Developing taxonomic and trait-based approaches for assessing and predicting macroinvertebrate responses to elevated fine sediments in the Tsitsa River and its tributaries, South Africa
- Authors: Ntloko, Pindiwe
- Date: 2022-04-08
- Subjects: Water quality South Africa Mzimvubu River Watershed , Sedimentation and deposition South Africa Mzimvubu River Watershed , Aquatic invertebrates Effect of sediments on South Africa Mzimvubu River Watershed , Aquatic invertebrates Classification , Environmental monitoring South Africa Mzimvubu River Watershed , Analysis of variance , Multivariate analysis
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294692 , vital:57245 , DOI 10.21504/10962/294692
- Description: Sedimentation of freshwater systems is one of the leading causes of water quality deterioration. The Mzimvubu River catchment, which includes the Tsitsa River and its tributaries, in the Eastern Cape is prone to elevated sediment impact due to dispersive soils that are easily erodible. In this study, taxonomy and trait-based approaches were used to assess the responses of macroinvertebrates to fine sediments in the Tsitsa River and its tributaries. Macroinvertebrates and environmental variables were sampled seasonally in winter, spring, summer and autumn of 2016 to 2018 in six selected sites, using the South African Scoring System version 5 as a collecting protocol. The sites were selected to represent a decreasing gradient of sediment influence from the highly impacted Sites 1 (Tsitsa upstream) 2 (Tsitsa downstream), and 3 (Qurana River) to moderately impacted Sites 4 (Millstream upstream) and 5 (Millstream downstream) and the least impacted Sites 6 (Pot River upstream), 7 (Little Pot River) and 8 (Pot River downstream), which were collectively referred to as the control sites. Analysis of basic physico-chemical variables, dissolved oxygen, pH, electrical conductivity, turbidity, total suspended solids, temperature and nutrients were undertaken seasonally over the study period. Sediments grain sizes were also analysed. All collected data were subjected to appropriate statistical tests – univariate and multivariate techniques. A fine-sediment-specific multimetric index was developed to monitor the impact of fine sediments on macroinvertebrate assemblages of the Tsitsa River and its tributaries. A total of 12 traits, resolved into 48 trait attributes, were selected to explore their distribution in relation to a fine-sediment stress gradient, and identify the trait-based signature of fine-sediment impact. A trait-based approach was then developed to classify South African macroinvertebrates into two groups: taxa that are potentially vulnerable to fine-sediment impact and those potentially resilient, based on the combination of traits possessed. Two-way analysis of variance (ANOVA) indicated that electrical conductivity, turbidity, embeddedness and total suspended solids were statistically significantly different between the sites. Apart from Dissolved oxygen, the remaining variables were statistically significantly lower at the control sites (P < 0.05). The two-way multivariate analysis of variance (MANOVA) indicated global significant differences between sites and seasons. The two-way MANOVA also revealed that the interaction between the sites and seasons were statistically significant. The MANOVA indicated global combined interactive effects across the sites for suspended fine-sediment grain sizes, two-way ANOVA, followed by a Tukey’s post-hoc test, was carried out to indicate where the significant differences lay. The one-way ANOVA results indicated that very fine sand, very coarse silt, medium silt, and fine silt were significantly higher at Tsitsa upstream, Tsitsa downstream, Qurana tributary that is at Millstream upstream, Millstream downstream and Control sites. The rest of the grain sizes did not differ statistically between the sites. In terms of the settled sediment grain sizes, the volumetric analysis did not show considerable differences across the sites. Settled fine-sediment grain sizes were evenly distributed across the sites. Statistically, MANOVA results indicated no significant differences across sites or across seasons. The developed Sediment Multimetric Index indicated that the sites in the Tsitsa River and those in the Qurana River were highly sedimented during the wet season, but became moderately sedimented during the dry season, indicating that the index responded to seasonality. The sediment multimetric index indicated that the control sites were less sedimented during both the wet season and dry seasons, suggesting minimal seasonal effects at the control sites. Traits such as an exposed and soft body, collector-filterers, shredding, feeding on coarse particulate organic matter and a high sensitivity to dissolved oxygen were identified as fine- sediment-sensitive indicator traits. Identified fine-sediment-tolerant traits and ecological preferences included complete sclerotisation, a cased/tubed body, a preference for fine particulate organic matter, a high tolerance to dissolved oxygen depletion, and climbing and skating behaviours. Regarding the trait-based approach followed for classifying macroinvertebrates into vulnerable taxa and resilient taxa, the results revealed that the relative abundance and richness of the vulnerable taxa decreased predictably along the increasing gradient of sediment impact. However, the relative abundance and richness of resilient taxa showed no marked response to the impact of an increasing gradient of fine sediments. Overall, the present study makes a contribution to the complementary application of trait-and taxonomy-based approaches to freshwater biomonitoring. The trait-based approach enables predictions to be made and tested based on the mechanistic understanding of the mediating roles of traits in organism- environment interaction. A fundamental challenge, which showcases the limitation of the current study, is the sparse trait data on Afrotropical macroinvertebrates at the species or generic levels. In this regard, the iv trait-based approaches developed here were the family level instead of species or genus. This is the first study in South Africa to develop explicit trait-based indicators of elevated fine sediments as well as an approach for predicting macroinvertebrate vulnerability and resilience to fine-sediment effects, thus advancing the science and practice of freshwater biomonitoring. , Thesis (PhD) -- Faculty of Science, Institute for Water Research, 2022
- Full Text:
- Authors: Ntloko, Pindiwe
- Date: 2022-04-08
- Subjects: Water quality South Africa Mzimvubu River Watershed , Sedimentation and deposition South Africa Mzimvubu River Watershed , Aquatic invertebrates Effect of sediments on South Africa Mzimvubu River Watershed , Aquatic invertebrates Classification , Environmental monitoring South Africa Mzimvubu River Watershed , Analysis of variance , Multivariate analysis
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294692 , vital:57245 , DOI 10.21504/10962/294692
- Description: Sedimentation of freshwater systems is one of the leading causes of water quality deterioration. The Mzimvubu River catchment, which includes the Tsitsa River and its tributaries, in the Eastern Cape is prone to elevated sediment impact due to dispersive soils that are easily erodible. In this study, taxonomy and trait-based approaches were used to assess the responses of macroinvertebrates to fine sediments in the Tsitsa River and its tributaries. Macroinvertebrates and environmental variables were sampled seasonally in winter, spring, summer and autumn of 2016 to 2018 in six selected sites, using the South African Scoring System version 5 as a collecting protocol. The sites were selected to represent a decreasing gradient of sediment influence from the highly impacted Sites 1 (Tsitsa upstream) 2 (Tsitsa downstream), and 3 (Qurana River) to moderately impacted Sites 4 (Millstream upstream) and 5 (Millstream downstream) and the least impacted Sites 6 (Pot River upstream), 7 (Little Pot River) and 8 (Pot River downstream), which were collectively referred to as the control sites. Analysis of basic physico-chemical variables, dissolved oxygen, pH, electrical conductivity, turbidity, total suspended solids, temperature and nutrients were undertaken seasonally over the study period. Sediments grain sizes were also analysed. All collected data were subjected to appropriate statistical tests – univariate and multivariate techniques. A fine-sediment-specific multimetric index was developed to monitor the impact of fine sediments on macroinvertebrate assemblages of the Tsitsa River and its tributaries. A total of 12 traits, resolved into 48 trait attributes, were selected to explore their distribution in relation to a fine-sediment stress gradient, and identify the trait-based signature of fine-sediment impact. A trait-based approach was then developed to classify South African macroinvertebrates into two groups: taxa that are potentially vulnerable to fine-sediment impact and those potentially resilient, based on the combination of traits possessed. Two-way analysis of variance (ANOVA) indicated that electrical conductivity, turbidity, embeddedness and total suspended solids were statistically significantly different between the sites. Apart from Dissolved oxygen, the remaining variables were statistically significantly lower at the control sites (P < 0.05). The two-way multivariate analysis of variance (MANOVA) indicated global significant differences between sites and seasons. The two-way MANOVA also revealed that the interaction between the sites and seasons were statistically significant. The MANOVA indicated global combined interactive effects across the sites for suspended fine-sediment grain sizes, two-way ANOVA, followed by a Tukey’s post-hoc test, was carried out to indicate where the significant differences lay. The one-way ANOVA results indicated that very fine sand, very coarse silt, medium silt, and fine silt were significantly higher at Tsitsa upstream, Tsitsa downstream, Qurana tributary that is at Millstream upstream, Millstream downstream and Control sites. The rest of the grain sizes did not differ statistically between the sites. In terms of the settled sediment grain sizes, the volumetric analysis did not show considerable differences across the sites. Settled fine-sediment grain sizes were evenly distributed across the sites. Statistically, MANOVA results indicated no significant differences across sites or across seasons. The developed Sediment Multimetric Index indicated that the sites in the Tsitsa River and those in the Qurana River were highly sedimented during the wet season, but became moderately sedimented during the dry season, indicating that the index responded to seasonality. The sediment multimetric index indicated that the control sites were less sedimented during both the wet season and dry seasons, suggesting minimal seasonal effects at the control sites. Traits such as an exposed and soft body, collector-filterers, shredding, feeding on coarse particulate organic matter and a high sensitivity to dissolved oxygen were identified as fine- sediment-sensitive indicator traits. Identified fine-sediment-tolerant traits and ecological preferences included complete sclerotisation, a cased/tubed body, a preference for fine particulate organic matter, a high tolerance to dissolved oxygen depletion, and climbing and skating behaviours. Regarding the trait-based approach followed for classifying macroinvertebrates into vulnerable taxa and resilient taxa, the results revealed that the relative abundance and richness of the vulnerable taxa decreased predictably along the increasing gradient of sediment impact. However, the relative abundance and richness of resilient taxa showed no marked response to the impact of an increasing gradient of fine sediments. Overall, the present study makes a contribution to the complementary application of trait-and taxonomy-based approaches to freshwater biomonitoring. The trait-based approach enables predictions to be made and tested based on the mechanistic understanding of the mediating roles of traits in organism- environment interaction. A fundamental challenge, which showcases the limitation of the current study, is the sparse trait data on Afrotropical macroinvertebrates at the species or generic levels. In this regard, the iv trait-based approaches developed here were the family level instead of species or genus. This is the first study in South Africa to develop explicit trait-based indicators of elevated fine sediments as well as an approach for predicting macroinvertebrate vulnerability and resilience to fine-sediment effects, thus advancing the science and practice of freshwater biomonitoring. , Thesis (PhD) -- Faculty of Science, Institute for Water Research, 2022
- Full Text:
Dynamics of charge movement in ∞-Al2O3:C,Mg using thermoluminescence phototransferred and optically stimulated luminescence
- Authors: Lontsi Sob, Aaron Joel
- Date: 2022-04-08
- Subjects: Thermoluminescence , Optically stimulated luminescence , Phototransfer , Deep traps , Phototransferred thermoluminescence (PTTL)
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294607 , vital:57237 , DOI 10.21504/10962/294607
