Decision analysis to inform invasive alien plant management in the Garden Route Biosphere Reserve
- Authors: Masunungure, Current
- Date: 2020
- Subjects: Invasive plants -- South Africa , Alien plants -- South Africa , Biodiversity -- South Africa -- Management , Ecosystem management -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49159 , vital:41606
- Description: Invasive alien plants (IAP) pose significant threats to global economies and biodiversity and are often considered as wicked problems. With an increasing number of IAP and limited resources, their management and decision-making processes are becoming difficult because of uncertainty, multiple and conflicting objectives, and diverse stakeholder views, facts and values. This is particularly challenging given the complex interactions between economic, ecological, and social elements that exist in invaded areas. Consequently, it is important to incorporate new ways of thinking and novel methodologies to improve our understanding of IAP management and the decision-making processes around them, which are currently inadequate. Decision analysis can help with dealing with these challenges and support decision-making under uncertainty. Drawing on the systems thinking approach and the concepts of leverage points, transition management and transformational change, the aim of this thesis was to explore the effectiveness of IAP management and the decision-making process in the Garden Route Biosphere Reserve (GRBR). This was achieved using a mixed methods approach involving: social-ecological inventory (identifying relevant stakeholders); review of literature on the available decision support tools; key informant interviews (stakeholder perspectives on the current decision-making process); and stakeholder workshop and expert consultation (casual loop modelling). The results of this thesis provide evidence that application of the proposed principles of robust decision-making has the potential to overcome the weaknesses of the current decision-making process and as such, enables decision-makers to efficiently allocate resources towards IAS management. A novel causal loop diagram (CLD) was developed to highlight the interconnections between key variables in IAP management and decision-making. This revealed that to transcend ‘policy resistance’ and ‘quickfixes that fail’ archetypes, and improve IAP management, the stakeholders need to consider deep leverage points, for example, fostering trust and shared understanding among different stakeholder groups. These can be realistically maintained over the long-term and can cause a fundamental change in IAP management, rather than focusing on shallow leverage points that are relatively easy to implement but do not result in significant systemic change. The findings of this thesis are flexible and could guide various stakeholder groups at local, national, and international scales in improving the effectiveness of IAP management and decision-making.
- Full Text:
- Date Issued: 2020
- Authors: Masunungure, Current
- Date: 2020
- Subjects: Invasive plants -- South Africa , Alien plants -- South Africa , Biodiversity -- South Africa -- Management , Ecosystem management -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49159 , vital:41606
- Description: Invasive alien plants (IAP) pose significant threats to global economies and biodiversity and are often considered as wicked problems. With an increasing number of IAP and limited resources, their management and decision-making processes are becoming difficult because of uncertainty, multiple and conflicting objectives, and diverse stakeholder views, facts and values. This is particularly challenging given the complex interactions between economic, ecological, and social elements that exist in invaded areas. Consequently, it is important to incorporate new ways of thinking and novel methodologies to improve our understanding of IAP management and the decision-making processes around them, which are currently inadequate. Decision analysis can help with dealing with these challenges and support decision-making under uncertainty. Drawing on the systems thinking approach and the concepts of leverage points, transition management and transformational change, the aim of this thesis was to explore the effectiveness of IAP management and the decision-making process in the Garden Route Biosphere Reserve (GRBR). This was achieved using a mixed methods approach involving: social-ecological inventory (identifying relevant stakeholders); review of literature on the available decision support tools; key informant interviews (stakeholder perspectives on the current decision-making process); and stakeholder workshop and expert consultation (casual loop modelling). The results of this thesis provide evidence that application of the proposed principles of robust decision-making has the potential to overcome the weaknesses of the current decision-making process and as such, enables decision-makers to efficiently allocate resources towards IAS management. A novel causal loop diagram (CLD) was developed to highlight the interconnections between key variables in IAP management and decision-making. This revealed that to transcend ‘policy resistance’ and ‘quickfixes that fail’ archetypes, and improve IAP management, the stakeholders need to consider deep leverage points, for example, fostering trust and shared understanding among different stakeholder groups. These can be realistically maintained over the long-term and can cause a fundamental change in IAP management, rather than focusing on shallow leverage points that are relatively easy to implement but do not result in significant systemic change. The findings of this thesis are flexible and could guide various stakeholder groups at local, national, and international scales in improving the effectiveness of IAP management and decision-making.
- Full Text:
- Date Issued: 2020
Design of metal ion-selective reagents for recovery of precious metals
- Authors: Moleko-Boyce, Pulleng
- Date: 2019
- Subjects: Bioinorganic chemistry , Metal complexes Speciation (Chemistry)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42510 , vital:36664
- Description: The study is divided into two sections; namely, (1) the design of rhodium(III) specific chelating ligands (tridentate bis-benzimidazole derivatives), and (2) the development of iridium(IV)-specific quaternary diammonium cations with electron donating and electron withdrawing groups. Bis-benzimidazole chelating ligands used were bis((1H-benzimidazol-2-yl)methyl)amine (NNN1), bis((1H-benzimidazol-2-yl)ethyl)amine (NNN2), bis((1H-benzimidazol-2-yl)methyl)sulfide (NSN1) and bis((1H-benzimidazol-2-yl)ethyl)sulfide (NSN2). Quaternary diammonium cations used were tetramethylbenzyl-1,10-diammonium chloride (QuatDMDAMeBnz), tetrabenzyl-1,10-diammonium chloride (QuatDMDABnz), tetratrifluoromethylbenzyl-1,10-diammonium chloride (QuatDMDACF3Bnz) and tetranitrobenzyl-1,10-diammonium chloride (QuatDMDANO2Bnz). For both studies, polyvinylbenzylchloride (PVBC) nanofibers were used as support material. The PVBC nanofibers which were functionalised with bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated for the selectivity for Rh(III) over Ir(III), Pt(II), Pd(II) and Ni(II), and for separation of Ir(IV) from Rh(III), respectively. The sorbent materials were characterised by FTIR, SEM, BET surface area, TGA, EDS and elemental analysis, and the results showed that the functionalization of the sorbent materials was successful.The efficiency of bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated in a column study under dynamic flow adsorption conditions. The adsorption kinetics and isotherms were investigated under batch conditions and fitted on pseudo-first-order and pseudo-second-order model, and Freundlich and Langmuir isotherm, respectively. It was observed that the bis-benzimidazole derivatives showed uptake of [RhCl3(H2O)3], and the loading capacities were observed in the following order; NSN1 (181.06 mg/g) > NSN2 (148.55 mg/g) > NNN1 (131.88 mg/g) > NNN2 (75.87 mg/g). The bis-benzimidazole derivatives preference for metal ions was further investigated with a multi-element solution containing Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II). The bis-benzimidazole derivatives showed the following order of loading capacity: NSN1 (47.28 mg/g) > NSN2 (23.89 mg/g) > NNN1 (17.47 mg/g) > NNN2 (14.91 mg/g) for Rh(III); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NNN2 (33.96 mg/g) > NSN1 (30.95 mg/g) > NSN2 (19.95 mg/g) > NNN1 (14.92 mg/g) for Pt(II); NNN1 (47.94 mg/g) > NNN2 (28.90 mg/g) > NSN1 (16.22 mg/g) > NSN2 (15.83 mg/g) for Pd(II). Bis-benzimidazole derivatives showed no uptake of nickel(II) under these conditions. It was observed the ligand-selectivity order for Rh(III) was similar in both single-element and multi-element studies. This order showed that the bis-benzimidazoles containing a sulfur atom showed a high preference for rhodium(III) compared to Pt(II) which had a high preference for NNN2 as well as Pd(II) which had a high preference for NNN1. Ir(III) generally had a lower preference for the ligands presumably due to its higher kinetic inertness compared with Rh(III). Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibers functionalized with diammonium cations was carried out and the loading capacities of [IrCl6]2- were obtained. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- with the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (60.29 mg/g) < F-QuatDMDABnz (67.61 mg/g) < F-QuatDMDACF3Bnz (107.59 mg/g) < F-QuatDMDANO2Bnz (140.47 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibers increased with an increase in the electron-withdrawing nature of the quaternizing group. The charge delocalizing ability of the nitrobenzyl group resulted in the best interaction of the diammonium cation with [IrCl6]2-. Batch equilibrium studies were carried out to assess the efficiency of bis-benzimidazole chelating derivatives as adsorbents using a multi-metal solution (Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II)) in 0.5 M HCl. The efficiency of the quaternary diammonium cations was tested using a binary metal solution (Ir(IV) and Rh(III)) in 6 M HCl. The isothermal batch adsorption studies of a multi-metal solution with bis-benzimidazoles derivatives fitted the Langmuir isotherm model which confirmed monolayer adsorption onto a homogeneous surface. The Langmuir isotherm parameter (qe (mg/g)), using functionalized nanofibers, showed the order of NNN2 (128.21 mg/g) > NSN1 (99.01 mg/g) > NSN2 (91.74 mg/g) > NNN1 (84.03 mg/g) for Pt(II); NNN1 (66.23 mg/g) > NNN2 (5.89 mg/g) > NSN1 (1.40 mg/g) > NSN2 (0.59 mg/g) for Pd(II); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NSN1 (140.85 mg/g) > NSN2 (109.89 mg/g) > NNN1 (104.17 mg/g) > NNN2 (91.74 mg/g) for Rh(III). The pseudo-first-order kinetics model was found to be the best fit to describe the adsorption kinetics of all metal ions onto all the sorbent materials. K1 (min-1) value in pseudo-first-order kinetics showed the same order of adsorption as observed in the Langmuir isotherms. The isothermal batch adsorption studies of [IrCl6]2- and [RhCl5(H2O)]2- with quaternary diammonium cations fitted the Freundlich isotherm model and confirmed to be effective for multiple-layered adsorption onto a heterogeneous surface. The Freundlich isotherm parameter (kf (mg/g)) using functionalized quaternary diammonium cationic nanofibers increased in the order of F-QuatDMDANO2Bnz (794.33 mg/g) > F-QuatDMDACF3Bnz (185.35 mg/g) > F-QuatDMDABnz (156.32 mg/g) > F-QuatDMDAMeBnz (112.46 mg/g) for Ir(IV) uptake. F-QuatDMDANO2Bnz resin showed the highest adsorption than that of F-QuatDMDAMeBnz, F-QuatDMDABnz and F-QuatDMDACF3Bnz and this order is similar to what was observed in column studies. The quaternary diammonium cations were shown to have the highest adsorption capacity for Ir(IV) compared with Rh(III). The adsorption of Rh(III) was also observed to increase in the order of F-QuatDMDANO2Bnz (177.83 mg/g) > F-QuatDMDACF3Bnz (40.37 mg/g) > F-QuatDMDABnz (36.98 mg/g) > F-QuatDMDAMeBnz (12.71 mg/g). The pseudo-second-order kinetic model was found to be the best fit to describe the adsorption kinetics of both metal ions onto all the sorbent materials. K2 (g.mg-1min-1) value in pseudo-second-order kinetics showed the same order of adsorption as observed in the Freundlich isotherms. The adsorption studies showed adsorption takes place via chemisorption process. This thesis presents PGMs and iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium, platinum and palladium with bis-benzimidazoles as well as in feed solutions from ore processing with diammonium cations for iridium recovery.
- Full Text:
- Date Issued: 2019
- Authors: Moleko-Boyce, Pulleng
- Date: 2019
- Subjects: Bioinorganic chemistry , Metal complexes Speciation (Chemistry)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42510 , vital:36664
- Description: The study is divided into two sections; namely, (1) the design of rhodium(III) specific chelating ligands (tridentate bis-benzimidazole derivatives), and (2) the development of iridium(IV)-specific quaternary diammonium cations with electron donating and electron withdrawing groups. Bis-benzimidazole chelating ligands used were bis((1H-benzimidazol-2-yl)methyl)amine (NNN1), bis((1H-benzimidazol-2-yl)ethyl)amine (NNN2), bis((1H-benzimidazol-2-yl)methyl)sulfide (NSN1) and bis((1H-benzimidazol-2-yl)ethyl)sulfide (NSN2). Quaternary diammonium cations used were tetramethylbenzyl-1,10-diammonium chloride (QuatDMDAMeBnz), tetrabenzyl-1,10-diammonium chloride (QuatDMDABnz), tetratrifluoromethylbenzyl-1,10-diammonium chloride (QuatDMDACF3Bnz) and tetranitrobenzyl-1,10-diammonium chloride (QuatDMDANO2Bnz). For both studies, polyvinylbenzylchloride (PVBC) nanofibers were used as support material. The PVBC nanofibers which were functionalised with bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated for the selectivity for Rh(III) over Ir(III), Pt(II), Pd(II) and Ni(II), and for separation of Ir(IV) from Rh(III), respectively. The sorbent materials were characterised by FTIR, SEM, BET surface area, TGA, EDS and elemental analysis, and the results showed that the functionalization of the sorbent materials was successful.The efficiency of bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated in a column study under dynamic flow adsorption conditions. The adsorption kinetics and isotherms were investigated under batch conditions and fitted on pseudo-first-order and pseudo-second-order model, and Freundlich and Langmuir isotherm, respectively. It was observed that the bis-benzimidazole derivatives showed uptake of [RhCl3(H2O)3], and the loading capacities were observed in the following order; NSN1 (181.06 mg/g) > NSN2 (148.55 mg/g) > NNN1 (131.88 mg/g) > NNN2 (75.87 mg/g). The bis-benzimidazole derivatives preference for metal ions was further investigated with a multi-element solution containing Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II). The bis-benzimidazole derivatives showed the following order of loading capacity: NSN1 (47.28 mg/g) > NSN2 (23.89 mg/g) > NNN1 (17.47 mg/g) > NNN2 (14.91 mg/g) for Rh(III); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NNN2 (33.96 mg/g) > NSN1 (30.95 mg/g) > NSN2 (19.95 mg/g) > NNN1 (14.92 mg/g) for Pt(II); NNN1 (47.94 mg/g) > NNN2 (28.90 mg/g) > NSN1 (16.22 mg/g) > NSN2 (15.83 mg/g) for Pd(II). Bis-benzimidazole derivatives showed no uptake of nickel(II) under these conditions. It was observed the ligand-selectivity order for Rh(III) was similar in both single-element and multi-element studies. This order showed that the bis-benzimidazoles containing a sulfur atom showed a high preference for rhodium(III) compared to Pt(II) which had a high preference for NNN2 as well as Pd(II) which had a high preference for NNN1. Ir(III) generally had a lower preference for the ligands presumably due to its higher kinetic inertness compared with Rh(III). Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibers functionalized with diammonium cations was carried out and the loading capacities of [IrCl6]2- were obtained. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- with the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (60.29 mg/g) < F-QuatDMDABnz (67.61 mg/g) < F-QuatDMDACF3Bnz (107.59 mg/g) < F-QuatDMDANO2Bnz (140.47 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibers increased with an increase in the electron-withdrawing nature of the quaternizing group. The charge delocalizing ability of the nitrobenzyl group resulted in the best interaction of the diammonium cation with [IrCl6]2-. Batch equilibrium studies were carried out to assess the efficiency of bis-benzimidazole chelating derivatives as adsorbents using a multi-metal solution (Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II)) in 0.5 M HCl. The efficiency of the quaternary diammonium cations was tested using a binary metal solution (Ir(IV) and Rh(III)) in 6 M HCl. The isothermal batch adsorption studies of a multi-metal solution with bis-benzimidazoles derivatives fitted the Langmuir isotherm model which confirmed monolayer adsorption onto a homogeneous surface. The Langmuir isotherm parameter (qe (mg/g)), using functionalized nanofibers, showed the order of NNN2 (128.21 mg/g) > NSN1 (99.01 mg/g) > NSN2 (91.74 mg/g) > NNN1 (84.03 mg/g) for Pt(II); NNN1 (66.23 mg/g) > NNN2 (5.89 mg/g) > NSN1 (1.40 mg/g) > NSN2 (0.59 mg/g) for Pd(II); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NSN1 (140.85 mg/g) > NSN2 (109.89 mg/g) > NNN1 (104.17 mg/g) > NNN2 (91.74 mg/g) for Rh(III). The pseudo-first-order kinetics model was found to be the best fit to describe the adsorption kinetics of all metal ions onto all the sorbent materials. K1 (min-1) value in pseudo-first-order kinetics showed the same order of adsorption as observed in the Langmuir isotherms. The isothermal batch adsorption studies of [IrCl6]2- and [RhCl5(H2O)]2- with quaternary diammonium cations fitted the Freundlich isotherm model and confirmed to be effective for multiple-layered adsorption onto a heterogeneous surface. The Freundlich isotherm parameter (kf (mg/g)) using functionalized quaternary diammonium cationic nanofibers increased in the order of F-QuatDMDANO2Bnz (794.33 mg/g) > F-QuatDMDACF3Bnz (185.35 mg/g) > F-QuatDMDABnz (156.32 mg/g) > F-QuatDMDAMeBnz (112.46 mg/g) for Ir(IV) uptake. F-QuatDMDANO2Bnz resin showed the highest adsorption than that of F-QuatDMDAMeBnz, F-QuatDMDABnz and F-QuatDMDACF3Bnz and this order is similar to what was observed in column studies. The quaternary diammonium cations were shown to have the highest adsorption capacity for Ir(IV) compared with Rh(III). The adsorption of Rh(III) was also observed to increase in the order of F-QuatDMDANO2Bnz (177.83 mg/g) > F-QuatDMDACF3Bnz (40.37 mg/g) > F-QuatDMDABnz (36.98 mg/g) > F-QuatDMDAMeBnz (12.71 mg/g). The pseudo-second-order kinetic model was found to be the best fit to describe the adsorption kinetics of both metal ions onto all the sorbent materials. K2 (g.mg-1min-1) value in pseudo-second-order kinetics showed the same order of adsorption as observed in the Freundlich isotherms. The adsorption studies showed adsorption takes place via chemisorption process. This thesis presents PGMs and iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium, platinum and palladium with bis-benzimidazoles as well as in feed solutions from ore processing with diammonium cations for iridium recovery.
