Graduate Theses & Dissertations

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Bio-based Polymers from Epoxidized Vegetable Oils Modified by Metathesis
The epoxides of oligomeric self-metathesized soybean oil (MSBO) and cross-metathesized palm oil (PMTAG) and canola oil (CMTAG) containing terminal double bonds were used to produce nonisocyanate polyurethanes (NIPUs) as well as anhydride, amine and thiol-cured epoxies. The synthesized NIPUs displayed metal adhesive properties for CMTAG and MSBO with MSBO being favoured probably due to its plasticizing nature as opposed to CMTAG. The relationship was reversed for the anhydride curing reaction where it was found that CMTAG, due to its lower degree of plasticizing content from the reduced dangling chains, produced higher tensile strengths than MSBO. Both MSBO and CMTAG led to fully cured amine and thiol products that were sticky gels, which prevented physical analyzses of their expected solidified products. PMTAG, due to its low number of reactive groups, was not suitable for the synthesis of these polymers. Author Keywords: Amine-cured epoxy, Anhydride-cured epoxy, Metathesis, Nonisocyanate Polyurethanes, Thiol-cured epoxy
An Evaluation of Wastewater Treatment by Ozonation for Reductions in Micropollutant Toxicity to Fish
Micropollutants are discharged into the aquatic environment with industrial and domestic wastewater and these compounds may cause toxic effects in aquatic organisms. In this study, the toxic effects to fish of micropollutants extracted from ozonated and nonozonated municipal wastewater effluent (MWWE) were measured in order to assess the effectiveness of ozonation in reducing toxicity. Juvenile rainbow trout (Oncorhynchus mykiss) injected with extracts prepared from ozonated MWWE had significantly reduced induction of plasma vitellogenin (VTG), significantly reduced hepatic total glutathione (tGSH) levels and an elevated oxidized-to-total glutathione (GSSG-to-tGSH) ratio. Exposure of Japanese medaka (Oryzias latipes) embryos to extracts prepared from both ozonated and non-ozonated MWWE resulted in elevated developmental toxicity in both treatment groups. These results indicate that wastewater treatment by ozonation reduces the estrogenicity of wastewater, but treatment may induce oxidative stress and embryonic developmental toxicity due to the production of toxic by-products. Author Keywords: Estrogenicity, Micropollutants, Oxidative stress, Ozonation, Toxic by-products, Wastewater
Doing it Right
The cyanidation technique is currently a viable technique for gold recovery that can replace the present amalgamation technique in Guyana. To implement this technique effectively, laboratory scale experiments and at scale runs were conducted to determine the best particle size of the ore, cyanide concentration, and leaching time. In addition, the profitability of cyanidation was compared to the amalgamation technique so as to describe the economic value of cyanidation. Results indicated that up to 94% of gold can be recovered from the ore using an ore particle size of 150 (105 µm), meshes, a cyanide concentration of 0.05% and leaching for 24 h. An economic comparison of this technique with the amalgamation technique indicated that although initial costs are high for the cyanidation technique, profits as high as 83% can be achieved after initializing this method whereas profits would be capped at approximately 25% for the amalgamation technique. Keywords: gold recovery, cyanidation, mercury amalgamation, activated car Author Keywords: activated carbon, cyanidation, gold recovery, mercury amalgamation
Regional Assessment of Soil Calcium Weathering Rates and the Factors that Influence Lake Calcium in the Muskoka River Catchment, Central Ontario
(MRC) in central Ontario was carried out to determine the range and spatial distribution of soil Ca weathering rates, and investigate the relationships between lake Ca and soil and catchment attributes. The MRC is acid-sensitive, and has a long history of impacts from industrial emission sources in Ontario and the United States. Small headwater catchments were sampled for soil and landscape attributes (e.g. elevation, slope, catchment area) at 84 sites. Soil Ca weathering rates, estimated with the PROFILE model, were low throughout the region (average: 188 eq/(ha·yr)) compared to global averages, and lower than Ca deposition (average: 292 eq/(ha·yr)). Multiple linear regression models of lake Ca (n= 306) were dominated by landscape variables such as elevation, which suggests that on a regional scale, landscape variables are better predictors of lake Ca than catchment soil variables. Author Keywords: Calcium, Lakes, Regional assessment, Regression, Soils, Weathering