- Description: The dosimetric features of ∞-Al2O3:C,Mg have been investigated for unannealed and annealed samples. The unannealed sample is referred to as sample A whereas the samples annealed at 700, 900 and 1200°C for 15 minutes each are referred to as samples B, C and D respectively. A glow curve of unannealed ∞-Al2O3:C,Mg measured at 1°C/s after irradiation to 2.0 Gy consists of peaks at 43, 73, 164, 195, 246, 284, 336 and 374°C respectively. For sample B (annealed at 700°C), a glow curve measured at 1°C/s after irradiation to 3.0 Gy has peaks at 46, 76, 100, 170, 199, 290, 330 and 375°C whereas the glow curve of sample C (annealed at 900°C) recorded under the same conditions consists of peaks at 49, 80, 100, 174, 206, 235, 290, 335 and 375°C respectively. Sample D (annealed at 1200°C) is the most sensitive of the four samples. A glow curve of sample D measured at 1°C/s after irradiation to 0.2 Gy has peaks at 52, 82, 102, 174, 234, 288 and 384°C respectively. The peaks are labelled I-VIII in order of appearance. The 100°C peak, labelled IIa, is induced by annealing at or above 700°C. The dose response of these peaks was studied for doses within 0.1-8.2 Gy. The reported peaks follow first-order kinetics irrespective of annealing temperature. Peaks I-III of each sample are reproduced under phototransfer for preheating up to 400°C. For the unannealed sample, the reproduced peaks are labelled A1-A3 whereas for the annealed samples, they are labelled B1-B3, C1-C3 and D1-D3 respectively. The annealing-induced peak at 100°C is reproduced as B2a, C2a and D2a for samples B, C and D respectively. A PTTL peak labelled C2b or D2b is also observed near 140°C in samples C and D. In addition to these PTTL peaks, a PTTL peak corresponding to peak IV is also found for sample D and for the unannealed sample. As the corresponding conventional peaks, the PTTL peaks of each sample follow first-order kinetics. Peak I and its corresponding PTTL peak for each sample are unstable and fade to a minimal level after 300 s of storage time. On the other hand, peak II of each sample and its corresponding PTTL peak could still be observed with delay up to 5000 s. Peak III of the unannealed sample remains stable with storage time up to 48 hours. Irrespective of annealing, the trap corresponding to peak III is the most sensitive to optical stimulation. Time-dependent profiles of PTTL from unannealed and annealed ∞-Al2O3:C,Mg were also studied. The mathematical analysis of the PTTL time-response profiles is based on experimental results. The role of various electron traps in PTTL was determined by using pulse annealing and by monitoring the dependence of peak intensity on duration of illumination for peaks not removed by preheating. The presence and role of deep traps were further demonstrated with thermally assisted optically stimulated luminescence. For the unannealed sample, the activation energy for thermal assistance is 0.033 ± 0.001 eV and the activation energy for thermal i quenching is 1.043 ± 0.001 eV. For sample C, the activation energy for thermal assistance is 0.044 ± 0.003 eV whereas that for thermal quenching is 1.110 ± 0.006 eV. The values for the activation energy for thermal assistance are lower than those reported in literature. Only the values for the activation energy for thermal quenching are somewhat comparable to values reported elsewhere. , Thesis (PhD) -- Faculty of Science, Physics and Electronics, 2022
- Full Text:
- Authors: Lontsi Sob, Aaron Joel
- Date: 2022-04-08
- Subjects: Thermoluminescence , Optically stimulated luminescence , Phototransfer , Deep traps , Phototransferred thermoluminescence (PTTL)
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294607 , vital:57237 , DOI 10.21504/10962/294607
- Description: The dosimetric features of ∞-Al2O3:C,Mg have been investigated for unannealed and annealed samples. The unannealed sample is referred to as sample A whereas the samples annealed at 700, 900 and 1200°C for 15 minutes each are referred to as samples B, C and D respectively. A glow curve of unannealed ∞-Al2O3:C,Mg measured at 1°C/s after irradiation to 2.0 Gy consists of peaks at 43, 73, 164, 195, 246, 284, 336 and 374°C respectively. For sample B (annealed at 700°C), a glow curve measured at 1°C/s after irradiation to 3.0 Gy has peaks at 46, 76, 100, 170, 199, 290, 330 and 375°C whereas the glow curve of sample C (annealed at 900°C) recorded under the same conditions consists of peaks at 49, 80, 100, 174, 206, 235, 290, 335 and 375°C respectively. Sample D (annealed at 1200°C) is the most sensitive of the four samples. A glow curve of sample D measured at 1°C/s after irradiation to 0.2 Gy has peaks at 52, 82, 102, 174, 234, 288 and 384°C respectively. The peaks are labelled I-VIII in order of appearance. The 100°C peak, labelled IIa, is induced by annealing at or above 700°C. The dose response of these peaks was studied for doses within 0.1-8.2 Gy. The reported peaks follow first-order kinetics irrespective of annealing temperature. Peaks I-III of each sample are reproduced under phototransfer for preheating up to 400°C. For the unannealed sample, the reproduced peaks are labelled A1-A3 whereas for the annealed samples, they are labelled B1-B3, C1-C3 and D1-D3 respectively. The annealing-induced peak at 100°C is reproduced as B2a, C2a and D2a for samples B, C and D respectively. A PTTL peak labelled C2b or D2b is also observed near 140°C in samples C and D. In addition to these PTTL peaks, a PTTL peak corresponding to peak IV is also found for sample D and for the unannealed sample. As the corresponding conventional peaks, the PTTL peaks of each sample follow first-order kinetics. Peak I and its corresponding PTTL peak for each sample are unstable and fade to a minimal level after 300 s of storage time. On the other hand, peak II of each sample and its corresponding PTTL peak could still be observed with delay up to 5000 s. Peak III of the unannealed sample remains stable with storage time up to 48 hours. Irrespective of annealing, the trap corresponding to peak III is the most sensitive to optical stimulation. Time-dependent profiles of PTTL from unannealed and annealed ∞-Al2O3:C,Mg were also studied. The mathematical analysis of the PTTL time-response profiles is based on experimental results. The role of various electron traps in PTTL was determined by using pulse annealing and by monitoring the dependence of peak intensity on duration of illumination for peaks not removed by preheating. The presence and role of deep traps were further demonstrated with thermally assisted optically stimulated luminescence. For the unannealed sample, the activation energy for thermal assistance is 0.033 ± 0.001 eV and the activation energy for thermal i quenching is 1.043 ± 0.001 eV. For sample C, the activation energy for thermal assistance is 0.044 ± 0.003 eV whereas that for thermal quenching is 1.110 ± 0.006 eV. The values for the activation energy for thermal assistance are lower than those reported in literature. Only the values for the activation energy for thermal quenching are somewhat comparable to values reported elsewhere. , Thesis (PhD) -- Faculty of Science, Physics and Electronics, 2022
- Full Text:
Inhibition of aluminium corrosion using phthalocyanines: Experimental and computational studies
- Authors: Nnaji, Nnaemeka Joshua
- Date: 2022-04-08
- Subjects: Aluminum Corrosion , Electrochemistry , Phthalocyanines , Corrosion and anti-corrosives , Protective coatings , Density functionals
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294643 , vital:57240 , DOI 10.21504/10962/294643
- Description: Metal deterioration over time is a process known as corrosion, an electrochemical process, which can occur by surface chemical actions on metals by its environment. Metal corrosion have great economic, security, and environmental consequences, and its control is a major research area in corrosion science. Amongst the different corrosion protecting approaches, the use of corrosion inhibitors and protective coatings have attracted enormous research interest in this area of scholasticism. This has necessitated the computational and electrochemical investigations of aluminium corrosion inhibitive potentials of some compounds in 1M HCl. Metal free (5_H2), ClGa(III) (5_Ga) and Co(II) (5_Co) tetrakis(4-acetamidophenoxy)phthalocyanines as well as Co(II) 2,9,16-tris(4-(tert-butyl)phenoxy)-23-(pyridin-4-yloxy)phthalocyanine (6) and Co(II) 2,9,16,24-tetrakis(4-(tert-butyl)phenoxy)phthalocyanine (7) were synthesized for the first time and studied for corrosion inhibition. The reported ClGa(III) tetrakis(benzo[d]thiazol-2-yl-thio)phthalocyaninine (1), ClGa(III) tetrakis(benzo[d]thiazol-2ylphenoxy)phthalocyanine (2), ClGa(III) tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyanine) (3) and ClGa(III) tetrakis-4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)-bis(phthalocyanine) (4) were also employed for corrosion inhibition of Al in HCl. Corrosion inhibition measurements using electrochemical techniques showed that increased π conjugation caused (1) to (2) to outperform (1a) and (2a) respectively as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. For similar reason, (4) outperformed 2. (1) and (2) were successfully electrodeposited onto aluminium for corrosion retardation in 1.0 M hydrochloric acid solution. Measurements obtained from electrochemical impedance spectroscopy gave corrosion inhibition efficiency values of 82% for 1 and 86% for 2 in 1.0 M hydrochloric acid solution and showed that electrodeposited phthalocyanines have enhanced aluminium corrosion retardation than when in solution. The use of reduced graphene oxide nanosheets (rGONS) alone as aluminium corrosion inhibitor is discouraged because of poor aluminium corrosion inhibition in 1M HCl. However, synergistic effects were observed when rGONS was mixed each with (4) and (3). (5_H2), (5_Ga) and (5_Co) decreased aluminium corrosion in 1M HCl and observation was that the heavier the atom the more decreased the protection and the free base performed best of the three. Studied tertbutylphenoxy-derived CoPcs (6 and 7) exhibited good aluminium corrosion inhibition properties in studied acidic solution and the unsymmetric CoPc (6) which has more heteroatoms, gave better performance. Quantum chemical calculations involved the use of density functional theoretical (DFT) approaches and gave results which corroborated with experimental findings. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Authors: Nnaji, Nnaemeka Joshua
- Date: 2022-04-08
- Subjects: Aluminum Corrosion , Electrochemistry , Phthalocyanines , Corrosion and anti-corrosives , Protective coatings , Density functionals
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294643 , vital:57240 , DOI 10.21504/10962/294643
- Description: Metal deterioration over time is a process known as corrosion, an electrochemical process, which can occur by surface chemical actions on metals by its environment. Metal corrosion have great economic, security, and environmental consequences, and its control is a major research area in corrosion science. Amongst the different corrosion protecting approaches, the use of corrosion inhibitors and protective coatings have attracted enormous research interest in this area of scholasticism. This has necessitated the computational and electrochemical investigations of aluminium corrosion inhibitive potentials of some compounds in 1M HCl. Metal free (5_H2), ClGa(III) (5_Ga) and Co(II) (5_Co) tetrakis(4-acetamidophenoxy)phthalocyanines as well as Co(II) 2,9,16-tris(4-(tert-butyl)phenoxy)-23-(pyridin-4-yloxy)phthalocyanine (6) and Co(II) 2,9,16,24-tetrakis(4-(tert-butyl)phenoxy)phthalocyanine (7) were synthesized for the first time and studied for corrosion inhibition. The reported ClGa(III) tetrakis(benzo[d]thiazol-2-yl-thio)phthalocyaninine (1), ClGa(III) tetrakis(benzo[d]thiazol-2ylphenoxy)phthalocyanine (2), ClGa(III) tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyanine) (3) and ClGa(III) tetrakis-4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)-bis(phthalocyanine) (4) were also employed for corrosion inhibition of Al in HCl. Corrosion inhibition measurements using electrochemical techniques showed that increased π conjugation caused (1) to (2) to outperform (1a) and (2a) respectively as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. For similar reason, (4) outperformed 2. (1) and (2) were successfully electrodeposited onto aluminium for corrosion retardation in 1.0 M hydrochloric acid solution. Measurements obtained from electrochemical impedance spectroscopy gave corrosion inhibition efficiency values of 82% for 1 and 86% for 2 in 1.0 M hydrochloric acid solution and showed that electrodeposited phthalocyanines have enhanced aluminium corrosion retardation than when in solution. The use of reduced graphene oxide nanosheets (rGONS) alone as aluminium corrosion inhibitor is discouraged because of poor aluminium corrosion inhibition in 1M HCl. However, synergistic effects were observed when rGONS was mixed each with (4) and (3). (5_H2), (5_Ga) and (5_Co) decreased aluminium corrosion in 1M HCl and observation was that the heavier the atom the more decreased the protection and the free base performed best of the three. Studied tertbutylphenoxy-derived CoPcs (6 and 7) exhibited good aluminium corrosion inhibition properties in studied acidic solution and the unsymmetric CoPc (6) which has more heteroatoms, gave better performance. Quantum chemical calculations involved the use of density functional theoretical (DFT) approaches and gave results which corroborated with experimental findings. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
Quantifying the impacts of cactus biological control agents in South Africa
- Authors: Mnqeta, Zezethu
- Date: 2022-04-08
- Subjects: Cactus Biological control South Africa , Noxious weeds South Africa , Invasive plants Biological control South Africa , Insects as biological pest control agents South Africa , Cochineal insect South Africa , Mealybugs South Africa , Agricultural productivity South Africa
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294631 , vital:57239 , DOI 10.21504/10962/294631