- Full Text:
- Date Issued: 2019
Development of high capacity lithium-manganese-rich cathode materials xLi2MnO3•(1-x)LiMn0.5Ni0.5O2 for lithium ion batteries
- Authors: Rapulenyane, Nomasonto
- Date: 2018
- Subjects: Lithium ion batteries , Electrochemistry Lithium cells
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34766 , vital:33442
- Description: In this study, a facile synthesis method was developed to produce layered-layered cathode materials with the formula xLi2MnO3•(1-x)LiMO2 (M= Ni and Mn) referred to as lithium-manganese-rich materials for lithium ion batteries. The prepared materials displayed high capacity ≥200 mAh/g at a current density of 20 mA/g in the voltage range of 2.0 V to 4.8 V. In particular the cathode material prepared at pH 10.0 delivered a high initial discharge capacity of 266 mAh/g at 20 mA/g current density and maintained a discharge capacity ≥220 mAh/g at 50 mA/g after 50 cycles. The synthesis method was used to further investigate the effect of lithium ratio in the layered-layered material. Li1+xMn0.6Ni0.2O2, x= 0.2, 0.25, 0.3 and 0.4 cathode materials were produced respectively. The BET surface area analysis results showed that Li1.3Mn0.6Ni0.2O2 material had comparatively higher surface area to the other cathode materials and also delivered good electrochemical results. XPS showed that the cation distribution is affected by the increase in lithium ratio, the Mn4+ percentages decreased significantly with an increase in lithium ratio. All materials peaks deconvoluted into two peaks namely Mn4+ and Mn3+, Li1.3Mn0.6Ni0.2O2 had the highest percentages of the stable Mn4+ 70.8%. Further investigation focused on the effect of the sintering temperature on the structure and the electrochemical performance of Li1+xMn0.6Ni0.2O2, x= 0.25, 0.3 and 0.4 cathode materials. X-ray diffraction showed the same patterns for all cathode materials sintered at 700˚C, 800˚C and 900˚C. Rietveld refined results however, showed that the increase in the sintering temperature, results in a decrease in the Li2MnO3 component percentage in the layered structures. Scanning electron microscopy images further proved that the particle size increases with increasing temperature. The charge–discharge tests of coin cells demonstrated that the materials sintered at 800˚C delivered higher discharge capacities above 200 mAh/g at 20 mA/g current density when compared to the materials made at the lower temperatures. Lastly the cathode material prepared at pH 10.0 was further evaluated in a cell using lithium titanate oxide Li4Ti5O12 as anode material. The cells delivered an initial discharge capacity of 213 mAh/g at 20 mA/g within a voltage range 3.3V-0.5V. The coin cells developed in this work delivered good cycling performance.
- Full Text:
- Date Issued: 2018
- Authors: Rapulenyane, Nomasonto
- Date: 2018
- Subjects: Lithium ion batteries , Electrochemistry Lithium cells
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34766 , vital:33442
- Description: In this study, a facile synthesis method was developed to produce layered-layered cathode materials with the formula xLi2MnO3•(1-x)LiMO2 (M= Ni and Mn) referred to as lithium-manganese-rich materials for lithium ion batteries. The prepared materials displayed high capacity ≥200 mAh/g at a current density of 20 mA/g in the voltage range of 2.0 V to 4.8 V. In particular the cathode material prepared at pH 10.0 delivered a high initial discharge capacity of 266 mAh/g at 20 mA/g current density and maintained a discharge capacity ≥220 mAh/g at 50 mA/g after 50 cycles. The synthesis method was used to further investigate the effect of lithium ratio in the layered-layered material. Li1+xMn0.6Ni0.2O2, x= 0.2, 0.25, 0.3 and 0.4 cathode materials were produced respectively. The BET surface area analysis results showed that Li1.3Mn0.6Ni0.2O2 material had comparatively higher surface area to the other cathode materials and also delivered good electrochemical results. XPS showed that the cation distribution is affected by the increase in lithium ratio, the Mn4+ percentages decreased significantly with an increase in lithium ratio. All materials peaks deconvoluted into two peaks namely Mn4+ and Mn3+, Li1.3Mn0.6Ni0.2O2 had the highest percentages of the stable Mn4+ 70.8%. Further investigation focused on the effect of the sintering temperature on the structure and the electrochemical performance of Li1+xMn0.6Ni0.2O2, x= 0.25, 0.3 and 0.4 cathode materials. X-ray diffraction showed the same patterns for all cathode materials sintered at 700˚C, 800˚C and 900˚C. Rietveld refined results however, showed that the increase in the sintering temperature, results in a decrease in the Li2MnO3 component percentage in the layered structures. Scanning electron microscopy images further proved that the particle size increases with increasing temperature. The charge–discharge tests of coin cells demonstrated that the materials sintered at 800˚C delivered higher discharge capacities above 200 mAh/g at 20 mA/g current density when compared to the materials made at the lower temperatures. Lastly the cathode material prepared at pH 10.0 was further evaluated in a cell using lithium titanate oxide Li4Ti5O12 as anode material. The cells delivered an initial discharge capacity of 213 mAh/g at 20 mA/g within a voltage range 3.3V-0.5V. The coin cells developed in this work delivered good cycling performance.
- Full Text:
- Date Issued: 2018
Development of InSb/GaSb quantum dots by MOVPE
- Authors: Ahia, Chinedu Christian
- Date: 2018
- Subjects: Semiconductors , Quantum electronics Organometallic compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23382 , vital:30537
- Description: There has been an increasing interest in the modification of semiconductor band structures through the reduction of their dimensions, which simultaneously increases the band gap energy of the material and gives rise to flexibility in device properties. Advances in III-V antimony (Sb) based semiconductor fabrication have triggered the quest for extension of the emission/absorption wavelength range of this family of compounds for optoelectronic devices operating in the mid-infrared region of the electromagnetic spectrum. An interesting material system for mid-infrared (MIR) applications is indium antimonide (InSb) quantum dots (QDs) within a gallium antimonide (GaSb) matrix. However, its band alignment and emission wavelength has been the subject of some interest and controversy over the years. This study focuses on the development of InSb/GaSb QDs by metal organic vapour phase epitaxy (MOVPE). The samples were grown on different substrates using various growth parameters in order to vary the size, density and aspect ratio of the dots. Interfacial growth interruptions while flowing various source precursors through the reactor were investigated in order to influence the chemical termination of the surface, and hence the resulting strain in the structures. The samples were characterized using photoluminescence spectroscopy, scanning probe microscopy, scanning electron microscopy, X-ray diffraction and transmission electron microscopy. Likewise, the band alignment, energy levels, and carrier wave functions of the samples in this work were modelled theoretically using the nextnanomat software (version 3.1.0.0). A comparison of growth on two different GaSb substrates [(100) 2° off towards <111>B ± 0.1ᵒ and (111) ± 0.1ᵒ] using similar growth conditions yielded a higher dot density on the (100) substrate compared to the (111) substrate. This was attributed to the presence of terraces/atomic steps induced by the misorientation on the (100) substrate, which invariably gives rise to increased adsorption and an enhanced sticking coefficient of adatoms. Studies on the influence of a buffer layer on the morphology of uncapped dots showed that the shape and size of the dots are sensitive to the thickness of the buffer layer. In some case a corrugated buffer surface resulted, which introduced order in the arrangement of the dots, which formed preferentially inside the troughs. An increase in the V/III ratio from 1.0 to 3.0 was found to reduce the areal density of the QDs, while an analysis of the diameter histograms showed a narrowing of the size distribution with an increase in V/III ratio. The larger size distribution at low V/III was ascribed to the increase in indium species and the increased indium adatom migration length. This leads to increased dot density and nucleation sites, and thus triggers an increase in the conversion of tiny QDs into thermodynamically more suitable larger dots via coalescence. However, as the V/III ratio increased, the number of indium adatoms available for growth on the surface reduced, which automatically led to a decrease in the migration length of indium species which is unfavourable for the production of nucleation sites and to a decrease in dot density. Low growth rates were found to be beneficial for the growth of a high density (~5×1010cm-2) of QDs. Photoluminescence (PL) analysis of the capped samples at low temperature (~10 K), using an excitation power of 2 mW, showed a PL peak at ∼732 meV. Upon an increase in laser power to 120 mW, a blue shift of ∼ 8 meV was noticed. This emission typically persisted up to 60–70 K. An increase in the number of InSb QD-layers, was observed to cause an increase in the luminescence spectral line width and a long-wavelength shift of the PL lines, together with an enhancement in the strength of the PL emission. However, high resolution transmission electron microscopy (HRTEM) of the capped dots revealed the formation of an InGaSb quantum well-like structure, ∼10 nm thick, which was responsible for the PL signal mentioned above. The absence of QDs in the capped sample was attributed to inter-diffusion of Ga and In during the deposition of the cap layer, giving rise to a quantum well (QW) instead of the intended QDs. The presence of threading dislocations and stacking faults were also observed in the TEM micrographs of the samples containing multilayers, which can account for the fast quenching of the PL emission with increasing temperature from these samples. Theoretical simulations of the band alignment, wave functions and energy levels were in good agreement with the data collected from the PL spectra of the samples.
- Full Text:
- Date Issued: 2018
- Authors: Ahia, Chinedu Christian
- Date: 2018
- Subjects: Semiconductors , Quantum electronics Organometallic compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23382 , vital:30537
- Description: There has been an increasing interest in the modification of semiconductor band structures through the reduction of their dimensions, which simultaneously increases the band gap energy of the material and gives rise to flexibility in device properties. Advances in III-V antimony (Sb) based semiconductor fabrication have triggered the quest for extension of the emission/absorption wavelength range of this family of compounds for optoelectronic devices operating in the mid-infrared region of the electromagnetic spectrum. An interesting material system for mid-infrared (MIR) applications is indium antimonide (InSb) quantum dots (QDs) within a gallium antimonide (GaSb) matrix. However, its band alignment and emission wavelength has been the subject of some interest and controversy over the years. This study focuses on the development of InSb/GaSb QDs by metal organic vapour phase epitaxy (MOVPE). The samples were grown on different substrates using various growth parameters in order to vary the size, density and aspect ratio of the dots. Interfacial growth interruptions while flowing various source precursors through the reactor were investigated in order to influence the chemical termination of the surface, and hence the resulting strain in the structures. The samples were characterized using photoluminescence spectroscopy, scanning probe microscopy, scanning electron microscopy, X-ray diffraction and transmission electron microscopy. Likewise, the band alignment, energy levels, and carrier wave functions of the samples in this work were modelled theoretically using the nextnanomat software (version 3.1.0.0). A comparison of growth on two different GaSb substrates [(100) 2° off towards <111>B ± 0.1ᵒ and (111) ± 0.1ᵒ] using similar growth conditions yielded a higher dot density on the (100) substrate compared to the (111) substrate. This was attributed to the presence of terraces/atomic steps induced by the misorientation on the (100) substrate, which invariably gives rise to increased adsorption and an enhanced sticking coefficient of adatoms. Studies on the influence of a buffer layer on the morphology of uncapped dots showed that the shape and size of the dots are sensitive to the thickness of the buffer layer. In some case a corrugated buffer surface resulted, which introduced order in the arrangement of the dots, which formed preferentially inside the troughs. An increase in the V/III ratio from 1.0 to 3.0 was found to reduce the areal density of the QDs, while an analysis of the diameter histograms showed a narrowing of the size distribution with an increase in V/III ratio. The larger size distribution at low V/III was ascribed to the increase in indium species and the increased indium adatom migration length. This leads to increased dot density and nucleation sites, and thus triggers an increase in the conversion of tiny QDs into thermodynamically more suitable larger dots via coalescence. However, as the V/III ratio increased, the number of indium adatoms available for growth on the surface reduced, which automatically led to a decrease in the migration length of indium species which is unfavourable for the production of nucleation sites and to a decrease in dot density. Low growth rates were found to be beneficial for the growth of a high density (~5×1010cm-2) of QDs. Photoluminescence (PL) analysis of the capped samples at low temperature (~10 K), using an excitation power of 2 mW, showed a PL peak at ∼732 meV. Upon an increase in laser power to 120 mW, a blue shift of ∼ 8 meV was noticed. This emission typically persisted up to 60–70 K. An increase in the number of InSb QD-layers, was observed to cause an increase in the luminescence spectral line width and a long-wavelength shift of the PL lines, together with an enhancement in the strength of the PL emission. However, high resolution transmission electron microscopy (HRTEM) of the capped dots revealed the formation of an InGaSb quantum well-like structure, ∼10 nm thick, which was responsible for the PL signal mentioned above. The absence of QDs in the capped sample was attributed to inter-diffusion of Ga and In during the deposition of the cap layer, giving rise to a quantum well (QW) instead of the intended QDs. The presence of threading dislocations and stacking faults were also observed in the TEM micrographs of the samples containing multilayers, which can account for the fast quenching of the PL emission with increasing temperature from these samples. Theoretical simulations of the band alignment, wave functions and energy levels were in good agreement with the data collected from the PL spectra of the samples.
- Full Text:
- Date Issued: 2018
Development of insulin resistance in a rat model and the effects of sutherlandia frutescens as treatment and prevention
- Authors: Mackenzie, Janine
- Date: 2010
- Subjects: Metabolic syndrome , Insulin resistance -- Animal models , Obesity -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10340 , http://hdl.handle.net/10948/d1016216
- Description: The global number of obese people has reached pandemic proportions. High caloric diets and reduced physical exercise are to blame for this growing epidemic. Obesity has a very complex association with several other metabolic disorders, such as insulin resistance (IR), diabetes mellitus type 2 (DMT2) and cardiovascular disease. This puts a huge burden on health care systems world wide and claims many lives. Sutherlandia frutescens is a traditionally used herb, which is known to have anti-diabetic properties. However, the direct mode of action of S. frutescens still remains to be elucidated. The aim of this study was to investigate the developmental stages of high fat diet (HFD)-induced IR, to illuminate the pathogenesis of IR with a focal point on modifications in the lipid metabolism. Furthermore, the effects of S. frutescens as a treatment or prevention drug for IR and associated metabolic changes were examined. Two sets of experiments were conducted on male Wistar rats. In the first experiment rats, one week post weaning received a low fat diet (LFD), high fat diet (HFD) or HFD supplemented with S. frutescens (50mg/kg BW/d). Rats were sacrificed at week 0, 1, 2, 4, 8 and 12 in the feeding regime. In a second experiment rats were fed with a LFD or a HFD for 12 weeks and treated thereafter with S. frutescens (50mg/kg BW/d), metformin (13mg/kg BW/d) or water (control) for 28 days. Rats in the second experiment were sacrificed at week 12 to confirm IR while concurrently run rats were sacrificed after 28 days of treatment. For all the experiments rats were anaesthetized, blood was removed and rats were dissected. Plasma samples were analyzed for insulin, glucose, blood lipid parameters and cytokines. Liver, muscle and adipose tissue were analyzed for glucose uptake, total lipid content, lipid profile and fatty acid profile. It was shown that the intake of HFD caused IR and hyperinsulinaemia. The developmental stages in experiment one confirmed that an increase in plasma free fatty acids preceeded the onset of IR. Plasma and tissue lipid parameters (free fatty acid-, triglyceride- and cholesterol concentrations) showed pathological modifications in the HFD group. An ectopic accumulation of fat was observed in muscle and liver, as well as a change in membrane fatty acid profile. The results for circulating cytokines were somewhat inconclusive. Rats supplemented with S. frutescens did not develop HFD-induced IR (study one) or IR was reversed (study two). S. frutescens treatment also resulted in positive changes in plasma and tissue lipid parameters. In summary, an animal model for HFD-induced IR was established and the detrimental effect of elevated plasma FFA on glucose and lipid metabolism was observed. A novel discovery suggests that the anti-diabetic mode of action of S. frutescens is through modulation of lipid metabolism. It was also established that S. frutescens has the potential to prevent IR in vivo.
