phenol biosensor. GCE modified with laccase SphereZyme™ entrapped in cellulose membrane was the best modification due to the broad catechol range (<0.950 mM), high correlation coefficient (R2, 0.995) and relative high sensitivity factor (0.305 μA.mM-1). This type of biosensor was also shown to be electroactive at pH 7.0 for which its control, free laccase, lacked electroactivity. From the catalytic constants calculated, GCE modified with laccase SphereZyme™ entrapped in cellulose membrane also gave the highest effectiveness factor (Imax/Km app) of 1.84 μA.mM-1. The modified GCE with Alcalase® SphereZyme™ was relatively more sensitive than GCE modified with free Alcalase®.
- Full Text:
- Date Issued: 2011
- Authors: Molawa, Letshego Gloria
- Date: 2011
- Subjects: Immobilized enzymes , Hydrolases , Hydrolysis , SphereZyme , Biosensors , Proteolytic enzymes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3989 , http://hdl.handle.net/10962/d1004048 , Immobilized enzymes , Hydrolases , Hydrolysis , SphereZyme , Biosensors , Proteolytic enzymes
- Description: Self-immobilisation enzyme technologies, such as SphereZyme™, suffer from the lack of applicability to hydrolyse large substrates. Solid support immobilisation is usually a method of choice, to produce a stable biocatalyst for large substrates hydrolysis in the industry. In order to investigate this limitation, a commercial protease called Alcalase® was chosen as a model enzyme due to its natural activity (hydrolysis of large substrates-proteins). Prior to immobilising through the SphereZyme™ technology, Alcalase® was partially purified through dialysis followed by CM Sepharose™ FF cation exchanger. Sample contaminants, such as salts and stabilisers can inhibit protein crosslinking by reacting with glutaraldehyde. Alcalase® was successfully separated into 3 proteases with the major peak correlating to a positive control run on native PAGE, indicating that it was likely subtilisin Carlsberg. A 16% alkaline protease activity for azo-casein hydrolysis was retained when 5% v/v PEI: 25% v/v glutaraldehyde solution was used as a crosslinking agent in Alcalase® SphereZyme™ production. An increase in activity was also observed for monomeric substrates (PNPA) where the highest was 55%. The highest % activities maintained when 0.33 M EDA: 25% v/v glutaraldehyde solution was initially used as crosslinking agent were 4.5% and 1.6% for monomeric and polymeric substrates, respectively. PEI is a hydrophilic branched polymer with an abundance of amine groups compared to EDA. A comparison study of immobilisation efficiencies of SphereZyme™, Eupergit® and Dendrispheres was also performed for large substrate biocatalysis. The two latter technologies are solid-support immobilisation methods. Dendrispheres reached its maximum loading capacity in the first 5 minute of the one hour binding time. Twenty minutes was chosen as a maximum binding time since there was constant protein maintained on the solid support and no enzyme loss was observed during the 1 hour binding time. PEI at pH 11.5, its native pH, gave the highest immobilisation yield and specific activity over the PEI pH range of 11.5 to 7. SphereZyme™ had the highest ratio for azocasein hydrolysis followed by Dendrispheres and Eupergit®. The SphereZyme™ was also shown to be applicable to biosensors for phenol detection. Different modifications of glassy carbon electrode (GCE) were evaluated as a benchmark for the fabrication of SphereZyme™ modified phenol biosensor. GCE modified with laccase SphereZyme™ entrapped in cellulose membrane was the best modification due to the broad catechol range (<0.950 mM), high correlation coefficient (R2, 0.995) and relative high sensitivity factor (0.305 μA.mM-1). This type of biosensor was also shown to be electroactive at pH 7.0 for which its control, free laccase, lacked electroactivity. From the catalytic constants calculated, GCE modified with laccase SphereZyme™ entrapped in cellulose membrane also gave the highest effectiveness factor (Imax/Km app) of 1.84 μA.mM-1. The modified GCE with Alcalase® SphereZyme™ was relatively more sensitive than GCE modified with free Alcalase®.
- Full Text:
- Date Issued: 2011
Statistical comparison of international size-based equity index using a mixture distribution
- Authors: Ngundze, Unathi
- Date: 2011
- Subjects: Mixture distributions (Probability theory) , Finance -- Statistics , Investment analysis , Portfolio management
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10576 , http://hdl.handle.net/10948/d1012367 , Mixture distributions (Probability theory) , Finance -- Statistics , Investment analysis , Portfolio management
- Description: Investors and financial analysts spend an inordinate amount of time, resources and effort in an attempt to perfect the science of maximising the level of financial returns. To this end, the field of distribution modelling and analysis of firm size effect is important as an investment analysis and appraisal tool. Numerous studies have been conducted to determine which distribution best fits stock returns (Mandelbrot, 1963; Fama, 1965 and Akgiray and Booth, 1988). Analysis and review of earlier research has revealed that researchers claim that the returns follow a normal distribution. However, the findings have not been without their own limitations in terms of the empirical results in that many also say that the research done does not account for the fat tails and skewness of the data. Some research studies dealing with the anomaly of firm size effect have led to the conclusion that smaller firms tend to command higher returns relative to their larger counterparts with a similar risk profile (Banz, 1981). Recently, Janse van Rensburg et al. (2009a) conducted a study in which both non- normality of stock returns and firm size effect were addressed simultaneously. They used a scale mixture of two normal distributions to compare the stock returns of large capitalisation and small capitalisation shares portfolios. The study concluded that in periods of high volatility, the small capitalisation portfolio is far more risky than the large capitalisation portfolio. In periods of low volatility they are equally risky. Janse van Rensburg et al. (2009a) identified a number of limitations to the study. These included data problems, survivorship bias, exclusion of dividends, and the use of standard statistical tests in the presence of non-normality. They concluded that it was difficult to generalise findings because of the use of only two (limited) portfolios. In the extension of the research, Janse van Rensburg (2009b) concluded that a scale mixture of two normal distributions provided a more superior fit than any other mixture. The scope of this research is an extension of the work by Janse van Rensburg et al. (2009a) and Janse van Rensburg (2009b), with a view to addressing several of the limitations and findings of the earlier studies. The Janse van rensburg (2009b) study was based on data from the Johannesburg Stock Exchange (JSE); this study seeks to compare their research by looking at the New York Stock Exchange (NYSE) to determine if similar results occur in developed markets. For analysis purposes, this study used the statistical software package R (R Development Core Team 2008) and its package mixtools (Young, Benaglia, Chauveau, Elmore, Hettmansperg, Hunter, Thomas, Xuan 2008). Some computation was also done using Microsoft Excel. This dissertation is arranged as follows: Chapter 2 is a literature review of some of the baseline studies and research that supports the conclusion that earlier research finding had serious limitations. Chapter 3 describes the data used in the study and gives a breakdown of portfolio formation and the methodology used in the study. Chapter 4 provides the statistical background of the methods used in this study. Chapter 5 presents the statistical analysis and distribution fitting of the data. Finally, Chapter 6 gives conclusions drawn from the results obtained in the analysis of data as well as recommendations for future work.
- Full Text:
- Date Issued: 2011
- Authors: Ngundze, Unathi
- Date: 2011
- Subjects: Mixture distributions (Probability theory) , Finance -- Statistics , Investment analysis , Portfolio management
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10576 , http://hdl.handle.net/10948/d1012367 , Mixture distributions (Probability theory) , Finance -- Statistics , Investment analysis , Portfolio management
- Description: Investors and financial analysts spend an inordinate amount of time, resources and effort in an attempt to perfect the science of maximising the level of financial returns. To this end, the field of distribution modelling and analysis of firm size effect is important as an investment analysis and appraisal tool. Numerous studies have been conducted to determine which distribution best fits stock returns (Mandelbrot, 1963; Fama, 1965 and Akgiray and Booth, 1988). Analysis and review of earlier research has revealed that researchers claim that the returns follow a normal distribution. However, the findings have not been without their own limitations in terms of the empirical results in that many also say that the research done does not account for the fat tails and skewness of the data. Some research studies dealing with the anomaly of firm size effect have led to the conclusion that smaller firms tend to command higher returns relative to their larger counterparts with a similar risk profile (Banz, 1981). Recently, Janse van Rensburg et al. (2009a) conducted a study in which both non- normality of stock returns and firm size effect were addressed simultaneously. They used a scale mixture of two normal distributions to compare the stock returns of large capitalisation and small capitalisation shares portfolios. The study concluded that in periods of high volatility, the small capitalisation portfolio is far more risky than the large capitalisation portfolio. In periods of low volatility they are equally risky. Janse van Rensburg et al. (2009a) identified a number of limitations to the study. These included data problems, survivorship bias, exclusion of dividends, and the use of standard statistical tests in the presence of non-normality. They concluded that it was difficult to generalise findings because of the use of only two (limited) portfolios. In the extension of the research, Janse van Rensburg (2009b) concluded that a scale mixture of two normal distributions provided a more superior fit than any other mixture. The scope of this research is an extension of the work by Janse van Rensburg et al. (2009a) and Janse van Rensburg (2009b), with a view to addressing several of the limitations and findings of the earlier studies. The Janse van rensburg (2009b) study was based on data from the Johannesburg Stock Exchange (JSE); this study seeks to compare their research by looking at the New York Stock Exchange (NYSE) to determine if similar results occur in developed markets. For analysis purposes, this study used the statistical software package R (R Development Core Team 2008) and its package mixtools (Young, Benaglia, Chauveau, Elmore, Hettmansperg, Hunter, Thomas, Xuan 2008). Some computation was also done using Microsoft Excel. This dissertation is arranged as follows: Chapter 2 is a literature review of some of the baseline studies and research that supports the conclusion that earlier research finding had serious limitations. Chapter 3 describes the data used in the study and gives a breakdown of portfolio formation and the methodology used in the study. Chapter 4 provides the statistical background of the methods used in this study. Chapter 5 presents the statistical analysis and distribution fitting of the data. Finally, Chapter 6 gives conclusions drawn from the results obtained in the analysis of data as well as recommendations for future work.
- Full Text:
- Date Issued: 2011
Studies in South African marine molluscan chemistry
- Authors: Bromley, Candice Leigh
- Date: 2011
- Subjects: Mollusks -- South Africa , Marine invertebrates -- South Africa , Marine metabolites -- South Africa , Chemical oceanography -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4356 , http://hdl.handle.net/10962/d1005021
- Description: This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.
- Full Text:
- Date Issued: 2011
- Authors: Bromley, Candice Leigh
- Date: 2011
- Subjects: Mollusks -- South Africa , Marine invertebrates -- South Africa , Marine metabolites -- South Africa , Chemical oceanography -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4356 , http://hdl.handle.net/10962/d1005021
- Description: This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.
