Graduate Theses & Dissertations


Effects of hydrologic seasonality on dissolved organic matter composition, export, and biodegradability in two contrasting streams
Environmental and seasonal processes are important watershed drivers controlling the amount, composition, and fate of dissolved organic matter (DOM) in aquatic ecosystems. We used ten months of water samples and eight months of bioassay incubations from two contrasting catchments (agriculture and natural, forested) to assess the effects of seasonal variability on the composition, export, and biodegradability of DOM. As expected, the DOM composition and exports were more allochthonous-like and autochthonous-like in the forest and agriculture streams, respectively. However, we found no relationship between DOM composition and biodegradability in our study, suggesting that broad environmental factors play a large part in determining bioavailability of DOM. We found that both differences between the catchments and seasonal variability in hydrology and water temperature cause shifts in DOM composition that can affect exports and potentially affect its susceptibility to microbial activity. More research is needed to fully understand the impact of land use and temporal variability on bioavailability and delivery to downstream ecosystems. Author Keywords: Bioavailable dissolved organic carbon, Biodegradability, Dissolved organic matter, Export, Seasonality, Streams
Effects of road salt sodium on soil
While previous studies have focused on how road salt affects water quality and vegetation, limited research has characterized road salt distribution through soil and the resulting impacts. The potential for sodium (Na+) to be retained and impact soil physical and chemical properties is likely to vary depending on the soil’s parent material, and more specifically on the extent of base saturation on the cation exchange complex. This thesis contrasted Na+ retention, impacts, and mobility in roadside soils in two different parent materials within southern Ontario. Soils were sampled (pits and deep cores) during fall 2013 and spring 2014 from two sites along highways within base-poor, Precambrian Shield soil and base-rich soil, respectively. Batch experiments were subsequently performed to investigate the influence of parent material and the effect of co-applied Ca2+-enriched grit on the longevity of Na+ retention in soils. Less Na+ is adsorbed upon the co-application of Ca2+, suggesting grit has a protective effect on soil by increasing cation exchange competition. Positive correlations between Na+ and pH, and negative correlations between Na+ and soil organic matter, % clay and base cations within Shield soils suggest that they are more vulnerable to Na+ impacts than calcareous soils due to less cation exchange competition. However, Na+ is more readily released from calcareous roadside soils, suggesting there is greater potential for Na+ transfer to waterways in regions dominated by calcareous soils. Author Keywords: cation exchange, parent material, road salt, sodium retention, urban soil
Effects of wood ash addition on soil chemical properties and sugar maple (Acer saccharum, Marsh.) seedling growth in two northern hardwood forest sites in central Ontario
One possible solution to acidification and losses of base cations in central Ontario forest soils may be the application of wood ash. Wood ash is generally high in pH and contains large amounts of calcium (Ca) and other nutrients essential for ecosystem health, however it also contains trace metals. Understanding the chemistry of soils following ash application to forests is crucial for future policy recommendations and remediation efforts. In this study, soil and soil water chemistry was measured at two acidic forest sites in central Ontario. Sugar maple (Acer saccharum, Marsh.) seedling growth and chemistry, as well as understory vegetation composition, were also measured. At site one, plots (2 m x 2 m) were established with sugar maple, white pine (Pinus strobus L.) and yellow birch (Betula alleghaniensis Britt.) residential wood ash treatments and applied at rates of 0 and 6 Mg ha-1. The effects of residential wood ash on soil and understory vegetation were measured three- and 12-months following ash addition. At site two, plots (5 m x 5 m) were established with both fly and bottom industrial grade bark ash treatments of 0, 4 and 8 Mg ha-1 (n=4), and tension lysimeters were positioned in each plot at 30, 50, and 100 cm depths. The effects of industrial grade wood ash on soil, soil water and understory vegetation were measured four years following ash addition. Metal concentrations in the ashes were generally low but were higher in the fly ash and yellow birch ash types. At site one, significant increase in soil pH, and Ca and magnesium (Mg) concentrations were observed after three months, however changes varied by treatment. Some metal concentrations increased in the upper organic horizons, but metals were likely immobilized in the soil due to increases in soil pH, electrical conductivity (EC) and high organic matter content of the soil. After one year, changes to metal concentrations in soils could be seen in mineral horizons, and a few metals (aluminum (Al), zinc (Zn), copper (Cu), chromium (Cr), strontium (Sr)) increased in treatment plots. At site two, the effects of industrial-grade bark ashes on soil pH could still be seen after four years and soil water metal concentrations were not elevated relative to controls. Changes to understory vegetation composition following ash application were observed, but ash addition had no significant effect on sugar maple seedling growth (root:shoot ratio) and