- Full Text:
- Date Issued: 2010
- Authors: Mackenzie, Janine
- Date: 2010
- Subjects: Metabolic syndrome , Insulin resistance -- Animal models , Obesity -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10340 , http://hdl.handle.net/10948/d1016216
- Description: The global number of obese people has reached pandemic proportions. High caloric diets and reduced physical exercise are to blame for this growing epidemic. Obesity has a very complex association with several other metabolic disorders, such as insulin resistance (IR), diabetes mellitus type 2 (DMT2) and cardiovascular disease. This puts a huge burden on health care systems world wide and claims many lives. Sutherlandia frutescens is a traditionally used herb, which is known to have anti-diabetic properties. However, the direct mode of action of S. frutescens still remains to be elucidated. The aim of this study was to investigate the developmental stages of high fat diet (HFD)-induced IR, to illuminate the pathogenesis of IR with a focal point on modifications in the lipid metabolism. Furthermore, the effects of S. frutescens as a treatment or prevention drug for IR and associated metabolic changes were examined. Two sets of experiments were conducted on male Wistar rats. In the first experiment rats, one week post weaning received a low fat diet (LFD), high fat diet (HFD) or HFD supplemented with S. frutescens (50mg/kg BW/d). Rats were sacrificed at week 0, 1, 2, 4, 8 and 12 in the feeding regime. In a second experiment rats were fed with a LFD or a HFD for 12 weeks and treated thereafter with S. frutescens (50mg/kg BW/d), metformin (13mg/kg BW/d) or water (control) for 28 days. Rats in the second experiment were sacrificed at week 12 to confirm IR while concurrently run rats were sacrificed after 28 days of treatment. For all the experiments rats were anaesthetized, blood was removed and rats were dissected. Plasma samples were analyzed for insulin, glucose, blood lipid parameters and cytokines. Liver, muscle and adipose tissue were analyzed for glucose uptake, total lipid content, lipid profile and fatty acid profile. It was shown that the intake of HFD caused IR and hyperinsulinaemia. The developmental stages in experiment one confirmed that an increase in plasma free fatty acids preceeded the onset of IR. Plasma and tissue lipid parameters (free fatty acid-, triglyceride- and cholesterol concentrations) showed pathological modifications in the HFD group. An ectopic accumulation of fat was observed in muscle and liver, as well as a change in membrane fatty acid profile. The results for circulating cytokines were somewhat inconclusive. Rats supplemented with S. frutescens did not develop HFD-induced IR (study one) or IR was reversed (study two). S. frutescens treatment also resulted in positive changes in plasma and tissue lipid parameters. In summary, an animal model for HFD-induced IR was established and the detrimental effect of elevated plasma FFA on glucose and lipid metabolism was observed. A novel discovery suggests that the anti-diabetic mode of action of S. frutescens is through modulation of lipid metabolism. It was also established that S. frutescens has the potential to prevent IR in vivo.
- Full Text:
- Date Issued: 2010
Development of MOVPE-grown InAsSb for barrier diode applications
- Authors: Dobson, Stephen R
- Date: 2020
- Subjects: Gallium arsenide semiconductors , Electronics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49071 , vital:41598
- Description: In this study, layers of GaSb, InAs and InAsSb are grown by metalorganic vapour phase epitaxy and characterised. Growth is conducted using the precursors of trimethylgallium, trimethylindium, trimethylantimony and tertiarybutylarsine. Focus is then placed on the characterisation of the materials, carried out by the techniques of X-ray diffraction, photoluminescence spectroscopy, Hall measurements and photocurrent spectroscopy. It is observed that V/III ratio plays a vital role in the growth of the GaSb and InAsSb layers. Epilayers of GaSb showed best crystalline quality when a V/III ratio of 1.2 was used at a growth temperature of 600 °C and a cell pressure of 600 Torr. Resultant Hall measurements indicated p-type GaSb. The Hall carrier concentrations of the p-type GaSb samples were analyzed considering electrical neutrality conditions and found to be highly compensated with evidence of band impurity conduction at low measurement temperatures. Both the donor and acceptor concentrations were determined to be of the order of 1016 cm−3 for all samples. For low temperature (< 150 K) a monovalent acceptor concentration is calculated to have an activation energy at approximately 20 meV. At high temperature (> 150 K) a divalent acceptor is extracted with an activation energy varying between samples based on compensation in a range of 90 meV to 70 meV. Photoluminescence measurements show four peaks with recombination mechanisms linked to the native acceptor identified in literature as either the gallium antisite and/or vacant gallium site. A fifth peak observed is attributed to the longitudinal phonon of the native acceptor. InAs and InAsSb epilayer are all grown at a temperature of 600 °C and cell pressure of 600 Torr. InAs is grown at a V/III ratio of 9.5 on GaAs substrate. Photoluminescence of the InAs layer shows two distinct peaks, one of which is an extrinsic band to band recombination. The other is attributed to free electron to acceptor or a donor-acceptor pair transition. An additional weak peak is also observed which is assigned to the longitudinal phonon of the band to band. InAsSb growth was conducted under a range of V/III ratios of 4.8 to 5, with a vapour phase composition of 0.4 to 0.435. Structural analysis via X-ray diffraction showed a 6 % to 12 % solid antimony content. Photoluminescence exhibited a single broad peak for all samples, with extended band tails. Temperature and power dependant analysis of luminescence indicated a convolution of extrinsic band to tail and band to band recombinations. Hall measurements indicated the InAsSb was n-type material with an apparent measured maximum mobility at 120 K of 9.5 × 103 cm2/V.s. and a room temperature apparent mobility of 7.5 × 103 cm2/V.s. Analysis of hall results using a two-layer model calculated a true bulk mobility of the epilayer at room temperature with an increased value of 15.4 × 103 cm2/V.s. The two-layer model details the effects of the surface conduction. From photoconductivity measurements and further analysis a resultant effective lifetime, at room temperature, was found to be on same order of magnitude as that of InAs materials. Application of a single Einstein oscillator extrapolated 0 K energy gaps for two samples of solid Sb contents of 6 % and 12 %, of 354 meV and 332 meV, respectively. Finally consideration was given to the growth of aluminium containing compounds, particularly AlGaSb. Multiple phases were observed under scanning electron microscope showing growth of GaSb regions surrounded by amorphous solid aluminium and/or aluminium oxide phases. The failure of the aluminium to incorporate into the desired crystal structure is speculated to be due to impure precursor introducing oxygen into the films. Additionally, the effectiveness of the gallium precursor compared to the aluminium precursor in helping the removal of the methyl groups at the growth surface, could also promote a preference for GaSb growth.
- Full Text:
- Date Issued: 2020
- Authors: Dobson, Stephen R
- Date: 2020
- Subjects: Gallium arsenide semiconductors , Electronics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49071 , vital:41598
- Description: In this study, layers of GaSb, InAs and InAsSb are grown by metalorganic vapour phase epitaxy and characterised. Growth is conducted using the precursors of trimethylgallium, trimethylindium, trimethylantimony and tertiarybutylarsine. Focus is then placed on the characterisation of the materials, carried out by the techniques of X-ray diffraction, photoluminescence spectroscopy, Hall measurements and photocurrent spectroscopy. It is observed that V/III ratio plays a vital role in the growth of the GaSb and InAsSb layers. Epilayers of GaSb showed best crystalline quality when a V/III ratio of 1.2 was used at a growth temperature of 600 °C and a cell pressure of 600 Torr. Resultant Hall measurements indicated p-type GaSb. The Hall carrier concentrations of the p-type GaSb samples were analyzed considering electrical neutrality conditions and found to be highly compensated with evidence of band impurity conduction at low measurement temperatures. Both the donor and acceptor concentrations were determined to be of the order of 1016 cm−3 for all samples. For low temperature (< 150 K) a monovalent acceptor concentration is calculated to have an activation energy at approximately 20 meV. At high temperature (> 150 K) a divalent acceptor is extracted with an activation energy varying between samples based on compensation in a range of 90 meV to 70 meV. Photoluminescence measurements show four peaks with recombination mechanisms linked to the native acceptor identified in literature as either the gallium antisite and/or vacant gallium site. A fifth peak observed is attributed to the longitudinal phonon of the native acceptor. InAs and InAsSb epilayer are all grown at a temperature of 600 °C and cell pressure of 600 Torr. InAs is grown at a V/III ratio of 9.5 on GaAs substrate. Photoluminescence of the InAs layer shows two distinct peaks, one of which is an extrinsic band to band recombination. The other is attributed to free electron to acceptor or a donor-acceptor pair transition. An additional weak peak is also observed which is assigned to the longitudinal phonon of the band to band. InAsSb growth was conducted under a range of V/III ratios of 4.8 to 5, with a vapour phase composition of 0.4 to 0.435. Structural analysis via X-ray diffraction showed a 6 % to 12 % solid antimony content. Photoluminescence exhibited a single broad peak for all samples, with extended band tails. Temperature and power dependant analysis of luminescence indicated a convolution of extrinsic band to tail and band to band recombinations. Hall measurements indicated the InAsSb was n-type material with an apparent measured maximum mobility at 120 K of 9.5 × 103 cm2/V.s. and a room temperature apparent mobility of 7.5 × 103 cm2/V.s. Analysis of hall results using a two-layer model calculated a true bulk mobility of the epilayer at room temperature with an increased value of 15.4 × 103 cm2/V.s. The two-layer model details the effects of the surface conduction. From photoconductivity measurements and further analysis a resultant effective lifetime, at room temperature, was found to be on same order of magnitude as that of InAs materials. Application of a single Einstein oscillator extrapolated 0 K energy gaps for two samples of solid Sb contents of 6 % and 12 %, of 354 meV and 332 meV, respectively. Finally consideration was given to the growth of aluminium containing compounds, particularly AlGaSb. Multiple phases were observed under scanning electron microscope showing growth of GaSb regions surrounded by amorphous solid aluminium and/or aluminium oxide phases. The failure of the aluminium to incorporate into the desired crystal structure is speculated to be due to impure precursor introducing oxygen into the films. Additionally, the effectiveness of the gallium precursor compared to the aluminium precursor in helping the removal of the methyl groups at the growth surface, could also promote a preference for GaSb growth.
- Full Text:
- Date Issued: 2020
Development of spunlaced nonwoven filters from PAN, PPS and PI fibres for industrial use
- Authors: Maduna, Lebo
- Date: 2019
- Subjects: Textile fibers -- Mechanical properties , Nonwoven fabrics --Technological innovations Textile fibers, Synthetic -- Mechanical properties
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/32610 , vital:32266
- Description: The aim of this work was to produce filter fabrics suitable for high temperature and other conditions encountered in coal power plants using the spunlacing manufacturing technique. Polyacrylonitrile (PAN), polyphenylene sulfide (PPS) and polyimide (PI) fibres being combined suitable for this purpose, each at three aerial density of (440, 500 and 560 g/m2) and each at three water jet pressures of (60, 80 and 90 bars) were produced. The effect of changing these on the fabric air permeability, tensile strength and filtration properties were investigated and optimized. For this purpose, the Box-Behnken experimental design (BBD) was considered the best and therefore used. The PPS/PI fabrics were found to consistently have the highest air permeability, tensile strength and filtration performance, followed by the PPS fabrics and the PAN fabrics. As could be expected, an increase in area weight and water jet pressure generally resulted in a decrease in air permeability irrespective of the fabric types, this being due to the increased number of fibres and therefore greater fibre surface area and entanglement respectively. For fabric tensile strength, the effects of varying fabric area weight and water jet pressure were not so straight forward. For cross direction (CD) an increase in water jet pressure resulted in an increase tensile strength whereas in the machine direction (MD) there was a decrease when the water jet pressure was increased. The filtration efficiency and dust holding capacity of the fabrics were found to be around 96% and 211g/m2, respectively, with the exception of the PPS (500 g/m2 80 bar) fabrics. Increasing the amount of dust being fed to the fabric during each loading cycle, it caused an increase in pressure drop, as the fabrics became increasingly clogged forming a cake layer.
- Full Text:
- Date Issued: 2019
- Authors: Maduna, Lebo
- Date: 2019
- Subjects: Textile fibers -- Mechanical properties , Nonwoven fabrics --Technological innovations Textile fibers, Synthetic -- Mechanical properties
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/32610 , vital:32266
- Description: The aim of this work was to produce filter fabrics suitable for high temperature and other conditions encountered in coal power plants using the spunlacing manufacturing technique. Polyacrylonitrile (PAN), polyphenylene sulfide (PPS) and polyimide (PI) fibres being combined suitable for this purpose, each at three aerial density of (440, 500 and 560 g/m2) and each at three water jet pressures of (60, 80 and 90 bars) were produced. The effect of changing these on the fabric air permeability, tensile strength and filtration properties were investigated and optimized. For this purpose, the Box-Behnken experimental design (BBD) was considered the best and therefore used. The PPS/PI fabrics were found to consistently have the highest air permeability, tensile strength and filtration performance, followed by the PPS fabrics and the PAN fabrics. As could be expected, an increase in area weight and water jet pressure generally resulted in a decrease in air permeability irrespective of the fabric types, this being due to the increased number of fibres and therefore greater fibre surface area and entanglement respectively. For fabric tensile strength, the effects of varying fabric area weight and water jet pressure were not so straight forward. For cross direction (CD) an increase in water jet pressure resulted in an increase tensile strength whereas in the machine direction (MD) there was a decrease when the water jet pressure was increased. The filtration efficiency and dust holding capacity of the fabrics were found to be around 96% and 211g/m2, respectively, with the exception of the PPS (500 g/m2 80 bar) fabrics. Increasing the amount of dust being fed to the fabric during each loading cycle, it caused an increase in pressure drop, as the fabrics became increasingly clogged forming a cake layer.
- Full Text:
- Date Issued: 2019
Development of Tio 2 nanostructure arrays for photonic extraction of hydrogen gas
- Authors: Suliali, Nyasha Joseph
- Date: 2020
- Subjects: Nanostructures , Nanostructured materials Hydrogen
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49314 , vital:41620
- Description: Amid the energy crisis of the 21st century, renewable energy is a thriving field of study, light harvesting materials being a central theme due to the abundance of solar energy. Nanostructured TiO2 is the most studied photocatalysis material, since the discovery of its energy harvesting properties by Fujishima and Honda in 1972. Environmentally friendly products such as hydrogen fuel, can be produced using TiO2 due to its non-toxicity, chemical stability and photocatalytic activity. The surprising aspect of this important material is that it can be prepared using cost-effective methods such as hydrothermal synthesis, solution gelation and anodic oxidation. This research focused on the three key elements required to develop TiO2 photoelectrodes i.e. the deposition of Ti films on transparent substrates, a thorough analysis of the chemistry of the anodic oxidation process and the development of the TiO2 thin films. Glass substrates that have Ti films are the base component for TiO2 photoelectrode production. Ti films with thicknesses up to 4 μm, were developed on commercial F-doped SnO2 (FTO) glass substrates using high-power impulse magnetron sputtering (HiPIMS). The sputter deposition experiments were performed in the 1 to 8 kW range at a substrate temperature of 500 °C and Ar pressure of 400 mPa. At higher powers, thicker films were deposited, resulting in increased intensity of Xray-diffraction peaks. However, on comparing the XRD patterns, the (001) peak outgrew the rest regardless of thickness of the film. The deposition process therefore favoured orientation of most of the α-Ti phase crystallites with the [001] axis perpendicular to the substrate surface. Surface roughness results were interesting, showing a non-linear dependence of the surface roughness on HiPIMS pulse energy in the 1 to 8 kW range. The surface roughness is highest at the starting deposition power of 1450 W and reduces to a minimum at 4500 W. From this minimum, it increases to its second highest value at 7900 W. From this data, the parameters required to produce Ti films of lowest surface roughness, for deposition on commercial Technistro® FTO glass, were deduced at the inflection point, where the deposition power was 4500 W. The surface roughness obtained is a critical result for the anodic production of quality TiO2 photoelectrodes, which if high, leads to uneven etching, thus irregular and inefficient photoelectrodes. Direct current magnetron sputtering was also carried out in the 1 to 5 kW range to obtain ratios of power-normalised growth rates of the Ti films. This investigation provided the Ti films on FTO glass, the transparent, conductive substrates which were used to develop TiO2 photoelectrodes. To elucidate the chemistry of anodic oxidation of Ti, a mathematical model of the anodic current density, which had not been reported at the time of its publication, was developed. The technique, a highlight of this research, is a predictive numerical computation of the instantaneous quantities of species that participate in the anodization process. From eleven chemical reactions, 14 first order ordinary differential equations were compiled using the principles of chemical reaction kinetics. The pattern, transient behaviour and response to anodization parameters of the current density signal, were successfully predicted. Strong agreement between the model and measurements was demonstrated in seven experiments. The results confirm that the current density signal is a numerical integral of the kinetics of redox reactions of water. The bulk of this research was on the development of TiO2 nanotubular arrays on Ti foil substrates and Ti films on FTO glass. TiO2 films with well-defined tubular structures were synthesised. The films were developed in anhydrous, polar organic hosts with water and etching agents in the range of 10 V to 70 V. The control of geometrical properties of the tubes such as the length, pore diameter, wall thickness, tube separation and number of nanotubes per unit area was demonstrated. Anatase only and mixed anatase-rutile phase compositions were obtained at different annealing temperatures. Nanotubes with diameters as small as 20 nm and thickness as high as 29 μm were produced. Apart from an increase in nanotube thickness, a decrease in distance between nanotubes grown in diethylene glycol was observed at longer anodization times. Studies of the effects of anodization parameters on the current density measured, morphological and crystallographic properties of the nanotube films were conducted in three main investigations. The first was the study of the effect of anodization parameters on current density. Besides the obvious increase of current density with anodic voltage, the first steady state of the growth process was found to depend on the NH4F concentration. The second investigation focused on the effect of accelerated growth of TiO2 nanotubular films. In the study, 9 μm-thick nanotube films were synthesised at twice the growth rate of a 9 μm-thick control sample. The array obtained by accelerated growth had distinguishable nanotubes, however, the morphological quality was reduced. The third investigation demonstrates the control of the number of nanotubes per unit area. By varying the etchant content, the anodic voltage and the viscosity of the electrolyte host, various distributions were obtained. The research ends with a photoelectrochemical application: measurement on photocurrents generated in a two-electrode setup. The photocurrent densities measured in the off and on conditions were 30 nA/cm2 and 2.57 μA/cm2, respectively, demonstrating photoactivity of the developed films.