- Full Text:
- Date Issued: 2011
Synthesis of bromochloromethane using phase transfer catalysis
- Authors: Brooks, Lancelot L
- Date: 2011
- Subjects: Chemistry, Analytic , Fire extinguishing agents , Chemical systems , Physical science
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10382 , http://hdl.handle.net/10948/d1008162 , Chemistry, Analytic , Fire extinguishing agents , Chemical systems , Physical science
- Description: The synthesis of bromochloromethane (BCM) in a batch reactor, using phase transfer catalysis, was investigated. During the synthetic procedure, sodium bromide (100.0g, 0.97mol) along with an excess amount of dichloromethane (265.0g, 3.12 mol) was charged to a reactor containing benzyl triethylammonium chloride (13 mmol), dissolved in 50 ml of water. The bench scale reactions were all carried out in a Parr 4520 bench top pressure reactor coupled to a Parr 4841 temperature controller. The method produced a 50.0 percent yield of the product BCM after a reaction time of 12 to 13 hours. The main objective for this investigation was to optimize the abovementioned reaction with respect to yield and reactor throughput. Quantitative analysis of BCM was performed on a Focus Gas Chromatograph, fitted with a flame ionization detector, and a BP20 column (30m × 0,32mm ID × 0,25 mm). Delta software, version 5.0, was applied for data collection and processing. The injector and detector port were set at 250°C and 280°C, respectively. The oven temperature was set and held at 40°C for a period of 2 minutes, then gradually increased at a rate of 10°C/min to 130°C, with the final hold time set for 1 minute. An analytical method for the quantitative analysis of BCM was developed, optimized and validated. Validation of the analytical method commenced over a period of three days, and focussed the following validation parameters: Accuracy, precision, and ruggedness. Statistical evaluation of the results obtained for precision showed that the error between individual injections is less than 2 percent for each component. However, ANOVA analysis showed a significant difference between the mean response factors obtained in the three day period (p-value < 0.05). Thus we could conclude that the response factors had to be determined on each day before quantitatively analyzing samples. The accuracy of the analytical method was assessed by using the percent recovery method. Results obtained showed that a mean percent recovery of 100.18 percent was obtained for BCM, with the absolute bias = 0.0004, and the percent bias = 0.18 percent. Hence the 95 confidence intervals for the percent recovery and percent bias are given by: (Lz, Uz) = (100.56 percent percent 102.15 percent), 13 (LPB, UPB) = (0.56 percent, 2.15 percent), respectively. Since the 95 percent confidence interval for the percent recovery contains 100, or equivalently, the 95 percent confidence interval for percent bias contains 0, the assay method is considered accurate and validated for BCM. In the same manner the accuracy and percent recovery for DCM and DBM was evaluated. The method was found to be accurate and validated for DBM, however, slightly biased in determining the recovered amount of DCM. With the analytical method validated, the batch production process could be evaluated. A total of six process variables, namely reaction time, water amount, temperature, volume of the two phases, stirring rate, and catalyst concentration, were selected for the study. The effects of the individual variables were determined in the classical manner, by varying only the one of interest while keeping all others constant. The experimental data generated was fit to a quadratic response surface model. The profile plots that were obtained from this model allowed a visual representation of the effect of the six variables. The experimental results obtained showed that the reaction follows pseudo zero-order kinetics and that the rate of the reaction is directly proportional to the concentration of the catalyst. The reaction obeys the Arrhenius equation, and the relatively high activation energy of 87kJ.mol -1 signifies that the rate constant is strongly dependent on the temperature of the reaction. The results also showed that the formation of BCM is favoured by an increase in the reaction temperature, catalyst concentration, and a high organic: aqueous phase ratio. Thus the synthesis of BCM using phase transfer catalyst could be optimised, to obtain a 100 percent yield BCM, by increasing both the reaction temperature to 105°C, and the concentration of the phase transfer catalyst -benzyl triethylammonium chloride - to 5.36 mol percent. The reaction time was also reduced to 6 hours.
- Full Text:
- Date Issued: 2011
- Authors: Brooks, Lancelot L
- Date: 2011
- Subjects: Chemistry, Analytic , Fire extinguishing agents , Chemical systems , Physical science
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10382 , http://hdl.handle.net/10948/d1008162 , Chemistry, Analytic , Fire extinguishing agents , Chemical systems , Physical science
- Description: The synthesis of bromochloromethane (BCM) in a batch reactor, using phase transfer catalysis, was investigated. During the synthetic procedure, sodium bromide (100.0g, 0.97mol) along with an excess amount of dichloromethane (265.0g, 3.12 mol) was charged to a reactor containing benzyl triethylammonium chloride (13 mmol), dissolved in 50 ml of water. The bench scale reactions were all carried out in a Parr 4520 bench top pressure reactor coupled to a Parr 4841 temperature controller. The method produced a 50.0 percent yield of the product BCM after a reaction time of 12 to 13 hours. The main objective for this investigation was to optimize the abovementioned reaction with respect to yield and reactor throughput. Quantitative analysis of BCM was performed on a Focus Gas Chromatograph, fitted with a flame ionization detector, and a BP20 column (30m × 0,32mm ID × 0,25 mm). Delta software, version 5.0, was applied for data collection and processing. The injector and detector port were set at 250°C and 280°C, respectively. The oven temperature was set and held at 40°C for a period of 2 minutes, then gradually increased at a rate of 10°C/min to 130°C, with the final hold time set for 1 minute. An analytical method for the quantitative analysis of BCM was developed, optimized and validated. Validation of the analytical method commenced over a period of three days, and focussed the following validation parameters: Accuracy, precision, and ruggedness. Statistical evaluation of the results obtained for precision showed that the error between individual injections is less than 2 percent for each component. However, ANOVA analysis showed a significant difference between the mean response factors obtained in the three day period (p-value < 0.05). Thus we could conclude that the response factors had to be determined on each day before quantitatively analyzing samples. The accuracy of the analytical method was assessed by using the percent recovery method. Results obtained showed that a mean percent recovery of 100.18 percent was obtained for BCM, with the absolute bias = 0.0004, and the percent bias = 0.18 percent. Hence the 95 confidence intervals for the percent recovery and percent bias are given by: (Lz, Uz) = (100.56 percent percent 102.15 percent), 13 (LPB, UPB) = (0.56 percent, 2.15 percent), respectively. Since the 95 percent confidence interval for the percent recovery contains 100, or equivalently, the 95 percent confidence interval for percent bias contains 0, the assay method is considered accurate and validated for BCM. In the same manner the accuracy and percent recovery for DCM and DBM was evaluated. The method was found to be accurate and validated for DBM, however, slightly biased in determining the recovered amount of DCM. With the analytical method validated, the batch production process could be evaluated. A total of six process variables, namely reaction time, water amount, temperature, volume of the two phases, stirring rate, and catalyst concentration, were selected for the study. The effects of the individual variables were determined in the classical manner, by varying only the one of interest while keeping all others constant. The experimental data generated was fit to a quadratic response surface model. The profile plots that were obtained from this model allowed a visual representation of the effect of the six variables. The experimental results obtained showed that the reaction follows pseudo zero-order kinetics and that the rate of the reaction is directly proportional to the concentration of the catalyst. The reaction obeys the Arrhenius equation, and the relatively high activation energy of 87kJ.mol -1 signifies that the rate constant is strongly dependent on the temperature of the reaction. The results also showed that the formation of BCM is favoured by an increase in the reaction temperature, catalyst concentration, and a high organic: aqueous phase ratio. Thus the synthesis of BCM using phase transfer catalyst could be optimised, to obtain a 100 percent yield BCM, by increasing both the reaction temperature to 105°C, and the concentration of the phase transfer catalyst -benzyl triethylammonium chloride - to 5.36 mol percent. The reaction time was also reduced to 6 hours.
- Full Text:
- Date Issued: 2011
Testing the existence and direction of "spill-over" of mussel recruits beyond the boundaries of marine protected areas
- Authors: Ludford, Adam
- Date: 2011
- Subjects: Marine parks and reserves -- South Africa -- Transkei , Marine resources conservation -- South Africa -- Transkei , Mussels -- Ecology -- South Africa -- Transkei , Mexilhao mussel -- Reproduction -- South Africa -- Transkei , Mexilhao mussel -- Behavior -- South Africa -- Transkei
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5786 , http://hdl.handle.net/10962/d1005474 , Marine parks and reserves -- South Africa -- Transkei , Marine resources conservation -- South Africa -- Transkei , Mussels -- Ecology -- South Africa -- Transkei , Mexilhao mussel -- Reproduction -- South Africa -- Transkei , Mexilhao mussel -- Behavior -- South Africa -- Transkei
- Description: Landscape ecology helps in predicting the influence of habitat fragmentation on populations. Marine protected areas (MPAs) are expected to create areas of good quality patches and so improve connectivity among shores. MPAs are believed not only to protect adult populations, but also to enhance recruitment both within MPAs and on surrounding exploited shores, therefore improving their ability to recover from overexploitation. As such, MPAs are a preferred management tool for the conservation of natural populations. Although MPAs have been demonstrated to enhance adult abundances, little work has been done on their ability to provide so called "spill-over" of recruits nor has the generality of the influence of MPAs been investigated in a single region with multiple control sites. The Transkei region, on the east coast of South Africa, and the intertidal mussel, Perna perna, offer an ideal system to test the generality of the influence of MPAs on surrounding shores, due to the presence of multiple MPAs and exploited control sites. Patterns of adult abundance were surveyed at four MPAs and two comparably sized exploited control sites. Adult abundances were, in general, found to be higher within MPAs than at exploited control sites, with adult abundances decreasing towards the edge of MPAs and decreasing even more on the outside shores. To simplify the sorting procedure for samples of mussel recruits, a new method using fractionated elutriation was devised and tested. This new method was found to be more accurate, although not statistically significant but also substantially more time consuming. The increase in accuracy although not statistically significant could be biologically significant, especially when looking at low numbers. This new method could, therefore, be very useful especially when [...] is low. Recruitment was estimated over three months during the main reproductive season at two of the MPAs and at appropriate control sites. I predicted that recruitment patterns would mirror the patterns found in adult abundances and that there would be directionality in patterns of recruitment, with northern sites having greater recruitment due to the direction of near-shore ocean currents. Contrary to this, there were no correlations between adult abundance and recruitment for any of the months or sites, with no clear spatial pattern of recruitment in any of the three months. There was, however, a slight trend of greater recruitment at northern sites. To explain the lack of consistency in recruitment and adult abundances, wind data were used to examine the near-shore surface currents in this area, with theoretical surface currents showing similar patterns to those observed for recruitment. From a landscape perspective, the good patches created by MPAs supply recruits to the surrounding matrix but the low quality of habitat in the matrix prevents rehabilitation. The quality of the matrix must therefore be first improved by reseeding these shores. These results emphasise that while MPAs may function in protecting adult abundances, their influence on supplying recruits and hence recovery of near-by exploited shores may be overestimated. This lack of influence on near-by exploited shores highlights the need for reseeding of shores in conjunction with suitable management plans.
