Graduate Theses & Dissertations

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Molecular Architectures for Improved Biomaterials Derived from Vegetable Oils – Application to Energy Storage and Lubricants
The replacement of petroleum with renewable feedstock for energy and materials has become a priority because of concerns over the environment and finite nature of petroleum. The structures of the available natural biomass feedstocks fall short in delivering key functionality required in materials such as lubricants and phase change energy storage materials (PCMs). The approach taken in this thesis was to combine select functional groups with vegetable oil derivatives to create novel PCMs and lubricantswhich deliver desired functionality. One series of diester PCMs were prepared with terephthalic acid and fatty alcohols to address known shortcomings of esters. The second class of PCMs are sulfones prepared from oxidation of fatty sulfides to improve thermal energy storage. Overall, the new PCMs presented narrow phase change temperature ranges, high transition temperature (between 67 to 110℃), high transition enthalpy (210 to 266J/g), minimal supercooling and congruent phase transitions unaffected by cooling rates. They also demonstrated higher thermal degradation stability with onset of degradation from 290 to 310℃. The series of lubricants studied consists of sulfide and sulfonyl functional groups attached to the unsaturation sites of oleyl oleate as pendant groups to improve the thermal and flow properties. The new lubricants present subzero crystallization temperatures, very low crystallization enthalpy and dynamic viscosity as high as 180mPas. Furthermore, they also presented high onset of degradation (up to 322℃) and oxidation (up to 298℃). The PCMs and lubricants of the present thesis demonstrate that select functional groups can be used with common structural elements of vegetable oil such as fatty acids, ester groups and unsaturation sites to make a variety of molecular structures capable of delivering desired properties Author Keywords: Crystal Structure, Lubricant, Phase Change Material, Renewable, Structure-Property Relationships, Vegetable Oil
Interseeded Cover Crops in Ontario Grain Corn Systems
Ontario grain corn is highly valuable, accounting for 60% of Canada’s total corn output. Grain producers are increasingly interested in including cover crops (CCs) in their cropping systems, but they have concerns regarding successful CC establishment and potential adverse competitive effects on corn yield and nutrient status. One option to improve the success of CC establishment is the interseeding in corn at the V4 -V6 stages. Interseeding improves the chances of good CC establishment, with potential benefits for soil health, weed control, and plant productivity. This thesis research was conducted to evaluate the short-term effectiveness of interseeding annual ryegrass (AR), red clover (RC), and their mixture (MIX) in grain corn at three locations in central and southwestern Ontario. Cover crop and corn yields, and their nitrogen (N) uptake, residual soil N, soil biological parameters, weed biomass, and residue decomposition rates were measured. CC biomass was highly variable (range: 0 - 1.6 Mg ha-1), influenced by climatic conditions, location, and CC type. Total carbon (C) and N contributions from CCs were similarly influenced by site-year and CC type. Regression analyses showed significant influence of corn biomass on CC establishment. Red clover had a significantly lower C/N ratio (11.8) than AR (18.2) and MIX (15.6). Strikingly, the amount of CC biomass accumulated in early spring reduced weeds by 50%. Moreover, CCs did not reduce corn grain or stover yield, nor N uptake, and soil mineral N in either fall or spring. Soil metabolic activity measured by BIOLOG Ecoplates was significantly greater in plots with AR than RC, MIX or NOCC. Soil biological parameters showed no CC effect. Results of residue decomposition i.e., C and N mineralization showed negligible CC residue effects on corn stover decomposition or N immobilization. The findings from this research suggest the need for assessing a more diverse range of CCs over longer durations to establish more specific CC niches for improving soil health in Ontario corn systems. Author Keywords: CLPP, cover crops, grain corn, nitrogen uptake, residue decomposition, soil health
Assessing effects and fate of environmental contaminants in invasive, native, and endangered macrophytes