- Full Text:
- Date Issued: 2020
- Authors: Suliali, Nyasha Joseph
- Date: 2020
- Subjects: Nanostructures , Nanostructured materials Hydrogen
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49314 , vital:41620
- Description: Amid the energy crisis of the 21st century, renewable energy is a thriving field of study, light harvesting materials being a central theme due to the abundance of solar energy. Nanostructured TiO2 is the most studied photocatalysis material, since the discovery of its energy harvesting properties by Fujishima and Honda in 1972. Environmentally friendly products such as hydrogen fuel, can be produced using TiO2 due to its non-toxicity, chemical stability and photocatalytic activity. The surprising aspect of this important material is that it can be prepared using cost-effective methods such as hydrothermal synthesis, solution gelation and anodic oxidation. This research focused on the three key elements required to develop TiO2 photoelectrodes i.e. the deposition of Ti films on transparent substrates, a thorough analysis of the chemistry of the anodic oxidation process and the development of the TiO2 thin films. Glass substrates that have Ti films are the base component for TiO2 photoelectrode production. Ti films with thicknesses up to 4 μm, were developed on commercial F-doped SnO2 (FTO) glass substrates using high-power impulse magnetron sputtering (HiPIMS). The sputter deposition experiments were performed in the 1 to 8 kW range at a substrate temperature of 500 °C and Ar pressure of 400 mPa. At higher powers, thicker films were deposited, resulting in increased intensity of Xray-diffraction peaks. However, on comparing the XRD patterns, the (001) peak outgrew the rest regardless of thickness of the film. The deposition process therefore favoured orientation of most of the α-Ti phase crystallites with the [001] axis perpendicular to the substrate surface. Surface roughness results were interesting, showing a non-linear dependence of the surface roughness on HiPIMS pulse energy in the 1 to 8 kW range. The surface roughness is highest at the starting deposition power of 1450 W and reduces to a minimum at 4500 W. From this minimum, it increases to its second highest value at 7900 W. From this data, the parameters required to produce Ti films of lowest surface roughness, for deposition on commercial Technistro® FTO glass, were deduced at the inflection point, where the deposition power was 4500 W. The surface roughness obtained is a critical result for the anodic production of quality TiO2 photoelectrodes, which if high, leads to uneven etching, thus irregular and inefficient photoelectrodes. Direct current magnetron sputtering was also carried out in the 1 to 5 kW range to obtain ratios of power-normalised growth rates of the Ti films. This investigation provided the Ti films on FTO glass, the transparent, conductive substrates which were used to develop TiO2 photoelectrodes. To elucidate the chemistry of anodic oxidation of Ti, a mathematical model of the anodic current density, which had not been reported at the time of its publication, was developed. The technique, a highlight of this research, is a predictive numerical computation of the instantaneous quantities of species that participate in the anodization process. From eleven chemical reactions, 14 first order ordinary differential equations were compiled using the principles of chemical reaction kinetics. The pattern, transient behaviour and response to anodization parameters of the current density signal, were successfully predicted. Strong agreement between the model and measurements was demonstrated in seven experiments. The results confirm that the current density signal is a numerical integral of the kinetics of redox reactions of water. The bulk of this research was on the development of TiO2 nanotubular arrays on Ti foil substrates and Ti films on FTO glass. TiO2 films with well-defined tubular structures were synthesised. The films were developed in anhydrous, polar organic hosts with water and etching agents in the range of 10 V to 70 V. The control of geometrical properties of the tubes such as the length, pore diameter, wall thickness, tube separation and number of nanotubes per unit area was demonstrated. Anatase only and mixed anatase-rutile phase compositions were obtained at different annealing temperatures. Nanotubes with diameters as small as 20 nm and thickness as high as 29 μm were produced. Apart from an increase in nanotube thickness, a decrease in distance between nanotubes grown in diethylene glycol was observed at longer anodization times. Studies of the effects of anodization parameters on the current density measured, morphological and crystallographic properties of the nanotube films were conducted in three main investigations. The first was the study of the effect of anodization parameters on current density. Besides the obvious increase of current density with anodic voltage, the first steady state of the growth process was found to depend on the NH4F concentration. The second investigation focused on the effect of accelerated growth of TiO2 nanotubular films. In the study, 9 μm-thick nanotube films were synthesised at twice the growth rate of a 9 μm-thick control sample. The array obtained by accelerated growth had distinguishable nanotubes, however, the morphological quality was reduced. The third investigation demonstrates the control of the number of nanotubes per unit area. By varying the etchant content, the anodic voltage and the viscosity of the electrolyte host, various distributions were obtained. The research ends with a photoelectrochemical application: measurement on photocurrents generated in a two-electrode setup. The photocurrent densities measured in the off and on conditions were 30 nA/cm2 and 2.57 μA/cm2, respectively, demonstrating photoactivity of the developed films.
- Full Text:
- Date Issued: 2020
Dynamics of macrophytes in the East Kleinemonde, a small temporarily open/closed South Afrcan Estuary
- Authors: Riddin, Taryn
- Date: 2011
- Subjects: Estuaries -- South Africa -- East Kleinemonde
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10605 , http://hdl.handle.net/10948/1529 , Estuaries -- South Africa -- East Kleinemonde
- Description: The East Kleinemonde Estuary is one of 175 temporarily open/closed estuaries (TOCEs) that represent 70 percent of estuaries in South Africa. TOCEs are small (mostly less than 100 ha), shallow estuaries (average depth < 2 m) that respond quickly to freshwater inflow events. Their connection to the sea can be highly variable resulting in considerable changes in abiotic and biotic conditions. Mouth status depends on a balance between freshwater inflow and marine influence, which in turn affects ambient abiotic conditions. The objective of the study was to identify the abiotic variables which influence macrophyte growth and habitat availability. It was hypothesised that water level and salinity were the two main drivers of macrophyte change and macrophyte habitat would respond very rapidly, in less than a month, when habitat was available. Macrophyte habitats would also have high sediment seed reserves to ensure persistence under highly variable abiotic conditions. Macrophyte cover was monitored monthly in the East Kleinemonde Estuary along three permanent transects. The dominant habitats were submerged macrophytes, intertidal salt marsh, supratidal salt marsh, reeds and sedges. The following abiotic variables; water level, water column salinity, water temperature, Secchi depth, air temperature and rainfall were also measured between March 2006 and January 2010. Time-lag responses of the macrophytes to water level and salinity changes up to four months prior to the sampling session were also assessed. The analysis of a one year dataset highlighted only water level as a driver of change in macrophyte cover, whereas the five year dataset identified salinity as an additional important abiotic driver. This is because during September 2008 to January 2010 a series of large marine overwash events maintained high salinity (> 30 ppt) and high water level (> 1.6 m amsl) in the estuary. Water level increased by up to 0.33 m due to large volumetric changes and salinity was significantly higher in the 16 month closed euhaline phase after the breach (31 ± 0.9 ppt) compared to 21.9 ± 0.9 ppt in the closed polyhaline phase before the September 2008 breach. This increase in salinity significantly reduced the cover of the submerged macrophytes Ruppia cirrhosa and Chara vulgaris. They were replaced by macroalgae during this high salinity phase. The cover of supratidal salt marsh and reed habitats was also significantly reduced during the high water level phase, which in turn would lead to the potential for bank destabilisation and erosion. Based on the average elevation above sea level position of the macrophytes in the East Kleinemonde iv Estuary, a threshold water level was identified as 1.55 amsl. This was taken to be the height above sea level at which there was a maximum cover change for each macrophyte habitat. Above this water level emergent macrophyte habitat would mainly be inundated. This, together with 30 ppt salinity, was identified as the two thresholds for macrophyte change in the East Kleinemonde Estuary. From these thresholds and the 5 year dataset four biotic states were identified as State A: open and tidal, State B: closed with a water level below 1.55 m amsl and salinity between 18 to 30 ppt, State C: closed and water level above 1.55 m amsl and salinity between 18 to 30 ppt and State D: closed and water level above 1.55 m amsl and salinity above 30 ppt. Intertidal salt marsh, reeds and sedges were dominant during the open phase. Submerged macrophytes were dominant during the closed polyhaline state and macroalgae during the closed euhaline state. The high variability of abiotic factors common in TOCEs and the response of macrophyte habitat indicated that macrophytes were resilient to changing states provided they were of relatively short (< 3 months) duration. Macrophytes in the East Kleinemonde Estuary were found to have fast growth rates and large seed reserves in the sediment. The seed banks in the East Kleinemonde, as well as the adjacent temporarily open/closed West Kleinemonde Estuary were quantified for the first time in a South African estuary. The averaged data from both estuaries showed that Charophyte öospores represented almost 72 percent of the sexual propagules in the sediment with a mean öospore density of 31 306 ± 2 293 m-2. This was despite the Charophytes being sparsely located and only representing a maximum of 32.5 percent cover in the above ground vegetation. Historically there must have been stands of Charophytes in the East Kleinemonde Estuary, such that öospores could accumulate to such high density found in this study. The second highest seed density was for the intertidal salt marsh plant Sarcocornia tegetaria (18 percent) (7 929 ± 688 seed m-2), followed by the submerged angiosperm Ruppia cirrhosa (7 percent) (2 852 ± 327 seeds m-2). Although seed density did not differ significantly with sediment depth, seeds still occurred at 20 cm below the surface of the sediment providing a regeneration source in the event of sediment scouring during a flood event. Germination studies in the greenhouse showed that most seeds were viable and Sarcocornia tegetaria began to germinate after 3 days to a maximum of 82 percent after 91 days. Submerged species only germinated after 18 days with a low maximum germination of between 11 and 15 percent. This study has made an original contribution to the field of knowledge on macrophyte responses in a small TOCE as it showed that macrophyte habitats in the East Kleinemonde Estuary have a high natural variability in cover over time, they respond quickly after a disturbance event such as a mouth breach and there are large sediment seed reserves that remain viable from 2 to more than 5 years. This ensures habitat persistence even under unfavourable conditions, such as prolonged periods of mouth closure with high water level and flooding which causes loss of salt marsh species. Given this natural variability it is necessary to predict responses both spatially and temporally in order to manage and maintain ecological functioning in TOCEs. This study identified dominant macrophyte habitat for different abiotic states through the use of water level and salinity thresholds. In the determination of the freshwater requirements of any South African estuary freshwater inflow rates are provided for each estuary's past, present and possible future freshwater inflow scenarios. These flow data are generated by hydrological models and simulated monthly inflow volumes for a period of about 72 years are provided. For the East Kleinemonde freshwater requirement study for any year in that 70-odd year period, the number of high flow and low flow mouth breaches were predicted, as well as the closed state periods. The threshold water level of 1.55 m amsl was also used to filter past, present and future inflow monthly volumes to determine the frequency of the four abiotic states identified in this study. It was based on a water level/water volume equation calculation from a digital elevation model. Results showed that the total closed period in the present state was 83 percent, made up of 48 percent of the time in a polyhaline state (State C) and 35 percent in a euahaline state (State D). A second method was used to quantify available spatial habitat under different water level scenarios. A spatial model was written in Model Builder, an application in ArcGIS that allowed a series of processes to be built. A habitat map was overlaid with a bathymetric map and by selecting water level, available habitat areas were determined and empirical equations of water level versus available habitat were produced. These equations were then used to calculate the available habitat areas for monthly water level conditions from the freshwater requirement study for the past, present and two future inflow scenarios. Using both the threshold water level method and the spatial availability model method it was possible to assess the effect of the two future inflow scenarios on macrophyte habitat vi response. Scenario 1 had a 16 percent reduction in mean annual runoff (MAR) generating low flows for 88.6 percent of the time and a 3.5 percent reduction in flood events. In Scenario 2 there would be a 12 percent reduction in MAR with low flows occurring for 87.5 percent of the year, a 5.3 percent reduction in floods and an 11.5 percent reduction in the open mouth state. The model showed that Scenario 1 would have the highest submerged macrophyte area (12.56 ha versus 12.48 ha in Scenario 2), whereas Scenario 2 produced the largest mudflat and intertidal salt marsh area (7.11 ha versus 7.34 ha) due to lower water level in conjunction with the bathymetry of the estuary. A reduction in freshwater inflow to TOCEs either due to anthropogenic influences or natural precipitation cycles is one of the main threats to the optimum functioning of these estuaries. The results from this study and the two methods of assessing the effect of freshwater inflow scenarios on macrophytes in TOCEs can be integrated into the current freshwater inflow assessment methodology in South Africa, as well as adding to our understanding of the ecological functioning of these small, highly variable estuaries. The methods provide a quick assessment of macrophyte habitat associated with abiotic states under past, present and future inflow scenarios. All that is required to predict macrophyte habitat for different freshwater inflow scenarios (present, past and future) is a habitat map, a bathymetric map and the elevation range of macrophytes in the TOCE being assessed. This, together with the knowledge of response rates, provides invaluable information for the management of TOCEs to maintain their ecological functioning under altered freshwater inflow regimes.
- Full Text:
- Date Issued: 2011
- Authors: Riddin, Taryn
- Date: 2011
- Subjects: Estuaries -- South Africa -- East Kleinemonde
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10605 , http://hdl.handle.net/10948/1529 , Estuaries -- South Africa -- East Kleinemonde
- Description: The East Kleinemonde Estuary is one of 175 temporarily open/closed estuaries (TOCEs) that represent 70 percent of estuaries in South Africa. TOCEs are small (mostly less than 100 ha), shallow estuaries (average depth < 2 m) that respond quickly to freshwater inflow events. Their connection to the sea can be highly variable resulting in considerable changes in abiotic and biotic conditions. Mouth status depends on a balance between freshwater inflow and marine influence, which in turn affects ambient abiotic conditions. The objective of the study was to identify the abiotic variables which influence macrophyte growth and habitat availability. It was hypothesised that water level and salinity were the two main drivers of macrophyte change and macrophyte habitat would respond very rapidly, in less than a month, when habitat was available. Macrophyte habitats would also have high sediment seed reserves to ensure persistence under highly variable abiotic conditions. Macrophyte cover was monitored monthly in the East Kleinemonde Estuary along three permanent transects. The dominant habitats were submerged macrophytes, intertidal salt marsh, supratidal salt marsh, reeds and sedges. The following abiotic variables; water level, water column salinity, water temperature, Secchi depth, air temperature and rainfall were also measured between March 2006 and January 2010. Time-lag responses of the macrophytes to water level and salinity changes up to four months prior to the sampling session were also assessed. The analysis of a one year dataset highlighted only water level as a driver of change in macrophyte cover, whereas the five year dataset identified salinity as an additional important abiotic driver. This is because during September 2008 to January 2010 a series of large marine overwash events maintained high salinity (> 30 ppt) and high water level (> 1.6 m amsl) in the estuary. Water level increased by up to 0.33 m due to large volumetric changes and salinity was significantly higher in the 16 month closed euhaline phase after the breach (31 ± 0.9 ppt) compared to 21.9 ± 0.9 ppt in the closed polyhaline phase before the September 2008 breach. This increase in salinity significantly reduced the cover of the submerged macrophytes Ruppia cirrhosa and Chara vulgaris. They were replaced by macroalgae during this high salinity phase. The cover of supratidal salt marsh and reed habitats was also significantly reduced during the high water level phase, which in turn would lead to the potential for bank destabilisation and erosion. Based on the average elevation above sea level position of the macrophytes in the East Kleinemonde iv Estuary, a threshold water level was identified as 1.55 amsl. This was taken to be the height above sea level at which there was a maximum cover change for each macrophyte habitat. Above this water level emergent macrophyte habitat would mainly be inundated. This, together with 30 ppt salinity, was identified as the two thresholds for macrophyte change in the East Kleinemonde Estuary. From these thresholds and the 5 year dataset four biotic states were identified as State A: open and tidal, State B: closed with a water level below 1.55 m amsl and salinity between 18 to 30 ppt, State C: closed and water level above 1.55 m amsl and salinity between 18 to 30 ppt and State D: closed and water level above 1.55 m amsl and salinity above 30 ppt. Intertidal salt marsh, reeds and sedges were dominant during the open phase. Submerged macrophytes were dominant during the closed polyhaline state and macroalgae during the closed euhaline state. The high variability of abiotic factors common in TOCEs and the response of macrophyte habitat indicated that macrophytes were resilient to changing states provided they were of relatively short (< 3 months) duration. Macrophytes in the East Kleinemonde Estuary were found to have fast growth rates and large seed reserves in the sediment. The seed banks in the East Kleinemonde, as well as the adjacent temporarily open/closed West Kleinemonde Estuary were quantified for the first time in a South African estuary. The averaged data from both estuaries showed that Charophyte öospores represented almost 72 percent of the sexual propagules in the sediment with a mean öospore density of 31 306 ± 2 293 m-2. This was despite the Charophytes being sparsely located and only representing a maximum of 32.5 percent cover in the above ground vegetation. Historically there must have been stands of Charophytes in the East Kleinemonde Estuary, such that öospores could accumulate to such high density found in this study. The second highest seed density was for the intertidal salt marsh plant Sarcocornia tegetaria (18 percent) (7 929 ± 688 seed m-2), followed by the submerged angiosperm Ruppia cirrhosa (7 percent) (2 852 ± 327 seeds m-2). Although seed density did not differ significantly with sediment depth, seeds still occurred at 20 cm below the surface of the sediment providing a regeneration source in the event of sediment scouring during a flood event. Germination studies in the greenhouse showed that most seeds were viable and Sarcocornia tegetaria began to germinate after 3 days to a maximum of 82 percent after 91 days. Submerged species only germinated after 18 days with a low maximum germination of between 11 and 15 percent. This study has made an original contribution to the field of knowledge on macrophyte responses in a small TOCE as it showed that macrophyte habitats in the East Kleinemonde Estuary have a high natural variability in cover over time, they respond quickly after a disturbance event such as a mouth breach and there are large sediment seed reserves that remain viable from 2 to more than 5 years. This ensures habitat persistence even under unfavourable conditions, such as prolonged periods of mouth closure with high water level and flooding which causes loss of salt marsh species. Given this natural variability it is necessary to predict responses both spatially and temporally in order to manage and maintain ecological functioning in TOCEs. This study identified dominant macrophyte habitat for different abiotic states through the use of water level and salinity thresholds. In the determination of the freshwater requirements of any South African estuary freshwater inflow rates are provided for each estuary's past, present and possible future freshwater inflow scenarios. These flow data are generated by hydrological models and simulated monthly inflow volumes for a period of about 72 years are provided. For the East Kleinemonde freshwater requirement study for any year in that 70-odd year period, the number of high flow and low flow mouth breaches were predicted, as well as the closed state periods. The threshold water level of 1.55 m amsl was also used to filter past, present and future inflow monthly volumes to determine the frequency of the four abiotic states identified in this study. It was based on a water level/water volume equation calculation from a digital elevation model. Results showed that the total closed period in the present state was 83 percent, made up of 48 percent of the time in a polyhaline state (State C) and 35 percent in a euahaline state (State D). A second method was used to quantify available spatial habitat under different water level scenarios. A spatial model was written in Model Builder, an application in ArcGIS that allowed a series of processes to be built. A habitat map was overlaid with a bathymetric map and by selecting water level, available habitat areas were determined and empirical equations of water level versus available habitat were produced. These equations were then used to calculate the available habitat areas for monthly water level conditions from the freshwater requirement study for the past, present and two future inflow scenarios. Using both the threshold water level method and the spatial availability model method it was possible to assess the effect of the two future inflow scenarios on macrophyte habitat vi response. Scenario 1 had a 16 percent reduction in mean annual runoff (MAR) generating low flows for 88.6 percent of the time and a 3.5 percent reduction in flood events. In Scenario 2 there would be a 12 percent reduction in MAR with low flows occurring for 87.5 percent of the year, a 5.3 percent reduction in floods and an 11.5 percent reduction in the open mouth state. The model showed that Scenario 1 would have the highest submerged macrophyte area (12.56 ha versus 12.48 ha in Scenario 2), whereas Scenario 2 produced the largest mudflat and intertidal salt marsh area (7.11 ha versus 7.34 ha) due to lower water level in conjunction with the bathymetry of the estuary. A reduction in freshwater inflow to TOCEs either due to anthropogenic influences or natural precipitation cycles is one of the main threats to the optimum functioning of these estuaries. The results from this study and the two methods of assessing the effect of freshwater inflow scenarios on macrophytes in TOCEs can be integrated into the current freshwater inflow assessment methodology in South Africa, as well as adding to our understanding of the ecological functioning of these small, highly variable estuaries. The methods provide a quick assessment of macrophyte habitat associated with abiotic states under past, present and future inflow scenarios. All that is required to predict macrophyte habitat for different freshwater inflow scenarios (present, past and future) is a habitat map, a bathymetric map and the elevation range of macrophytes in the TOCE being assessed. This, together with the knowledge of response rates, provides invaluable information for the management of TOCEs to maintain their ecological functioning under altered freshwater inflow regimes.