- Full Text:
- Date Issued: 2011
- Authors: Ludford, Adam
- Date: 2011
- Subjects: Marine parks and reserves -- South Africa -- Transkei , Marine resources conservation -- South Africa -- Transkei , Mussels -- Ecology -- South Africa -- Transkei , Mexilhao mussel -- Reproduction -- South Africa -- Transkei , Mexilhao mussel -- Behavior -- South Africa -- Transkei
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5786 , http://hdl.handle.net/10962/d1005474 , Marine parks and reserves -- South Africa -- Transkei , Marine resources conservation -- South Africa -- Transkei , Mussels -- Ecology -- South Africa -- Transkei , Mexilhao mussel -- Reproduction -- South Africa -- Transkei , Mexilhao mussel -- Behavior -- South Africa -- Transkei
- Description: Landscape ecology helps in predicting the influence of habitat fragmentation on populations. Marine protected areas (MPAs) are expected to create areas of good quality patches and so improve connectivity among shores. MPAs are believed not only to protect adult populations, but also to enhance recruitment both within MPAs and on surrounding exploited shores, therefore improving their ability to recover from overexploitation. As such, MPAs are a preferred management tool for the conservation of natural populations. Although MPAs have been demonstrated to enhance adult abundances, little work has been done on their ability to provide so called "spill-over" of recruits nor has the generality of the influence of MPAs been investigated in a single region with multiple control sites. The Transkei region, on the east coast of South Africa, and the intertidal mussel, Perna perna, offer an ideal system to test the generality of the influence of MPAs on surrounding shores, due to the presence of multiple MPAs and exploited control sites. Patterns of adult abundance were surveyed at four MPAs and two comparably sized exploited control sites. Adult abundances were, in general, found to be higher within MPAs than at exploited control sites, with adult abundances decreasing towards the edge of MPAs and decreasing even more on the outside shores. To simplify the sorting procedure for samples of mussel recruits, a new method using fractionated elutriation was devised and tested. This new method was found to be more accurate, although not statistically significant but also substantially more time consuming. The increase in accuracy although not statistically significant could be biologically significant, especially when looking at low numbers. This new method could, therefore, be very useful especially when [...] is low. Recruitment was estimated over three months during the main reproductive season at two of the MPAs and at appropriate control sites. I predicted that recruitment patterns would mirror the patterns found in adult abundances and that there would be directionality in patterns of recruitment, with northern sites having greater recruitment due to the direction of near-shore ocean currents. Contrary to this, there were no correlations between adult abundance and recruitment for any of the months or sites, with no clear spatial pattern of recruitment in any of the three months. There was, however, a slight trend of greater recruitment at northern sites. To explain the lack of consistency in recruitment and adult abundances, wind data were used to examine the near-shore surface currents in this area, with theoretical surface currents showing similar patterns to those observed for recruitment. From a landscape perspective, the good patches created by MPAs supply recruits to the surrounding matrix but the low quality of habitat in the matrix prevents rehabilitation. The quality of the matrix must therefore be first improved by reseeding these shores. These results emphasise that while MPAs may function in protecting adult abundances, their influence on supplying recruits and hence recovery of near-by exploited shores may be overestimated. This lack of influence on near-by exploited shores highlights the need for reseeding of shores in conjunction with suitable management plans.
- Full Text:
- Date Issued: 2011
The critical natural capital of the Buffalo City Municipality, South Africa : harnessing local action for biodiversity conservation
- Authors: Hagen, Brett
- Date: 2011
- Subjects: Natural resources -- South Africa -- Buffalo City , Biodiversity conservation -- South Africa -- Buffalo City , Ecosystem services -- South Africa -- Buffalo City , Nature conservation -- South Africa -- Buffalo City , Environmental protection -- South Africa -- Buffalo City , Environmental degradation -- South Africa -- Buffalo City , Restoration ecology -- South Africa -- Buffalo City
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4753 , http://hdl.handle.net/10962/d1007075 , Natural resources -- South Africa -- Buffalo City , Biodiversity conservation -- South Africa -- Buffalo City , Ecosystem services -- South Africa -- Buffalo City , Nature conservation -- South Africa -- Buffalo City , Environmental protection -- South Africa -- Buffalo City , Environmental degradation -- South Africa -- Buffalo City , Restoration ecology -- South Africa -- Buffalo City
- Description: Globally, ecosystems provide services of almost twice the value of global gross national product (Costanza et al., 2006). The Buffalo City Municipality (BCM), South Africa contains biodiversity of national and international importance (Pierce, 2003; Pierce et al., 2005). Despite this, the municipality continues to experience loss of both urban and rural biodiversity (Buffalo City Municipality, 2006a). This study sought to determine the status of biodiversity, and the potential for ecosystem services to contribute to conservation, within the BCM. Biodiversity features, including ecosystem type, species of special concern and biodiversity processes, were identified and mapped using a GIS to produce a biodiversity priority index for the BCM. Current transformation status was then mapped to determine the level of ecosystem degradation within the BCM. Priority biodiversity areas as well as individual biodiversity features were spatially overlain against current transformation status and protected areas and analysed using a GIS to determine the level of degradation and protection of BCM biodiversity. In total 3.5 % of total BCM biodiversity was protected. Of the 24 ecosystem types, 11 (45%) had less than 1% under protection, while 16 (67%) had less than five percent protected. Not restorable areas, thus completely lost to biodiversity conservation, comprised just less than a quarter of the total BCM area while un-impacted areas comprised just 12.3%. Twenty five ecosystem services were identified as being provided by intact natural ecosystems within the BCM. The natural capital providing these services was identified and mapped to produce an ecosystem service index (ESI) using a GIS. This ecosystem service index and the biodiversity priority index were overlain to determine their level of correlation. Overall ESI correlation with priority biodiversity was weak although several individual ecosystem services, including carbon sequestration, showed correlation. Using the above data layers an implementation plan and conservation framework was proposed to assist the coordination of local conservation action within the BCM. It is concluded that ecosystem services are a potentially useful tool for conservationists at the local level seeking to ensure that biodiversity has relevance to and receives protection from broader society.
- Full Text:
- Date Issued: 2011
- Authors: Hagen, Brett
- Date: 2011
- Subjects: Natural resources -- South Africa -- Buffalo City , Biodiversity conservation -- South Africa -- Buffalo City , Ecosystem services -- South Africa -- Buffalo City , Nature conservation -- South Africa -- Buffalo City , Environmental protection -- South Africa -- Buffalo City , Environmental degradation -- South Africa -- Buffalo City , Restoration ecology -- South Africa -- Buffalo City
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4753 , http://hdl.handle.net/10962/d1007075 , Natural resources -- South Africa -- Buffalo City , Biodiversity conservation -- South Africa -- Buffalo City , Ecosystem services -- South Africa -- Buffalo City , Nature conservation -- South Africa -- Buffalo City , Environmental protection -- South Africa -- Buffalo City , Environmental degradation -- South Africa -- Buffalo City , Restoration ecology -- South Africa -- Buffalo City
- Description: Globally, ecosystems provide services of almost twice the value of global gross national product (Costanza et al., 2006). The Buffalo City Municipality (BCM), South Africa contains biodiversity of national and international importance (Pierce, 2003; Pierce et al., 2005). Despite this, the municipality continues to experience loss of both urban and rural biodiversity (Buffalo City Municipality, 2006a). This study sought to determine the status of biodiversity, and the potential for ecosystem services to contribute to conservation, within the BCM. Biodiversity features, including ecosystem type, species of special concern and biodiversity processes, were identified and mapped using a GIS to produce a biodiversity priority index for the BCM. Current transformation status was then mapped to determine the level of ecosystem degradation within the BCM. Priority biodiversity areas as well as individual biodiversity features were spatially overlain against current transformation status and protected areas and analysed using a GIS to determine the level of degradation and protection of BCM biodiversity. In total 3.5 % of total BCM biodiversity was protected. Of the 24 ecosystem types, 11 (45%) had less than 1% under protection, while 16 (67%) had less than five percent protected. Not restorable areas, thus completely lost to biodiversity conservation, comprised just less than a quarter of the total BCM area while un-impacted areas comprised just 12.3%. Twenty five ecosystem services were identified as being provided by intact natural ecosystems within the BCM. The natural capital providing these services was identified and mapped to produce an ecosystem service index (ESI) using a GIS. This ecosystem service index and the biodiversity priority index were overlain to determine their level of correlation. Overall ESI correlation with priority biodiversity was weak although several individual ecosystem services, including carbon sequestration, showed correlation. Using the above data layers an implementation plan and conservation framework was proposed to assist the coordination of local conservation action within the BCM. It is concluded that ecosystem services are a potentially useful tool for conservationists at the local level seeking to ensure that biodiversity has relevance to and receives protection from broader society.
- Full Text:
- Date Issued: 2011
The demography and population dynamics of a re-introduced black rhinoceros population on the Great Fish River Reserve, Eastern Cape Province
- Authors: Fike, Bradley Robin
- Date: 2011
- Subjects: Black rhinoceros -- South Africa -- Great Fish River Valley , Population biology -- South Africa -- Great Fish River Valley , Black rhinoceros -- Habitat -- South Africa -- Great Fish River Valley , Black rhinoceros -- Adaptation -- South Africa -- Great Fish River Valley , Black rhinoceros -- Ecology -- South Africa -- Great Fish River Valley
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5948 , http://hdl.handle.net/10962/d1020869
- Description: The re-introduction of black rhinoceros onto the Great Fish River Reserve in the Eastern Cape, following the species absence for over a century, created an opportunity to study this species in the thicket biome, and in particular the succulent thicket of the Great Fish River valley. The thicket biome is quite different from the habitats in which other extant populations of these animals are found and where studies of their demography have been undertaken. Data collection occurred from May 1986, with the arrival of the first four animals to December 2008, when the population was estimated to be 144 individuals. A variety of monitoring techniques were used including direct ground observations, aerial helicopter census, aerial monitoring by microlight aircraft, camera traps and opportunistic observations, each with its own advantages and disadvantages. The combination of methods and effort has resulted in the population being recognized as completely known with up to 97% of the animals being located at least once per year with a mean frequency of sightings of 11.5 per animal per year. In 2008, the population was about 20% juvenile, 36% sub-adult and 44% adult with a female biased sex ratio of 1.3 females per male. Mean age at first birth was about 80 months and this increased significantly with increasing density of black rhinoceroses. Mean intercalf interval was about 28 months and 41% of adult females gave birth each year. Mortality rates were low for juveniles, higher for sub-adults and higher for males than females. There was a weak but significant positive effect of density on male mortality. Population growth rate was about 10% and was not significantly affected by density. These results suggest that this population is beginning to show the first indications of density dependant constraints and that harvesting should be implemented in order to maintain the productive tempo. A secondary goal of the Management Plan will then be realized as the population functions as a donor to establish founder populations elsewhere within the Diceros bicornis minor range.