Macrophytes play an important role in aquatic ecosystems, and thus are integral to ecological risk assessments of environmental contaminants. In this dissertation, I address gaps in the assessments of contaminant fate and effects in macrophytes, with focus on glyphosate herbicide use for invasive plant control. First, I evaluated the suitability of Typha as future standard test species to represent emergent macrophytes in risk assessments. I concluded that Typha is ecologically relevant, straight-forward to grow, and its sensitivity can be assessed with various morphological and physiological endpoints. Second, I assessed effects from glyphosate (Roundup WeatherMAX® formulation) spray drift exposure on emergent non-target macrophytes. I performed toxicity tests with five taxa, Phragmites australis, Typha × glauca, Typha latifolia, Ammannia robusta, and Sida hermaphrodita, which in Canada collectively represent invasive, native, and endangered species. I found significant differences in glyphosate sensitivity among genera, and all species’ growth was adversely affected at concentrations as low as 0.1% (0.54 g/L), much below the currently used rate (5%, 27 g/L). Third, I assessed the potential for glyphosate accumulation in and release from treated plant tissues. I found that P. australis and T. × glauca accumulate glyphosate following spray treatment, and that accumulated glyphosate can leach out of treated plant tissues upon their submergence in water. Finally, I assessed effects of released glyphosate on non-target macrophytes. I found that P. australis and T. × glauca leachate containing glyphosate residues can stimulate the germination and seedling growth of T. latifolia, but can exert an inhibiting effect on A. robusta, although leachate without glyphosate caused similar responses in both plants. Additionally, I found no negative effects in A. robusta when exposed to glyphosate residues in surface water, or when grown with rhizosphere contact to an invasive plant that was wicked (touched) with glyphosate. My results show that non-target macrophytes can be at risk from glyphosate spray for invasive plant control, but risks can be mitigated through informed ecosystem management activities, such as targeted wick-applications or removing plant litter. Integrating contaminant fate and effect assessments with emergent macrophytes into ecological risk assessments can support the protection of diverse macrophyte communities. Author Keywords: Ecosystem management, Ecotoxicology, Glyphosate, Herbicide, Invasive plant, Species at risk
Automated Separation and Preconcentration of Ultra-Trace Levels of Radionuclides in Complex Matrices by Online Ion Exchange Chromatography Coupled with Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Radionuclides occur in the environment both naturally and artificially. Along with weapons testing and nuclear reactor operations, activities such as mining, fuel fabrication and fuel reprocessing are also major contributors to nuclear waste in the environment. In terms of nuclear safety, the concentration of radionuclides in nuclear waste must be monitored and reported before storage and/or discharge. Similarly, radionuclide waste from mining activities also contains radionuclides that need to be monitored. In addition, a knowledge of ongoing radionuclide concentrations is often required under certain ‘special’ conditions, for example in the area surrounding nuclear and mining operations, or when nuclear and other accidents occur. Thus, there is a huge demand for new methods that are suitable for continuously monitoring and rapidly analyzing radionuclide levels, especially in emergency situations. In this study, new automated analytical methods were successfully developed to measure ultra trace levels of single or multiple radionuclides in various environmental samples with the goal of faster analysis times and less analyst involvement while achieving detection limits suitable for typical environmental concentrations. Author Keywords: automation, ICP-MS, ion exchange, radionuclide
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
Ecosystem Response to Above Canopy Nitrogen Addition in a Jack Pine (Pinus banksiana) Forest in the Athabasca Bituminous Sands Region of Northeastern Alberta, Canada
In this study we seek to better understand the potential effects of short-term (5-year) N fertilization on jack pine forest biogeochemistry, vascular plant community composition and to project a temporal endpoint of nitrogen leaching below the major rooting zone. Aqueous ammonium nitrate (NH4NO3) was applied above the forest canopy across five treatment plots (20 x 80 m) four times annually. The experimental deposition gradient followed those known for localized areas around the major open pit operations at 0, 5, 10, 15, 20 and 25 kg N ha-1 yr-1 over a five-year period (2011 – 2015). Nitrate recovery in throughfall was significantly higher than NH4+ (p < 0.05), indicating canopy NH4+ immobilization. There was a strong treatment effect (p < 0.05) of N on the epiphytic lichen thalli concentrations of Hypogymnia physodes and Evernia mesomorpha after five years. The canopy appeared to approach saturation at the highest deposition load (25 kg N ha-1 yr-1) during the fifth year of N additions as most N added above the canopy was accounted for in throughfall and stemflow. The non-vascular (lichen and moss) vegetation pool above the forest floor was the largest receptor of N as cryptogam foliar and thalli N concentrations showed a significant treatment effect (p < 0.05). Nitrogen in decomposing litter (25 kg N ha-1 yr-1) remained immobilized after five years, while treatments ≤ 20 kg N ha-1 yr-1 started to mobilize. Understory vascular plant cover expansion was muted when deposition was ≥ 10 kg N ha-1 yr-1. Finally, modeling suggests the forest may not leach N below the rooting zone until around 50 years after chronic addition begin (25 kg N ha-1 yr-1). The modeling results are consistent with empirical data from a high exposure (~20 - 25 kg N ha-1 yr-1) jack pine site approximately 12 km west of the experimental site that has not yet experienced N leaching. Author Keywords: Biogeochemistry, Canopy, Deposition, Jack Pine, Nitrogen, Understory