- Description: Invasive alien cacti are prominent weeds that threaten indigenous biodiversity and have a negative impact on agricultural productivity in South Africa. These plants are problematic because they form dense thickets that reduce the carrying capacity of rangelands; restrict the movement of livestock and wildlife thus reducing access to shade and water sources; and are directly harmful to livestock, wildlife and people due to their sharp spines. Biological control is the most effective, affordable and environmentally friendly method to control invasive alien cacti and minimize their negative impacts. Cochineal insects (Dactylopius spp.: Dactylopiidae) and the gall-forming mealybug, Hypogeococcus sp. (Pseudococcidae) are used as biological control agents for cacti. The agents are however poor dispersers, so mass-rearing and augmentative releases are required in order to establish the agents at sites where they are needed. This study aimed to evaluate the mass-rearing and release efforts of cactus biological control in South Africa, quantify the impact of the biological control agents on cactus plant populations through long-term monitoring, and assess the benefits accrued due to the biological control agents through the perceptions of land-users. An assessment of the effectiveness of the release effort for cactus biological control agents was conducted by comparing where biological control agents have been released with the known distribution of the target weeds. Only 26% of the quarter degree squares that are known to be occupied by invasive alien cacti have had biological control agents released in them. This indicated that the mass-rearing and release efforts in South Africa are inadequate and should be increased, especially in areas where few releases have been made and many cacti are present, such as the Limpopo Province. The impact of the biological control agents on cactus plant populations was assessed by monitoring agent densities, target plant densities and target plant reproductive outputs before and after releases. Plant biomass and reproductive output were reduced by biological control agents for three of the target weeds that were assessed, while the duration of the study was too short to measure reductions for the fourth target weed. Benefits to land-users were then quantified through a questionnaire survey. Land-users perceived biological control as an effective management option, with 81% of the land-users reporting that there was less invasive alien cactus after releasing biological control agents on their land. Forty-nine percent of the land-users believed that the negative impacts of the cactus had been reduced and that they benefited more from their land since control was achieved. Since land-users were only interviewed within four years of the releases being conducted, it is expected that the percentage of land-users who gained benefits from biological control will increase in future. Ninety-seven percent of the land-users stated that the agents were safe and had not fed on any other plants or had any detrimental impacts. These perceptions indicated that land-users regarded biological control as a safe and effective method of controlling invasive alien cacti. This study confirms that biological control is an effective and safe way of controlling invasive alien Cactaceae. It is also the first to assess some of the benefits that land-users have accrued due to biological control of cactus weeds. It is however evident that a greater mass-rearing and release effort is required for South Africa to get the maximum benefits possible from the use of the biological control agents for cactus weeds that are available in the country. , Izityalo ze-cactus ezisuka kwamanye amazwe zilukhula olubalaseleyo, olwenza ingxaki kwintlobo ngeentlobo zezityalo nezilwanyana kwaye ezizityalo zinefuthe neziphumo ezingalunganga kwimveliso yezolimo eMzantsi Afrika. Ezi zizityalo ziyingxaki kuba zenza amatyholo ashinyeneyo athi anciphise umthamo wokusebenzisa umhlaba: zinqanda ukuhamba nogkukhululekileyo kwemfuyo nezilwanyana zasendle ngokwenza oko zingakwazi ukufikelela emthuzini xa kutshisa nakwimithombo yamanzi yokusela; zikwayiyo nengozi kwimfuyo, izilwanyana zasendle kunye nabantu ngenxa yamave abukhali afumaneka kwezizityalo. Ukulawula nokwehliza ubunzini nezinga lemigcipheko yezizityalo, kusetyenziswa indlela ekuthiwa yi-biological control. Lendlela yeyona ndlela isebenza ngokuphucukileyo, efikelelayo, nengenabungozi kokusingqongileyo. Izinambuzane ze- cochineal (i-Dactylopius spp.: Dactylopiidae) kunye ne-mealybug, i-Hypogeococcus sp. (Pseudococcidae) zisetyenziswe njengezixhobo ze-biological control ezinceda ukulawula ezizityalo ze-cactus zingafunekiyo. Ingxaki yazo ezizinambuzane zizixhobo ze-biological control zingentla kukuba azikwazi kuzisasaza ngokwazo ukuba zifikelele nakwizityalo ezikude ngoko ke ukukhuliswa nokukhutshwa ngobuninzi bazo kuyafuneka ukukhawulelana nalengxaki kunye nokwandisa amathuba wokuba zifikelele kuzozonke izityalo ze-cactus ekufuneka zizilawule. Olu phononongo lujolise ekuvavanyeni iinzame zokukhulisa ngobuninzi nokukhupha ezezinambuzane zizixhobo ze-bioloigical control zokulawula izityalo ze-cactus eMzantsi Afrika, ukujonga ubungakanani befuthe notshintsho elenziwa zezinambuzane zizixhobo ze-bioloigical control kwizityalo ze-cactus emva kwexesha elide lokuzijonga, kunye nokuvavanya inzuzo efunyenwe ngenxa yokulawula ezizityalo ze-cactus ngokwemibono yabasebenzisi bomhlaba. Uvavanyo lweenzame zokukhutshwa kwezixhobo zezixhobo zezinambuzane ze-bioloigical control kwizityalo ze-cactus lwenziwa ngokuthelekisa iindawo apho izixhobo zezinambuzane ze-biological control zikhutshwe khona kunye neendawo apho izityalo ze-cactus kwaziwayo ukuba ziyafumaneka khona. Yi-26% kuphela yesikwere sekota eyaziwayo ukuba kukhona izityalo ze-cactus nalapho kukhutshwe khona kwezinambuzane ezizixhobo ze-biological control. Oku kubonisa ukuba iinzame zokukhulisa nokukhutshwa kwezinambuzane ezizixhobo ze-biological control eMzantsi Afrika azanelanga kwaye kufuneka zandiswe, ngakumbi kwiindawo apho kukho ukhutsho olumbalwa olwenziweyo kunye nezityalo ze-cactus ezininzi ezifumaneka khona, njengePhondo laseLimpopo. Iimpembelelo yokukhutshwa kwezinambuzane ezizixhobo ze-biological control kwizityalo ze-cactus zavavanywa ngokujonga ubunizi bezinambuzane ezizixhobo ze-biological control, ukuxinana kwezityalo ze-cactus ekujoliswe kuzo kunye nemveliso yokuzala kwezityalo ze-cactus phambi nasemva kokuba kukhutshwe izinambuzane ezizixhobo ze-biological control. Ubungakanani bezityalo ze-cactus kunye nemveliso yokuzala ziye zacutheka emva kokukhutshwa kwezinambuzane ezizixhobo ze-biological control kwinzityalo ezintathu ze-cactus ebekujoliswe uvavanyo kuzo, ngelixa ixesha lophononongo lalifutshane kakhulu ukuvavanya unciphiso kwisityalo se-cactus sesine. Izibonelelo zabasebenzisi bomhlaba zaye zavavanywa kusetyenziswa uhlobo lwemibuzo. Abasebenzisi bomhlaba balubona ukusetyenziswa kwezinambuzane ezizixhobo ze-biological control njengendlela yolawulo olusebenzayo, yi81% yabasebenzisi bomhlaba echaze ukuba izityalo ze-cactus zecuthekile emva kokukhutshwa kwezinambuzane ezizixhobo ze-biological control emhlabeni wabo. Amashumi amane anesithoba eepesenti zabasebenzisi bomhlaba bakholelwa ukuba impembelelo ezingalunganga ze-cactus zincitshisiwe kwaye baxhamle kakhulu kumhlaba wabo okoko lwaphunyenzwa. Oludliwano-ndlebe belwenziwe kubasebenzisi bomhlaba kwisithuba seminyaka emine emva kokuba kukhutshwe izinambuzane ezizixhobo ze-biological control, kulindeleke ukuba ipesenti yabasebenzisi bomhlaba abathe bafumana izibonelelo kwi-biological control lonyuke kwixesha elizayo. Amashumi alithoba anesixhenxe ekhulwini abasebenzisi bomhlaba bachaze ukuba izinambuzane ezizixhobo ze-biological control zikhuselekile kwaye khange zidle kuzo naziphi na ezinye izityalo ezingezi eze-cactus ebekujoliswe kuzo okanye zineempembelelo eyingozi. Ezi mbono ziyabonisa ukuba abasebenzi bomhlaba bayithatha i-biological control njengendlela ekhuselekileyo nesebenzayo yokulawula izityalo ze-cactus zamanye amazwe. Olu phononongo luqinisekisa ukuba ulawulo olusebenzisa izinambuzane ezizixhobo ze-biological control yindlela esebenzayo nekhuselekileyo yokulawula iCactaceae yamanye amazwe. Ikwangolokuqala ukuvavanya ezinye zezibonelelo ezizuzwe ngabasebenzisi bomhlaba ngenxa ye-biological control yezityalo ze-cactus. Nangona kunjalo kucacile ukuba ukwandisa inzame zokukhulisa nokukhupha ngobuninzi izinambuzane ezizixhobo ze-biological control kuyafuneka ukuze uMzantsi Afrika ufumane izibonelelo eziphakamileyo enokubakho ngokusetyenziswa kwe zinambuzane ezizixhobo ze-biological control zokulawula ukhula lwe-cactus olukhoyo kweli lizwe. , Thesis (PhD) -- Faculty of Science, Zoology and Entomology, 2022
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- Authors: Mnqeta, Zezethu
- Date: 2022-04-08
- Subjects: Cactus Biological control South Africa , Noxious weeds South Africa , Invasive plants Biological control South Africa , Insects as biological pest control agents South Africa , Cochineal insect South Africa , Mealybugs South Africa , Agricultural productivity South Africa
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294631 , vital:57239 , DOI 10.21504/10962/294631
- Description: Invasive alien cacti are prominent weeds that threaten indigenous biodiversity and have a negative impact on agricultural productivity in South Africa. These plants are problematic because they form dense thickets that reduce the carrying capacity of rangelands; restrict the movement of livestock and wildlife thus reducing access to shade and water sources; and are directly harmful to livestock, wildlife and people due to their sharp spines. Biological control is the most effective, affordable and environmentally friendly method to control invasive alien cacti and minimize their negative impacts. Cochineal insects (Dactylopius spp.: Dactylopiidae) and the gall-forming mealybug, Hypogeococcus sp. (Pseudococcidae) are used as biological control agents for cacti. The agents are however poor dispersers, so mass-rearing and augmentative releases are required in order to establish the agents at sites where they are needed. This study aimed to evaluate the mass-rearing and release efforts of cactus biological control in South Africa, quantify the impact of the biological control agents on cactus plant populations through long-term monitoring, and assess the benefits accrued due to the biological control agents through the perceptions of land-users. An assessment of the effectiveness of the release effort for cactus biological control agents was conducted by comparing where biological control agents have been released with the known distribution of the target weeds. Only 26% of the quarter degree squares that are known to be occupied by invasive alien cacti have had biological control agents released in them. This indicated that the mass-rearing and release efforts in South Africa are inadequate and should be increased, especially in areas where few releases have been made and many cacti are present, such as the Limpopo Province. The impact of the biological control agents on cactus plant populations was assessed by monitoring agent densities, target plant densities and target plant reproductive outputs before and after releases. Plant biomass and reproductive output were reduced by biological control agents for three of the target weeds that were assessed, while the duration of the study was too short to measure reductions for the fourth target weed. Benefits to land-users were then quantified through a questionnaire survey. Land-users perceived biological control as an effective management option, with 81% of the land-users reporting that there was less invasive alien cactus after releasing biological control agents on their land. Forty-nine percent of the land-users believed that the negative impacts of the cactus had been reduced and that they benefited more from their land since control was achieved. Since land-users were only interviewed within four years of the releases being conducted, it is expected that the percentage of land-users who gained benefits from biological control will increase in future. Ninety-seven percent of the land-users stated that the agents were safe and had not fed on any other plants or had any detrimental impacts. These perceptions indicated that land-users regarded biological control as a safe and effective method of controlling invasive alien cacti. This study confirms that biological control is an effective and safe way of controlling invasive alien Cactaceae. It is also the first to assess some of the benefits that land-users have accrued due to biological control of cactus weeds. It is however evident that a greater mass-rearing and release effort is required for South Africa to get the maximum benefits possible from the use of the biological control agents for cactus weeds that are available in the country. , Izityalo ze-cactus ezisuka kwamanye amazwe zilukhula olubalaseleyo, olwenza ingxaki kwintlobo ngeentlobo zezityalo nezilwanyana kwaye ezizityalo zinefuthe neziphumo ezingalunganga kwimveliso yezolimo eMzantsi Afrika. Ezi zizityalo ziyingxaki kuba zenza amatyholo ashinyeneyo athi anciphise umthamo wokusebenzisa umhlaba: zinqanda ukuhamba nogkukhululekileyo kwemfuyo nezilwanyana zasendle ngokwenza oko zingakwazi ukufikelela emthuzini xa kutshisa nakwimithombo yamanzi yokusela; zikwayiyo nengozi kwimfuyo, izilwanyana zasendle kunye nabantu ngenxa yamave abukhali afumaneka kwezizityalo. Ukulawula nokwehliza ubunzini nezinga lemigcipheko yezizityalo, kusetyenziswa indlela ekuthiwa yi-biological control. Lendlela yeyona ndlela isebenza ngokuphucukileyo, efikelelayo, nengenabungozi kokusingqongileyo. Izinambuzane ze- cochineal (i-Dactylopius spp.: Dactylopiidae) kunye ne-mealybug, i-Hypogeococcus sp. (Pseudococcidae) zisetyenziswe njengezixhobo ze-biological control ezinceda ukulawula ezizityalo ze-cactus zingafunekiyo. Ingxaki yazo ezizinambuzane zizixhobo ze-biological control zingentla kukuba azikwazi kuzisasaza ngokwazo ukuba zifikelele nakwizityalo ezikude ngoko ke ukukhuliswa nokukhutshwa ngobuninzi bazo kuyafuneka ukukhawulelana nalengxaki kunye nokwandisa amathuba wokuba zifikelele kuzozonke izityalo ze-cactus ekufuneka zizilawule. Olu phononongo lujolise ekuvavanyeni iinzame zokukhulisa ngobuninzi nokukhupha ezezinambuzane zizixhobo ze-bioloigical control zokulawula