- Full Text:
- Date Issued: 2011
- Authors: Fike, Bradley Robin
- Date: 2011
- Subjects: Black rhinoceros -- South Africa -- Great Fish River Valley , Population biology -- South Africa -- Great Fish River Valley , Black rhinoceros -- Habitat -- South Africa -- Great Fish River Valley , Black rhinoceros -- Adaptation -- South Africa -- Great Fish River Valley , Black rhinoceros -- Ecology -- South Africa -- Great Fish River Valley
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5948 , http://hdl.handle.net/10962/d1020869
- Description: The re-introduction of black rhinoceros onto the Great Fish River Reserve in the Eastern Cape, following the species absence for over a century, created an opportunity to study this species in the thicket biome, and in particular the succulent thicket of the Great Fish River valley. The thicket biome is quite different from the habitats in which other extant populations of these animals are found and where studies of their demography have been undertaken. Data collection occurred from May 1986, with the arrival of the first four animals to December 2008, when the population was estimated to be 144 individuals. A variety of monitoring techniques were used including direct ground observations, aerial helicopter census, aerial monitoring by microlight aircraft, camera traps and opportunistic observations, each with its own advantages and disadvantages. The combination of methods and effort has resulted in the population being recognized as completely known with up to 97% of the animals being located at least once per year with a mean frequency of sightings of 11.5 per animal per year. In 2008, the population was about 20% juvenile, 36% sub-adult and 44% adult with a female biased sex ratio of 1.3 females per male. Mean age at first birth was about 80 months and this increased significantly with increasing density of black rhinoceroses. Mean intercalf interval was about 28 months and 41% of adult females gave birth each year. Mortality rates were low for juveniles, higher for sub-adults and higher for males than females. There was a weak but significant positive effect of density on male mortality. Population growth rate was about 10% and was not significantly affected by density. These results suggest that this population is beginning to show the first indications of density dependant constraints and that harvesting should be implemented in order to maintain the productive tempo. A secondary goal of the Management Plan will then be realized as the population functions as a donor to establish founder populations elsewhere within the Diceros bicornis minor range.
- Full Text:
- Date Issued: 2011
The design and synthesis of multidentate N-heterocyclic carbenes as metathesis catalyst ligands
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
The development and assessment of a fixed dose combination tablet of Ranitidine and Metronidazole
- Authors: King'ori, Loti David
- Date: 2011 , 2011-04-07
- Subjects: Ulcers -- Treatment , Ranitidine -- Evaluation , Metronidazole -- Evaluation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3858 , http://hdl.handle.net/10962/d1013359
- Description: The oral route of drug administration is convenient since it is acceptable to most patients and the manufacturing processes used to produce tablets and capsules are relatively simple when compared to those used to manufacture other types of dosage forms. Metronidazole (MTZ) and Ranitidine (RTD) have been used in combination, as part of triple therapy for the treatment of ulcers. However the use of large numbers of tablets and long duration of therapy makes adherence to drug treatment challenging for patients. Therefore the formulation of a fixed dose combination (FDC) of MTZ and RTD may improve patient adherence to therapy and consequently may reduce morbidity and mortality due to ulcers. A stability indicating HPLC method for the simultaneous analysis of MTZ and RTD was developed and validated according to the International Conference on Harmonization (ICH) guidelines. The method was sensitive, selective, precise, accurate and linear.Preformulation studies were performed on the active pharmaceutical ingredients (API) alone and in combination with potential excipients. Differential scanning calorimetry (DSC) studies revealed a potential interaction between MTZ and RTD, however the interaction was not apparent following IR analysis of the same samples. DSC analyses of the API in combination with potential excipients revealed that the compounds were compatible with most materials with the exception of a binary mixture of RTD and Dibasic calcium phosphate (DCP) that exhibited a potential interaction. Thermal gravimetric analysis (TGA) of MTZ and RTD revealed that both compounds exhibited thermal stability. The Carrs Index (CI) and Hausner Ratio (HR) values of MTZ and RTD indicated that both compounds exhibited poor flow and compressibility properties, whereas the CI and HR values for (Microcrystalline cellulose) MCC and DCP indicated better flowability and compressibility characteristics.Direct compression and wet granulation processes were assessed to identify a suitable method of manufacture of FDC tablets of MTZ and RTD. The blends were evaluated using bulk and tapped density and the resultant tablets were evaluated for weight uniformity, crushing strength, tensile strength and disintegration time. The wet granulation method of manufacture produced tablets that showed acceptable pharmacotechnical properties: this approach was therefore used as the method of manufacture of FDC tablets of MTZ and RTD. Tablet formulations comprised of API, viz. MTZ and RTD and different compositions of MCC, DCP, Sodium starch glycolate (SSG) and Croscarmellose sodium (CCS), were manufactured in order to screen for an appropriate diluent and disintegrant composition for use in response surface studies. Assays of tablet content and in vitro drug release were undertaken using the validated HPLC method. Tablets in which MCC and CCS were used appeared to produce better assay and dissolution results as compared to those manufactured using DCP and SSG. Consequently a formulation comprised of MCC and CCS was selected and used in studies in which the effect(s) of level two formulation and composition changes as described in the Scale and Post Approval Changes for Immediate Release (SUPAC-IR) Guidelines on tablet disintegration and in vitro release were assessed. A Box-Behnken statistical design was used for the investigation of the effect of input factors, viz. CCS, (Polyvinyl pyrollidone K30) PVP-K30 and magnesium stearate on measured responses, viz. disintegration time and percent drug release in 10 minutes (Q10). CCS appeared to have an inverse linear relationship on disintegration time and a linear relationship with the Q10 for MTZ and RTD, whereas PVP-K30 and magnesium stearate appeared to have an antagonistic effect on the measured responses. Furthermore CCS and magnesium stearate exhibited an interaction that had an agonistic effect on the Q10 value for RTD. A numerical optimization approach was used to predict a formulation composition that would produce tablets that exhibited a disintegration time and Q10 values for MTZ and RTD that fell within the constraints set in our laboratory. The resultant model was found to be accurate and had a percent prediction error of < 5% for all measured response variables.FDC tablets of MTZ and RTD have been successfully produced. The disintegration of the tablet and dissolution of the API were within compendial specifications and the tablets are of suitable quality and have the potential to be further investigated to reduce the pill burden in the treatment of ulcers.
- Full Text:
- Date Issued: 2011
- Authors: King'ori, Loti David
- Date: 2011 , 2011-04-07
- Subjects: Ulcers -- Treatment , Ranitidine -- Evaluation , Metronidazole -- Evaluation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3858 , http://hdl.handle.net/10962/d1013359
- Description: The oral route of drug administration is convenient since it is acceptable to most patients and the manufacturing processes used to produce tablets and capsules are relatively simple when compared to those used to manufacture other types of dosage forms. Metronidazole (MTZ) and Ranitidine (RTD) have been used in combination, as part of triple therapy for the treatment of ulcers. However the use of large numbers of tablets and long duration of therapy makes adherence to drug treatment challenging for patients. Therefore the formulation of a fixed dose combination (FDC) of MTZ and RTD may improve patient adherence to therapy and consequently may reduce morbidity and mortality due to ulcers. A stability indicating HPLC method for the simultaneous analysis of MTZ and RTD was developed and validated according to the International Conference on Harmonization (ICH) guidelines. The method was sensitive, selective, precise, accurate and linear.Preformulation studies were performed on the active pharmaceutical ingredients (API) alone and in combination with potential excipients. Differential scanning calorimetry (DSC) studies revealed a potential interaction between MTZ and RTD, however the interaction was not apparent following IR analysis of the same samples. DSC analyses of the API in combination with potential excipients revealed that the compounds were compatible with most materials with the exception of a binary mixture of RTD and Dibasic calcium phosphate (DCP) that exhibited a potential interaction. Thermal gravimetric analysis (TGA) of MTZ and RTD revealed that both compounds exhibited thermal stability. The Carrs Index (CI) and Hausner Ratio (HR) values of MTZ and RTD indicated that both compounds exhibited poor flow and compressibility properties, whereas the CI and HR values for (Microcrystalline cellulose) MCC and DCP indicated better flowability and compressibility characteristics.Direct compression and wet granulation processes were assessed to identify a suitable method of manufacture of FDC tablets of MTZ and RTD. The blends were evaluated using bulk and tapped density and the resultant tablets were evaluated for weight uniformity, crushing strength, tensile strength and disintegration time. The wet granulation method of manufacture produced tablets that showed acceptable pharmacotechnical properties: this approach was therefore used as the method of manufacture of FDC tablets of MTZ and RTD. Tablet formulations comprised of API, viz. MTZ and RTD and different compositions of MCC, DCP, Sodium starch glycolate (SSG) and Croscarmellose sodium (CCS), were manufactured in order to screen for an appropriate diluent and disintegrant composition for use in response surface studies. Assays of tablet content and in vitro drug release were undertaken using the validated HPLC method. Tablets in which MCC and CCS were used appeared to produce better assay and dissolution results as compared to those manufactured using DCP and SSG. Consequently a formulation comprised of MCC and CCS was selected and used in studies in which the effect(s) of level two formulation and composition changes as described in the Scale and Post Approval Changes for Immediate Release (SUPAC-IR) Guidelines on tablet disintegration and in vitro release were assessed. A Box-Behnken statistical design was used for the investigation of the effect of input factors, viz. CCS, (Polyvinyl pyrollidone K30) PVP-K30 and magnesium stearate on measured responses, viz. disintegration time and percent drug release in 10 minutes (Q10). CCS appeared to have an inverse linear relationship on disintegration time and a linear relationship with the Q10 for MTZ and RTD, whereas PVP-K30 and magnesium stearate appeared to have an antagonistic effect on the measured responses. Furthermore CCS and magnesium stearate exhibited an interaction that had an agonistic effect on the Q10 value for RTD. A numerical optimization approach was used to predict a formulation composition that would produce tablets that exhibited a disintegration time and Q10 values for MTZ and RTD that fell within the constraints set in our laboratory. The resultant model was found to be accurate and had a percent prediction error of < 5% for all measured response variables.FDC tablets of MTZ and RTD have been successfully produced. The disintegration of the tablet and dissolution of the API were within compendial specifications and the tablets are of suitable quality and have the potential to be further investigated to reduce the pill burden in the treatment of ulcers.
