Graduate Theses & Dissertations

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Enhanced weathering and carbonation of kimberlite residues from South African diamond mines
Mafic and ultramafic mine wastes have the potential to sequester atmospheric carbon dioxide (CO2) through enhanced weathering and CO2 mineralization. In this study, kimberlite residues from South African diamond mines were investigated to understand how weathering of these wastes leads to the formation of secondary carbonate minerals, a stable sink for CO2. Residues from Venetia Diamond Mine were fine-grained with high surface areas, and contained major abundances of lizardite, diopside, and clinochlore providing a maximum CO2 sequestration capacity of 3–6% of the mines emissions. Experiments utilized flux chambers to measure CO2 drawdown within residues and unweathered kimberlite exhibited greater negative fluxes (-790 g CO2/m2/year) compared to residues previously exposed to process waters (-190 g CO2/m2/year). Long-term weathering of kimberlite residues was explored using automated wet-dry cycles (4/day) over one year. Increases in the δ13C and δ18O values of carbonate minerals and unchanged amount of inorganic carbon indicate CO2 cycling as opposed to a net increase in carbon. Kimberlite collected at Voorspoed Diamond Mine contained twice as much carbonate in yellow ground (weathered) compared to blue ground, demonstrating the ability of kimberlite to store CO2 through prolonged weathering. This research is contributing towards the utilization of kimberlite residues and waste rock for CO2 sequestration. Author Keywords: CO2 fluxes, CO2 mineralization, CO2 sequestration, Enhanced weathering, Kimberlite, Passive carbonation
Fungal pathogen emergence
The emergence of fungal hybrid pathogens threatens sustainable crop production worldwide. To investigate hybridization, the related smut fungi, Ustilago maydis and Sporisorium reilianum, were selected because they infect a common host (Zea mays), can hybridize, and tools are available for their analysis. Hybrid dikaryons exhibited filamentous growth on plates but reduced virulence and limited colonization in Z. mays. Select virulence genes in the hybrid had similar transcript levels on plates and altered levels during infection of Z. mays relative to each parental dikaryon. Virulence genes were constitutively expressed in the hybrid to determine if its pathogenic development could be influenced. Little impact was observed in hybrids with increased expression of effectors known to modify host response and metabolism. However, increased expression of transcriptional regulators of stage specific pathogenic development increased the hybrid’s capacity to induce symptoms. These results establish a base for investigating molecular aspects of fungal hybrid pathogen emergence. Author Keywords: effectors, hybrid pathogenesis assays, Sporisorium reilianum, transcription factors, Ustilago maydis, virulence factors
Extraction and Characterization of Hyaluronic Acid and Collagen from Eggshell Membrane Waste
Connecting academia to industry is one important way to advance towards meeting the United Nations (UN) Sustainability Goals (SDGs).1 Sustainability can be applied to all industrial sectors with the SDGs being implemented by 2030.2 This research contributes to the SDGs by investigating a way to remediate an industrial waste stream in the egg-breaking industry. If adopted, this would reduce the amount of eggshell membrane (ESM) waste placed in landfill where it does not decompose properly. The work described in this thesis specifically targets extraction of collagen and hyaluronic acid (HA), two components of the ESM that are of commercial value in the cosmetic, pharmaceutical, and biomedical industries3,4 . Deliverables from this research include economically viable extraction methods, developed based on green chemistry approaches, that can be transferred from lab bench to industrial scale. The extraction development process was guided by the 12 Principles of Green Chemistry5,6,7 and the 12 Principles of Green Engineering.8 HA was most successfully extracted using a sodium acetate solution on ground ESM. Filtrate was collected, exhaustively dialyzed and lyophilized. High molecular weight HA was recovered. Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and proton nuclear magnetic resonance (NMR) spectroscopy compared extracted material to reference HA identifying successful extraction. Collagen was extracted using acetic acid or pepsin enzyme digestion. Hydrophilic interaction liquid chromatography (HILIC) coupled with mass spectrometry (MS) compared amino acid composition of extracted materials to reference collagen material. FTIR-ATR spectra also supported successful extraction of collagen. This work identifies that HA and collagen can be conveniently extracted from ESM using an economical approach that can be implemented into egg-breaking facilities. This work highlights the benefits of connecting academia to industry to advance green chemical approaches while implementing sustainable practices into existing industry. Author Keywords: collagen, eggshell membrane waste, extraction, green chemistry, hyaluronic acid, sustainability