izityalo ze-cactus eMzantsi Afrika, ukujonga ubungakanani befuthe notshintsho elenziwa zezinambuzane zizixhobo ze-bioloigical control kwizityalo ze-cactus emva kwexesha elide lokuzijonga, kunye nokuvavanya inzuzo efunyenwe ngenxa yokulawula ezizityalo ze-cactus ngokwemibono yabasebenzisi bomhlaba. Uvavanyo lweenzame zokukhutshwa kwezixhobo zezixhobo zezinambuzane ze-bioloigical control kwizityalo ze-cactus lwenziwa ngokuthelekisa iindawo apho izixhobo zezinambuzane ze-biological control zikhutshwe khona kunye neendawo apho izityalo ze-cactus kwaziwayo ukuba ziyafumaneka khona. Yi-26% kuphela yesikwere sekota eyaziwayo ukuba kukhona izityalo ze-cactus nalapho kukhutshwe khona kwezinambuzane ezizixhobo ze-biological control. Oku kubonisa ukuba iinzame zokukhulisa nokukhutshwa kwezinambuzane ezizixhobo ze-biological control eMzantsi Afrika azanelanga kwaye kufuneka zandiswe, ngakumbi kwiindawo apho kukho ukhutsho olumbalwa olwenziweyo kunye nezityalo ze-cactus ezininzi ezifumaneka khona, njengePhondo laseLimpopo. Iimpembelelo yokukhutshwa kwezinambuzane ezizixhobo ze-biological control kwizityalo ze-cactus zavavanywa ngokujonga ubunizi bezinambuzane ezizixhobo ze-biological control, ukuxinana kwezityalo ze-cactus ekujoliswe kuzo kunye nemveliso yokuzala kwezityalo ze-cactus phambi nasemva kokuba kukhutshwe izinambuzane ezizixhobo ze-biological control. Ubungakanani bezityalo ze-cactus kunye nemveliso yokuzala ziye zacutheka emva kokukhutshwa kwezinambuzane ezizixhobo ze-biological control kwinzityalo ezintathu ze-cactus ebekujoliswe uvavanyo kuzo, ngelixa ixesha lophononongo lalifutshane kakhulu ukuvavanya unciphiso kwisityalo se-cactus sesine. Izibonelelo zabasebenzisi bomhlaba zaye zavavanywa kusetyenziswa uhlobo lwemibuzo. Abasebenzisi bomhlaba balubona ukusetyenziswa kwezinambuzane ezizixhobo ze-biological control njengendlela yolawulo olusebenzayo, yi81% yabasebenzisi bomhlaba echaze ukuba izityalo ze-cactus zecuthekile emva kokukhutshwa kwezinambuzane ezizixhobo ze-biological control emhlabeni wabo. Amashumi amane anesithoba eepesenti zabasebenzisi bomhlaba bakholelwa ukuba impembelelo ezingalunganga ze-cactus zincitshisiwe kwaye baxhamle kakhulu kumhlaba wabo okoko lwaphunyenzwa. Oludliwano-ndlebe belwenziwe kubasebenzisi bomhlaba kwisithuba seminyaka emine emva kokuba kukhutshwe izinambuzane ezizixhobo ze-biological control, kulindeleke ukuba ipesenti yabasebenzisi bomhlaba abathe bafumana izibonelelo kwi-biological control lonyuke kwixesha elizayo. Amashumi alithoba anesixhenxe ekhulwini abasebenzisi bomhlaba bachaze ukuba izinambuzane ezizixhobo ze-biological control zikhuselekile kwaye khange zidle kuzo naziphi na ezinye izityalo ezingezi eze-cactus ebekujoliswe kuzo okanye zineempembelelo eyingozi. Ezi mbono ziyabonisa ukuba abasebenzi bomhlaba bayithatha i-biological control njengendlela ekhuselekileyo nesebenzayo yokulawula izityalo ze-cactus zamanye amazwe. Olu phononongo luqinisekisa ukuba ulawulo olusebenzisa izinambuzane ezizixhobo ze-biological control yindlela esebenzayo nekhuselekileyo yokulawula iCactaceae yamanye amazwe. Ikwangolokuqala ukuvavanya ezinye zezibonelelo ezizuzwe ngabasebenzisi bomhlaba ngenxa ye-biological control yezityalo ze-cactus. Nangona kunjalo kucacile ukuba ukwandisa inzame zokukhulisa nokukhupha ngobuninzi izinambuzane ezizixhobo ze-biological control kuyafuneka ukuze uMzantsi Afrika ufumane izibonelelo eziphakamileyo enokubakho ngokusetyenziswa kwe zinambuzane ezizixhobo ze-biological control zokulawula ukhula lwe-cactus olukhoyo kweli lizwe. , Thesis (PhD) -- Faculty of Science, Zoology and Entomology, 2022
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Singlet oxygen and optical limiting applications of BODIPYs and other molecular dyes
- Authors: May, Aviwe Khanya
- Date: 2022-04-08
- Subjects: Dyes and dyeing Chemistry , Phthalocyanines , Photochemotherapy , Active oxygen , Nonlinear optics , Time-dependent density functional theory , Photochemistry
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294618 , vital:57238 , DOI 10.21504/10962/294620
- Description: A series of structurally diverse novel and previously synthesized BODIPY core dyes are synthesized and characterized in this thesis. These BODIPYs were synthesized using 2-methylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole and 3-ethyl-2,4-dimethylpyrrole as the starting pyrroles. The combination of different pyrroles with the same aldehyde results in BODIPY core dyes that are structural analogues. These core dyes were used as precursors to synthesise halogenated BODIPYs and novel styrylBODIPY dyes, which were successfully characterized using FT-IR and 1H NMR spectroscopy. The halogenated BODIPY core dyes and the styrylBODIPY dyes were also characterized using MALDI-TOF mass spectrometry. The introduction of heavy atoms on the BODIPY core leads to a red shift of the main spectral. In the presence of styryl groups, the main spectral band red shifts to the far red end of the visible region. As expected, the halogenated BODIPY core dyes also had moderate singlet oxygen quantum yields. These halogenated core dyes were found to be suitable as photosensitizers as all the dyes reduced bacterial viability to below 50% during photodynamic antimicrobial chemotherapy (PACT) studies against Staphylococcus aureus. The structure-property relationships studied demonstrate that the presence of protons rather than methyls at the 1,7-positions or iodines at the 2,6-positions results in more favorable PACT activity. This is likely to be related to the greater ability of the meso-aryl to rotate into the plane of the dipyrromethene ligand and suggests that there should be a stronger focus on dyes of this type in future studies in this field. During nonlinear optical (NLO) studies, all the styrylBODIPYs exhibited favorable reverse saturable absorption (RSA) responses. In the absence of methyl groups at the 1,7-positions, the meso-aryl ring lies closer to the π-system of the BODIPY core, enhancing donor (D)–π–acceptor (A) properties and resulting in slightly enhanced optical limiting (OL) parameters. Additionally, there is no evidence that the introduction of heavy atoms at the 2,6-positions significantly enhances OL properties. In a similar manner, alkyl substituents at these positions also do not significantly enhance OL properties; this was studied for the first time using 15 with ethyl groups at the 2,6-positions. The combination of z-scan data and transient spectroscopy for 16 demonstrated that the main mechanism responsible for the NLO properties of nonhalogenated BODIPY dyes is one-photon absorption from the ground state followed by ESA in the singlet manifold. From the NLO studies of 25, OL parameters of 1,3,5-tristyrylBODIPY dyes were found to be similar in magnitude to properties of distyrylBODIPY dyes, but to have less favorable optical properties for OL applications. The OL properties of scandium phthalocyanines were assessed for the first time, since the Sc(III) ion, unusually for a first row transition metal ion, is known to readily form sandwich complexes. The presence of a Sc(III) ion does not significantly enhance the OL properties of phthalocyanines relative to those of rare earth metal ions that also form complexes of this type. Because BODIPYs and phthalocyanines typically absorb significantly in the visible region, transparent PBC polymer thin films of disilane-bridged compounds with minimal absorption in this region were studied and exhibited an excellent RSA response. These compounds may be useful in the design of OL materials that can protect the human eye. The optimized geometries and spectroscopic properties of selected BODIPYs were studied. As expected, the presence of bromine, iodine, ethyl and styryl groups at different positions of the BODIPY core leads to a narrowing of the HOMO–LUMO band gap, which results in a red-shift of the main spectral band. Partial atomic charges have also been calculated for some of the styrylBODIPY dyes studied for application in OL, and electrostatic potential energy maps were also visualized to better assess how the dipole moment of BODIPY dyes can be modulated since this can affect the OL properties. For all the BODIPYs studied, the electronegativity of the atoms present influences charge distribution on the BODIPY structure. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Authors: May, Aviwe Khanya
- Date: 2022-04-08
- Subjects: Dyes and dyeing Chemistry , Phthalocyanines , Photochemotherapy , Active oxygen , Nonlinear optics , Time-dependent density functional theory , Photochemistry
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294618 , vital:57238 , DOI 10.21504/10962/294620
- Description: A series of structurally diverse novel and previously synthesized BODIPY core dyes are synthesized and characterized in this thesis. These BODIPYs were synthesized using 2-methylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole and 3-ethyl-2,4-dimethylpyrrole as the starting pyrroles. The combination of different pyrroles with the same aldehyde results in BODIPY core dyes that are structural analogues. These core dyes were used as precursors to synthesise halogenated BODIPYs and novel styrylBODIPY dyes, which were successfully characterized using FT-IR and 1H NMR spectroscopy. The halogenated BODIPY core dyes and the styrylBODIPY dyes were also characterized using MALDI-TOF mass spectrometry. The introduction of heavy atoms on the BODIPY core leads to a red shift of the main spectral. In the presence of styryl groups, the main spectral band red shifts to the far red end of the visible region. As expected, the halogenated BODIPY core dyes also had moderate singlet oxygen quantum yields. These halogenated core dyes were found to be suitable as photosensitizers as all the dyes reduced bacterial viability to below 50% during photodynamic antimicrobial chemotherapy (PACT) studies against Staphylococcus aureus. The structure-property relationships studied demonstrate that the presence of protons rather than methyls at the 1,7-positions or iodines at the 2,6-positions results in more favorable PACT activity. This is likely to be related to the greater ability of the meso-aryl to rotate into the plane of the dipyrromethene ligand and suggests that there should be a stronger focus on dyes of this type in future studies in this field. During nonlinear optical (NLO) studies, all the styrylBODIPYs exhibited favorable reverse saturable absorption (RSA) responses. In the absence of methyl groups at the 1,7-positions, the meso-aryl ring lies closer to the π-system of the BODIPY core, enhancing donor (D)–π–acceptor (A) properties and resulting in slightly enhanced optical limiting (OL) parameters. Additionally, there is no evidence that the introduction of heavy atoms at the 2,6-positions significantly enhances OL properties. In a similar manner, alkyl substituents at these positions also do not significantly enhance OL properties; this was studied for the first time using 15 with ethyl groups at the 2,6-positions. The combination of z-scan data and transient spectroscopy for 16 demonstrated that the main mechanism responsible for the NLO properties of nonhalogenated BODIPY dyes is one-photon absorption from the ground state followed by ESA in the singlet manifold. From the NLO studies of 25, OL parameters of 1,3,5-tristyrylBODIPY dyes were found to be similar in magnitude to properties of distyrylBODIPY dyes, but to have less favorable optical properties for OL applications. The OL properties of scandium phthalocyanines were assessed for the first time, since the Sc(III) ion, unusually for a first row transition metal ion, is known to readily form sandwich complexes. The presence of a Sc(III) ion does not significantly enhance the OL properties of phthalocyanines relative to those of rare earth metal ions that also form complexes of this type. Because BODIPYs and phthalocyanines typically absorb significantly in the visible region, transparent PBC polymer thin films of disilane-bridged compounds with minimal absorption in this region were studied and exhibited an excellent RSA response. These compounds may be useful in the design of OL materials that can protect the human eye. The optimized geometries and spectroscopic properties of selected BODIPYs were studied. As expected, the presence of bromine, iodine, ethyl and styryl groups at different positions of the BODIPY core leads to a narrowing of the HOMO–LUMO band gap, which results in a red-shift of the main spectral band. Partial atomic charges have also been calculated for some of the styrylBODIPY dyes studied for application in OL, and electrostatic potential energy maps were also visualized to better assess how the dipole moment of BODIPY dyes can be modulated since this can affect the OL properties. For all the BODIPYs studied, the electronegativity of the atoms present influences charge distribution on the BODIPY structure. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
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Synthesis and evaluation of the medicinal potential of novel 4-hydroxycoumarin derivatives
- Authors: Manyeruke, Meloddy Hlatini
- Date: 2022-04-08
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/164458 , vital:41120 , doi:10.21504/10962/164458