- Full Text:
- Date Issued: 2011
The development of an in vitro system for the production of drug metabolites using microsomal enzymes from bovine liver
- Authors: Morrison, Roxanne
- Date: 2011
- Subjects: Drugs -- Metabolism , Xenobiotics -- Metabolism , Metabolites , Drugs -- Testing , Toxicity testing -- In vitro , Doping in horse racing -- Control -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4087 , http://hdl.handle.net/10962/d1007698 , Drugs -- Metabolism , Xenobiotics -- Metabolism , Metabolites , Drugs -- Testing , Toxicity testing -- In vitro , Doping in horse racing -- Control -- Research
- Description: Drug metabolism is a specialised subset of xenobiotic metabolism, pertaining to the breakdown and elimination of pharmaceutical drugs. The enzymes involved in these pathways are the cytochrome P450 family of isozymes. Metabolism is an important factor in determining the pharmacological effects of drugs. The main aim of this study was to develop a system whereby the major metabolites of drugs can be produced in vitro. An in vitro system was developed and optimised using commercially prepared microsomes from rat liver and coumarin (by monitoring its conversion to 7-hydroxycoumarin) as a model. The optimum running conditions for the incubations were 50 μM coumarin, 50 μg protein/ml microsomes, 1 mM NADP⁺, 5 mM G6P and 1U/ml G6PDH incubated for 30 minutes at 38℃. The HPLC method for the detection of coumarin and 7-hydroxycoumarin was also validated with respect to linearity, reproducibility, precision, accuracy and lower limits of detection and quantification. The system developed was then tested using microsomes prepared from fresh bovine liver on these ten drugs of interest in doping control in horse racing: diazepam, nordiazepam, oxazepam, promazine, acepromazine, chlorpromazine, morphine, codeine, etoricoxib and lumiracoxib. The bovine liver microsomes were prepared using differential centrifugation and had activity on a par with the commercial preparations. This in vitro system metabolised the drugs and produced both phase I and II metabolites, similar to those observed in humans and horses in vivo. For example, the major metabolites of the benzodiazepine drug, diazepam, nordiazepam, temazepam and oxazepam as well as the glucuronidated phase II products were all found after incubations with the bovine liver microsomes. The metabolism of the drugs was also investigated in silico using the computational procedure, MetaSite. MetaSite was able to successfully predict known metabolites for most of the drugs studied. Differences were observed from the in vitro incubations and this is most likely due to MetaSite using only human cytochrome P450s for analysis.
- Full Text:
- Date Issued: 2011
- Authors: Morrison, Roxanne
- Date: 2011
- Subjects: Drugs -- Metabolism , Xenobiotics -- Metabolism , Metabolites , Drugs -- Testing , Toxicity testing -- In vitro , Doping in horse racing -- Control -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4087 , http://hdl.handle.net/10962/d1007698 , Drugs -- Metabolism , Xenobiotics -- Metabolism , Metabolites , Drugs -- Testing , Toxicity testing -- In vitro , Doping in horse racing -- Control -- Research
- Description: Drug metabolism is a specialised subset of xenobiotic metabolism, pertaining to the breakdown and elimination of pharmaceutical drugs. The enzymes involved in these pathways are the cytochrome P450 family of isozymes. Metabolism is an important factor in determining the pharmacological effects of drugs. The main aim of this study was to develop a system whereby the major metabolites of drugs can be produced in vitro. An in vitro system was developed and optimised using commercially prepared microsomes from rat liver and coumarin (by monitoring its conversion to 7-hydroxycoumarin) as a model. The optimum running conditions for the incubations were 50 μM coumarin, 50 μg protein/ml microsomes, 1 mM NADP⁺, 5 mM G6P and 1U/ml G6PDH incubated for 30 minutes at 38℃. The HPLC method for the detection of coumarin and 7-hydroxycoumarin was also validated with respect to linearity, reproducibility, precision, accuracy and lower limits of detection and quantification. The system developed was then tested using microsomes prepared from fresh bovine liver on these ten drugs of interest in doping control in horse racing: diazepam, nordiazepam, oxazepam, promazine, acepromazine, chlorpromazine, morphine, codeine, etoricoxib and lumiracoxib. The bovine liver microsomes were prepared using differential centrifugation and had activity on a par with the commercial preparations. This in vitro system metabolised the drugs and produced both phase I and II metabolites, similar to those observed in humans and horses in vivo. For example, the major metabolites of the benzodiazepine drug, diazepam, nordiazepam, temazepam and oxazepam as well as the glucuronidated phase II products were all found after incubations with the bovine liver microsomes. The metabolism of the drugs was also investigated in silico using the computational procedure, MetaSite. MetaSite was able to successfully predict known metabolites for most of the drugs studied. Differences were observed from the in vitro incubations and this is most likely due to MetaSite using only human cytochrome P450s for analysis.
- Full Text:
- Date Issued: 2011
The diversity of aquatic insects in the Tsitsikamma region, with implications for aquatic ecosystem conservation
- Authors: Bellingan, Terence Andrew
- Date: 2011
- Subjects: Aquatic insects -- South Africa -- Tsitsikamma , Aquatic insects -- Classification -- South Africa -- Tsitsikamma , Aquatic ecology -- South Africa -- Tsitsikamma , Ecosystem management -- South Africa -- Tsitsikamma , Stream conservation -- South Africa -- Tsitsikamma
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5664 , http://hdl.handle.net/10962/d1005348 , Aquatic insects -- South Africa -- Tsitsikamma , Aquatic insects -- Classification -- South Africa -- Tsitsikamma , Aquatic ecology -- South Africa -- Tsitsikamma , Ecosystem management -- South Africa -- Tsitsikamma , Stream conservation -- South Africa -- Tsitsikamma
- Description: As a result of research carried out within the last decade to assess the diversity of macroinvertebrates of the Salt River in the Western Cape Province, South Africa, surveys of macroinvertebrates of 20 sites on 11 selected rivers from the same mountain range source were undertaken. This was done to make a preliminary assessment of the conservation status of the rivers of this region. Aquatic insects from the orders Ephemeroptera, Odonata, Plecoptera, Megaloptera, Trichoptera and the dipteran family Simuliidae were collected using techniques to maximize the number of taxa found. The insects collected were identified to species level where possible. Water physicochemical parameters were recorded at all sites for each sampling trip to characterize these rivers and to establish a set of baseline data for future comparisons. These parameters included measurements made on site and analysis of the concentrations of all the major ions in water samples in the laboratory. Multivariate analyses including Principle Components Analysis and Canonical Correspondence Analysis were used to reveal patterns within the water physicochemistry and species distributional data. Results include the identification of 123 species from 70 genera and 30 families. A total of 31 species were found to be undescribed, of which 17 were not previously collected and are thus completely new to science. In addition, four of these species could not be placed into any known genus. The analysis of water physicochemistry showed a clear distinction between rivers of Table Mountain sandstone and Bokkeveld shale origin. Downstream effects of anthropogenic influences were discernable too. Distinct macroinvertebrate assemblages were found based upon stream order and water chemistry composition. pH proved to be the most important driver of invertebrate assemblage composition. The high levels of endemism of the macroinvertebrates found within the upper reaches of these rivers and their degree of ecological specialization make these systems a priority for the conservation of aquatic biodiversity on a national and global scale.
- Full Text:
- Date Issued: 2011
- Authors: Bellingan, Terence Andrew
- Date: 2011
- Subjects: Aquatic insects -- South Africa -- Tsitsikamma , Aquatic insects -- Classification -- South Africa -- Tsitsikamma , Aquatic ecology -- South Africa -- Tsitsikamma , Ecosystem management -- South Africa -- Tsitsikamma , Stream conservation -- South Africa -- Tsitsikamma
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5664 , http://hdl.handle.net/10962/d1005348 , Aquatic insects -- South Africa -- Tsitsikamma , Aquatic insects -- Classification -- South Africa -- Tsitsikamma , Aquatic ecology -- South Africa -- Tsitsikamma , Ecosystem management -- South Africa -- Tsitsikamma , Stream conservation -- South Africa -- Tsitsikamma
- Description: As a result of research carried out within the last decade to assess the diversity of macroinvertebrates of the Salt River in the Western Cape Province, South Africa, surveys of macroinvertebrates of 20 sites on 11 selected rivers from the same mountain range source were undertaken. This was done to make a preliminary assessment of the conservation status of the rivers of this region. Aquatic insects from the orders Ephemeroptera, Odonata, Plecoptera, Megaloptera, Trichoptera and the dipteran family Simuliidae were collected using techniques to maximize the number of taxa found. The insects collected were identified to species level where possible. Water physicochemical parameters were recorded at all sites for each sampling trip to characterize these rivers and to establish a set of baseline data for future comparisons. These parameters included measurements made on site and analysis of the concentrations of all the major ions in water samples in the laboratory. Multivariate analyses including Principle Components Analysis and Canonical Correspondence Analysis were used to reveal patterns within the water physicochemistry and species distributional data. Results include the identification of 123 species from 70 genera and 30 families. A total of 31 species were found to be undescribed, of which 17 were not previously collected and are thus completely new to science. In addition, four of these species could not be placed into any known genus. The analysis of water physicochemistry showed a clear distinction between rivers of Table Mountain sandstone and Bokkeveld shale origin. Downstream effects of anthropogenic influences were discernable too. Distinct macroinvertebrate assemblages were found based upon stream order and water chemistry composition. pH proved to be the most important driver of invertebrate assemblage composition. The high levels of endemism of the macroinvertebrates found within the upper reaches of these rivers and their degree of ecological specialization make these systems a priority for the conservation of aquatic biodiversity on a national and global scale.