Adoption of a Finite Element Model of Material Deformation Relevant to Studying Corneal Biomechanics
The human cornea is required to exhibit specific material properties to maintain its regular shape under typical intraocular pressures which then allow for its correct optical functionality. In this thesis, the basis of continuum solid mechanics and the finite element method are introduced. We use finite element modelling to simulate the extension of an effective-1d, linear-elastic bar, a cornea-like body governed by Poisson’s equation, and the deformation of a loaded, linear-elastic, cube. Preliminary results for the deformation of a simulated, linear-elastic, cornea have also been achieved using the finite element approach. Author Keywords: continuum solid mechanics, corneal biomechanics, finite element method, intraocular pressure
Modelling Depressive Symptoms in Emerging Adulthood
Depression during the transition into adulthood is a growing mental health concern, with overwhelming evidence linking the developmental risk for depressive symptoms with maternal depression. In addition, there is a lack of research on the protective role of socioemotional competencies in this context. This study examines independent and joint effects of maternal depression and trait emotional intelligence (TEI) on the longitudinal trajectory of depressive symptoms during emerging adulthood. A series of latent growth models was applied to three biennial cycles of data from a nationally representative sample (N=933) from the Canadian National Longitudinal Survey of Children and Youth. We assessed the trajectory of self-reported depressive symptoms from age 20 to 24 years, as well as whether it was moderated by maternal depression at age 10 to 11 and TEI at age 20, separately by gender. The results indicated that mean levels of depression declined during the emerging adulthood in females, but remained relatively stable in males. Maternal depressive symptoms significantly positively predicted depressive symptoms across the entire emerging adulthood in females, but only at age 20-21 for males. In addition, likelihood of developing depressive symptoms was attenuated by higher global TEI in both females and males, and additionally by higher interpersonal skills in males. Our findings suggest that interventions for depressive symptoms in emerging adulthood should consider development of socioemotional competencies. Author Keywords: Depression, Depressive Symptoms, Emerging Adulthood, Intergenerational Risk, Longitudinal, Trait Emotional Intelligence
Academic Efficiency
Universities produce a significant and increasing share of basic research that is later commercialized by firms. We argue that the university's prominence as a producer of basic research is the result of a differential efficiency in research production that cannot be replicated by firms or individual agents - teaching. By using research accomplishments to signal knowledge and attract tuition-paying students, universities are uniquely positioned to undertake certain types of research projects. However, in a market for innovation without patent rights, a significant and increasing number of basic research projects, that are social welfare improving, cannot be initiated by firms or universities. The extension of patent rights to university-generated research elegantly redresses this issue and leaves us to ponder important questions about the future of our innovation-driven economies. Author Keywords: Innovation, Intellectual Property Rights, Research, Science Technology and Innovation Policy
UV-Curable hybrid sol-gel materials
This thesis describes the synthesis, application and evaluation of a UV crosslinked 3-methacryloxypropyltrimethoxysilane-derived coating formulation. This is a two-component sol-gel system with 3-methacryloxypropyltrimethoxysilane (MaPTMS) and tetraethoxysilane (TEOS). Herein we show that if we change the co-solvent required for solubilizing MaPTMS from the more common methanol and ethanol to isopropanol we change the rate of hydrolysis from days or weeks to minutes. With the assistance of 2D 29Si-NMR we demonstrate that the system undergoes extensive condensation in twenty minutes. Using standard UV irradiation, the material can be extensively UV crosslinked with 70% of the methacryloxy functionality being consumed in 5 minutes upon irradiation in the presence of a photo-initiator. When this material is used to coat low carbon steel and immersed in an accelerated corrosion solution (dilute Harrison’s solution); this material affords low carbon steel 25 hours of protection when crosslinked and 17 hours of protection when uncrosslinked. The material was then used to encapsulate polyaniline (PANI), an intrinsic conductive polymer used in the corrosion protection of metal substrates. PANI has been encapsulated previously in sol-gel material, but due to the pH dependence of the solubility of PANI, it can not be encapsulated in more commonly chemically crosslinked sol-gel. As our system is UV crosslinked rather than chemically crosslinked, we were able to successfully demonstrate the inclusion of PANI into our coating system. Finally, this thesis includes a thorough computational investigation into the structure and band gap of PANI. Through the analysis of the band gap it was shown that the structure of the polymer commonly displayed in literature is not the correct structure of the polymer. Our results suggest that when PANI is made electrochemically, the oligomer contains two quinoid units next to one another instead of the more usually represented regularly alternating benzoid and quinoid units. The results also suggest that when PANI is made using the oxidant ammonium persulfate, the polymer most likely contains a Michael adduct structure somewhere in the polymer chain which dominates PANI’s electronic properties. Author Keywords: 3-Methacryloxypropyltrimethoxysilane, Computational Chemistry , Corrosion , Polyaniline, Tetraethoxysilane