Soil mineralizable nitrogen as an indicator of soil nitrogen supply for grain corn in southwestern Ontario
Soil mineralizable nitrogen (N) is the main component of soil N supply in humid temperate regions and should be considered in N fertilizer recommendations. The objectives of this study were to determine the potentially mineralizable N parameters, and improve N fertilizer recommendations by evaluating a suite of soil N tests in southwestern Ontario. The study was conducted over the 2013 and 2014 growing seasons using 19 field sites across southwestern Ontario. The average potentially mineralizable N (N0) and readily mineralizable N (Pool I) were 147 mg kg-1 and 42 mg kg-1, respectively. Pool I was the only soil N test that successfully predicted RY in 2013. The PPNT and water soluble N (WSN) concentration (0-30cm depth) at planting were the best predictors of fertilizer N requirement when combing data from 2013 and 2014. When soils were categorized based on soil texture, the relationships also improved. Our findings suggest that N fertilizer recommendations for grain corn can be improved, however, further field validations are required. Author Keywords: corn, nitrogen, nitrogen mineralization, soil nitrogen supply, soil N test, southwestern Ontario
Factors affecting road mortality of reptiles and amphibians on the Bruce Peninsula
Road mortality is one of the leading causes of global population declines in reptiles and amphibians. Stemming losses from reptile and amphibian road mortality is a conservation priority and mitigation is a key recovery measure. I developed a model of road mortalities relative to non-­‐mortalities, based on predictors varying across space (road surface type, traffic volume, speed limit, distance to wetland) and time (weather conditions, traffic volume). Herpetofauna road mortalities were recorded during daily bicycle and vehicle surveys to investigate the impact of roads on reptiles and amphibians within the Bruce Peninsula, Ontario in 2012 and 2013. A total of 2541 observations of herpetofauna on roads were recorded, 79% of which were dead. The major factor influencing turtle road mortality was proximity to the nearest wetland and dates early in the season (spring). For the Massasauga, high daily temperatures and low daily precipitation were associated with road mortality. The major factors driving colubrid snake mortality were also high daily temperature, low daily precipitation, as well as low speeds and paved roads. Frog and toad mortality was driven by proximity to wetland and late summer dates. These models will increase our understanding of factors affecting road losses of herpetofauna and serve as a basis for planned, experimental mitigation within the Bruce Peninsula. Author Keywords: amphibians, hotspot, mitigation, reptiles, road ecology, road mortality
Hormonal Algae
Based on an endogenous hormone study, three cytokinin type phytohormones; benzyladenine (BA), trans-zeatin (tZ) and methylthiol trans-zeatin (MeSZ), as well as abscisic acid (ABA) were exogenously added at three concentrations (10-7, 10-6 and 10-5 M) to cultures of Chlorella vulgaris in an attempt to alter growth rate, total lipid and fatty acid yields and fatty acid profile. Growth stimulation was highest at 10-6 M for BA, MeSZ and ABA and 10-5 M for tZ. All treatments caused changes in total lipid and fatty acid content, with BA causing an increase to lipid content. The most significant change in the fatty acid profile was observed with the addition of MeSZ at 10-7 and 10-6 M causing increases of 204% and 457% in linolenic acid respectively above the control. These results are novel and potentially highly impactful, as MeSZ has never been added exogenously to algae and may be used to stimulate overproduction of linolenic acid for pharmaceutical or industrial purposes. Author Keywords: Abscisic Acid, Chlorella vulgaris, Cytokinin, Fatty acid, Linolenic Acid, Methylthiol trans-Zeatin
Impact of Wetland Disturbance on Phosphorus Loadings to Lakes