- Full Text:
- Date Issued: 2011
The effect of mussel bed structure on the associated infauna in South Africa and the interaction between mussel and epibiotic barnacles
- Jordaan, Tembisa Nomathamsanqa
- Authors: Jordaan, Tembisa Nomathamsanqa
- Date: 2011
- Subjects: Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5675 , http://hdl.handle.net/10962/d1005360 , Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Description: Mussels are important ecological engineers on intertidal rocks where they create habitat that contributes substantially to overall biodiversity. They provide secondary substratum for other free-living, infaunal or epifaunal organisms, and increase the surface area for settlement by densely packing together into complex multilayered beds. The introduction of the alien invasive mussel Mytilus galloprovincialis has extended the upper limit of mussels on the south coast of South Africa, potentially increasing habitat for associated fauna. The aim of this study was to describe the structure of mussel beds, the general biodiversity associated with multi- and monolayered mussel beds of indigenous Perna perna and alien M. galloprovincialis, and to determine the relationship between mussels and epibiotic barnacles. This was done to determine the community structure of associated macrofauna and the role of mussels as biological facilitators. Samples were collected in Plettenberg Bay, South Africa, where M. galloprovincialis dominates the high mussel zone and P. perna the low zone. Three 15 X 15 cm quadrats were scraped off the rock in the high and low zones, and in the mid zone where the two mussel species co-exist. The samples were collected on 3 occasions. In the laboratory mussel-size was measured and sediment trapped within the samples was separated through 75 μm, 1 mm and 5 mm mesh. The macrofauna was sorted from the 1 mm and 5 mm sieves and identified to species level where possible. The epibiotic relationship between mussels and barnacles was assessed by measuring the prevalence and intensity of barnacle infestation and the condition index of infested mussels. Multivariate analysis was used on the mean abundance data of the species for each treatment (Hierarchical clustering, multidimensional scaling, analysis of similarity and similarity of percentages) and ANOVA was used for most of the statistical analyses. Overall, the results showed that tidal height influences the species composition and abundance of associated fauna. While mussel bed layering influenced the accumulation of sediments; it had no significant effect on the associated fauna. Time of collection also had a strong effect. While there was an overlap of species among samples from January, May and March, the principal species contributing to similarity among the March samples were not found in the other two months. The outcomes of this study showed that low shore mussel beds not only supported a higher abundance and diversity of species, but were also the most structurally complex. Although the condition index of mussels did not correlate to the percentage cover of barnacle epibionts, it was also evident that low shore mussels had the highest prevalence. The levels of barnacle infestation (intensity) for each mussel species were highest where it was common and lowest where it was least abundant. This is viewed as a natural artefact of the distribution patterns of P. perna and M. galloprovincialis across the shore. Mussels are more efficient as facilitators on the low mussel zone than the high mussel zone possibly because they provide habitats that are more effective in protecting the associated macrofauna from the effects of competition and predation, than they are at eliminating the effects of physical stress on the high shore. Although mussels create less stressful habitats and protect organisms from the physical stress of the high shore, there are clear limitations in their ability to provide ideal habitats. The biological associations in an ecosystem can be made weak or strong depending on the external abiotic factors and the adaptability of the affected organisms.
- Full Text:
- Date Issued: 2011
- Authors: Jordaan, Tembisa Nomathamsanqa
- Date: 2011
- Subjects: Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5675 , http://hdl.handle.net/10962/d1005360 , Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Description: Mussels are important ecological engineers on intertidal rocks where they create habitat that contributes substantially to overall biodiversity. They provide secondary substratum for other free-living, infaunal or epifaunal organisms, and increase the surface area for settlement by densely packing together into complex multilayered beds. The introduction of the alien invasive mussel Mytilus galloprovincialis has extended the upper limit of mussels on the south coast of South Africa, potentially increasing habitat for associated fauna. The aim of this study was to describe the structure of mussel beds, the general biodiversity associated with multi- and monolayered mussel beds of indigenous Perna perna and alien M. galloprovincialis, and to determine the relationship between mussels and epibiotic barnacles. This was done to determine the community structure of associated macrofauna and the role of mussels as biological facilitators. Samples were collected in Plettenberg Bay, South Africa, where M. galloprovincialis dominates the high mussel zone and P. perna the low zone. Three 15 X 15 cm quadrats were scraped off the rock in the high and low zones, and in the mid zone where the two mussel species co-exist. The samples were collected on 3 occasions. In the laboratory mussel-size was measured and sediment trapped within the samples was separated through 75 μm, 1 mm and 5 mm mesh. The macrofauna was sorted from the 1 mm and 5 mm sieves and identified to species level where possible. The epibiotic relationship between mussels and barnacles was assessed by measuring the prevalence and intensity of barnacle infestation and the condition index of infested mussels. Multivariate analysis was used on the mean abundance data of the species for each treatment (Hierarchical clustering, multidimensional scaling, analysis of similarity and similarity of percentages) and ANOVA was used for most of the statistical analyses. Overall, the results showed that tidal height influences the species composition and abundance of associated fauna. While mussel bed layering influenced the accumulation of sediments; it had no significant effect on the associated fauna. Time of collection also had a strong effect. While there was an overlap of species among samples from January, May and March, the principal species contributing to similarity among the March samples were not found in the other two months. The outcomes of this study showed that low shore mussel beds not only supported a higher abundance and diversity of species, but were also the most structurally complex. Although the condition index of mussels did not correlate to the percentage cover of barnacle epibionts, it was also evident that low shore mussels had the highest prevalence. The levels of barnacle infestation (intensity) for each mussel species were highest where it was common and lowest where it was least abundant. This is viewed as a natural artefact of the distribution patterns of P. perna and M. galloprovincialis across the shore. Mussels are more efficient as facilitators on the low mussel zone than the high mussel zone possibly because they provide habitats that are more effective in protecting the associated macrofauna from the effects of competition and predation, than they are at eliminating the effects of physical stress on the high shore. Although mussels create less stressful habitats and protect organisms from the physical stress of the high shore, there are clear limitations in their ability to provide ideal habitats. The biological associations in an ecosystem can be made weak or strong depending on the external abiotic factors and the adaptability of the affected organisms.
- Full Text:
- Date Issued: 2011
The effectiveness of livestock guarding dogs for livestock production and conservation in Namibia
- Authors: Potgieter, Gail Christine
- Date: 2011
- Subjects: Livestock protection dogs -- Namibia , Herding dogs -- Namibia , Livestock -- Predators of -- Control -- Namibia , Livestock -- Losses -- Namibia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10680 , http://hdl.handle.net/10948/1666 , Livestock protection dogs -- Namibia , Herding dogs -- Namibia , Livestock -- Predators of -- Control -- Namibia , Livestock -- Losses -- Namibia
- Description: The use of livestock guarding dogs (LGDs) to mitigate farmer-predator conflict in Namibia was evaluated. As farmer-predator conflict has two sides, LGDs were evaluated in terms of livestock production and conservation. The main objectives in terms of livestock production were to document: 1) the perceived ability of LGDs to reduce livestock losses in a cost-effective manner; 2) the farmers’ satisfaction with LGD performance; and 3) factors influencing LGD behaviour. The main objectives in terms of conservation were to record: 1) predator killing by farmers relative to LGD introduction; 2) direct impacts of LGDs on target (damage-causing) species; and 3) the impact of LGDs on non-target species. This evaluation was conducted on LGDs bred by the Cheetah Conservation Fund (CCF) and placed on farms in Namibia. The data were collected during face-to-face interviews with farmers using LGDs. Historical data from the CCF programme were used in conjunction with a complete survey of the farmers in the CCF LGD programme during 2009-2010. In terms of livestock production, 91 percent of the LGDs (n = 65) eliminated or reduced livestock losses. Subsequently, 73 percent of the farmers perceived their LGDs as economically beneficial, although a cost-benefit analysis showed that only 59 percent of the LGDs were cost-effective. Farmers were generally satisfied with the performance of their LGDs. However, farmer satisfaction was more closely linked to good LGD behaviour than the perceived reduction in livestock losses. The most commonly-reported LGD behavioural problems (n = 195) were staying at home rather than accompanying the livestock (21 percent) and chasing wildlife (19 percent). LGD staying home behaviour was linked to a lack of care on subsistence farms, as high quality dog food was not consistently provided. Care for LGDs declined with LGD age on subsistence, but not commercial, farms. In terms of conservation, predator-killing farmers killed fewer individuals in the year since LGD introduction than previously; this result was only significant for black-backed jackal Canis mesomelas. However, 37 LGDs killed jackals, nine killed baboons Papio ursinus, three killed caracals Caracal caracal and one killed a cheetah Acinonyx jubatus (n = 83). Farmers and LGDs combined killed significantly more jackals in the survey year than the same farmers (n = 36) killed before LGD introduction. Conversely, five farmers killed 3.2 ± 2.01 cheetahs each in the year before LGD introduction, whereas LGDs and these farmers combined killed only 0.2 ± 0.2 cheetahs per farm in the survey year. Only 16 LGDs (n = 83) killed non-target species. The high LGD success rate in terms of livestock production was facilitated by livestock husbandry practices in the study area. In terms of conservation, LGDs were more beneficial for apex predators than for mesopredators and had a minor impact on non-target species.
- Full Text:
- Date Issued: 2011
- Authors: Potgieter, Gail Christine
- Date: 2011
- Subjects: Livestock protection dogs -- Namibia , Herding dogs -- Namibia , Livestock -- Predators of -- Control -- Namibia , Livestock -- Losses -- Namibia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10680 , http://hdl.handle.net/10948/1666 , Livestock protection dogs -- Namibia , Herding dogs -- Namibia , Livestock -- Predators of -- Control -- Namibia , Livestock -- Losses -- Namibia
- Description: The use of livestock guarding dogs (LGDs) to mitigate farmer-predator conflict in Namibia was evaluated. As farmer-predator conflict has two sides, LGDs were evaluated in terms of livestock production and conservation. The main objectives in terms of livestock production were to document: 1) the perceived ability of LGDs to reduce livestock losses in a cost-effective manner; 2) the farmers’ satisfaction with LGD performance; and 3) factors influencing LGD behaviour. The main objectives in terms of conservation were to record: 1) predator killing by farmers relative to LGD introduction; 2) direct impacts of LGDs on target (damage-causing) species; and 3) the impact of LGDs on non-target species. This evaluation was conducted on LGDs bred by the Cheetah Conservation Fund (CCF) and placed on farms in Namibia. The data were collected during face-to-face interviews with farmers using LGDs. Historical data from the CCF programme were used in conjunction with a complete survey of the farmers in the CCF LGD programme during 2009-2010. In terms of livestock production, 91 percent of the LGDs (n = 65) eliminated or reduced livestock losses. Subsequently, 73 percent of the farmers perceived their LGDs as economically beneficial, although a cost-benefit analysis showed that only 59 percent of the LGDs were cost-effective. Farmers were generally satisfied with the performance of their LGDs. However, farmer satisfaction was more closely linked to good LGD behaviour than the perceived reduction in livestock losses. The most commonly-reported LGD behavioural problems (n = 195) were staying at home rather than accompanying the livestock (21 percent) and chasing wildlife (19 percent). LGD staying home behaviour was linked to a lack of care on subsistence farms, as high quality dog food was not consistently provided. Care for LGDs declined with LGD age on subsistence, but not commercial, farms. In terms of conservation, predator-killing farmers killed fewer individuals in the year since LGD introduction than previously; this result was only significant for black-backed jackal Canis mesomelas. However, 37 LGDs killed jackals, nine killed baboons Papio ursinus, three killed caracals Caracal caracal and one killed a cheetah Acinonyx jubatus (n = 83). Farmers and LGDs combined killed significantly more jackals in the survey year than the same farmers (n = 36) killed before LGD introduction. Conversely, five farmers killed 3.2 ± 2.01 cheetahs each in the year before LGD introduction, whereas LGDs and these farmers combined killed only 0.2 ± 0.2 cheetahs per farm in the survey year. Only 16 LGDs (n = 83) killed non-target species. The high LGD success rate in terms of livestock production was facilitated by livestock husbandry practices in the study area. In terms of conservation, LGDs were more beneficial for apex predators than for mesopredators and had a minor impact on non-target species.