- Description: This research has focused on the synthesis and biological evaluation of a broad range of compounds characterised by the presence of the pharmacologically significant 4-hydroxycoumalin scaffold. The compounds were designed to contain additional pharmachophoric centres to enhance bioactivity and generate lead compounds with dualaction potential. The use of 4-hydroxycoumarin as the primary synthon enabled access to various series of 4-hydroxycoumarin conjugates, the reactive 3-position on the 4-hydroxycoumarin moiety being exploited for regioselective construction of the targeted compounds in several steps. Some of the reactants required in the construction of these compounds were specially synthesised and included propargyloxy benzaldehydes, benzyloxy benzaldehydes and 2,3-dihydroxysuccino-dihydride. Overall, eight different families of novel compounds were accessed, comprising conjugates of 4-hydroxycoumarin with bisethylidenesuccinohyrazide, trifluoroacetamide, amino, benzyloxyphenyl-iminoethyl, benzylidenehyrazinyl-thiazoyl, benzylidenehydrazonoethyl, propargyloxybenzylidenehydrazonoethyl and phenylacryloyl moieties using protocols that required minimal work-up and purification. The eighty novel compounds synthesised in the study were fully characterised using HMRS and advanced NMR techniques. Cytotoxicity, HIV-1 IN and PR inhibitory, and antitrypanosomal, antimalarial and anti-Mtb assays were conducted on the synthesised coumarin derivatives. Several compounds exhibited activity against HIV-1 IN, the most potent being a bis-ethylidenesuccinohyrazide with an IC50 value of 3.5 μM. Various compounds exhibited anti-malarial activity (% pLDH viability in the range 62-77%), anti-trypanosomal activity (the most potent with an IC50 = 0.9 μM against T.b. brucei) and a measure of anti-Mtb activity. Apart from two chalconyl derivatives, none of the synthesised compounds exhibited significant cytotoxicity. Conflicting results were obtained from the in silico docking studies; in some cases supporting the observed in vitro assay data while, in others, exhibiting no correlation. , Thesis (PhD) -- Faculty of Science, Chemistry, 2020
- Full Text:
- Authors: Manyeruke, Meloddy Hlatini
- Date: 2022-04-08
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/164458 , vital:41120 , doi:10.21504/10962/164458
- Description: This research has focused on the synthesis and biological evaluation of a broad range of compounds characterised by the presence of the pharmacologically significant 4-hydroxycoumalin scaffold. The compounds were designed to contain additional pharmachophoric centres to enhance bioactivity and generate lead compounds with dualaction potential. The use of 4-hydroxycoumarin as the primary synthon enabled access to various series of 4-hydroxycoumarin conjugates, the reactive 3-position on the 4-hydroxycoumarin moiety being exploited for regioselective construction of the targeted compounds in several steps. Some of the reactants required in the construction of these compounds were specially synthesised and included propargyloxy benzaldehydes, benzyloxy benzaldehydes and 2,3-dihydroxysuccino-dihydride. Overall, eight different families of novel compounds were accessed, comprising conjugates of 4-hydroxycoumarin with bisethylidenesuccinohyrazide, trifluoroacetamide, amino, benzyloxyphenyl-iminoethyl, benzylidenehyrazinyl-thiazoyl, benzylidenehydrazonoethyl, propargyloxybenzylidenehydrazonoethyl and phenylacryloyl moieties using protocols that required minimal work-up and purification. The eighty novel compounds synthesised in the study were fully characterised using HMRS and advanced NMR techniques. Cytotoxicity, HIV-1 IN and PR inhibitory, and antitrypanosomal, antimalarial and anti-Mtb assays were conducted on the synthesised coumarin derivatives. Several compounds exhibited activity against HIV-1 IN, the most potent being a bis-ethylidenesuccinohyrazide with an IC50 value of 3.5 μM. Various compounds exhibited anti-malarial activity (% pLDH viability in the range 62-77%), anti-trypanosomal activity (the most potent with an IC50 = 0.9 μM against T.b. brucei) and a measure of anti-Mtb activity. Apart from two chalconyl derivatives, none of the synthesised compounds exhibited significant cytotoxicity. Conflicting results were obtained from the in silico docking studies; in some cases supporting the observed in vitro assay data while, in others, exhibiting no correlation. , Thesis (PhD) -- Faculty of Science, Chemistry, 2020
- Full Text:
The role of angling-guides in promoting pro-environmental catch-and-release attitudes and behaviours in the recreational angling community
- Authors: Farthing, Matthew William
- Date: 2022-04-08
- Subjects: Fishing , Fishing Catch effort , Fishing guides , Fishers , Human behavior , Role models
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294583 , vital:57235 , DOI 10.21504/10962/294585
- Description: Angling-guides are respected as opinion leaders of the recreational angling community, but nothing is known of their influence on angler behaviour. Given their social-standing, angling-guides may be perceived as role-models by angling-clients – thereby promoting the adoption of best and/or poor catch-and-release (C&R) practices, depending on their individual knowledge, attitudes and behaviour. It is critical to understand their potential influence, their knowledge and their behaviours to inform effective intervention strategies which could exploit their extensive networking potential. The aim of this thesis was to better understand the potential utility of angling-guides in efforts to improve angler behaviour. Firstly, this was done by investigating whether angling-guides are perceived as role-models by angling-clients (Chapter 2). Secondly, it was done by assessing the current level of knowledge, attitudes and behaviours of angling-guides from around the world (Chapter 3). Thirdly, it was done by exploring the relationship between angling-guide knowledge, attitudes, intentions and actual behaviour in a case-study of guided-angling trips (Chapter 4). Lastly, it was done by exploring intervention frameworks and incorporating insights into potential strategies for promoting pro-environmental angling behaviours to angling-guides (Chapter 5). To understand if angling-guides are perceived as role-models by the recreational angling community (Chapter 2), a digital survey was designed to assess previous angling-clients’ attitudes towards angling-guides serving the three role-model functions proposed in the Motivational Theory of Role-Modelling, namely as Behavioural models, Representations of the Possible and Inspiration. Of the 492 angling-clients (27 countries), most agreed that angling-guides were competent, skilled, and worth emulating (91.1%), suggesting they are perceived as Behavioural Models. Less agreed that angling-guides were Inspirational or Representations of the Possible (54.8%), suggesting they are less likely to motivate anglers to adopt and/or pursue new goals. As Behavioural Models, angling-guide C&R practices are likely to be emulated, which is of both utility and concern to managers. As angling-guides are likely to be emulated, a digital survey was designed to assess their knowledge, attitudes and behaviours (particularly C&R best-practices) (Chapter 3). Of the 342 angling-guides (47 countries), few had accredited training (9.4%). However, most were deemed “knowledgeable of best-practices” (69.0%), but pervasive misconceptions of key C&R best-practices were observed. Attitudes towards best-practices were generally pro-environmental, and those deemed knowledgeable had significantly more pro-environmental attitudes (p = 0.003). Most angling-guides had pro-environmental attitudes towards their environmental responsibilities (87.1 - 89.5%), but these broad attitudes cannot predict specific pro-environmental behaviours during guided-angling trips where angler satisfaction is often at odds with best-practice. Angling-client satisfaction has important financial implications for angling-guides, and even those with pro-environmental intentions may struggle to adhere to C&R best-practices with inherent sacrifices for the angling-client’s enjoyment. Observation of behaviour in context is critical for understanding the behaviour to be changed. To explore the relationship between angling-guide knowledge, intentions and actual behaviour (Chapter 4), five angling-guides were observed (and filmed) interacting with groups of angling-clients during their guided-angling trips over a 30 day period. Five angling behaviours of interest were identified, and a survey focussed on these behaviours was disseminated (18 months later) to the five angling-guides previously observed to assess their knowledge, attitudes, reported behaviours and perceptions of the norm. Generally the subjects’ reported behaviours aligned well with their knowledge of best-practice, but their actual behaviour was not well aligned (24.4%). Instead, their actual behaviour aligned better with their perceptions of the norm (80.9%), which was generally a “worse” practice than what they reported. Angling-guides appeared to favour client-satisfaction over pro-environmental behaviour. Gaps between angling-guides’ knowledge of best-practice and their actual behaviour indicate that there may be obscure and complex barriers to pro-environmental angling-guide behaviour. Many barriers are seemingly impossible to overcome, such as economic limitations and financial disincentives. These barriers may limit the efficacy of traditional knowledge-attitude-behaviour (KAB) change interventions. The strong alignment of angling-guide behaviour with social norms, and the strong community orientation of recreational angling suggests that the Community-Based Social Marketing (CBSM) approach may be a more effective framework for interventions that aim to promote pro-environmental catch-and-release behaviours at angling-guide level. The CBSM approach allows interventionists to leverage a larger suite of cognitive biases than KAB approaches, provided that sufficient understanding of the context, barriers and benefits for a given segment of the angling-guide community (likely defined by style-of-participation) are obtained. Furthermore, the success of the CBSM approach will depend on the ability of interventionists to effectively recruit and incentivise disjunct and isolated communities of angling-guides to participate in training and workshops in order to achieve the important in-person contact on which the CBSM approach depends. , Thesis (PhD) -- Faculty of Science, Ichthyology and Fisheries Science, 2022
- Full Text:
- Authors: Farthing, Matthew William
- Date: 2022-04-08
- Subjects: Fishing , Fishing Catch effort , Fishing guides , Fishers , Human behavior , Role models
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294583 , vital:57235 , DOI 10.21504/10962/294585
- Description: Angling-guides are respected as opinion leaders of the recreational angling community, but nothing is known of their influence on angler behaviour. Given their social-standing, angling-guides may be perceived as role-models by angling-clients – thereby promoting the adoption of best and/or poor catch-and-release (C&R) practices, depending on their individual knowledge, attitudes and behaviour. It is critical to understand their potential influence, their knowledge and their behaviours to inform effective intervention strategies which could exploit their extensive networking potential. The aim of this thesis was to better understand the potential utility of angling-guides in efforts to improve angler behaviour. Firstly, this was done by investigating whether angling-guides are perceived as role-models by angling-clients (Chapter 2). Secondly, it was done by assessing the current level of knowledge, attitudes and behaviours of angling-guides from around the world (Chapter 3). Thirdly, it was done by exploring the relationship between angling-guide knowledge, attitudes, intentions and actual behaviour in a case-study of guided-angling trips (Chapter 4). Lastly, it was done by exploring intervention frameworks and incorporating insights into potential strategies for promoting pro-environmental angling behaviours to angling-guides (Chapter 5). To understand if angling-guides are perceived as role-models by the recreational angling community (Chapter 2), a digital survey was designed to assess previous angling-clients’ attitudes towards angling-guides serving the three role-model functions proposed in the Motivational Theory of Role-Modelling, namely as Behavioural models, Representations of the Possible and Inspiration. Of the 492 angling-clients (27 countries), most agreed that angling-guides were competent, skilled, and worth emulating (91.1%), suggesting they are perceived as Behavioural Models. Less agreed that angling-guides were Inspirational or Representations of the Possible (54.8%), suggesting they are less likely to motivate anglers to adopt and/or pursue new goals. As Behavioural Models, angling-guide C&R practices are likely to be emulated, which is of both utility and concern to managers. As angling-guides are likely to be emulated, a digital survey was designed to assess their knowledge, attitudes and behaviours (particularly C&R best-practices) (Chapter 3). Of the 342 angling-guides (47 countries), few had accredited training (9.4%). However, most were deemed “knowledgeable of best-practices” (69.0%), but pervasive misconceptions of key C&R best-practices were observed. Attitudes towards best-practices were generally pro-environmental, and those deemed knowledgeable had significantly more pro-environmental attitudes (p = 0.003). Most angling-guides had pro-environmental attitudes towards their environmental responsibilities (87.1 - 89.5%), but these broad attitudes cannot predict specific pro-environmental behaviours during guided-angling trips where angler satisfaction is often at odds with best-practice. Angling-client satisfaction has important financial implications for angling-guides, and even those with pro-environmental intentions may struggle to adhere to C&R best-practices with inherent sacrifices for the angling-client’s enjoyment. Observation of behaviour in context is critical for understanding the behaviour to be changed. To explore the relationship between angling-guide knowledge, intentions and actual behaviour (Chapter 4), five angling-guides were observed (and filmed) interacting with groups of angling-clients during their guided-angling trips over a 30 day period. Five angling behaviours of interest were identified, and a survey focussed on these behaviours was disseminated (18 months later) to the five angling-guides previously observed to assess their knowledge, attitudes, reported behaviours and perceptions of the norm. Generally the subjects’ reported behaviours aligned well with their knowledge of best-practice, but their actual behaviour was not well aligned (24.4%). Instead, their actual behaviour aligned better with their perceptions of the norm (80.9%), which was generally a “worse” practice than what they reported. Angling-guides appeared to favour client-satisfaction over pro-environmental behaviour. Gaps between angling-guides’ knowledge of best-practice and their actual behaviour indicate that there may be obscure and complex barriers to pro-environmental angling-guide behaviour. Many barriers are seemingly impossible to overcome, such as economic limitations and financial disincentives. These barriers may limit the efficacy of traditional knowledge-attitude-behaviour (KAB) change interventions. The strong alignment of angling-guide behaviour with social norms, and the strong community orientation of recreational angling suggests that the Community-Based Social Marketing (CBSM) approach may be a more effective framework for interventions that aim to promote pro-environmental catch-and-release behaviours at angling-guide level. The CBSM approach allows interventionists to leverage a larger suite of cognitive biases than KAB approaches, provided that sufficient understanding of the context, barriers and benefits for a given segment of the angling-guide community (likely defined by style-of-participation) are obtained. Furthermore, the success of the CBSM approach will depend on the ability of interventionists to effectively recruit and incentivise disjunct and isolated communities of angling-guides to participate in training and workshops in order to achieve the important in-person contact on which the CBSM approach depends. , Thesis (PhD) -- Faculty of Science, Ichthyology and Fisheries Science, 2022