Using ultra high-resolution mass spectrometry to characterize the biosorbent Euglena gracilis and its application to dysprosium biosorption
Euglena gracilis is an enigmatic and adaptable organism that has great bioremediationpotential and is best known for its metabolic flexibility. The research done in this dissertation addresses (1) how growth conditions impact cellular composition, and (2) how chemometric approaches (such as statistical design of experiments and artificial neural networks) are viable alternatives to the conventional biosorption models for process optimization. Using high-resolution mass spectrometry for biosorbent characterization is a powerful way to assess the chemical characteristics of lyophilized and fractionated cells with high precision, especially to screen for compound classes that may have potentiality for rare earth element removal. Growth conditions impacted cellular composition and separated size fractions of cells yielded different molecular/chemical properties as described by compositional abundances, thus different biosorptive potential. Untargeted analysis demonstrated that exponential dark-grown cells with glucose supplementation were abundant in polyphenolic- and carbohydrate-like compounds, molecular species highly involved in rare earth element binding. Light grown cells had more heterogeneity and the highest molecular weighted fractions from light grown cells (fraction D) had the most abundances of polyphenolic- and protein-like structures. Chemometric modeling used identified the best and worst conditions for iii dysprosium sorption and showed that pH had the most significant influence on bioremoval. Bioremoval ranged from 37% at pH 8 to 91% at pH 3 at Dy concentration ranging from 1 to 100 μg L-1. The work presented in the PhD dissertation will aid in understanding the chemical characteristics of biosorbents by using a Van krevelen analysis of elemental ratios whether algal cells are grown in different environmental growth conditions, or when algal cell are size fractionated. This is especially applied for the screening for metal binding potentiality to Dysprosium. Chemometric methods provide an alternative method for the investigating factors for bioremoval, and applications for process optimization and for real-world applications. This dissertation will aid in understanding chemical characteristics when a biosorbent is grown in a given condition and which factors are important for rare earth element (REE) bioremoval. The significance of this work aims to look for alternate ways to screen biosorbents and using a more efficient experimental design for REE bioremoval. Author Keywords: bioremoval, biosorption, chemometrics, dysprosium, euglena, mass spectrometry
Composition and Transformation of Dissolved Organic Matter in Hudson Bay, Canada
The Hudson Bay region is a sensitive environment, where anthropogenic (e.g., dams, diversions, and/or reservoirs) impacts have increased in recent decades, potentially influencing the functioning of the ecosystem. Dissolved organic matter (DOM) entering Hudson Bay comes from both terrestrial (allochthonous) and aquatic (autochthonous) sources. The chemical composition of DOM is important, as it controls carbon biogeochemistry, nutrient cycling, and heat exchange. In rivers, estuaries, and oceans, photochemical processes and microbial degradation play a significant role in the chemical composition of DOM. Yet, our knowledge is scarce into how photochemical and microbial processes effect DOM composition specifically in Arctic aquatic systems making it difficult to predict how the carbon cycle will respond to a changing environment. This Ph.D. thesis addresses: (1) the composition of photochemically altered autochthonous and allochthonous DOM; (2) the photochemical transformations of DOM in surface waters of Hudson Bay; and (3) the microbial transformations of DOM in Hudson Bay surface waters. Using multiple analytical techniques, this work demonstrated that photochemical and microbial effects were different for light absorbing DOM compounds and ionisable DOM analyzed by Fourier transform-ion cyclotron-resonance-mass spectrometry (FT-ICR-MS). Based on FT-ICR-MS analysis, microbial processes had a greater impact on the molecular composition of allochthonous DOM originating from riverine sources and estuary whereas photochemical processes were the dominant mechanism for degradation of autochthonous DOM in Hudson Bay. Photochemical processes significantly decreased colored dissolved organic matter (CDOM) and fluorescence dissolved organic matter (FDOM) loss whereas microbial degradation was minimal in Hudson Bay river, estuary, and coastal waters. The results of this thesis highlight the importance of photochemical and microbial alteration of DOM in Arctic regions, two processes that are expected to be enhanced under climate change conditions. Author Keywords: Carbon cycle, Field flow fractionation, Microbial transformation, Optical properties, Photochemical degradation
collaborative ecotoxicological risk assessment of in-place pollutants in Owen Sound Bay, Lake Huron within the Saugeen Ojibway Nation Territory