- Full Text:
- Date Issued: 2011
Ecophysiology and nutrient uptake mechanisms facilitating the prolonged bloom persistence by Cyanothece sp. in Lake St Lucia, South Africa
- Authors: Du Plooy, Schalk Jacobus
- Date: 2017
- Subjects: Cyanobacterial blooms , Cyanobacteria -- Physiology , Cyanobacteria
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/7344 , vital:21324
- Description: Cyanobacterial blooms are becoming more frequent worldwide, with possible negative effects on human health. The effects of climate change and eutrophication have been associated with persistent cyanobacterial blooms becoming more frequent. Altered water characteristics, salinity in particular, influence ecosystem dynamics that may lead to conditions conducive to cyanobacterial blooms. The occurrence of an 18-month long Cyanothece sp. bloom (the longest for any cyanobacterium recorded so far worldwide and the first of the genus) from June 2009 to December 2010 in Africa’s largest estuarine lake, St Lucia, highlighted the susceptibility of ecosystems to anthropogenic alterations. This study investigated the long-term survival and physiological adaptations of Cyanothece sp. to various and dynamic environmental conditions that contributed towards its bloom persistence. The main findings are the high salinities at which Cyanothece sp. could perform important physiological processes such as N uptake, N2 fixation and photosynthesis. Nutrient uptake (both nitrogen and phosphorus) was observed over the full experimental salinity range (0-300) while N2 fixation was only observed up to a salinity of 120. Nutrient uptake rates significantly decreased at this threshold salinity of 120. Interestingly, photosystem II activity was not observed in Cyanothece sp. during this study, but photosystem I activity was robust. Salinity had a minor influence on electron transport rates by photosystem I, high temperature (> 30°C) did however increase electron transport rates. Rapid responses to hypo-osmotic shock (i.e. osmotic downshift during freshening events) by Cyanothece sp. cells also helped minimize cell rupture due to high turgor pressure. Zooplankton abundance within the St Lucia system was negatively correlated with salinity, while grazing experiments indicated that the typical estuarine zooplankton species are able to graze on Cyanothece sp. cells. Therefore, the disappearance of zooplankton at salinities above 60 must have been an important factor in the bloom persistence. Apart from the ecological factors that were at play in St Lucia during the bloom period, the persistence of the Cyanothece sp. bloom can be attributed to the robust nature of their nutrient uptake, nitrogen fixation and photosynthetic systems to maintain activity despite extreme hypersalinity levels.
- Full Text:
- Date Issued: 2017
- Authors: Du Plooy, Schalk Jacobus
- Date: 2017
- Subjects: Cyanobacterial blooms , Cyanobacteria -- Physiology , Cyanobacteria
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/7344 , vital:21324
- Description: Cyanobacterial blooms are becoming more frequent worldwide, with possible negative effects on human health. The effects of climate change and eutrophication have been associated with persistent cyanobacterial blooms becoming more frequent. Altered water characteristics, salinity in particular, influence ecosystem dynamics that may lead to conditions conducive to cyanobacterial blooms. The occurrence of an 18-month long Cyanothece sp. bloom (the longest for any cyanobacterium recorded so far worldwide and the first of the genus) from June 2009 to December 2010 in Africa’s largest estuarine lake, St Lucia, highlighted the susceptibility of ecosystems to anthropogenic alterations. This study investigated the long-term survival and physiological adaptations of Cyanothece sp. to various and dynamic environmental conditions that contributed towards its bloom persistence. The main findings are the high salinities at which Cyanothece sp. could perform important physiological processes such as N uptake, N2 fixation and photosynthesis. Nutrient uptake (both nitrogen and phosphorus) was observed over the full experimental salinity range (0-300) while N2 fixation was only observed up to a salinity of 120. Nutrient uptake rates significantly decreased at this threshold salinity of 120. Interestingly, photosystem II activity was not observed in Cyanothece sp. during this study, but photosystem I activity was robust. Salinity had a minor influence on electron transport rates by photosystem I, high temperature (> 30°C) did however increase electron transport rates. Rapid responses to hypo-osmotic shock (i.e. osmotic downshift during freshening events) by Cyanothece sp. cells also helped minimize cell rupture due to high turgor pressure. Zooplankton abundance within the St Lucia system was negatively correlated with salinity, while grazing experiments indicated that the typical estuarine zooplankton species are able to graze on Cyanothece sp. cells. Therefore, the disappearance of zooplankton at salinities above 60 must have been an important factor in the bloom persistence. Apart from the ecological factors that were at play in St Lucia during the bloom period, the persistence of the Cyanothece sp. bloom can be attributed to the robust nature of their nutrient uptake, nitrogen fixation and photosynthetic systems to maintain activity despite extreme hypersalinity levels.
- Full Text:
- Date Issued: 2017
Evaluating the effectiveness of public participation in the environmental impact assessment process in South Africa
- Authors: Uithaler, Eldrid Marlon
- Date: 2015
- Subjects: Environmental impact analysis -- South Africa , Environmental policy -- Citizen participation
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/5928 , vital:21015
- Description: This research is based on reflections of various practitioners and their views on how public participation processes may or may not contribute to effective EIA decisions. It is therefore grounded in what is described as practitioner-based research. To study comparative development activities effectively, one must draw on many disciplines and construct a balanced understanding of historical and contemporary development processes. No single conventional disciplinary area of research is able to integrate the issues of public participation, EIA and decision-making in the context of the current development debate. The emergence of Trans-disciplinary areas of research allows for such integration. The Africa Earth Observatory Network (AEON) institute creates the space for this study to achieve an integrated response to the question of the effectiveness of public participation in EIA and decision-making. This further creates the opportunity to contribute and expand the growing body of knowledge and literature of public participation in the earth stewardship science discipline. Making use of triangulation, this study fulfils four major tasks: firstly, an assessment is made on the historical and theoretical importance, process and outcome of both EIA and public participation internationally and in South Africa. Secondly, three prominent case studies (i) the Coega IDZ, (ii) the Pondoland N2 Toll Road, and (iii) the anticipated Hydraulic Fracturing in the Karoo each focusses on concerns of an environmental, socio-economic, and political nature to assess if the public participation process has had influence, if any, on the final decisions for these projects to go-ahead. Thirdly, a survey was conducted to establish the views and perceptions of practitioners in the EIA and public participation domain on the effectiveness of public participation in EIA processes. Lastly, face-to-face interviews were conducted with various ‘pracademics’, i.e. consultants, practitioners, government, and non-governmental officials to establish their views on how public participation may or may not influence EIA decisions. Utilising the International Association for Public Participation’s (IAP2) participation spectrum as an evaluation tool, this research explores thirteen key criteria normally attributed to effective public participation. This provides a scale (inform, involve, consult, collaborate) to assess whether public participation in EIA in South Africa is least effective (inform) or most effective (collaborate). My research confirms that in South Africa an enabling environment to address impacts on our environment is emerging. One of the main challenges remains putting in place robust, clear and effective regulations, models or approaches that provide for effective public participation and decision-making in EIAs. My research also suggests that the legislation on which EIA is based cannot by itself guarantee the effectiveness of public participation processes. In practice, EIA is an institutional process of power division between different actors, and the practitioner or ‘pracademic’ has to play a more fundamental role to ensure effectiveness and fairness in the public participation process. Academic commentators should therefore call for new approaches that emphasise collaborative interaction between decision-makers and the public as well as deliberation amongst participants.
- Full Text:
- Date Issued: 2015
- Authors: Uithaler, Eldrid Marlon
- Date: 2015
- Subjects: Environmental impact analysis -- South Africa , Environmental policy -- Citizen participation
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/5928 , vital:21015
- Description: This research is based on reflections of various practitioners and their views on how public participation processes may or may not contribute to effective EIA decisions. It is therefore grounded in what is described as practitioner-based research. To study comparative development activities effectively, one must draw on many disciplines and construct a balanced understanding of historical and contemporary development processes. No single conventional disciplinary area of research is able to integrate the issues of public participation, EIA and decision-making in the context of the current development debate. The emergence of Trans-disciplinary areas of research allows for such integration. The Africa Earth Observatory Network (AEON) institute creates the space for this study to achieve an integrated response to the question of the effectiveness of public participation in EIA and decision-making. This further creates the opportunity to contribute and expand the growing body of knowledge and literature of public participation in the earth stewardship science discipline. Making use of triangulation, this study fulfils four major tasks: firstly, an assessment is made on the historical and theoretical importance, process and outcome of both EIA and public participation internationally and in South Africa. Secondly, three prominent case studies (i) the Coega IDZ, (ii) the Pondoland N2 Toll Road, and (iii) the anticipated Hydraulic Fracturing in the Karoo each focusses on concerns of an environmental, socio-economic, and political nature to assess if the public participation process has had influence, if any, on the final decisions for these projects to go-ahead. Thirdly, a survey was conducted to establish the views and perceptions of practitioners in the EIA and public participation domain on the effectiveness of public participation in EIA processes. Lastly, face-to-face interviews were conducted with various ‘pracademics’, i.e. consultants, practitioners, government, and non-governmental officials to establish their views on how public participation may or may not influence EIA decisions. Utilising the International Association for Public Participation’s (IAP2) participation spectrum as an evaluation tool, this research explores thirteen key criteria normally attributed to effective public participation. This provides a scale (inform, involve, consult, collaborate) to assess whether public participation in EIA in South Africa is least effective (inform) or most effective (collaborate). My research confirms that in South Africa an enabling environment to address impacts on our environment is emerging. One of the main challenges remains putting in place robust, clear and effective regulations, models or approaches that provide for effective public participation and decision-making in EIAs. My research also suggests that the legislation on which EIA is based cannot by itself guarantee the effectiveness of public participation processes. In practice, EIA is an institutional process of power division between different actors, and the practitioner or ‘pracademic’ has to play a more fundamental role to ensure effectiveness and fairness in the public participation process. Academic commentators should therefore call for new approaches that emphasise collaborative interaction between decision-makers and the public as well as deliberation amongst participants.
- Full Text:
- Date Issued: 2015
Factors affecting effective ecological restoration of Portulacaria afra (spekboom)-rich subtropical thicket and aboveground carbon endpoint projections
- Van der Vyver, Marius Lodewyk
- Authors: Van der Vyver, Marius Lodewyk
- Date: 2018
- Subjects: Restoration ecology , Plant conservation -- South Africa Portulacaria afra -- South Africa Shrubs -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23250 , vital:30468
- Description: Among the requirements to achieve effective ecological restoration on a landscape scale are a scientific underpinning, strong adaptive management and the setting of realistic endpoints. Efficacy and success depend on a complex interplay of factors of both local and regional influence. Biome-wide restoration experiments are rare, but valuable for evaluating efficacy of different protocols according to local context. The Thicket-wide Plot (TWP) experiment was initiated by the Subtropical Thicket Restoration Programme to inform landscape-scale ecological restoration of degraded Portulacaria afra (spekboom)-rich Subtropical Thicket. Thirteen different planting treatments of Portulacaria afra (spekboom) truncheons were planted as replicated rows on 0.25 ha fenced plots across the distribution range of spekboom-rich thicket habitat to better establish effective restoration protocols. I used a rule-based learning ensemble algorithm to evaluate 60 different predictors that potentially impact effective restoration, covering a range of climatic, topographic, edaphic, ecological and management related factors observed at 227 of these TWP plots. Percentage survivorship and aboveground biomass carbon sequestration rate (ABCsr) were taken as proxies for efficacy derived from subsequent monitoring data gathered 2 - 5 years after establishment, and a new allometric model I developed for spekboom. I found herbivory and identification of target habitat the two most important predictors of restoration efficacy, both well within the control of the practitioner. Highest survivorship and ABCsr were associated with larger truncheons planted deeper. The only exception to this pattern was found amongst the two smallest size truncheon categories. The application of external rooting hormone or watering treatment to truncheons were found of no significance to effective restoration, while all the pruned treatments were, in association with lesser planting depth, found to be significantly less effective than untreated truncheons planted deeper. When the restoration protocol is optimal (largest truncheons planted deepest in target habitats and protected from herbivory), my results show higher annual carbon sequestration rates (1.46 - 3.7 t C ha−1 yr−1 in aboveground biomass) than most older restoration sites that have been identified as benchmarks of success. In order to project ABC endpoints, I generated 40 new species-specific allometric models and used them to estimate biomass and carbon of intact and degraded stands on five sites spread out across the region. The highest AGC for stands in both intact and degraded states were estimated at 42.96 t Cha−1 and 12.98 t C ha−1 respectively, and the lowest at 26.32 t C ha−1 and 2.52 t C ha−1. Large canopy dominant (LCD) species contributed the largest AGC portion at three intact stands. The second largest portion was recorded for spekboom. The difference between paired stands on each sample site ranged between 23.8 and 32.8 t C ha−1, which provide a realistic target for biome-wide restoration that, when adopted together with current protocols, may be reached within three decades of inception.