Total phosphorus (TP) concentrations have declined in many lakes and streams across south- central Ontario, Canada over the past three decades and changes have been most pronounced in wetland-dominated catchments. In this study, long-term (1980-2007) patterns in TP concentrations in streams were assessed at four wetland-dominated catchments that drain into Dickie Lake (DE) in south-central Ontario. Two of the sub-catchments (DE5 and DE6) have particularly large wetland components (31-34 % of catchment area), and wetlands are characterised by numerous standing dead trees and many young live trees (18 – 27 year old). These two streams exhibited large peaks in TP and potassium (K) export in the early 1980s. In contrast, TP and K export from DE8 and DE10 (wetland cover 19 – 20 %) were relatively flat over the entire record (1980-2007), and field surveys indicated negligible standing dead biomass in these wetlands, and a relatively healthy, mixed-age tree community. Furthermore, K:TP ratios in the DE5 and DE6 streams were around 5 in the early 1980s; very similar to the K:P ratio found in biomass, and as stream TP levels fell through the 1980s, K:TP ratios in DE5 and DE6 stream water increased. The coincidence of high TP and K concentrations in the DE5 and DE6 streams as well as evidence of a disturbance event in their wetlands during the early 1980s suggest that the two are related. The diameter of standing dead trees and allometric equations were used to estimate the amount of TP that would have been held in readily decomposed tree tissues in the DE5 wetland. The amount of P that would have been held in the bark, twig, root and foliage compartments of just the standing dead trees at DE5 was approximately half of the amount of excess stream TP export that occurred in the 1980s. This work suggests that disturbance events that lead to wetland tree mortality may contribute to patterns in surface water TP observed in this region. Author Keywords: Chemistry, Disurbance, Nutrients, Tree Death, Water, Wetland
Testing for Interspecific Hybridization and a Latitudinal Cline Within the Clock Gene Per1 of the Deer Mouse (Peromyscus maniculatus) and the White-Footed Mouse (Peromyscus leucopus)
The recent northward expansion of the white-footed mouse (Peromyscus leucopus) in response to climatic changes provides a natural experiment to explore potential adaptive genetic variation within the clock gene Per1 in Peromyscus undergoing latitudinal shifts, as well as, the possibility of hybridization and introgression related to novel secondary contact with its sister species the deer mouse (Peromyscus maniculatus). Because clock genes influence the timing of behaviors critical for survival, variations in genotype may reflect an organism’s ability to persist in different environments. Hybridization followed by introgression may increase the adaptive potential of a species by quickly generating adaptive variation through novel genetic recombination or by the transfer of species-specific alleles that have evolved in response to certain environments. In chapter 2, I used microsatellite and mtDNA markers to test for hybridization and introgression between P. maniculatus and P. leucopus and found that interbreeding is occurring at a low frequency (<1%). In chapter 3, I tested for a latitudinal cline in a polyglycine repeat located within the Per1 gene of Peromyscus and discovered a putative cline in the Per1-142 and Per1-157 allele of P. leucopus and P. maniculatus, respectively. Chapter 4, further expands upon these findings, limitations, and the lack of evidence supporting introgression at the Per1 locus. Despite this lack of evidence, it is possible that novel hybridization has or could lead to adaptive introgression of other genes, allowing for the exchange of adaptive alleles or traits that could be advantageous for range expansion and adaption to future environmental changes. Author Keywords: Clock genes, Hybridization, Latitudinal gradient, Per1, Peromyscus, Range Expansion
Adaptive Genetic Markers Reveal the Biological Significance and Evolutionary History of Woodland Caribou (Rangifer tarandus caribou) Ecotypes