Owen Sound Bay, which is located within the traditional territory of the Saugeen Ojibway Nation (SON), is contaminated as a result of historical industrial and shipping activity. Gross contamination of the sediments in the inner part of the Bay (i.e., Owen Sound Harbour) includes high concentrations of polycyclic aromatic hydrocarbons (PAHs) and other organic compounds, as well as metals that may pose a risk to the SON fishery for lake whitefish (Coregonus clupeaformis). However, evaluating the environmental risks posed by contaminated sediments is a challenge, as these risks are dependent upon several factors and require multiple lines of evidence. Including Indigenous communities in environmental risk assessment and the management of those risks is vital for sustaining ecosystem integrity, as well as respecting Treaty Rights. In this study, a risk assessment framework was developed that included several risk assessment tools used in Western science and also encompassed the concerns and values of the SON, including the application of SON-ecological knowledge. Methods for risk evaluation included gathering lines of evidence though community workshops, as well as field sampling in the Bay to determine the concentrations of PAHs and other organic contaminants in sediments and in the water column. Laboratory studies of toxicity to early life stages of lake whitefish and Japanese medaka (Oryzias latipes) and sediment disturbance simulations to evaluate biological responses in juvenile lake whitefish were also completed as lines of evidence. The results indicate that leaving the harbour “as is” without a thorough analysis of remediation options fails to address the concerns of the people within the SON communities. Overall, this research demonstrated a successful process for developing a collaborative risk assessment framework that recognizes the sovereignty of Indigenous peoples and promotes Nation-to-Nation decision making. Author Keywords: biomarkers, Coregonus clupeaformis, Indigenous knowledge, polycyclic aromatic hydrocarbons, risk assessment, source tracking
Population Dynamics of Eastern Coyotes in Southeastern Ontario
The ability of animal populations to compensate for harvest mortality provides the basis for sustainable harvesting. Coyote populations are resilient to exploitation, but the underlying mechanisms of compensation and how they inter-relate are not fully understood. Moreover, deficiencies in the quality and quantity of information about eastern coyotes preclude effective management. I combined field work, laboratory work, and genetic profiling to investigate the population dynamics of eastern coyotes in southeastern Ontario. Specifically, I conducted research on coyotes during 2010–2013 in Prince Edward County where coyote hunting and trapping seasons were open all year. First, I investigated their social status dynamics and space-use patterns. Transients exhibited extensive space-use relative to residents, potentially encountering vacant territories and/or breeding positions, and some transients became residents, potentially filling vacant territories and/or breeding positions. Accordingly, the study population demonstrated the potential to compensate for harvest mortality via source-sink dynamics and/or buffering reproductive capacity. Second, I investigated their survival and cause-specific mortality. Residents exhibited greater survival than transients, probably partly because of the benefits of holding a territory, and transients seemingly exhibited greater vulnerability to harvest than residents, probably partly because their movements exposed them to greater cumulative mortality risks over time. Accordingly, harvest mortality disproportionately impacted the non-reproductive segment of the study population and thus may have failed to substantially limit reproduction, and thus recruitment. Third, I investigated their reproduction and breeding histories. Females in the study population exhibited age-specific reproductive rates and litter sizes generally typical of those in exploited coyote populations. Accordingly, increased reproductive rates and increased litter sizes may have offset losses due to harvest mortality. There was at least some breeder turnover in the study population due to harvest mortality, but many breeders survived to reproduce for multiple years and those that died were quickly replaced. My findings have important management implications for eastern coyotes and contribute significantly to better understanding of their resilience to harvest. Indiscriminate killing of coyotes through liberal harvest is unlikely to be effective in reducing their abundance. Management strategies should consider non-lethal alternatives and/or targeted lethal control for dealing with problem coyotes. Author Keywords: Canis latrans var., eastern coyotes, population dynamics, Prince Edward County, southeastern Ontario
Icelandic Dust Entrainment, Emission & Deposition