Surface temperature regulation during stress exposure
The influence of stress exposure on the body temperature of vertebrates has been known for nearly two-thousand years. While the proximate mechanisms supporting this phenomenon are well described, the ultimate mechanisms remain enigmatic. In this thesis, I propose a novel hypothesis which states that changes in body surface temperature (henceforth "surface temperature") following stress exposure occur to reduce energetic expenditure toward thermoregulation, thus freeing energy for use in the stress response (hereafter, the "Thermoprotective Hypothesis"). Using a paired experimental design, I first show that black-capped chickadees (Poecile atricapillus, Linnaeus, 1766) exposed to repeated stressors decrease their surface temperatures at low ambient temperatures, and increase their surface temperatures at high ambient temperatures relative to unstressed controls. These changes in surface temperature contribute to a relative reduction in heat loss in the cold, and a relative increase in heat dissipation in the warmth among stress-exposed individuals, thus reducing their energetic demands toward more costly thermoregulatory strategies. Next, I show that stress-induced changes in surface temperature are most pronounced in chickadees that experience naturally-occurring resource-restrictions, suggesting that this response occurs to balance allocation of energy among the stress response and thermoregulation (i.e. a true energetic trade-off ). Third, I show that the magnitudes of chronic, stress-induced changes in surface temperature are highly variable among, and highly consistent within, chickadees, therefore suggesting that this response could hold adaptive significance if such variation among individuals is heritable. Finally, using domestic pigeons (Columba livia domestica, Gmelin, 1789) as a model species, I show that stress-induced changes in surface temperature are highly pronounced at bare tissues with a critical role in thermoregulation for some avian species (the bill), when compared with responses at surrounding bare tissues (the eye region). Together, these findings strongly support the Thermoprotective Hypothesis and suggest that endotherms may trade energetic investment toward thermoregulation with that toward the stress response in resource-limiting environments. Author Keywords: heat transfer, infrared thermography, stress physiology, surface temperature, thermoregulation, trade-off
Drink my beer, smoke my weed, my good friends are all I need
Past research has predominately supported an association between insecure attachment and substance use. More recent research has found that while individuals with secure attachment may use substances, they do so with less risk. The current study attempted to replicate the finding regarding secure attachment and substance use and examined the motivational drives behind why students use substances. A total of 318 undergraduate students completed self-report questionnaires examining peer attachment, alcohol and marijuana use, as well as motivations for use. Results indicated that students who reported low frequency use of alcohol or marijuana did not have significantly higher security ratings compared to students who reported increased use. Additionally, although hypothesized, secure attachment ratings were not associated with social facilitation or enhancement motivations. However, fearful and dismissing attachment ratings were both significantly associated with coping motives as predicted, while preoccupied and fearful attachment ratings were significantly associated with conformity motives. Lastly, results from multiple regressions suggest that coping and enhancement motivations are significant predictors of alcohol use, while enhancement motivations are marginally significant in predicting marijuana use. Author Keywords: alcohol, attachment, marijuana, motivation
Characteristics of Models for Representation of Mathematical Structure in Typesetting Applications and the Cognition of Digitally Transcribing Mathematics