- Full Text:
- Date Issued: 2011
The experiences of professional nurses regarding the management of health services rendered to tuberculosis patients
- Authors: Jantjies, Leigh-Anne Rene
- Date: 2011
- Subjects: Tuberculosis -- Nursing -- South Africa -- Port Elizabeth , Health services administration -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10025 , http://hdl.handle.net/10948/1399 , Tuberculosis -- Nursing -- South Africa -- Port Elizabeth , Health services administration -- South Africa -- Port Elizabeth
- Description: The World Health Organisation (WHO) declared tuberculosis (TB) a global emergency, and this infectious disease remains a health threat by being the leading cause of death amongst adults (Naidoo, Dick & Cooper, 2008:55). In 2005, South Africa was ranked seventh in the world for having the highest TB rate and the lowest TB success rate in the world. As a professional nurse involved in the tuberculosis programme at a clinic in the Nelson Mandela Bay Municipality at local government level for approximately three years, the researcher observed that the morale of professional nurses who provide TB services appeared to be low. They also appeared to be frustrated because they feel that they are not winning the battle with regard to the TB epidemic in their communities irrespective of their efforts to try and curb the spread of the disease. The extent of the workload per person also appeared to add to the low morale and frustration of the professional nurses rendering TB health services because they feel that they are unable to manage everything. The objectives of the study were therefore to explore and describe how professional nurses experienced the management of health services being rendered to TB patients in Sub district B of the Nelson Mandela Bay Municipality (NMBM) in order to make recommendations that could be used by the district manager to address the research findings. The research study was based on a qualitative, explorative, descriptive and contextual research design. The research population consisted of all professional nurses who worked in the TB services of Sub district B. Non-probability, purposive sampling was used to select the participants for the study. Seven in-depth and three follow-up interviews were conducted before data saturation was achieved. The data gathered during the interview process by the researcher were transcribed and coded by an independent coder using Tech’s model for data analysis. Ethical considerations were adhered to throughout the research study. The aspect of trustworthiness according to Guba’s model was implemented in the research study and included credibility, applicability, consistency and neutrality. iii One theme, two sub themes and categories were identified relating to the diverse experiences expressed by the participants relating to the management of health services being rendered to TB patients. The experiences expressed by the professional nurses included both negative and positive experiences. The negative experiences expressed by the participants were for example, a lack of resources as hampering adequate service delivery, a concern regarding the number of staff contracting TB due to a lack of infection control measures, a difference in conditions of service between the two local authorities and the DOTS supporters as being a threat to patient confidentiality. The positive experiences expressed by the participants included experiences relating to job satisfaction in rendering TB health services, the DOTS supporters as being supportive to the staff, the TB meetings serving as an appropriate platform for problem solving and the audits conducted by managers as being remedial. The study concludes with recommendations made with regard to the areas of nursing practice, education and research.
- Full Text:
- Date Issued: 2011
- Authors: Jantjies, Leigh-Anne Rene
- Date: 2011
- Subjects: Tuberculosis -- Nursing -- South Africa -- Port Elizabeth , Health services administration -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10025 , http://hdl.handle.net/10948/1399 , Tuberculosis -- Nursing -- South Africa -- Port Elizabeth , Health services administration -- South Africa -- Port Elizabeth
- Description: The World Health Organisation (WHO) declared tuberculosis (TB) a global emergency, and this infectious disease remains a health threat by being the leading cause of death amongst adults (Naidoo, Dick & Cooper, 2008:55). In 2005, South Africa was ranked seventh in the world for having the highest TB rate and the lowest TB success rate in the world. As a professional nurse involved in the tuberculosis programme at a clinic in the Nelson Mandela Bay Municipality at local government level for approximately three years, the researcher observed that the morale of professional nurses who provide TB services appeared to be low. They also appeared to be frustrated because they feel that they are not winning the battle with regard to the TB epidemic in their communities irrespective of their efforts to try and curb the spread of the disease. The extent of the workload per person also appeared to add to the low morale and frustration of the professional nurses rendering TB health services because they feel that they are unable to manage everything. The objectives of the study were therefore to explore and describe how professional nurses experienced the management of health services being rendered to TB patients in Sub district B of the Nelson Mandela Bay Municipality (NMBM) in order to make recommendations that could be used by the district manager to address the research findings. The research study was based on a qualitative, explorative, descriptive and contextual research design. The research population consisted of all professional nurses who worked in the TB services of Sub district B. Non-probability, purposive sampling was used to select the participants for the study. Seven in-depth and three follow-up interviews were conducted before data saturation was achieved. The data gathered during the interview process by the researcher were transcribed and coded by an independent coder using Tech’s model for data analysis. Ethical considerations were adhered to throughout the research study. The aspect of trustworthiness according to Guba’s model was implemented in the research study and included credibility, applicability, consistency and neutrality. iii One theme, two sub themes and categories were identified relating to the diverse experiences expressed by the participants relating to the management of health services being rendered to TB patients. The experiences expressed by the professional nurses included both negative and positive experiences. The negative experiences expressed by the participants were for example, a lack of resources as hampering adequate service delivery, a concern regarding the number of staff contracting TB due to a lack of infection control measures, a difference in conditions of service between the two local authorities and the DOTS supporters as being a threat to patient confidentiality. The positive experiences expressed by the participants included experiences relating to job satisfaction in rendering TB health services, the DOTS supporters as being supportive to the staff, the TB meetings serving as an appropriate platform for problem solving and the audits conducted by managers as being remedial. The study concludes with recommendations made with regard to the areas of nursing practice, education and research.
- Full Text:
- Date Issued: 2011
The genetic diversity and conservation biology of the rare terrestrial snail genus Prestonella
- Authors: Fearon, Janine Lee
- Date: 2011
- Subjects: Snails -- South Africa , Snails -- Conservation -- South Africa , Snails -- Variation -- South Africa , Biodiversity -- South Africa , Snails -- Genetics -- South Africa , Snails -- Habitat -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4191 , http://hdl.handle.net/10962/d1003760 , Snails -- South Africa , Snails -- Conservation -- South Africa , Snails -- Variation -- South Africa , Biodiversity -- South Africa , Snails -- Genetics -- South Africa , Snails -- Habitat -- South Africa
- Description: Prestonella bowkeri and Prestonella nuptialis are montane specialists endemic to the southern Great Escarpment of South Africa. Phylogeographic analyses of these species based on mitochondrial markers CO1 and 16S reveal extremely high levels of divergence between populations indicating a lack of gene flow between populations. This is not surprising, because P. nuptialis and P. bowkeri have limited dispersal capacity, low vagility, a highly fragmented distribution and are habitat specialists that are restricted to isolated mesic refugia associated with waterfalls and montane seepages. A relaxed Bayesian clock estimate suggests that populations diverged from one another during the mid-late Miocene (12.5-7 MYA) which coincides with the modern trends of seasonal aridity which began during the Miocene. This result should be viewed with caution because the rates used are at best imprecise estimates of mutation rates in snails. There is no clear dichotomy between the two species and P. bowkeri is paraphyletic with respect to P. nuptialis, as a consequence the taxonomy is unclear. Due to the high levels of sequence divergence between populations they may be considered as evolutionary significant units (ESU’s). An assessment of haplotype diversity (h) and nucleotide diversity (π) reveals that populations in the western part of the Great Escarpment are more genetically depauperate than populations in the east. Correlations between genetic diversity and climatic variables show that genetically depauperate populations are found in areas that have lower annual rainfall, less reliable rainfall and higher potential evaporation, all factors associated with a drier, less mesic environment that increases the chances of a population bottleneck. This indicates that a shift towards a more arid environment may be a driver of genetic erosion. Historical climate change may thus have affected the amount and distribution of genetic diversity across the Great Escarpment since the Miocene. This has serious future implications for the survival of Prestonella. With predicted increase in global temperatures, climate change in South Africa is likely to result in range contraction and an eastward range shift for many species in the drier central and western areas (Erasmus et al. 2002) and regions along the Great Escarpment are likely to become more arid. Prestonella populations found living on inselbergs along the Great Escarpment are already restricted to site specific watercourses and seepages. An increase in the periods between stream flow, and increasing rainfall variability and mean annual potential evaporation are likely to have an adverse affect on species living in these habitats, resulting in further bottlenecks and possibly local extinction. An IUCN assessment of P. nuptialis and P. bowkeri suggests that these two species are probably endangered. The issue surrounding the conservation of Prestonella species is that they are threatened by global climate change, which cannot be simply restricted or prevented, which makes dealing with the threat of climate change difficult. Assisted migration (MA) may be considered as a method to prevent possible future extinctions of Prestonella populations, but will only be considered as a last resort. The thermal tolerance (Arrhenius breaking temperature and flat-line temperature) of individual snails from three Prestonella populations (one forest population and two thicket populations) were assessed using infrared sensors that detected changes in heart rate with increasing temperature. The forest population had a significantly lower Arrhenius breaking temperature (ABT) and flat-line temperature (FLT) than the two thicket population (p<0.05). Our results do not show a correlation between upper thermal limits and maximum habitat temperatures or other climatic variables in Prestonella populations. Although no correlation is found between ABT and maximum habitat temperature, it is likely that the differences seen between these populations are due to local micro-climate adaptation. The climatic variables used in this experiment are coarse estimates from GIS data and do not reflect actual microhabitat conditions. Forest environments are less heat stressed than thicket environments due to the forest canopy which may explain the lower ABT and FLT of the forest population.