- Full Text:
The transformative potential of intersecting arts-based inquiry and environmental learning in urban South Africa: a focus on socio-ecological water pedagogies
- Authors: James, Anna Katharine
- Date: 2022-04-08
- Subjects: Environmental education South Africa , Water conservation Study and teaching South Africa , Art in environmental education South Africa , Social learning South Africa , Educational sociology South Africa , Water-supply Social aspects South Africa , Critical realism , Socio-ecological education
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/290660 , vital:56772 , DOI 10.21504/10962/290660
- Description: In this study I explore and explain transformative potential in arts-based environmental learning with a focus on water pedagogy. The study took place over a period of four years, where approximately 40 school pupils between the ages of 10 and 17 years-old were engaged in participatory arts-based inquiries into water located across unequal neighbourhoods in Cape Town, South Africa. Educators, school learners, citizens and decision-makers hold different historical, cultural, political and spiritual perspectives on water. These play a role in shaping what is termed in this research the ‘hydro-social cycle’. Yet, due to dominant ideas of what counts as knowing and truth, educators in educational settings struggle to account for the complexity of water, limiting educational encounters to a partial knowing leading mostly to limited unimaginative framings of problems and solutions. My focus on transformative potential in learning is derived from a concern for how environmental education encounters and the sense-making they enable, are infused by socio-economic, political, and historical elements, specifically colonialism, capitalism, and white supremacist racism. The connections between the multiple layers of capitalist crisis and the ever-urgent environmental crisis are not adequately made in mainstream forms of water education. The research explores how arts-based pedagogy could enable a productive meeting of critical environmental education with ecological literacies. Within this positioning, transformative potential considers how educational engagements position questions about water within the social life of participants/learners and inform learning that leads to fuller and more nuanced greater knowledge. Theoretically, I work with an interrogation of critical education theory, underlaboured by critical realism which enabled me to rigorously consider how claims to knowing are shaped by their accompanying assumptions of what is real. Drawing on recent debates in critical education theory, I resist the notion of critique as ideology and engage instead in the craftsmanship of contextual and responsive inquiry practice. This has enabled me to articulate processes and relationships in water education encounters with meaningful understandings of the effects of simultaneous crises rooted in racial capitalism and environmental crisis. My methodological approach is arts-based educational research with a directive to reflect upon educational encounters in an integrated way. It includes two parts informing the facilitation and analysis of open-ended learning processes. One component was arts-based inquiry practice developed for exploring complexity, drawing on the thinking of Norris (2009, 2011) and Finley (2016, 2017). The second part holds reflective space for these encounters guided by the practice of pedagogical narration inspired by the Reggio Amelia approach, demonstrated by Pacini-Ketchabaw, Nxumalo, Kocher, Elliot and Sanchez (2014). Clarifying the intellectual work of a responsive educator-researcher, pedagogical narration brings multiple theoretical lenses into conversation with emergent dimensions of educational process. In practice, in order to transgress the dominance of colonial white supremacist knowledge frames of water, I needed to be curious, to be confounded, to expect the unexpected in the educational encounters with participants and this mirroring of practice was emulated by the participants as they followed their own questions about water in Mzansi (South Africa). In our work together we came up against assumptions we had previously not questioned as individuals. Together we explored the implications of this by, for example, questioning who is responsible for saving water. These explorations required bringing together science knowledge and everyday knowledge at multiple scales: the household, catchment, government and global. It required us to be critical of how language and images are mobilized in public communication and school curriculums; for example, representations of water are infused with history and power in a way that impacts how we know and teach about water. The transformative potential of this pedagogical space is generated through acts of creative expression which are seen as acts of absenting absence, for example exhibiting through play how water use in the household interconnects with gender and age relationships. As such, creative expression through multiple mediums or more-than-text enables a deeper understanding of water as well as openings for interdisciplinary engagement with learning about water. My research found that in bringing together the contributions of critical education and environmental education in practice, two shifts are needed: environmental educators need to view ecological literacy as inseparable from the social and political. The knowledge that is shared about water in the classroom has social and political implications. On the other hand, critical educators need to better locate justice concerns in the material and ecological world at scale. Arts-based inquiry, as a kind of scaffolding for pedagogical process, has the potential to enable these shifts by opening up fixed analytical frames. Making these shifts requires a reflective practice on the part of the educator to navigate the inherited blind spots in environmental learning and critical education, such as dualities. One way to do this is for the educator to identify absences, as articulated in the Critical Realist tradition, and consider how these absences might be absented. This differs from a simplistic process of critique in the possibilities it opens up for collaboration between different schools of thought rather than further polarisation and alienation between educators and knowledge keepers on social ecologies. These insights have relevance for many sites of environmental education practice, such as natural science lecturers, school teachers or community activists. It is knowledge-learning work emergent from and responsive to complex ecological crisis, which requires everyone to rethink and open up to new ways of being, seeing and doing around these issues. The transformative potential of this work is that the thinking and transforming at all scales can be catalysed and grounded through the arts based educational encounters with the participants. , Thesis (PhD) -- Faculty of Education, Education, 2022
- Full Text:
- Authors: James, Anna Katharine
- Date: 2022-04-08
- Subjects: Environmental education South Africa , Water conservation Study and teaching South Africa , Art in environmental education South Africa , Social learning South Africa , Educational sociology South Africa , Water-supply Social aspects South Africa , Critical realism , Socio-ecological education
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/290660 , vital:56772 , DOI 10.21504/10962/290660
- Description: In this study I explore and explain transformative potential in arts-based environmental learning with a focus on water pedagogy. The study took place over a period of four years, where approximately 40 school pupils between the ages of 10 and 17 years-old were engaged in participatory arts-based inquiries into water located across unequal neighbourhoods in Cape Town, South Africa. Educators, school learners, citizens and decision-makers hold different historical, cultural, political and spiritual perspectives on water. These play a role in shaping what is termed in this research the ‘hydro-social cycle’. Yet, due to dominant ideas of what counts as knowing and truth, educators in educational settings struggle to account for the complexity of water, limiting educational encounters to a partial knowing leading mostly to limited unimaginative framings of problems and solutions. My focus on transformative potential in learning is derived from a concern for how environmental education encounters and the sense-making they enable, are infused by socio-economic, political, and historical elements, specifically colonialism, capitalism, and white supremacist racism. The connections between the multiple layers of capitalist crisis and the ever-urgent environmental crisis are not adequately made in mainstream forms of water education. The research explores how arts-based pedagogy could enable a productive meeting of critical environmental education with ecological literacies. Within this positioning, transformative potential considers how educational engagements position questions about water within the social life of participants/learners and inform learning that leads to fuller and more nuanced greater knowledge. Theoretically, I work with an interrogation of critical education theory, underlaboured by critical realism which enabled me to rigorously consider how claims to knowing are shaped by their accompanying assumptions of what is real. Drawing on recent debates in critical education theory, I resist the notion of critique as ideology and engage instead in the craftsmanship of contextual and responsive inquiry practice. This has enabled me to articulate processes and relationships in water education encounters with meaningful understandings of the effects of simultaneous crises rooted in racial capitalism and environmental crisis. My methodological approach is arts-based educational research with a directive to reflect upon educational encounters in an integrated way. It includes two parts informing the facilitation and analysis of open-ended learning processes. One component was arts-based inquiry practice developed for exploring complexity, drawing on the thinking of Norris (2009, 2011) and Finley (2016, 2017). The second part holds reflective space for these encounters guided by the practice of pedagogical narration inspired by the Reggio Amelia approach, demonstrated by Pacini-Ketchabaw, Nxumalo, Kocher, Elliot and Sanchez (2014). Clarifying the intellectual work of a responsive educator-researcher, pedagogical narration brings multiple theoretical lenses into conversation with emergent dimensions of educational process. In practice, in order to transgress the dominance of colonial white supremacist knowledge frames of water, I needed to be curious, to be confounded, to expect the unexpected in the educational encounters with participants and this mirroring of practice was emulated by the participants as they followed their own questions about water in Mzansi (South Africa). In our work together we came up against assumptions we had previously not questioned as individuals. Together we explored the implications of this by, for example, questioning who is responsible for saving water. These explorations required bringing together science knowledge and everyday knowledge at multiple scales: the household, catchment, government and global. It required us to be critical of how language and images are mobilized in public communication and school curriculums; for example, representations of water are infused with history and power in a way that impacts how we know and teach about water. The transformative potential of this pedagogical space is generated through acts of creative expression which are seen as acts of absenting absence, for example exhibiting through play how water use in the household interconnects with gender and age relationships. As such, creative expression through multiple mediums or more-than-text enables a deeper understanding of water as well as openings for interdisciplinary engagement with learning about water. My research found that in bringing together the contributions of critical education and environmental education in practice, two shifts are needed: environmental educators need to view ecological literacy as inseparable from the social and political. The knowledge that is shared about water in the classroom has social and political implications. On the other hand, critical educators need to better locate justice concerns in the material and ecological world at scale. Arts-based inquiry, as a kind of scaffolding for pedagogical process, has the potential to enable these shifts by opening up fixed analytical frames. Making these shifts requires a reflective practice on the part of the educator to navigate the inherited blind spots in environmental learning and critical education, such as dualities. One way to do this is for the educator to identify absences, as articulated in the Critical Realist tradition, and consider how these absences might be absented. This differs from a simplistic process of critique in the possibilities it opens up for collaboration between different schools of thought rather than further polarisation and alienation between educators and knowledge keepers on social ecologies. These insights have relevance for many sites of environmental education practice, such as natural science lecturers, school teachers or community activists. It is knowledge-learning work emergent from and responsive to complex ecological crisis, which requires everyone to rethink and open up to new ways of being, seeing and doing around these issues. The transformative potential of this work is that the thinking and transforming at all scales can be catalysed and grounded through the arts based educational encounters with the participants. , Thesis (PhD) -- Faculty of Education, Education, 2022