The digital typesetting of mathematics can present many challenges to users, especially those of novice to intermediate experience levels. Through a series of experiments, we show that two models used to represent mathematical structure in these typesetting applications, the 1-dimensional structure based model and the 2-dimensional freeform model, cause interference with users' working memory during the process of transcribing mathematical content. This is a notable finding as a connection between working memory and mathematical performance has been established in the literature. Furthermore, we find that elements of these models allow them to handle various types of mathematical notation with different degrees of success. Notably, the 2-dimensional freeform model allows users to insert and manipulate exponents with increased efficiency and reduced cognitive load and working memory interference while the 1-dimensional structure based model allows for handling of the fraction structure with greater efficiency and decreased cognitive load. Author Keywords: mathematical cognition, mathematical software, user experience, working memory
influence of tree species litterfall on soil chemistry and implications for modelling soil recovery from acidification
Decades of acidic deposition have depleted base cation pools in soil over large parts of eastern north America, including the Muskoka-Haliburton region of central Ontario. This region has also experienced a shift in forest species composition over the past 200 years, favouring sugar maple (Acer saccharum Marsh.) at the expense of species such as white pine (Pinus strobus L.) and eastern hemlock (Tsuga canadensis (L.) Carr.). This shift in species composition may have changed soil chemistry over time due to differences in nutrient and metal inputs in litterfall. An analysis of litterfall and soil chemistry was conducted for five tree species commonly found across central Ontario. Stands were established in the Haliburton Forest & Wild Life Reserve and were dominated by one of balsam fir (Abies balsamea (L.) Mill.), eastern hemlock, white pine, sugar maple, or yellow birch (Betula alleghaniensis Britt.). Analysis of mineral soil oxides suggested that these stands were established on similar parent material. Deciduous dominated stands (maple and birch) had greater litterfall mass compared with conifer stands (fir, hemlock, and pine), generally leading to greater macronutrient inputs to the soil. Elemental cycling through the organic horizons was more rapid in deciduous stands, with base cations having the shortest residence times. This suggests that a change from greater conifer dominance to mixed hardwood forests may lead to more rapid elemental cycling and alter the distribution of elements in soil. Forests in the region are typically mixed and the resulting differences in soil chemistry may influence model predictions of soil recovery from acidification. Laboratory leaching tests indicated that both stand type and the acidity of simulated rainwater inputs influenced soil solution chemistry, with deciduous stands generally having a greater buffering capacity than sites dominated by coniferous species. Changes in soil chemistry were examined for each stand type using the Very Simple Dynamic (VSD) biogeochemical model. Simulations showed that soil base saturation began to increase following lows reached around the year 2000, and similar patterns were observed for all stands. When sulphur (S) and nitrogen (N) deposition were held constant at present rates, soil base saturation recovery (toward pre-1900 levels) was marginal by 2100. With additional deposition reductions, further increases in base saturation were minor at all sites. In conjunction with additional deposition reductions, the elimination of future forest harvesting allowed for the greatest potential for recovery in all stands. Overall, these results suggest that changes in forest cover may influence soil chemistry over time, most notably in the organic soil horizons. However, forecasted recovery from acidification is expected to follow similar patterns among stands, since differences in soil chemistry were less significant in the mineral soil horizons which compose a greater proportion of the soil profile. Author Keywords: base cation decline, forest harvesting, litterfall, mineral weathering, soil acidification, VSD model
Short photoperiod lowers visceral adiposity and shifts the molecular clock in Peromyscus leucopus
The length of photoperiod can alter circadian rhythms and change fat depot mass whencombined with environmental temperatures below thermoneutral. To isolate photoperiod effects, we compared the effects of long and short photoperiod exposure at thermoneutrality in photoperiod sensitive, F1 generation adult male white-footed mice (P. leucopus). Mice were housed in long-day or short-day photoperiod conditions at thermoneutrality for 4 weeks. Short photoperiod decreased vWAT mass without changing body weight, scWAT or iBAT mass, or calorie consumption. Short photoperiod increased Adrβ3 and Lpl mRNA expression in vWAT with no change in Ucp1, Pgc1a or Hsl. vWAT Per1, Per2 and Nr1d1 mRNA expression were aligned to the onset of dark and food intake, while Bmal1 and Clock were misaligned. These findings suggest that short photoperiod per se can decrease visceral fat accumulation, without activating thermogenesis, reinforcing that environmental photoperiod should be considered when researching cause and prevention of obesity. Author Keywords: adiposity, circadian rhythm, clock genes, obesity, Peromyscus, photoperiod

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Format: 2024/04/24