- Full Text:
- Date Issued: 2011
- Authors: Fearon, Janine Lee
- Date: 2011
- Subjects: Snails -- South Africa , Snails -- Conservation -- South Africa , Snails -- Variation -- South Africa , Biodiversity -- South Africa , Snails -- Genetics -- South Africa , Snails -- Habitat -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4191 , http://hdl.handle.net/10962/d1003760 , Snails -- South Africa , Snails -- Conservation -- South Africa , Snails -- Variation -- South Africa , Biodiversity -- South Africa , Snails -- Genetics -- South Africa , Snails -- Habitat -- South Africa
- Description: Prestonella bowkeri and Prestonella nuptialis are montane specialists endemic to the southern Great Escarpment of South Africa. Phylogeographic analyses of these species based on mitochondrial markers CO1 and 16S reveal extremely high levels of divergence between populations indicating a lack of gene flow between populations. This is not surprising, because P. nuptialis and P. bowkeri have limited dispersal capacity, low vagility, a highly fragmented distribution and are habitat specialists that are restricted to isolated mesic refugia associated with waterfalls and montane seepages. A relaxed Bayesian clock estimate suggests that populations diverged from one another during the mid-late Miocene (12.5-7 MYA) which coincides with the modern trends of seasonal aridity which began during the Miocene. This result should be viewed with caution because the rates used are at best imprecise estimates of mutation rates in snails. There is no clear dichotomy between the two species and P. bowkeri is paraphyletic with respect to P. nuptialis, as a consequence the taxonomy is unclear. Due to the high levels of sequence divergence between populations they may be considered as evolutionary significant units (ESU’s). An assessment of haplotype diversity (h) and nucleotide diversity (π) reveals that populations in the western part of the Great Escarpment are more genetically depauperate than populations in the east. Correlations between genetic diversity and climatic variables show that genetically depauperate populations are found in areas that have lower annual rainfall, less reliable rainfall and higher potential evaporation, all factors associated with a drier, less mesic environment that increases the chances of a population bottleneck. This indicates that a shift towards a more arid environment may be a driver of genetic erosion. Historical climate change may thus have affected the amount and distribution of genetic diversity across the Great Escarpment since the Miocene. This has serious future implications for the survival of Prestonella. With predicted increase in global temperatures, climate change in South Africa is likely to result in range contraction and an eastward range shift for many species in the drier central and western areas (Erasmus et al. 2002) and regions along the Great Escarpment are likely to become more arid. Prestonella populations found living on inselbergs along the Great Escarpment are already restricted to site specific watercourses and seepages. An increase in the periods between stream flow, and increasing rainfall variability and mean annual potential evaporation are likely to have an adverse affect on species living in these habitats, resulting in further bottlenecks and possibly local extinction. An IUCN assessment of P. nuptialis and P. bowkeri suggests that these two species are probably endangered. The issue surrounding the conservation of Prestonella species is that they are threatened by global climate change, which cannot be simply restricted or prevented, which makes dealing with the threat of climate change difficult. Assisted migration (MA) may be considered as a method to prevent possible future extinctions of Prestonella populations, but will only be considered as a last resort. The thermal tolerance (Arrhenius breaking temperature and flat-line temperature) of individual snails from three Prestonella populations (one forest population and two thicket populations) were assessed using infrared sensors that detected changes in heart rate with increasing temperature. The forest population had a significantly lower Arrhenius breaking temperature (ABT) and flat-line temperature (FLT) than the two thicket population (p<0.05). Our results do not show a correlation between upper thermal limits and maximum habitat temperatures or other climatic variables in Prestonella populations. Although no correlation is found between ABT and maximum habitat temperature, it is likely that the differences seen between these populations are due to local micro-climate adaptation. The climatic variables used in this experiment are coarse estimates from GIS data and do not reflect actual microhabitat conditions. Forest environments are less heat stressed than thicket environments due to the forest canopy which may explain the lower ABT and FLT of the forest population.
- Full Text:
- Date Issued: 2011
The genetic integrity of Labeo capensis and L. umbratus (Cyprinidae) in South Africa in relation to inter-basin water transfer schemes
- Authors: Ramoejane, Mpho
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Darlington Dam , Cyprinidae -- Namibia -- Hardap Dam , Labeo -- South Africa -- Darlington Dam , Labeo -- Namibia -- Hardap Dam , Fishes -- Hybridisation -- South Africa -- Darlington Dam , Fishes -- Hybridisation -- Namibia -- Hardap Dam , Fishes -- Anatomy -- South Africa -- Darlington Dam , Fishes -- Anatomy -- Namibia -- Hardap Dam , Water transfer -- South Africa-- Darlington Dam , Water transfer -- Namibia -- Hardap Dam
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5367 , http://hdl.handle.net/10962/d1013049
- Description: The Orange-Fish and Cookhouse tunnels that are part of a major inter-basin water transfer scheme (IBT) act as a pathway for several fish species from the Orange River system to enter the Great Fish and Sundays River systems in South Africa. These include Labeo capensis and L. umbratus. Labeo capensis was restricted to the Orange River system before the inter-basin water transfer scheme. Labeo umbratus occurred naturally in the Orange River and in southern flowing river systems. Previous studies showed that the two species hybridise in Hardap Dam, located in a tributary of the Orange River system in Namibia. There are also unconfirmed reports of hybrids from Darlington Dam on the Sundays River system. The aim of the thesis was to confirm hybridisation in Hardap Dam, assess whether hybridisation between L. capensis and L. umbratus has occurred in Darlington Dam and to gain a better understanding of the diversity of these two species. Morphology (morphometrics and meristics), a nuclear S7 intron and the mitochondrial cytochrome ♭ gene were used to assess for hybridisation. A total of 275 specimens were analysed from across the geographical range of the two species. The two species could be distinguished using morphometrics (dorsal fin base, interorbital width and operculum to eye distance) and meristics (lateral line, origin of the dorsal fin to lateral line, origin of the pelvic fin to lateral line and caudal peduncle scale counts) characters. Hybrids from Hardap and Darlington dams were placed between the two species clusters. Labeo umbratus from the Orange River and southern flowing rivers formed a single cluster. The two species could also be distinguished from each other with six nuclear DNA mutations and hybrids were heterozygous at such sites in both dams. Labeo umbratus populations from the Orange River and southern flowing rivers (Gouritz, Gamtoos, Sundays, Bushmans, Great Fish and Nahoon) formed a single lineage. Analysis of mitochondrial DNA, however, revealed that L. umbratus populations from the Orange River and southern flowing rivers were two lineages that differ from each other by 5 mutations. Labeo capensis could be differentiated from both these lineages. Being maternally inherited, mitochondrial DNA did not reveal hybridisation, but ten specimens with L. capensis haplotypes were found in the Darlington Dam. In Hardap Dam, however, it appears that only L. capensis mitochondrial DNA haplotypes persist, despite morphological and nuclear DNA analysis suggesting that both morphs and hybrids of the two species occur. The genetic integrity of these Labeo species has therefore been compromised in at least Hardap and Darlington dams. The Great Fish and Sundays populations are considered to be under threat of complete introgression. The Kat River and Slagboom Dam populations that were isolated before the IBTs have to remain isolated to protect the genetic integrity of the southern lineage of L. umbratus in these two systems.
- Full Text:
- Date Issued: 2011
- Authors: Ramoejane, Mpho
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Darlington Dam , Cyprinidae -- Namibia -- Hardap Dam , Labeo -- South Africa -- Darlington Dam , Labeo -- Namibia -- Hardap Dam , Fishes -- Hybridisation -- South Africa -- Darlington Dam , Fishes -- Hybridisation -- Namibia -- Hardap Dam , Fishes -- Anatomy -- South Africa -- Darlington Dam , Fishes -- Anatomy -- Namibia -- Hardap Dam , Water transfer -- South Africa-- Darlington Dam , Water transfer -- Namibia -- Hardap Dam
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5367 , http://hdl.handle.net/10962/d1013049
- Description: The Orange-Fish and Cookhouse tunnels that are part of a major inter-basin water transfer scheme (IBT) act as a pathway for several fish species from the Orange River system to enter the Great Fish and Sundays River systems in South Africa. These include Labeo capensis and L. umbratus. Labeo capensis was restricted to the Orange River system before the inter-basin water transfer scheme. Labeo umbratus occurred naturally in the Orange River and in southern flowing river systems. Previous studies showed that the two species hybridise in Hardap Dam, located in a tributary of the Orange River system in Namibia. There are also unconfirmed reports of hybrids from Darlington Dam on the Sundays River system. The aim of the thesis was to confirm hybridisation in Hardap Dam, assess whether hybridisation between L. capensis and L. umbratus has occurred in Darlington Dam and to gain a better understanding of the diversity of these two species. Morphology (morphometrics and meristics), a nuclear S7 intron and the mitochondrial cytochrome ♭ gene were used to assess for hybridisation. A total of 275 specimens were analysed from across the geographical range of the two species. The two species could be distinguished using morphometrics (dorsal fin base, interorbital width and operculum to eye distance) and meristics (lateral line, origin of the dorsal fin to lateral line, origin of the pelvic fin to lateral line and caudal peduncle scale counts) characters. Hybrids from Hardap and Darlington dams were placed between the two species clusters. Labeo umbratus from the Orange River and southern flowing rivers formed a single cluster. The two species could also be distinguished from each other with six nuclear DNA mutations and hybrids were heterozygous at such sites in both dams. Labeo umbratus populations from the Orange River and southern flowing rivers (Gouritz, Gamtoos, Sundays, Bushmans, Great Fish and Nahoon) formed a single lineage. Analysis of mitochondrial DNA, however, revealed that L. umbratus populations from the Orange River and southern flowing rivers were two lineages that differ from each other by 5 mutations. Labeo capensis could be differentiated from both these lineages. Being maternally inherited, mitochondrial DNA did not reveal hybridisation, but ten specimens with L. capensis haplotypes were found in the Darlington Dam. In Hardap Dam, however, it appears that only L. capensis mitochondrial DNA haplotypes persist, despite morphological and nuclear DNA analysis suggesting that both morphs and hybrids of the two species occur. The genetic integrity of these Labeo species has therefore been compromised in at least Hardap and Darlington dams. The Great Fish and Sundays populations are considered to be under threat of complete introgression. The Kat River and Slagboom Dam populations that were isolated before the IBTs have to remain isolated to protect the genetic integrity of the southern lineage of L. umbratus in these two systems.
- Full Text:
- Date Issued: 2011