Migratory and sedentary ecotypes are phenotypic distinctions of woodland caribou. I explored whether I could distinguish between these ecotypes in Manitoba and Ontario using genetic signatures of adaptive differentiation. I anticipated that signatures of selection would indicate genetic structure and permit ecotype assignment of individuals. Cytochrome-b, a functional portion of the mitochondrial genome, was tested for evidence of adaptation using Tajima’s D and by comparing variations in protein physiology. Woodland caribou ecotypes were compared for evidence of contemporary adaptive differentiation in relation to mitochondrial lineages. Trinucleotide repeats were also tested for differential selection between ecotypes and used to assign individuals to genetic clusters. Evidence of adaptive variation in the mitochondrial genome suggests woodland caribou ecotypes of Manitoba and Ontario corresponded with an abundance of functional variation. Woodland caribou ecotypes coincide with genetic clusters, and there is evidence of adaptive differentiation between migratory caribou and certain sedentary populations. Previous studies have not described adaptive variation in caribou using the methods applied in this study. Adaptive differences between caribou ecotypes suggest selection may contribute to the persistence of ecotypes and provides new genetic tools for population assessment. Author Keywords: Adaptation, Cytochrome-B, Ecotype, RANGIFER TARANDUS CARIBOU, Selection, TRINUCLEOTIDE REPEAT
An Assessment of Spatial Trends in the Accumulation of Oil Sands Related Metals in the Clearwater River Valley and Temporal Trends in Six Northern Saskatchewan Lakes
The objective of this thesis was to assess current spatial trends and historic trends in the accumulation of trace metals related to the Athabasca Oil Sands Region (AOSR). The AOSR hosts some of the largest industrial developments in Canada, yet relatively little is known about the transport and fate of trace metal emissions from the region – particularly in the relatively remote areas to the east of the AOSR. Lichens are widely used as biomonitors and are employed in this thesis to assess the range of metals deposition within the Clearwater River and Athabasca River Valleys. Lake sediment cores can retain a historical record of the long-range transport and deposition of metals but can also respond to large regional metal emissions sources. This thesis used lake sediment cores to assess temporal trends in metals accumulation in six road accessible lakes in NW Saskatchewan that are likely to be used by local residents. Results show that metal concentrations (V, Co, Cu, Ni, Pb, Zn, Zr and Cd ) in lichen decline exponentially with distance from the AOSR and approach background levels within a few kilometers . Results from lake sediment cores show that there was no evidence that metal concentrations had increased due to industrial activities in the AOSR. Author Keywords: Air Emissions, Lakes, Lichens, Oil Sands, Saskatchewan, Trace Metals
Impact of Invasive Earthworms on Soil Respiration and Soil Carbon within Temperate Hardwood Forests
Improving current understanding of the factors that control soil carbon (C) dynamics in forest ecosystems remains an important topic of research as it plays an integral role in the fertility of forest soils and the global carbon cycle. Invasive earthworms have the potential to alter soil C dynamics, though mechanisms and effects remain poorly understood. To investigate potential effects of invasive earthworms on forest C the forest floor, mineral soil, fine root biomass, litterfall and litter decomposition rates and total soil respiration (TSR) over a full year were measured at two invaded and one uninvaded deciduous forest sites in southern Ontario. The uninvaded site was approximately 300m from one of the invaded sites and a distinct invasion front between the sites was present. Along the invasion front, the biomass of the forest floor was negatively correlated with earthworm abundance and biomass. There was no significant difference between litterfall, litter decomposition and TSR between the invaded and uninvaded sites, but fine root biomass was approximately 30% lower at the invaded site. There was no significant difference in soil C pools between the invaded and uninvaded sites. Despite profound impacts on forest floor soil C pools, earthworm invasion does not significantly increase TSR, most likely because increased heterotrophic respiration associated with earthworms is largely offset by a decrease in autotrophic respiration caused by lower fine root biomass. Author Keywords: Biological Invasions, Carbon, Earthworms, Forest Ecosystems, Forest Floor, Soil Respiration

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