did not lead to significant increases in foliar metal concentrations. There were significant differences in root chemistry, suggesting metal translocation and uptake could be restricted. Mass balance estimates indicate that the organic horizon is a sink for all metals and simulated drought in this horizon led to a decrease in soil pH and increase in soil water metal concentration, but this occurred in all treatments including control. These results suggest that application of industrial and residential wood ash in moderate doses with trace metal concentrations below or near regulatory limits will increase soil pH and base cation concentrations, as well as increase seedling tissue nutrient concentrations in northern hardwood forest soils. However, depending on the parent material of the ash, increased metal availability can also occur. Author Keywords: Acer saccharum, calcium decline, forest soil amendment, Haliburton Forest and Wildlife Reserve, heavy metal, wood ash
Electrochemical Biosensors for Neurodegenerative Disease Biomarkers
The onset of neurodegenerative diseases such as Alzheimer’s disease (AD) and amyotrophic lateral sclerosis (ALS) are typically characterised by the aggregation of protein biomarkers into cytotoxic fibrils. Novel means of analysing these biomarkers are needed to expand the literature toward earlier diagnosis of these conditions. Electrochemical sensors could offer the sensitivity and selectivity needed for specialised analysis, including potential point-of-care applications. The AD biomarker Tau, and ALS biomarker TDP-43 proteins are explored here by using a label-free electrochemical sensors. Tau protein was covalently bound to gold electrode surface to study the in vitro mechanisms of aggregation for this protein. An immunosensor to TDP-43 was developed by covalently binding primary TDP-43 antibodies (Abs) on gold electrode surface. A novel direct ELISA sensor for TDP-43 with visual detection and electrochemical quantification was also developed. The results validated the experimental designs toward specialised and selective analysis of these biomarkers and their aggregation mechanisms. Author Keywords: ALS, Alzheimer's, Biosensors, Electrochemistry, Tau, TDP-43
Electrochemical Characterization of Giardia Intestinalis Cytochromes b5
Giardia intestinalis is a protozoan parasite that causes waterborne diarrheal disease in animals and humans. It is an unusual eukaryote as it lacks the capacity for heme biosynthesis; nonetheless it encodes heme proteins, including three cytochrome b5 isotypes (gCYTB5s) of similar size. Homology modelling of their structures predicts increased heme pocket polarity compared to mammalian isotypes, which would favour the oxidized state and lower their reduction potentials (E°’). This was confirmed by spectroelectrochemical experiments, which measured E°’ of -171 mV, -140 mV and -157 mV for gCYTB5-I, II, III respectively, compared to +7 mV for bovine microsomal cytochrome b5. To explore the influence of heme pocket polarity in more detail, five gCYTB5-I mutants in which polar residues were replaced by nonpolar residues at one of three positions were investigated. While these substitutions all increased the reduction potential, replacement of a conserved tyrosine residue at position-61 with phenylalanine had the most significant effect, raising E°’ by 106 mV. This tyrosine residue occurs in all gCYTB5s and is likely the greatest contributor to their low reduction potentials. Finally, complementary substitutions were made into a bovine microsomal cytochrome b5 triple mutant to lower its reduction potential. These not only lowered the E°’ by more than 140 mV but also weakened the interaction of heme with the protein. The lower reduction potentials of the gCYTB5s may indicate that these proteins have different roles from their more well-known mammalian counterparts. Author Keywords:
Electrochemical versus Chemical Oxidation of Bulky Phenols
Phenolic compounds are used in industry, such as agriculture and biotechnology, and inevitably end up in our environment. These compounds may serve as a phenolic precursor to produce raw materials for a wide range of applications. Chemical oxidation has been the common synthetic pathway to oxidize phenols and related compounds. However, traditional chemical approaches suffer from use of harsh chemicals, waste generation, and lack of reaction selectivity. Electrochemical synthesis has emerged as an alternative method to mitigate common challenges associated with organic synthesis. Herein, electrochemical oxidation of 2,6-diphenylphenol (DPP) and 2,2-dihydroxybiphenol (DHBP) was carried out and compared to traditional chemical oxidation. Contrasted with chemical oxidation, cyclic voltammetry of DPP resulted in a range of products based on the specific potential ranges used, whereas chemical oxidation of DHBP yield a dark-coloured polymeric product. The electrooxidation and chemical oxidation of DPP and DHBP resulted in a solution colour change, indicative of the formation of new, but different products monitored by UV-vis, and characterized by nuclear magnetic spectroscopy (NMR), X-ray single crystal diffraction, IR spectroscopy, transmission electron microscopy (TEM), and gas chromatography-mass spectrometry (GC-MS). The data indicate that the synthetic outcomes are dependent on the synthetic methodology employed, and that electrooxidation and chemical oxidation can form products unique to the pathway utilized. Author Keywords: chemoselectivity, electrochemistry, phenols, radical, synthesis
Emotional Competencies in Mothers and Children and their Relationship with Health Care Utilization, Somatization and Health Anxiety.