- Full Text:
- Date Issued: 2018
- Authors: Van der Vyver, Marius Lodewyk
- Date: 2018
- Subjects: Restoration ecology , Plant conservation -- South Africa Portulacaria afra -- South Africa Shrubs -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23250 , vital:30468
- Description: Among the requirements to achieve effective ecological restoration on a landscape scale are a scientific underpinning, strong adaptive management and the setting of realistic endpoints. Efficacy and success depend on a complex interplay of factors of both local and regional influence. Biome-wide restoration experiments are rare, but valuable for evaluating efficacy of different protocols according to local context. The Thicket-wide Plot (TWP) experiment was initiated by the Subtropical Thicket Restoration Programme to inform landscape-scale ecological restoration of degraded Portulacaria afra (spekboom)-rich Subtropical Thicket. Thirteen different planting treatments of Portulacaria afra (spekboom) truncheons were planted as replicated rows on 0.25 ha fenced plots across the distribution range of spekboom-rich thicket habitat to better establish effective restoration protocols. I used a rule-based learning ensemble algorithm to evaluate 60 different predictors that potentially impact effective restoration, covering a range of climatic, topographic, edaphic, ecological and management related factors observed at 227 of these TWP plots. Percentage survivorship and aboveground biomass carbon sequestration rate (ABCsr) were taken as proxies for efficacy derived from subsequent monitoring data gathered 2 - 5 years after establishment, and a new allometric model I developed for spekboom. I found herbivory and identification of target habitat the two most important predictors of restoration efficacy, both well within the control of the practitioner. Highest survivorship and ABCsr were associated with larger truncheons planted deeper. The only exception to this pattern was found amongst the two smallest size truncheon categories. The application of external rooting hormone or watering treatment to truncheons were found of no significance to effective restoration, while all the pruned treatments were, in association with lesser planting depth, found to be significantly less effective than untreated truncheons planted deeper. When the restoration protocol is optimal (largest truncheons planted deepest in target habitats and protected from herbivory), my results show higher annual carbon sequestration rates (1.46 - 3.7 t C ha−1 yr−1 in aboveground biomass) than most older restoration sites that have been identified as benchmarks of success. In order to project ABC endpoints, I generated 40 new species-specific allometric models and used them to estimate biomass and carbon of intact and degraded stands on five sites spread out across the region. The highest AGC for stands in both intact and degraded states were estimated at 42.96 t Cha−1 and 12.98 t C ha−1 respectively, and the lowest at 26.32 t C ha−1 and 2.52 t C ha−1. Large canopy dominant (LCD) species contributed the largest AGC portion at three intact stands. The second largest portion was recorded for spekboom. The difference between paired stands on each sample site ranged between 23.8 and 32.8 t C ha−1, which provide a realistic target for biome-wide restoration that, when adopted together with current protocols, may be reached within three decades of inception.
- Full Text:
- Date Issued: 2018
Fertility decline among Abagusii women : the application of an adapted proximate determinants model
- Authors: Onsongo, Francis Omweri
- Date: 2012
- Subjects: Fertility, Human -- Kenya , Birth control -- Kenya , Women, Gusii -- Social conditions , Women's rights -- Kenya , Gusii (African people) -- Social conditions
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10669 , http://hdl.handle.net/10948/d1019924
- Description: The primary objective of this thesis is to account for the fertility decline among Abagusii women in South-western Kenya. The motivation behind the study was based on the fact that the fertility trends associated with this group of people had not been studied before. This is surprising because the Abagusii recorded one of the world's highest total fertility rates of 10.4 in 1979 (Omosa 1994; Osiemo 1986; Oucho 1990), but has also experienced significant fertility decline. The total fertility rate in 2004 stood at 4.7, (Anyara 2009). The analytical framework that is adopted is Stover's (1998) adaptation of the Bongaarts et. al. (1984) Proximate Determinants Model. These determinants such as contraceptive use, post-partum insusceptibility, sexual activity, abortion and sterility represent behavioural and biological variables that affect fertility directly. The manner in which they are employed involves using the index which indicates the extent to which each proximate determinant reduces the fertility of the group in question.
- Full Text:
- Date Issued: 2012
- Authors: Onsongo, Francis Omweri
- Date: 2012
- Subjects: Fertility, Human -- Kenya , Birth control -- Kenya , Women, Gusii -- Social conditions , Women's rights -- Kenya , Gusii (African people) -- Social conditions
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10669 , http://hdl.handle.net/10948/d1019924
- Description: The primary objective of this thesis is to account for the fertility decline among Abagusii women in South-western Kenya. The motivation behind the study was based on the fact that the fertility trends associated with this group of people had not been studied before. This is surprising because the Abagusii recorded one of the world's highest total fertility rates of 10.4 in 1979 (Omosa 1994; Osiemo 1986; Oucho 1990), but has also experienced significant fertility decline. The total fertility rate in 2004 stood at 4.7, (Anyara 2009). The analytical framework that is adopted is Stover's (1998) adaptation of the Bongaarts et. al. (1984) Proximate Determinants Model. These determinants such as contraceptive use, post-partum insusceptibility, sexual activity, abortion and sterility represent behavioural and biological variables that affect fertility directly. The manner in which they are employed involves using the index which indicates the extent to which each proximate determinant reduces the fertility of the group in question.
- Full Text:
- Date Issued: 2012
Foraging ecology of gentoo penguins pygoscelis papua at the Falkland Islands
- Authors: Handley, Jonathan Murray
- Date: 2017
- Subjects: Gentoo penguin -- Food -- Falkland Islands Gentoo penguin -- Ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/14113 , vital:27431
- Description: Marine top predators often occupy broad geographical ranges that encompass varied habitats. Therefore, a pre-requisite towards conserving these animals is to determine the components of their realized niche, and investigate whether a species is a specialist or a generalist. For generalist species, it is also necessary to understand if local specialisation occurs. Uncovering these components can allow us to build models of a species realized niche that may then be used to infer habitat use in unsampled locations. However, fully understanding the components of a marine top predators realized niche is challenging owing to the limited opportunity for in situ observations. Overcoming these limitations is a key step in marine top predator research. It will enhance our understanding of trophic coupling in marine systems, and aid in the development of tools to better study these predators in their dynamic environment. Seabirds, penguins (Spheniscids) in particular, are a group of animals for which investigating their realized niche is of vital importance. This is because numerous species face growing uncertainty in the Anthropocene, and in a time of rapid environmental change there is furthermore a need to better understand the potential use of these birds as indicators of ecosystem health. The aim of this thesis, therefore, is to investigate the foraging ecology of gentoo penguins (Pygoscelis papua) at the Falkland Islands. At the Falkland Islands, limited historical information exists regarding this species foraging ecology, with most information coming from a single location at the Falklands. As the Falkland Islands have the world’s largest population of gentoo penguins, elucidating factors influencing this population will have global relevance. Furthermore, historical information indicated potential competition with fisheries, and with prospecting for hydrocarbons and an inshore fishery, there is a need to understand the distribution of these birds across the islands. Penguins are also well suited to carry biologging devices allowing for in situ observations of inter and intraspecific interactions, as well as habitat specific interactions. In this study, I sampled birds over three breeding seasons, from four breeding colonies - chosen for their varied surrounding at sea habitat - across the Falkland Islands. I investigated the diet with stomach content and stable isotope analysis, the at-sea distribution with GPS and time depth recorders, and how these birds behaved at sea using custom made animal-borne camera loggers. Furthermore, I developed a method to recognise prey encounter events from back mounted accelerometers, using a supervised machine learning approach. As part of the first species specific description of diet at this scale for the Falklands, I revealed six key prey items for the birds: rock cod (Patagonotothen spp.), lobster krill (Munida spp.), Falkland herring (Sprattus fuegensis), Patagonian squid (Doryteuthis gahi), juvenile fish (likely all nototheniids), and southern blue whiting (Micromesistius australis). The use of animal-borne camera loggers verified that not only do gentoo penguins consume a diverse array of prey items, but they adopted various methods to capture and pursue prey, with evidence of birds following optimal foraging theory. Prey composition varied significantly between study sites with the at-sea distribution and habitat use of penguins reflecting that of local prey. Birds from colonies close to gently sloping, shallow waters, foraged primarily in a benthic manner and had larger niche widths. However, those at a colony surrounded by steeply sloping, deeper waters, typically foraged in a pelagic manner. Contrasting diet patterns were also prevalent from stable isotope data, and the niche widths of birds relating to both stomach content and stable isotope data were larger at colonies where benthic foraging was prevalent. Therefore, it was clear that surrounding bathymetry played a key role in shaping this species’ foraging ecology, and that at the population level at the Falkland Islands birds are generalists. However, at individual colonies some specialisation occurs to take advantage of locally available prey. I developed habitat distribution models - via boosted regression trees – which transferred well in time but poorly across space. Reasons for poor model transfer might relate to the generalist foraging nature of these birds and the reduced availability of environmental predictors owing to the limited range of these birds. I furthermore developed a method to identify prey encounter events that can also, to a degree, distinguish between prey items. This method will be a promising approach to refine habitat distribution models in future. These habitat distribution models could potentially contribute to marine spatial planning at the Falkland Islands. Footage from animal-borne camera loggers clearly showed that prey behaviour can significantly influence trophic coupling in marine systems and should be accounted for in studies using marine top predators as samplers of mid to lower trophic level species. Ultimately, flexibility in foraging strategies and inter-colony variation will play a critical role when assessing factors such as interspecific competition or overlap with anthropogenic activities.
- Full Text:
- Date Issued: 2017
- Authors: Handley, Jonathan Murray
- Date: 2017
- Subjects: Gentoo penguin -- Food -- Falkland Islands Gentoo penguin -- Ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/14113 , vital:27431
- Description: Marine top predators often occupy broad geographical ranges that encompass varied habitats. Therefore, a pre-requisite towards conserving these animals is to determine the components of their realized niche, and investigate whether a species is a specialist or a generalist. For generalist species, it is also necessary to understand if local specialisation occurs. Uncovering these components can allow us to build models of a species realized niche that may then be used to infer habitat use in unsampled locations. However, fully understanding the components of a marine top predators realized niche is challenging owing to the limited opportunity for in situ observations. Overcoming these limitations is a key step in marine top predator research. It will enhance our understanding of trophic coupling in marine systems, and aid in the development of tools to better study these predators in their dynamic environment. Seabirds, penguins (Spheniscids) in particular, are a group of animals for which investigating their realized niche is of vital importance. This is because numerous species face growing uncertainty in the Anthropocene, and in a time of rapid environmental change there is furthermore a need to better understand the potential use of these birds as indicators of ecosystem health. The aim of this thesis, therefore, is to investigate the foraging ecology of gentoo penguins (Pygoscelis papua) at the Falkland Islands. At the Falkland Islands, limited historical information exists regarding this species foraging ecology, with most information coming from a single location at the Falklands. As the Falkland Islands have the world’s largest population of gentoo penguins, elucidating factors influencing this population will have global relevance. Furthermore, historical information indicated potential competition with fisheries, and with prospecting for hydrocarbons and an inshore fishery, there is a need to understand the distribution of these birds across the islands. Penguins are also well suited to carry biologging devices allowing for in situ observations of inter and intraspecific interactions, as well as habitat specific interactions. In this study, I sampled birds over three breeding seasons, from four breeding colonies - chosen for their varied surrounding at sea habitat - across the Falkland Islands. I investigated the diet with stomach content and stable isotope analysis, the at-sea distribution with GPS and time depth recorders, and how these birds behaved at sea using custom made animal-borne camera loggers. Furthermore, I developed a method to recognise prey encounter events from back mounted accelerometers, using a supervised machine learning approach. As part of the first species specific description of diet at this scale for the Falklands, I revealed six key prey items for the birds: rock cod (Patagonotothen spp.), lobster krill (Munida spp.), Falkland herring (Sprattus fuegensis), Patagonian squid (Doryteuthis gahi), juvenile fish (likely all nototheniids), and southern blue whiting (Micromesistius australis). The use of animal-borne camera loggers verified that not only do gentoo penguins consume a diverse array of prey items, but they adopted various methods to capture and pursue prey, with evidence of birds following optimal foraging theory. Prey composition varied significantly between study sites with the at-sea distribution and habitat use of penguins reflecting that of local prey. Birds from colonies close to gently sloping, shallow waters, foraged primarily in a benthic manner and had larger niche widths. However, those at a colony surrounded by steeply sloping, deeper waters, typically foraged in a pelagic manner. Contrasting diet patterns were also prevalent from stable isotope data, and the niche widths of birds relating to both stomach content and stable isotope data were larger at colonies where benthic foraging was prevalent. Therefore, it was clear that surrounding bathymetry played a key role in shaping this species’ foraging ecology, and that at the population level at the Falkland Islands birds are generalists. However, at individual colonies some specialisation occurs to take advantage of locally available prey. I developed habitat distribution models - via boosted regression trees – which transferred well in time but poorly across space. Reasons for poor model transfer might relate to the generalist foraging nature of these birds and the reduced availability of environmental predictors owing to the limited range of these birds. I furthermore developed a method to identify prey encounter events that can also, to a degree, distinguish between prey items. This method will be a promising approach to refine habitat distribution models in future. These habitat distribution models could potentially contribute to marine spatial planning at the Falkland Islands. Footage from animal-borne camera loggers clearly showed that prey behaviour can significantly influence trophic coupling in marine systems and should be accounted for in studies using marine top predators as samplers of mid to lower trophic level species. Ultimately, flexibility in foraging strategies and inter-colony variation will play a critical role when assessing factors such as interspecific competition or overlap with anthropogenic activities.
- Full Text:
- Date Issued: 2017
Foraging in a dynamic environment: movement and stable isotope ecology of marine top predators breeding at the Prince Edward Archipelago
- Authors: Carpenter-Kling, Tegan
- Date: 2020
- Subjects: Marine ecology , Stable isotope tracers , Estuarine ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49049 , vital:41596
- Description: Marine ecosystems are experiencing rapid changes due to climate change. The associated temporal and spatial changes in resource distribution impacts on the foraging behaviour of marine top predators. If these changes negatively affect the ability of marine predators to forage efficiently, there may be dire consequences for their populations. However, evidence of foraging plasticity during adverse conditions, or generalist foraging behaviour, can allow inference about the resilience of species to environmental change and provide essential knowledge towards effective and proactive conservation measures. I examined plasticity in the trophic ecology of 12 marine predator species breeding on Marion Island, southern Indian Ocean, over three years (2015 – 2018), a period characterized by pronounced environmental variability. Firstly, I correlated behavioural states inferred along the GPS tracks of incubating wandering, grey-headed, sooty and light-mantled albatrosses to environmental variables that are indicative of biologically productive oceanographic features. Secondly, I analysed δ13C and δ15N blood values in 12 marine predator species (the afore-mentioned albatrosses as well as king, gentoo, macaroni and eastern rockhopper penguins, northern and southern giant petrels and Antarctic and sub-Antarctic fur seals) over two seasons: summer and autumn. My results revealed that the foraging behaviour of all the species is, to some degree, either plastic (temporally variable isotopic niche) or general (large isotopic niche which remained similar over time), except for the king penguin (small isotopic niche which remained similar over time), a known foraging specialist. Furthermore, despite their dynamic foraging behaviour, resource partitioning among the predators was maintained over time. Due to the ease and relatively low cost of collecting tissues for stable isotope analysis it has the potential to be a powerful tool to monitor the trophic ecology of marine predators. I thus used my simultaneously collected dataset of GPS tracks with the stable isotope blood compositions to investigate some of the assumptions underlying the inferences made from marine predator δ13C and δ15N blood values. I reconstructed species- and guild- specific δ13C and δ15N isoscapes for eight seabird species. Following this, I coupled individual-based movement models of northern giant petrels with global marine isotope models to explore the sensitivity of tissue δ13C values to a range of extrinsic (environmental) and intrinsic (behavioural, physiological) drivers. My results demonstrate the strong influence of reference isoscapes on the inference of stable isotope compositions of marine predators. Furthermore, I show that caution should be used when using non-species-specific or temporally inaccurate isoscapes. I furthermore demonstrate that biological interactions, such as competition for food resources, either past or present, as well as spatio-temporal distribution of food patches strongly influence the foraging behaviour of marine predators. These findings highlight the importance of integrating biological interactions in species distribution models which are used to predict possible distributional shifts of marine predators in the context of global changes. My thesis further developed previously available methods and presents a novel approach to investigate sources of variance in the stable isotopic composition of animals’ tissues.
- Full Text:
- Date Issued: 2020
- Authors: Carpenter-Kling, Tegan
- Date: 2020
- Subjects: Marine ecology , Stable isotope tracers , Estuarine ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49049 , vital:41596
- Description: Marine ecosystems are experiencing rapid changes due to climate change. The associated temporal and spatial changes in resource distribution impacts on the foraging behaviour of marine top predators. If these changes negatively affect the ability of marine predators to forage efficiently, there may be dire consequences for their populations. However, evidence of foraging plasticity during adverse conditions, or generalist foraging behaviour, can allow inference about the resilience of species to environmental change and provide essential knowledge towards effective and proactive conservation measures. I examined plasticity in the trophic ecology of 12 marine predator species breeding on Marion Island, southern Indian Ocean, over three years (2015 – 2018), a period characterized by pronounced environmental variability. Firstly, I correlated behavioural states inferred along the GPS tracks of incubating wandering, grey-headed, sooty and light-mantled albatrosses to environmental variables that are indicative of biologically productive oceanographic features. Secondly, I analysed δ13C and δ15N blood values in 12 marine predator species (the afore-mentioned albatrosses as well as king, gentoo, macaroni and eastern rockhopper penguins, northern and southern giant petrels and Antarctic and sub-Antarctic fur seals) over two seasons: summer and autumn. My results revealed that the foraging behaviour of all the species is, to some degree, either plastic (temporally variable isotopic niche) or general (large isotopic niche which remained similar over time), except for the king penguin (small isotopic niche which remained similar over time), a known foraging specialist. Furthermore, despite their dynamic foraging behaviour, resource partitioning among the predators was maintained over time. Due to the ease and relatively low cost of collecting tissues for stable isotope analysis it has the potential to be a powerful tool to monitor the trophic ecology of marine predators. I thus used my simultaneously collected dataset of GPS tracks with the stable isotope blood compositions to investigate some of the assumptions underlying the inferences made from marine predator δ13C and δ15N blood values. I reconstructed species- and guild- specific δ13C and δ15N isoscapes for eight seabird species. Following this, I coupled individual-based movement models of northern giant petrels with global marine isotope models to explore the sensitivity of tissue δ13C values to a range of extrinsic (environmental) and intrinsic (behavioural, physiological) drivers. My results demonstrate the strong influence of reference isoscapes on the inference of stable isotope compositions of marine predators. Furthermore, I show that caution should be used when using non-species-specific or temporally inaccurate isoscapes. I furthermore demonstrate that biological interactions, such as competition for food resources, either past or present, as well as spatio-temporal distribution of food patches strongly influence the foraging behaviour of marine predators. These findings highlight the importance of integrating biological interactions in species distribution models which are used to predict possible distributional shifts of marine predators in the context of global changes. My thesis further developed previously available methods and presents a novel approach to investigate sources of variance in the stable isotopic composition of animals’ tissues.