Extremely active dust sources within selected areas of Iceland that are comprised of particles supplied from both glacio-fluvial outwash systems and volcanic eruptions (Bullard et al., 2016; Gassó et al., 2018). The supply of sediments, sparsity of vegetation, high frequency of surface winds, and lack of adequate gravel pavement to reduce sand drifting are believed to influence the duration, frequency, and magnitude of these dust events in Iceland. Apart from recent collaborative efforts to measure and model dust entrainment, emission and deposition (Prospero et al., 2012; Zwaaftink et al., 2017), several underlying physical mechanisms that are unique to cold, humid climates and the geology of Iceland are not well understood. This study specifically aims to assess and understand the physics of Icelandic dust entrainment and deposition with an emphasis on the influence of climate and the physical characteristics of the particles. A series of laboratory experiments of different configurations were carried out on several sediments collected from some of the most emissive sources in Iceland in order to understand these dust processes. The results from this study show that the increasing particle sphericity is associated with progressively smaller particle size; and an abundance of amorphous glass increases the surface area and roughness of the particles, which contributes to high porosity that alters the particle skeletal density. The particle features and climate are interlinked with the entrainment and deposition rates. For instance, coarse sediments emit higher PM concentrations than sediments containing more clay. The strong wind shear at the bed surface acts to disperse many of the tiny particle aggregates and coated liquid droplets contained within a splash structure created by the impact of a single water droplet. The deposition of suspended dust particulates is dependent on the particle characteristics and relative humidity. The retreat of glaciers and ice-cap masses in Iceland are expected to expose new dust particulate sources as the global mean temperature continues to rise (Cannone et al., 2008; Radic and Hock, 2011). Therefore, the influence of the particle characteristics and climate on the dust entrainment, emission and de- position must be accounted for in the parameterization of dust dispersion models related to suspended volcaniclastic particles. Author Keywords: High latitude cold climate environments, Icelandic dust particle characteristics, Laser Doppler anemometer, Rain droplet impact, Settling velocity, Wind tunnel
Novel Aliphatic Amides from Vegetable Oils as Bio-Based Phase Change Materials
Energy storage efficiency and sustainability require advanced technologies and novel materials. Recently, bio-based phase change materials (PCMs) have received significant attention for thermal energy storage (TES) uses. Vegetable oils are versatile renewable feedstocks that are well suited for the development of sustainable, functional PCMs. PCMs derived from vegetable oil, which compares favorably with paraffin waxes, the industry standard, are currently available. However, their melting points are typically below 80 °C preventing their wider integration in TES applications, particularly those requiring higher temperatures. The present work manipulated the structural building blocks of fatty acids to advantageously affect the intermolecular forces and increase the properties relevant to TES. The polar amide functional group was incorporated into fatty moieties to take advantage of the strong hydrogen bonds that it forms to increase intermolecular attractions and hence increase the phase change temperature and enthalpy as well as to improve thermal stability and thermal conductivity. A series of carefully designed lipid-derived monoamides and four series of lipid-derived diamides were synthesized via benign and simple amidation reactions. The purity of the amides and the intermolecular hydrogen bond strength were assessed using 1H NMR and FTIR. The properties relevant to TES such as thermal transition, crystal structure and polymorphism, thermal stability and thermal conductivity were measured using DSC, XRD, TGA and a thermal conductivity analyzer, respectively. The complex roles of the PCM’s constituting molecular building blocks in the phase behavior were elucidated and correlations between structure, processing conditions and macroscopic physicochemical properties, never before elucidated, were assembled in predictive relationships, drawing a unified picture of the rules that generally govern the phase behavior of lipid-derived PCMs. Practically, the prepared amides demonstrated desirable TES properties with substantial performance improvement over current bio-based PCMs. They presented increased phase change temperatures (79 - 159 °C), enthalpies of fusion (155 - 220 J/g) and thermal stability (234 - 353 °C). More importantly, the predictive structure-function relationships established in this work will allow the straightforward engineering of lipid-derived amide PCM architectures with judicious selection of molecular building blocks to extend the range of organic PCMs and deliver thermal properties desirable for TES applications. Author Keywords: LATENT HEAT THERMAL ENERGY STORAGE, LIPID-DERIVED AMIDES, PHASE CHANGE MATERIALS, RENEWABLE, SOLID LIQUID AMIDE PCMS, THERMAL PROPERTIES

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Graduate student theses produced at Trent University. You may also browse theses and dissertations by year, program, or author.

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