Young children learn their emotion regulation skills by modeling and internalizing their caregivers' emotional competencies. Inadequate or problematic emotional competencies in parents can result in insufficient development of these competencies in children, which can have severe consequences on multiple domains of their lives, including physical wellbeing. This study examined the relationship between emotional competencies, health care usage rates, somatization and health anxiety in the context of a family with young children. Participants were mothers of children 4-11 years old recruited in the community. The results revealed a relationship between mother’s emotional competencies and mother and child’s health care usage rates. Mother’s health care usage rates were also linked to mother’s health anxiety and child’s somatic symptoms. These findings add to our understanding of the relationship between emotional competencies of parents and children, and the effects it can have on both mother’s and child’s physical wellbeing. Implications and avenues for future research are discussed. Author Keywords: emotional competencies, health care usage, mother and child, somatization
Emotional Intelligence and Bullying Victimization
Previous research has found that bullying and victimization is related to poor socioemotional competencies. The present study examined the relationship between emotional intelligence (EI) and bullying and victimization in a large community-based sample of adolescents. Specifically, we explored the EI of bullies, victims, bully-victims, and those uninvolved. We also examined whether the relationship between EI and types of bullying and victimization activities were consistent across age and gender. We found that stress management and interpersonal skills are important EI dimensions to predicting both bullying and victimization. Moreover, intrapersonal skills were predictive of boys’ bullying behaviours and adaptability was the strongest EI dimension in bullies and victims. Age did not contribute much to the overall prediction of bullying and victimization in either gender. Results are discussed in terms of future implications regarding anti-bullying interventions. Author Keywords: Adolescents, age, Bullying, Emotional Intelligence, gender, social emotional competencies
Endocannabinoid Treatment for the Behavioural and Histopathological Alterations of Epilepsy
Epilepsy is associated with a variety of cognitive, emotional, and pain-related symptoms, such as impaired memory and learning, increased risk of anxiety and depression, and increased pain sensitivity. Unfortunately, these symptoms are generally untreated with typical pharmacological interventions, which tend to target seizure activity (i.e., ictogenesis) and not the subsequent histopathological and behavioural alterations resulting from epilepsy (i.e., epileptogenesis). Evidence has demonstrated that targeting the endocannabinoid system can alleviate seizure symptoms as well as cognitive, emotional, and pain-related impairments independent of epilepsy. However, research examining the use of endocannabinoid-based treatment for these behavioural symptoms when they are associated with epilepsy is sparse. In the following thesis, two animal models of epilepsy, several behavioural assessments, and immunohistochemical techniques are utilized to assess the effectiveness of endocannabinoid-based treatment for epilepsy’s interictal symptoms. The findings expand our knowledge and offer encouraging evidence for the usefulness of endocannabinoid-based treatment as an epileptogenesis-targeting pharmacological intervention. Author Keywords: animal models, endocannabinoid system, histopathological alterations, interictal symptoms, temporal lobe epilepsy, treatment
Enduring Attack
Numerous prey taxa employ defensive postures for protection against attack by predators. Defensive postures mitigate predation risk at various stages of the predator-prey sequence, including through crypsis, mimicry, thanatosis, aposematism, and deflection. In terrestrial salamanders, defensive postures may be aposematic, or deflect attacks away from vital body parts and towards the tail, however the extent to which these strategies act exclusively or synergistically remains poorly understood. Herein I demonstrate a novel approach to study the function of salamander defensive postures through experimental manipulation of predator response to antipredator behaviour in a natural field setting. I deployed 1600 clay salamander prey on Pelee Island, Ontario, manipulating prey size (small, large) and posture (resting, defensive) and documented attack rates across three predator types to further assess the effect of prey body size and predator type on antipredator efficacy. My research suggests that irrespective of prey body size, defensive posture does not function through aposematism, but rather acts to deflect predator attacks to the tail, which is commonly noxious and expendable in terrestrial salamanders. An intriguing possibility is that this behaviour facilitates taste-rejection by predators. Overall, my research should further contribute to our understanding of the importance and potential evolutionary significance of defensive posturing in Ambystoma salamanders, and more broadly, on the determinants of prey vulnerability to predation. I also briefly discuss the implications of my results to the conservation of Ambystoma populations on Pelee Island. Author Keywords: Anti-predator behaviour, Aposematism, Attack deflection, Predator avoidance, Small-mouthed salamander, Taste-rejection
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
Enhancing forensic entomology applications
The purpose of this thesis is to enhance forensic entomology applications through identifications and ecological research with samples collected in collaboration with the OPP and RCMP across Canada. For this, we focus on blow flies (Diptera: Calliphoridae) and present data collected from 2011-2013 from different terrestrial habitats to analyze morphology and species composition. Specifically, these data were used to: 1) enhance and simplify morphological identifications of two commonly caught forensically relevant species; Phormia regina and Protophormia terraenovae, using their frons-width to head-width ratio as an additional identifying feature where we found distinct measurements between species, and 2) to assess habitat specificity for urban and rural landscapes, and the scale of influence on species composition when comparing urban and rural habitats across all locations surveyed where we found an effect of urban habitat on blow fly species composition. These data help refine current forensic entomology applications by adding to the growing knowledge of distinguishing morphological features, and our understanding of habitat use by Canada’s blow fly species which may be used by other researchers or forensic practitioners. Author Keywords: Calliphoridae, Ecology, Forensic Entomology, Forensic Science, Morphology, Urban


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