- Full Text:
- Date Issued: 2020
Habitat use of important juvenile fish species in temperate Earnestine nursery areas with notes on feeding ecology and historical shifts to assist with conservation planning, South Africa
- Authors: Nel, Larize
- Date: 2018
- Subjects: Mariculture -- South Africa , Fishes -- Ecology -- South Africa Fishes -- Food -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/32904 , vital:32396
- Description: Estuaries are among the most productive ecosystems worldwide as they provide important refuge and feeding areas for the juveniles of many marine species, many of which have recreational importance. The use of these nursery areas by juvenile fishes in South Africa are in need of further investigation and many critical areas such as shallow water creeks and vegetated habitats remain understudied. By using mixed-methods, estuarine fish assemblages were assessed in five permanently open estuaries in the Eastern Cape Province of South Africa. A total of 81 428 comprising 24 families and 40 species of fishes were sampled by means of a 50 m seine net (12 mm mesh) along the length of these systems that comprised of six equidistant sites during the summer recruitment period (October - December) of 2014 and 2015. A higher catch per unit effort (CPUE) was recorded in 2014 (68 875) compared to the following year where a decline of approximately 82% was observed in the catch (12 553) for all estuaries except the Kromme Estuary. Catches were mainly dominated by the marine estuarine dependent sparid, Rhabdosargus holubi and the solely estuarine clupeid, Gilchristella aestuaria. Species compositions and catch abundance with regards to historical catches showed that the abundance of many marine estuarine dependent juveniles as well as important recreational species have declined within these systems and are mainly attributed to marine overfishing and the exploitation of undersized individuals in estuarine nurseries. Juvenile fishes that occur in these estuaries utilize a range of vegetated habitats ranging from salt marsh creeks, Zostera capensis beds, Spartina maritima and previously unexplored Phragmites australis areas. Sampling was achieved by using passive, double-winged, six-hooped fyke nets, 1 mm mesh size that was secured in placed on the nocturnal flood tide at each inundated vegetated and adjacent unvegetated habitat types. Higher catches were frequently recorded in vegetated areas for solely estuarine and marine estuarine dependent species and supports evidence of plasticity within these habitats. In general, the previously unstudied reed, P. australis showed the highest species richness and abundance of juvenile fishes overall, followed by, Z. capensis and the intertidal salt marsh species, S. maritima. These findings relate to many international trends on the value of vegetated areas as refugia for young fishes in estuaries. Fishes were also showing evidence of feeding and sheltering in these areas. By using conventional stomach contents and stable isotope methods (δ13C and δ15N signatures) on the abundant R. holubi in previously selected vegetation sites, it was clear that this species has a significant reliance on any of these habitats as their diets was largely comprised of a mixture of epiphytic algae and aquatic macrophytes. In addition, the diet of larger individuals (>80 mm) showed a greater component of invertebrates in previously unexplored habitats, which proves their omnivorous diet related to ontogenetic niche use. Knowledge of fine-scale habitat use by fishes is essential for conservation planning as exclusion zones can be optimised to limit anthropogenic influence on nursery use patterns in fishes. The availability of shallow water habitats (<60 cm) was assessed as an additional driver to explain the species diversity and richness of juvenile fishes within the lower reaches. These habitats are known as important nursery habitats providing numerous marine and estuarine spawned fishes with adequate refuge and food supply. This shallow water volume was measured by means of a two-man kayak using both the spring high and low tides in the lower reaches of these systems to assess juvenile assemblages. It was clear from the results that aquatic vegetation significantly adds to the volume of these areas and as a result, much greater fish density and species richness were observed. Generalized additive models showed that marine spawned species were particularly reliant on the availability of this shallow water along with submerged vegetation and additional environmental variables. The presence of structurally submerged vegetation typically characterized within shallow estuarine waters is commonly believed to reduce predation risk resulting in elevated densities of biota. Based on the current stock status and percentage of pristine breeding stock, five fish species classified as collapsed/overexploited was consistently found within these systems with an additional 14 species currently classified as exploited/vulnerable. Based on the current species richness and diversity, available habitat cover and knowledge regarding important recreational species, priority areas that require some form of legal protection in order to meet potential biodiversity targets, could be identified. It is a legal requirement in South Africa that all estuaries require management plans that should be based on good knowledge of priority habitats for fauna and flora. The identification of estuarine protected areas is seen as a mechanism for protecting a representative sample of the biodiversity accompanied by a complete range of environmental gradients and habitat types at a reasonable scale in order to maximize the protection of estuarine species.
- Full Text:
- Date Issued: 2018
- Authors: Nel, Larize
- Date: 2018
- Subjects: Mariculture -- South Africa , Fishes -- Ecology -- South Africa Fishes -- Food -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/32904 , vital:32396
- Description: Estuaries are among the most productive ecosystems worldwide as they provide important refuge and feeding areas for the juveniles of many marine species, many of which have recreational importance. The use of these nursery areas by juvenile fishes in South Africa are in need of further investigation and many critical areas such as shallow water creeks and vegetated habitats remain understudied. By using mixed-methods, estuarine fish assemblages were assessed in five permanently open estuaries in the Eastern Cape Province of South Africa. A total of 81 428 comprising 24 families and 40 species of fishes were sampled by means of a 50 m seine net (12 mm mesh) along the length of these systems that comprised of six equidistant sites during the summer recruitment period (October - December) of 2014 and 2015. A higher catch per unit effort (CPUE) was recorded in 2014 (68 875) compared to the following year where a decline of approximately 82% was observed in the catch (12 553) for all estuaries except the Kromme Estuary. Catches were mainly dominated by the marine estuarine dependent sparid, Rhabdosargus holubi and the solely estuarine clupeid, Gilchristella aestuaria. Species compositions and catch abundance with regards to historical catches showed that the abundance of many marine estuarine dependent juveniles as well as important recreational species have declined within these systems and are mainly attributed to marine overfishing and the exploitation of undersized individuals in estuarine nurseries. Juvenile fishes that occur in these estuaries utilize a range of vegetated habitats ranging from salt marsh creeks, Zostera capensis beds, Spartina maritima and previously unexplored Phragmites australis areas. Sampling was achieved by using passive, double-winged, six-hooped fyke nets, 1 mm mesh size that was secured in placed on the nocturnal flood tide at each inundated vegetated and adjacent unvegetated habitat types. Higher catches were frequently recorded in vegetated areas for solely estuarine and marine estuarine dependent species and supports evidence of plasticity within these habitats. In general, the previously unstudied reed, P. australis showed the highest species richness and abundance of juvenile fishes overall, followed by, Z. capensis and the intertidal salt marsh species, S. maritima. These findings relate to many international trends on the value of vegetated areas as refugia for young fishes in estuaries. Fishes were also showing evidence of feeding and sheltering in these areas. By using conventional stomach contents and stable isotope methods (δ13C and δ15N signatures) on the abundant R. holubi in previously selected vegetation sites, it was clear that this species has a significant reliance on any of these habitats as their diets was largely comprised of a mixture of epiphytic algae and aquatic macrophytes. In addition, the diet of larger individuals (>80 mm) showed a greater component of invertebrates in previously unexplored habitats, which proves their omnivorous diet related to ontogenetic niche use. Knowledge of fine-scale habitat use by fishes is essential for conservation planning as exclusion zones can be optimised to limit anthropogenic influence on nursery use patterns in fishes. The availability of shallow water habitats (<60 cm) was assessed as an additional driver to explain the species diversity and richness of juvenile fishes within the lower reaches. These habitats are known as important nursery habitats providing numerous marine and estuarine spawned fishes with adequate refuge and food supply. This shallow water volume was measured by means of a two-man kayak using both the spring high and low tides in the lower reaches of these systems to assess juvenile assemblages. It was clear from the results that aquatic vegetation significantly adds to the volume of these areas and as a result, much greater fish density and species richness were observed. Generalized additive models showed that marine spawned species were particularly reliant on the availability of this shallow water along with submerged vegetation and additional environmental variables. The presence of structurally submerged vegetation typically characterized within shallow estuarine waters is commonly believed to reduce predation risk resulting in elevated densities of biota. Based on the current stock status and percentage of pristine breeding stock, five fish species classified as collapsed/overexploited was consistently found within these systems with an additional 14 species currently classified as exploited/vulnerable. Based on the current species richness and diversity, available habitat cover and knowledge regarding important recreational species, priority areas that require some form of legal protection in order to meet potential biodiversity targets, could be identified. It is a legal requirement in South Africa that all estuaries require management plans that should be based on good knowledge of priority habitats for fauna and flora. The identification of estuarine protected areas is seen as a mechanism for protecting a representative sample of the biodiversity accompanied by a complete range of environmental gradients and habitat types at a reasonable scale in order to maximize the protection of estuarine species.
- Full Text:
- Date Issued: 2018
Immobilization of catalyst in a wall-coated micro-structured reactor for gas/liquid oxidation of p-cymene
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
In vivo toxicological evaluation of peptide conjugated gold nanoparticles for potential application in colorectal cancer diagnosis
- Authors: Adewale, Olusola Bolaji
- Date: 2018
- Subjects: Nanostructured materials -- Toxicology , Colon (Anatomy) -- Cancer Rectum -- Cancer
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/50133 , vital:42050
- Description: Colorectal cancer (CRC) is among the leading cause of cancer-related deaths in South Africa and worldwide. Efforts are being made at finding improved diagnostic tools, as early detection (before metastasis) is a major factor in CRC treatment. Colonoscopy is the most reliable detection method, but is a specialised and expensive procedure, which is invasive, not readily available and not patient-friendly. There is a risk of developing interval cancers, as colonoscopies are performed every 10 years after the age of 40. The development of non-invasive, cost efficient and readily available diagnostic tools to CRC, which can be performed at more regular intervals, using tumour-targeting molecular imaging agents, is of urgent attention. Gold nanoparticles (AuNPs) possess several physicochemical properties, including ease of synthesis, biocompatibility, and the ability to be conjugated by ligands or biomolecules such as polyethylene glycol (PEG) and peptides for improved stability, tissue targeting and selectivity. These factors potentiate the role in biomedical applications, including cancer theranostics. Conjugation of AuNPs with a targeting molecule (e.g. antibody or peptide) is directed against cancer cell receptors. The peptides, p.C, p.L, and p.14, bind to CRC cells in vitro. Conjugation of AuNPs with these peptides should be investigated for CRC diagnosis in vivo, as it is hypothesised to allow examinations at shorter intervals through imaging techniques. This could reduce the risk of interval cancers, but before developing this novel tool, in vivo toxicity evaluations are essential. This study was therefore aimed at investigating the short- and long-term toxicological effects of a single intravenous injection of peptides (p.C, p.L, and p.14) conjugated to AuNPs in a healthy rat model. Citrate-capped AuNPs were synthesised by the citrate-reduction method, and conjugated with each peptide (biotinylated) using a combination of PEG (99% PEG-OH and 1% PEG-biotin) as a stabilising agent and linker, via biotin-streptavidin interaction. Healthy male Wistar rats were intravenously injected with 14 nm citrate-AuNPs, PEG-, p.C-PEG, p.L-PEG, and p.14-PEG-AuNPs (100 μg/kg body weight), and the control rats were injected with phosphate buffered saline. The animals were monitored for behavioural, physiological, biochemical, haematological and histological changes, as well as inflammatory responses. Phase 1 rats were sacrificed 2 weeks post-injection to determine the immediate or acute toxicity of the AuNPs, while phase 2 animals were sacrificed 12 weeks post-injection, to investigate the delayed or persistence toxicity of the AuNPs. Results revealed no significant toxicities with the citrate, PEG-, p.C-PEG and p.14-PEG-AuNPs over 12 weeks post-exposure, as evidenced by biochemical assays such as serum marker enzymes, liver and kidney function markers, and cholestatic indicators; haematological parameters; oxidative stress markers; and histopathological examinations. P.L-PEG-AuNPs, however, caused significant toxicity (p<0.05) to rats, as evidenced by increased relative liver weight, increased malondialdehyde levels, and total white blood cell counts 2 weeks post-exposure when compared to the control group. This was, however, reversed during the 12 weeks post-exposure. Further, there were no evidence of inflammatory responses, using pro-inflammatory markers including phospho interleukin 18 (IL-18) and interferon-γ (IFN-γ), as indicated by immunohistochemical staining of the liver, spleen, kidney and colon of rats 2 weeks post-injection of AuNPs. Citrate, PEG-, p.C-PEG, and p.14-PEG-AuNPs did not induce immediate, acute or persistent toxicity, while p.L-PEG-AuNPs induced a transient acute toxicity. It can be concluded that 14 nm spherical citrate-AuNPs at 100 μg/kg body weight is a good candidate for biomedical applications, and as a suitable carrier for diagnostic and/or therapeutic molecules. Combination of 99% PEG-OH and 1% PEG-biotin is an appropriate option for stabilising AuNPs in biological environment, and conjugating secondary diagnostic or therapeutic biomolecules or agents to citrate-capped AuNPs. Peptide-conjugated AuNPs are suitable for the development into a diagnostic tool for CRC in vivo.
- Full Text:
- Date Issued: 2018
- Authors: Adewale, Olusola Bolaji
- Date: 2018
- Subjects: Nanostructured materials -- Toxicology , Colon (Anatomy) -- Cancer Rectum -- Cancer
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/50133 , vital:42050
- Description: Colorectal cancer (CRC) is among the leading cause of cancer-related deaths in South Africa and worldwide. Efforts are being made at finding improved diagnostic tools, as early detection (before metastasis) is a major factor in CRC treatment. Colonoscopy is the most reliable detection method, but is a specialised and expensive procedure, which is invasive, not readily available and not patient-friendly. There is a risk of developing interval cancers, as colonoscopies are performed every 10 years after the age of 40. The development of non-invasive, cost efficient and readily available diagnostic tools to CRC, which can be performed at more regular intervals, using tumour-targeting molecular imaging agents, is of urgent attention. Gold nanoparticles (AuNPs) possess several physicochemical properties, including ease of synthesis, biocompatibility, and the ability to be conjugated by ligands or biomolecules such as polyethylene glycol (PEG) and peptides for improved stability, tissue targeting and selectivity. These factors potentiate the role in biomedical applications, including cancer theranostics. Conjugation of AuNPs with a targeting molecule (e.g. antibody or peptide) is directed against cancer cell receptors. The peptides, p.C, p.L, and p.14, bind to CRC cells in vitro. Conjugation of AuNPs with these peptides should be investigated for CRC diagnosis in vivo, as it is hypothesised to allow examinations at shorter intervals through imaging techniques. This could reduce the risk of interval cancers, but before developing this novel tool, in vivo toxicity evaluations are essential. This study was therefore aimed at investigating the short- and long-term toxicological effects of a single intravenous injection of peptides (p.C, p.L, and p.14) conjugated to AuNPs in a healthy rat model. Citrate-capped AuNPs were synthesised by the citrate-reduction method, and conjugated with each peptide (biotinylated) using a combination of PEG (99% PEG-OH and 1% PEG-biotin) as a stabilising agent and linker, via biotin-streptavidin interaction. Healthy male Wistar rats were intravenously injected with 14 nm citrate-AuNPs, PEG-, p.C-PEG, p.L-PEG, and p.14-PEG-AuNPs (100 μg/kg body weight), and the control rats were injected with phosphate buffered saline. The animals were monitored for behavioural, physiological, biochemical, haematological and histological changes, as well as inflammatory responses. Phase 1 rats were sacrificed 2 weeks post-injection to determine the immediate or acute toxicity of the AuNPs, while phase 2 animals were sacrificed 12 weeks post-injection, to investigate the delayed or persistence toxicity of the AuNPs. Results revealed no significant toxicities with the citrate, PEG-, p.C-PEG and p.14-PEG-AuNPs over 12 weeks post-exposure, as evidenced by biochemical assays such as serum marker enzymes, liver and kidney function markers, and cholestatic indicators; haematological parameters; oxidative stress markers; and histopathological examinations. P.L-PEG-AuNPs, however, caused significant toxicity (p<0.05) to rats, as evidenced by increased relative liver weight, increased malondialdehyde levels, and total white blood cell counts 2 weeks post-exposure when compared to the control group. This was, however, reversed during the 12 weeks post-exposure. Further, there were no evidence of inflammatory responses, using pro-inflammatory markers including phospho interleukin 18 (IL-18) and interferon-γ (IFN-γ), as indicated by immunohistochemical staining of the liver, spleen, kidney and colon of rats 2 weeks post-injection of AuNPs. Citrate, PEG-, p.C-PEG, and p.14-PEG-AuNPs did not induce immediate, acute or persistent toxicity, while p.L-PEG-AuNPs induced a transient acute toxicity. It can be concluded that 14 nm spherical citrate-AuNPs at 100 μg/kg body weight is a good candidate for biomedical applications, and as a suitable carrier for diagnostic and/or therapeutic molecules. Combination of 99% PEG-OH and 1% PEG-biotin is an appropriate option for stabilising AuNPs in biological environment, and conjugating secondary diagnostic or therapeutic biomolecules or agents to citrate-capped AuNPs. Peptide-conjugated AuNPs are suitable for the development into a diagnostic tool for CRC in vivo.