- Full Text:
Towards the Common Good: An expansive post-abyssal (Re)stor(y)ing of the epistemic cultures of the citizen sciences
- Authors: Vallabh, Priya
- Date: 2022-04-08
- Subjects: Science Citizen participation , Decolonization , Social epistemology , Hegemony , Common good , Traditional ecological knowledge , Ethnoscience
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/290671 , vital:56773 , DOI 10.21504/10962/290671
- Description: In this study I explore and explain transformatiThe citizen sciences convene complex and reflexive ecologies of knowledges in response to a range of social-ecological risks. Their epistemic cultures seem to be assembled in ways which increase potential mobilisation of the common knowledges being produced, thereby producing knowledges in forms that are more strongly aligned with a range of implementation strategies. However, much of such processes of knowledge production have been ‘cleaned out’ of official accounts through scientifically hegemonic systems of legitimation, deepening hegemonically-entrenched systems of epistemic, contributory and distributive injustices, and undermining the potential for stronger enactments of participatory and radical democracies. The engagement of sociologies of absences and emergences in this study evidence these epistemic insights, thereby evidencing an expansive post-abyssal (re)stor(y)ing of the citizen sciences. Through this research, I consider knowledge production as ‘commoning', towards the constitution of the common good. To date, most accounts of knowledge production within citizen science projects primarily focus on scientific processes of knowledge production and legitimation. Such accounts neglect the ecologies of diverse knowledges through which knowledge is being collaboratively produced, the forms of learning that occur, or the ways in which such ecologies are mobilised in response to specific socialecological risks. To better understand the ways in which citizen science projects build risk-responsive common knowledge, I bring a focus to the diversity of epistemic cultures convened, speaking to this gap. My primary research question is: How do the epistemic cultures within citizen science projects enable commoning in response to social-ecological risk? To begin, I establish a particular vantage point from which the remainder of the thesis is launched, one which centres as the primary interest of knowledge production, an interest in social-ecological justice and the constitution of the common good. From this vantage point, knowledge co-production and learning can be viewed as acts of commoning, which themselves constitute common goods. I draw on the work of Karin Knorr Cetina to conceptualise and frame notions of epistemic cultures and their epistemic features. Expanding notions of epistemic cultures from a post-abyssal perspective, I draw on the work of Bruno Latour and Boaventura de Sousa Santos. Latour’s distinctions between the production of ‘matters of fact’ and ‘matters of concern’ provide a way to challenge hegemonic systems of scientific knowledge production, while preserving the potential emergence of multiplicity in the context of evolving risk, thereby enabling a greater degree of situated reflexivity. Santos argues for the reclamation of all ways of knowing, including but not limited to scientific ways of knowing the world. He argues that other forms of knowledge are produced as nonexistent, and that they might be reclaimed through engaging sociologies of absences and emergences. Both authors enable a stronger analysis of knowledge production in terms of its ability to intervene into context in response to manifest risks. These three theoretical approaches are convened into an analytical framework for the study. To enact sociologies of absences and emergences, I engage two forms of immanent critique, complemented by an epistemic mapping of 50 South African citizen science projects, and an analysis of three illustrative case studies. The first critique is one of produced nonexistence, through which I consider three aspects of the general knowledge cultures within which the epistemic cultures of citizen science projects are situated. This critique makes evident the ways in which the ontological and related conceptual structures of hegemonic scientific knowledge production actively produce as nonexistent, other onto-epistemic contributions to knowledge production in response to social-ecological risks. The second critique reviews the field of peer-reviewed literature through a reading of presence and absence, with a focus on the articulation of epistemic cultures. Predictably, a key finding is that this form of scientific reporting primarily foregrounds legitimated scientifically processed knowledge, while once again producing as nonexistent, other forms of knowledges. However, there is evidence of increasing accounts of citizen science which recognise both a diversity of knowledge contributions, and epistemic, contributory and distributive justice issues as regards hegemonic forms of reporting. The epistemic mapping evidences a highly diversified field of citizen sciences, whose epistemic cultures are convened to produce distinct forms of scientifically-informed knowledges in response to diverse contexts, scales and notions of risk. The three illustrative case studies engage sociologies of absences and emergences, with particular focus on articulating the ecologies of knowledges evidenced in project documentation, including both official and unofficial accounts of epistemic activity. This analysis highlights the significant contributions of diverse forms of knowledges, including scientific, situated, embodied, governance, indigenous, spiritual and relational knowledges, and the ways in which these knowledge are convened to respond to specific configurations of risk. It once again highlights issues of epistemic, contributory and distributive justice, and makes evident the need for stronger integrity in processes of producing and reporting common knowledges. The case studies also illustrate the increased effectiveness of leveraging an ecology of knowledges (in contrast to a monoculture of scientific knowledge) in response to situated risks, including how such ecologies have a tendency to be generative and enable multiple forms of intervention into structures and applied contexts of intervention. In response to the collective research findings, a think-piece on rigour-as-integrity is offered as a contribution to commoning, in response to social-ecological risk. The piece draws together a postabyssal system of rigour intended to strengthen knowledge production in ways which actively centre forms of justice and commoning. ve potential in arts-based environmental learning with a focus on water pedagogy. The study took place over a period of four years, where approximately 40 school pupils between the ages of 10 and 17 years-old were engaged in participatory arts-based inquiries into water located across unequal neighbourhoods in Cape Town, South Africa. Educators, school learners, citizens and decision-makers hold different historical, cultural, political and spiritual perspectives on water. These play a role in shaping what is termed in this research the ‘hydro-social cycle’. Yet, due to dominant ideas of what counts as knowing and truth, educators in educational settings struggle to account for the complexity of water, limiting educational encounters to a partial knowing leading mostly to limited unimaginative framings of problems and solutions. My focus on transformative potential in learning is derived from a concern for how environmental education encounters and the sense-making they enable, are infused by socio-economic, political, and historical elements, specifically colonialism, capitalism, and white supremacist racism. The connections between the multiple layers of capitalist crisis and the ever-urgent environmental crisis are not adequately made in mainstream forms of water education. The research explores how arts-based pedagogy could enable a productive meeting of critical environmental education with ecological literacies. Within this positioning, transformative potential considers how educational engagements position questions about water within the social life of participants/learners and inform learning that leads to fuller and more nuanced greater knowledge. Theoretically, I work with an interrogation of critical education theory, underlaboured by critical realism which enabled me to rigorously consider how claims to knowing are shaped by their accompanying assumptions of what is real. Drawing on recent debates in critical education theory, I resist the notion of critique as ideology and engage instead in the craftsmanship of contextual and responsive inquiry practice. This has enabled me to articulate processes and relationships in water education encounters with meaningful understandings of the effects of simultaneous crises rooted in racial capitalism and environmental crisis. My methodological approach is arts-based educational research with a directive to reflect upon educational encounters in an integrated way. It includes two parts informing the facilitation and analysis of open-ended learning processes. One component was arts-based inquiry practice developed for exploring complexity, drawing on the thinking of Norris (2009, 2011) and Finley (2016, 2017). The second part holds reflective space for these encounters guided by the practice of pedagogical narration inspired by the Reggio Amelia approach, demonstrated by Pacini-Ketchabaw, Nxumalo, Kocher, Elliot and Sanchez (2014). Clarifying the intellectual work of a responsive educator-researcher, pedagogical narration brings multiple theoretical lenses into conversation with emergent dimensions of educational process. In practice, in order to transgress the dominance of colonial white supremacist knowledge frames of water, I needed to be curious, to be confounded, to expect the unexpected in the educational encounters with participants and this mirroring of practice was emulated by the participants as they followed their own questions about water in Mzansi (South Africa). In our work together we came up against assumptions we had previously not questioned as individuals. Together we explored the implications of this by, for example, questioning who is responsible for saving water. These explorations required bringing together science knowledge and everyday knowledge at multiple scales: the household, catchment, government and global. It required us to be critical of how language and images are mobilized in public communication and school curriculums; for example, representations of water are infused with history and power in a way that impacts how we know and teach about water. The transformative potential of this pedagogical space is generated through acts of creative expression which are seen as acts of absenting absence, for example exhibiting through play how water use in the household interconnects with gender and age relationships. As such, creative expression through multiple mediums or more-than-text enables a deeper understanding of water as well as openings for interdisciplinary engagement with learning about water. My research found that in bringing together the contributions of critical education and environmental education in practice, two shifts are needed: environmental educators need to view ecological literacy as inseparable from the social and political. The knowledge that is shared about water in the classroom has social and political implications. On the other hand, critical educators need to better locate justice concerns in the material and ecological world at scale. Arts-based inquiry, as a kind of scaffolding for pedagogical process, has the potential to enable these shifts by opening up fixed analytical frames. Making these shifts requires a reflective practice on the part of the educator to navigate the inherited blind spots in environmental learning and critical education, such as dualities. One way to do this is for the educator to identify absences, as articulated in the Critical Realist tradition, and consider how these absences might be absented. This differs from a simplistic process of critique in the possibilities it opens up for collaboration between different schools of thought rather than further polarisation and alienation between educators and knowledge keepers on social ecologies. These insights have relevance for many sites of environmental education practice, such as natural science lecturers, school teachers or community activists. It is knowledge-learning work emergent from and responsive to complex ecological crisis, which requires everyone to rethink and open up to new ways of being, seeing and doing around these issues. The transformative potential of this work is that the thinking and transforming at all scales can be catalysed and grounded through the arts based educational encounters with the participants. , Thesis (PhD) -- Faculty of Education, Education, 2022
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- Authors: Vallabh, Priya
- Date: 2022-04-08
- Subjects: Science Citizen participation , Decolonization , Social epistemology , Hegemony , Common good , Traditional ecological knowledge , Ethnoscience
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/290671 , vital:56773 , DOI 10.21504/10962/290671
- Description: In this study I explore and explain transformatiThe citizen sciences convene complex and reflexive ecologies of knowledges in response to a range of social-ecological risks. Their epistemic cultures seem to be assembled in ways which increase potential mobilisation of the common knowledges being produced, thereby producing knowledges in forms that are more strongly aligned with a range of implementation strategies. However, much of such processes of knowledge production have been ‘cleaned out’ of official accounts through scientifically hegemonic systems of legitimation, deepening hegemonically-entrenched systems of epistemic, contributory and distributive injustices, and undermining the potential for stronger enactments of participatory and radical democracies. The engagement of sociologies of absences and emergences in this study evidence these epistemic insights, thereby evidencing an expansive post-abyssal (re)stor(y)ing of the citizen sciences. Through this research, I consider knowledge production as ‘commoning', towards the constitution of the common good. To date, most accounts of knowledge production within citizen science projects primarily focus on scientific processes of knowledge production and legitimation. Such accounts neglect the ecologies of diverse knowledges through which knowledge is being collaboratively produced, the forms of learning that occur, or the ways in which such ecologies are mobilised in response to specific socialecological risks. To better understand the ways in which citizen science projects build risk-responsive common knowledge, I bring a focus to the diversity of epistemic cultures convened, speaking to this gap. My primary research question is: How do the epistemic cultures within citizen science projects enable commoning in response to social-ecological risk? To begin, I establish a particular vantage point from which the remainder of the thesis is launched, one which centres as the primary interest of knowledge production, an interest in social-ecological justice and the constitution of the common good. From this vantage point, knowledge co-production and learning can be viewed as acts of commoning, which themselves constitute common goods. I draw on the work of Karin Knorr Cetina to conceptualise and frame notions of epistemic cultures and their epistemic features. Expanding notions of epistemic cultures from a post-abyssal perspective, I draw on the work of Bruno Latour and Boaventura de Sousa Santos. Latour’s distinctions between the production of ‘matters of fact’ and ‘matters of concern’ provide a way to challenge hegemonic systems of scientific knowledge production, while preserving the potential emergence of multiplicity in the context of evolving risk, thereby enabling a greater degree of situated reflexivity. Santos argues for the reclamation of all ways of knowing, including but not limited to scientific ways of knowing the world. He argues that other forms of knowledge are produced as nonexistent, and that they might be reclaimed through engaging sociologies of absences and emergences. Both authors enable a stronger analysis of knowledge production in terms of its ability to intervene into context in response to manifest risks. These three theoretical approaches are convened into an analytical framework for the study. To enact sociologies of absences and emergences, I engage two forms of immanent critique, complemented by an epistemic mapping of 50 South African citizen science projects, and an analysis of three illustrative case studies. The first critique is one of produced nonexistence, through which I consider three aspects of the general knowledge cultures within which the epistemic cultures of citizen science projects are situated. This critique makes evident the ways in which the ontological and related conceptual structures of hegemonic scientific knowledge production actively produce as nonexistent, other onto-epistemic contributions to knowledge production in response to social-ecological risks. The second critique reviews the field of peer-reviewed literature through a reading of presence and absence, with a focus on the articulation of epistemic cultures. Predictably, a key finding is that this form of scientific reporting primarily foregrounds legitimated scientifically processed knowledge, while once again producing as nonexistent, other forms of knowledges. However, there is evidence of increasing accounts of citizen science which recognise both a diversity of knowledge contributions, and epistemic, contributory and distributive justice issues as regards hegemonic forms of reporting. The epistemic mapping evidences a highly diversified field of citizen sciences, whose epistemic cultures are convened to produce distinct forms of scientifically-informed knowledges in response to diverse contexts, scales and notions of risk. The three illustrative case studies engage sociologies of absences and emergences, with particular focus on articulating the ecologies of knowledges evidenced in project documentation, including both official and unofficial accounts of epistemic activity. This analysis highlights the significant contributions of diverse forms of knowledges, including scientific, situated, embodied, governance, indigenous, spiritual and relational knowledges, and the ways in which these knowledge are convened to respond to specific configurations of risk. It once again highlights issues of epistemic, contributory and distributive justice, and makes evident the need for stronger integrity in processes of producing and reporting common knowledges. The case studies also illustrate the increased effectiveness of leveraging an ecology of knowledges (in contrast to a monoculture of scientific knowledge) in response to situated risks, including how such ecologies have a tendency to be generative and enable multiple forms of intervention into structures and applied contexts of intervention. In response to the collective research findings, a think-piece on rigour-as-integrity is offered as a contribution to commoning, in response to social-ecological risk. The piece draws together a postabyssal system of rigour intended to strengthen knowledge production in ways which actively centre forms of justice and commoning. ve potential in arts-based environmental learning with a focus on water pedagogy. The study took place over a period of four years, where approximately 40 school pupils between the ages of 10 and 17 years-old were engaged in participatory arts-based inquiries into water located across unequal neighbourhoods in Cape Town, South Africa. Educators, school learners, citizens and decision-makers hold different historical, cultural, political and spiritual perspectives on water. These play a role in shaping what is termed in this research the ‘hydro-social cycle’. Yet, due to dominant ideas of what counts as knowing and truth, educators in educational settings struggle to account for the complexity of water, limiting educational encounters to a partial knowing leading mostly to limited unimaginative framings of problems and solutions. My focus on transformative potential in learning is derived from a concern for how environmental education encounters and the sense-making they enable, are infused by socio-economic, political, and historical elements, specifically colonialism, capitalism, and white supremacist racism. The connections between the multiple layers of capitalist crisis and the ever-urgent environmental crisis are not adequately made in mainstream forms of water education. The research explores how arts-based pedagogy could enable a productive meeting of critical environmental education with ecological literacies. Within this positioning, transformative potential considers how educational engagements position questions about water within the social life of participants/learners and inform learning that leads to fuller and more nuanced greater knowledge. Theoretically, I work with an interrogation of critical education theory, underlaboured by critical realism which enabled me to rigorously consider how claims to knowing are shaped by their accompanying assumptions of what is real. Drawing on recent debates in critical education theory, I resist the notion of critique as ideology and engage instead in the craftsmanship of contextual and responsive inquiry practice. This has enabled me to articulate processes and relationships in water education encounters with meaningful understandings of the effects of simultaneous crises rooted in racial capitalism and environmental crisis. My methodological approach is arts-based educational research with a directive to reflect upon educational encounters in an integrated way. It includes two parts informing the facilitation and analysis of open-ended learning processes. One component was arts-based inquiry practice developed for exploring complexity, drawing on the thinking of Norris (2009, 2011) and Finley (2016, 2017). The second part holds reflective space for these encounters guided by the practice of pedagogical narration inspired by the Reggio Amelia approach, demonstrated by Pacini-Ketchabaw, Nxumalo, Kocher, Elliot and Sanchez (2014). Clarifying the intellectual work of a responsive educator-researcher, pedagogical narration brings multiple theoretical lenses into conversation with emergent dimensions of educational process. In practice, in order to transgress the dominance of colonial white supremacist knowledge frames of water, I needed to be curious, to be confounded, to expect the unexpected in the educational encounters with participants and this mirroring of practice was emulated by the participants as they followed their own questions about water in Mzansi (South Africa). In our work together we came up against assumptions we had previously not questioned as individuals. Together we explored the implications of this by, for example, questioning who is responsible for saving water. These explorations required bringing together science knowledge and everyday knowledge at multiple scales: the household, catchment, government and global. It required us to be critical of how language and images are mobilized in public communication and school curriculums; for example, representations of water are infused with history and power in a way that impacts how we know and teach about water. The transformative potential of this pedagogical space is generated through acts of creative expression which are seen as acts of absenting absence, for example exhibiting through play how water use in the household interconnects with gender and age relationships. As such, creative expression through multiple mediums or more-than-text enables a deeper understanding of water as well as openings for interdisciplinary engagement with learning about water. My research found that in bringing together the contributions of critical education and environmental education in practice, two shifts are needed: environmental educators need to view ecological literacy as inseparable from the social and political. The knowledge that is shared about water in the classroom has social and political implications. On the other hand, critical educators need to better locate justice concerns in the material and ecological world at scale. Arts-based inquiry, as a kind of scaffolding for pedagogical process, has the potential to enable these shifts by opening up fixed analytical frames. Making these shifts requires a reflective practice on the part of the educator to navigate the inherited blind spots in environmental learning and critical education, such as dualities. One way to do this is for the educator to identify absences, as articulated in the Critical Realist tradition, and consider how these absences might be absented. This differs from a simplistic process of critique in the possibilities it opens up for collaboration between different schools of thought rather than further polarisation and alienation between educators and knowledge keepers on social ecologies. These insights have relevance for many sites of environmental education practice, such as natural science lecturers, school teachers or community activists. It is knowledge-learning work emergent from and responsive to complex ecological crisis, which requires everyone to rethink and open up to new ways of being, seeing and doing around these issues. The transformative potential of this work is that the thinking and transforming at all scales can be catalysed and grounded through the arts based educational encounters with the participants. , Thesis (PhD) -- Faculty of Education, Education, 2022
- Full Text:
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