- Full Text:
- Date Issued: 2018
Indigenous knowledge and climate change : insights from Muzarabani, Zimbabwe
- Authors: Chanza, Nelson
- Date: 2014
- Subjects: Indigenous peoples – Ecology – Zimbabwe -- Centenary District , Climatic changes -- Social aspects – Zimbabwe -- Centenary District , Climatic changes – Zimbabwe -- Centenary District
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10671 , http://hdl.handle.net/10948/d1020299
- Description: Discourse characterising climate change has largely revolved around aspects within the realm of impact identification, mitigation and adaptation. Apparently, a burgeoning appetite to examine the role of indigenous knowledge (IK) now confronts the fronts of climate science, policy and practice. The surge in attention to localbased knowledge is attributed to growing challenges posed by change and variability in the climate system. This study argues that indigenous-based knowledge is capable of filling knowledge gaps and validating current understanding about climate change particularly at local levels. Essentially, the paucity of knowledge about local climatic events can be circumvented by engaging indigenous ‘scientists’ whose many years of direct contact with the environment have equipped them with the indispensable knowledge, skills and experiences to understand the same. Primarily, the thesis’ objectives were threefold. One, it captured useful indicators of climate change and variability from the understanding of the indigenous people, which can also be used to enhance understanding of climate change impacts.Two, it drew from the knowledge, experiences, skills and practices of the locals in order to inform appropriate community level mitigation and adaptation interventions. And, three, it highlighted the fact that knowledge of the indigenous people can be used to direct research on climate change. The study area (Muzarabani in Zimbabwe) experiences recurrent droughts and floods and its villagers rely predominantly on climate-sensitive livelihoods. As such, it was selected to provide a reliable case on IK practices and experiences of the people witnessing climatic events. The study was framed within an epistemological and methodological configuration of emancipatory pedagogy that looks at the generators of climate knowledge as ‘scientists’ in their own right. A qualitative elicitation interviewing technique involving in-depth discussions with traditional leaders and elderly knowledgeable citizens was conducted. The participants were selected through chain referrals until the level of theoretical saturation. In addition, directed field observations, document analysis and key informant interviews with other respondents selected through theoretical sampling enhanced the robustness of data acquisition methods. Group-based participatory data analysis and reflexive pragmatism also enhanced rigour and quality of research findings intended to balance between the strictures of the scientific audience and the views of the knowledge generators. Three key themes were derived from IK-climate change linkages as: indigenous based indicators of climate change, indigenous-based mitigation and indigenous based adaptation. A range of indigenous-based indicators identified pointed to a progressively drier climate with shorter growing seasons that are also punctuated by mid-season dry spells. A trend towards increased desiccation of water bodies (rivers, ponds and vleis) was further observed. There is also an upsurge in the abundance and pestiferous nature of Macrotermes spp, Quelea quelea and Acanthoplus discoidalis, which are most likely related to climate change. Some of these indicators closely match with those used in mainstream climate science and they also serve to understand climate change impacts at a finer local level of analysis. Indigenous-based mitigation is mainly driven by the notion of sacredness where the locals regard forestry, certain trees and vleis as sacrosanct. Tampering with these is believed to upset the spirits who have powers to influence climate. Opportunities associated with IK deployment in climate mitigation are understood from the viewpoint of enhancing greenhouse gas (GHG) sinks and that of reducing vulnerability to extreme climatic events. Specifically, this can be achieved through enhancing GHG sequestration through forestry and land-use management initiatives; that is, reducing emissions from deforestation and forestry related degradation (REDD+) and Land Use and Land-Use Cover and Forestry (LULUCF). These two are the dominant schemes adopted by the Intergovernmental Panel on Climate Change (IPCC) to govern climate mitigation. Indigenous disaster risk management (DRM) strategies abound in drought, famine, flood and violent storms through various forms such as Zunde raMambo, nhimbe, rain-making ceremonies and community early warning systems (EWS).The locals in Muzarabani are not passive observers of the changing climate system. Increasing environmental risks necessitates them to devise countermeasures for responding to climatic stimuli with the intention of minimising harm and/or enhancing the benefits brought about by the same. Thus, a portfolio of IK-based adaptation strategies best described as an assortment of short-term coping practices and longterm adaptive strategies were identified. These range from exploitation of ecosystem services, agricultural based interventions, riverine farming, traditional phonological knowledge (TPK) to migration. Therefore, it was revealed that community-based adaptation (CBA) can adequately leverage on IK to improve adaptive capacity and build community resilience against climate change. Clearly, the complementary role of indigenous-based knowledge cannot be disputed, given the demonstrated range of applications from identifying several indicators of change and variability in the climate system, examination of climate change impacts, to identification and assessment of mitigation and adaptation options. The study advises that exogenous climate interventions need to be congruent with indigenous based strategies to avoid maladaptation. To the climate research community therefore, it should be realised that IK is useful both as leads and as baseline knowledge for future work on the impacts of climate change, and in the assessment of climate interventions. In this regard, the remaining challenge is to formulate a framework of constructive dialogue between indigenous scientists and conventional scientists so as to make sure that the mutual benefits of the two knowledge forms are adequately harnessed. Handled well, such collaborative effort would ensure enhanced climate change knowledge for successful mitigation and adaptation strategies. Handled poorly, there is a risk that the developmental needs of communities exposed to climatic events would not be addressed.
- Full Text:
- Date Issued: 2014
- Authors: Chanza, Nelson
- Date: 2014
- Subjects: Indigenous peoples – Ecology – Zimbabwe -- Centenary District , Climatic changes -- Social aspects – Zimbabwe -- Centenary District , Climatic changes – Zimbabwe -- Centenary District
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10671 , http://hdl.handle.net/10948/d1020299
- Description: Discourse characterising climate change has largely revolved around aspects within the realm of impact identification, mitigation and adaptation. Apparently, a burgeoning appetite to examine the role of indigenous knowledge (IK) now confronts the fronts of climate science, policy and practice. The surge in attention to localbased knowledge is attributed to growing challenges posed by change and variability in the climate system. This study argues that indigenous-based knowledge is capable of filling knowledge gaps and validating current understanding about climate change particularly at local levels. Essentially, the paucity of knowledge about local climatic events can be circumvented by engaging indigenous ‘scientists’ whose many years of direct contact with the environment have equipped them with the indispensable knowledge, skills and experiences to understand the same. Primarily, the thesis’ objectives were threefold. One, it captured useful indicators of climate change and variability from the understanding of the indigenous people, which can also be used to enhance understanding of climate change impacts.Two, it drew from the knowledge, experiences, skills and practices of the locals in order to inform appropriate community level mitigation and adaptation interventions. And, three, it highlighted the fact that knowledge of the indigenous people can be used to direct research on climate change. The study area (Muzarabani in Zimbabwe) experiences recurrent droughts and floods and its villagers rely predominantly on climate-sensitive livelihoods. As such, it was selected to provide a reliable case on IK practices and experiences of the people witnessing climatic events. The study was framed within an epistemological and methodological configuration of emancipatory pedagogy that looks at the generators of climate knowledge as ‘scientists’ in their own right. A qualitative elicitation interviewing technique involving in-depth discussions with traditional leaders and elderly knowledgeable citizens was conducted. The participants were selected through chain referrals until the level of theoretical saturation. In addition, directed field observations, document analysis and key informant interviews with other respondents selected through theoretical sampling enhanced the robustness of data acquisition methods. Group-based participatory data analysis and reflexive pragmatism also enhanced rigour and quality of research findings intended to balance between the strictures of the scientific audience and the views of the knowledge generators. Three key themes were derived from IK-climate change linkages as: indigenous based indicators of climate change, indigenous-based mitigation and indigenous based adaptation. A range of indigenous-based indicators identified pointed to a progressively drier climate with shorter growing seasons that are also punctuated by mid-season dry spells. A trend towards increased desiccation of water bodies (rivers, ponds and vleis) was further observed. There is also an upsurge in the abundance and pestiferous nature of Macrotermes spp, Quelea quelea and Acanthoplus discoidalis, which are most likely related to climate change. Some of these indicators closely match with those used in mainstream climate science and they also serve to understand climate change impacts at a finer local level of analysis. Indigenous-based mitigation is mainly driven by the notion of sacredness where the locals regard forestry, certain trees and vleis as sacrosanct. Tampering with these is believed to upset the spirits who have powers to influence climate. Opportunities associated with IK deployment in climate mitigation are understood from the viewpoint of enhancing greenhouse gas (GHG) sinks and that of reducing vulnerability to extreme climatic events. Specifically, this can be achieved through enhancing GHG sequestration through forestry and land-use management initiatives; that is, reducing emissions from deforestation and forestry related degradation (REDD+) and Land Use and Land-Use Cover and Forestry (LULUCF). These two are the dominant schemes adopted by the Intergovernmental Panel on Climate Change (IPCC) to govern climate mitigation. Indigenous disaster risk management (DRM) strategies abound in drought, famine, flood and violent storms through various forms such as Zunde raMambo, nhimbe, rain-making ceremonies and community early warning systems (EWS).The locals in Muzarabani are not passive observers of the changing climate system. Increasing environmental risks necessitates them to devise countermeasures for responding to climatic stimuli with the intention of minimising harm and/or enhancing the benefits brought about by the same. Thus, a portfolio of IK-based adaptation strategies best described as an assortment of short-term coping practices and longterm adaptive strategies were identified. These range from exploitation of ecosystem services, agricultural based interventions, riverine farming, traditional phonological knowledge (TPK) to migration. Therefore, it was revealed that community-based adaptation (CBA) can adequately leverage on IK to improve adaptive capacity and build community resilience against climate change. Clearly, the complementary role of indigenous-based knowledge cannot be disputed, given the demonstrated range of applications from identifying several indicators of change and variability in the climate system, examination of climate change impacts, to identification and assessment of mitigation and adaptation options. The study advises that exogenous climate interventions need to be congruent with indigenous based strategies to avoid maladaptation. To the climate research community therefore, it should be realised that IK is useful both as leads and as baseline knowledge for future work on the impacts of climate change, and in the assessment of climate interventions. In this regard, the remaining challenge is to formulate a framework of constructive dialogue between indigenous scientists and conventional scientists so as to make sure that the mutual benefits of the two knowledge forms are adequately harnessed. Handled well, such collaborative effort would ensure enhanced climate change knowledge for successful mitigation and adaptation strategies. Handled poorly, there is a risk that the developmental needs of communities exposed to climatic events would not be addressed.
- Full Text:
- Date Issued: 2014
Investigation of the potential separation of isomers and related compounds using host compound (2R,3R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol
- Authors: Pohl, Pieter Lourens
- Date: 2018
- Subjects: Chemistry, Organic , Clathrate compounds Thermal analysis
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23131 , vital:30432
- Description: In this study, we investigated the potential of a host compound, (2R,3R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT), for use in the separation of isomers and related compounds using host-guest chemistry. The title molecule, DMT, is composed of a butane chain bearing hydroxyl moieties on the terminal carbons and methoxy moieties on the two internal, chiral carbon atoms. In addition, there are two phenyl rings on each of the terminal carbons. The synthesis of DMT was carried out by subjecting the diester of naturally-occurring optically active tartaric acid to a Grignard reaction employing phenylmagnesium bromide. Subsequent methylation of the secondary hydroxy groups with dimethyl sulfate afforded DMT. The resulting host molecule was investigated for its inclusion abilities by crystallizing with a number of potential aromatic, aliphatic and alicyclic guests such as toluene, aniline, nitrobenzene, anisole, cyclohexane, ethyl acetate and ethanol. Host:guest ratios were determined by means of 1H-NMR spectroscopy. Of the hosts investigated, DMT favoured a host:guest ratio of 2:1 for all included guests investigated. It complexed with most non-polycyclic aromatic guests as well as cyclohexane, cyclohexene and cyclohexanone. It was not able to include short chain or branched alcohols such as methanol, ethanol or 2-propanol, or other hetero-aliphatic or hetero- cyclic compounds such as diethyl ether, acetonitrile, morpholine or dioxane. Competition inclusion experiments were performed in which DMT was crystallized from equimolar and non-equimolar binary, ternary and quaternary mixtures of appropriate guests. The mother liquor mixtures and resultant crystals were subjected to GC-MS analysis in order to determine whether DMT showed discriminatory behaviour towards the guests from a mixture. It was observed that DMT was able to differentiate between related compounds, for example, the host preferred to include N,N-dimethylaniline compared with N-methylaniline and aniline. The host also discriminated against isomers, for example, p-xylene was preferentially included over o-xylene and m-xylene, while o-cresol was included in preference to p-cresol and m-cresol. Single crystal X-ray analysis was used to investigate the host–guest interactions responsible for guest inclusion, as well as to discern reasons for the host’s selective behaviour. X-ray data for the inclusion complexes indicated that each complex was isostructural, crystallizing in the monoclinic C2 crystal system. A pair of 1,3- and 2,4- intramolecular hydrogen bonds, as well as intramolecular non-classic hydrogen bonds between adjacent ortho-aromatic hydrogens and hydroxy moieties was a significant stabilizing factor for the geometry of the host. Guests were held within discrete cavities in the crystal lattice, and experienced only π–π stacking, CH–π interactions and other short contacts. Thermal analyses were used to determine the relative thermal stabilities of the complexes, and these data compared to the selectivity preference of DMT, obtained from the competition experiments, in order to assess the reasons for any discriminatory behaviour. Finally, Hirshfeld surface analysis data was used to determine if the thermal stability of the complexes was related to the number and type of interactions between host and guest.
- Full Text:
- Date Issued: 2018
- Authors: Pohl, Pieter Lourens
- Date: 2018
- Subjects: Chemistry, Organic , Clathrate compounds Thermal analysis
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23131 , vital:30432
- Description: In this study, we investigated the potential of a host compound, (2R,3R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT), for use in the separation of isomers and related compounds using host-guest chemistry. The title molecule, DMT, is composed of a butane chain bearing hydroxyl moieties on the terminal carbons and methoxy moieties on the two internal, chiral carbon atoms. In addition, there are two phenyl rings on each of the terminal carbons. The synthesis of DMT was carried out by subjecting the diester of naturally-occurring optically active tartaric acid to a Grignard reaction employing phenylmagnesium bromide. Subsequent methylation of the secondary hydroxy groups with dimethyl sulfate afforded DMT. The resulting host molecule was investigated for its inclusion abilities by crystallizing with a number of potential aromatic, aliphatic and alicyclic guests such as toluene, aniline, nitrobenzene, anisole, cyclohexane, ethyl acetate and ethanol. Host:guest ratios were determined by means of 1H-NMR spectroscopy. Of the hosts investigated, DMT favoured a host:guest ratio of 2:1 for all included guests investigated. It complexed with most non-polycyclic aromatic guests as well as cyclohexane, cyclohexene and cyclohexanone. It was not able to include short chain or branched alcohols such as methanol, ethanol or 2-propanol, or other hetero-aliphatic or hetero- cyclic compounds such as diethyl ether, acetonitrile, morpholine or dioxane. Competition inclusion experiments were performed in which DMT was crystallized from equimolar and non-equimolar binary, ternary and quaternary mixtures of appropriate guests. The mother liquor mixtures and resultant crystals were subjected to GC-MS analysis in order to determine whether DMT showed discriminatory behaviour towards the guests from a mixture. It was observed that DMT was able to differentiate between related compounds, for example, the host preferred to include N,N-dimethylaniline compared with N-methylaniline and aniline. The host also discriminated against isomers, for example, p-xylene was preferentially included over o-xylene and m-xylene, while o-cresol was included in preference to p-cresol and m-cresol. Single crystal X-ray analysis was used to investigate the host–guest interactions responsible for guest inclusion, as well as to discern reasons for the host’s selective behaviour. X-ray data for the inclusion complexes indicated that each complex was isostructural, crystallizing in the monoclinic C2 crystal system. A pair of 1,3- and 2,4- intramolecular hydrogen bonds, as well as intramolecular non-classic hydrogen bonds between adjacent ortho-aromatic hydrogens and hydroxy moieties was a significant stabilizing factor for the geometry of the host. Guests were held within discrete cavities in the crystal lattice, and experienced only π–π stacking, CH–π interactions and other short contacts. Thermal analyses were used to determine the relative thermal stabilities of the complexes, and these data compared to the selectivity preference of DMT, obtained from the competition experiments, in order to assess the reasons for any discriminatory behaviour. Finally, Hirshfeld surface analysis data was used to determine if the thermal stability of the complexes was related to the number and type of interactions between host and guest.
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- Date Issued: 2018