Graduate Theses & Dissertations

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Near-road assessment of traffic related air pollutants along a major highway in Southern Ontario
The spatial and temporal variation in atmospheric nitrogen dioxide (NO2), ammonia (NH3), and 17 elements (V, Cr, Fe, Ni, Cu, Zn, As, Cd, Pb, Mg, Al, Ca, Co, Se, Sb, Mn, and Na) were measured at 40 road side locations along a ~250 km traffic density gradient of 40,000–400,000 vehicles on the King’s Highway 401, in Ontario, Canada. Elemental concentrations were measured over a year, using moss bags as passive samplers, for four quarterly three-month exposure periods (October 2015 – October 2016). Gaseous NO2 and NH3 concentrations were measured using Willem’s badge passive diffusive samplers for twelve one-week exposure periods (one per month: October 2015–October 2016). Dry deposition of nitrogen was estimated using the inferential method. There were significant linear relationships between NO2 and NH3 and average annual daily traffic (AADT) volumes across the study area; higher concentrations corresponded to higher volume traffic sites. Average NO2 concentrations at sites ranged from 23.5 to 73 μg/m3, with an annual average of 43.7 μg/m3. Ammonia ranged from 2.56 to 13.55 μg/m3, with an annual average of 6.44 μg/m3. There were significant quarterly variations in NO2, with concentrations peaking during the winter months. In contrast, NH3 showed no significant quarterly variation, but a slight peak occurred during the summer. Gaseous NO2 and NH3 were highly positively correlated (r = 0.63), suggesting a common emission source from traffic. Concentrations in exposed moss were determined by subtracting the total concentration of each metal in the exposed sample from the background concentration present in the moss. Relative accumulation factors (RAF) and contamination factors were also calculated to determine the anthropogenic influence on tissue concentrations in exposed moss. All metals showed elevated levels versus background concentrations, with all metals except Ni and Co showing considerable enrichment. The highest levels of contamination were from V, Cr, Fe, Zn, Cd, Sb, Pb and Na. Principal component analysis indicated 5 clear clusters of related elements, with PC1 accounting for 36.2% and PC2 accounting for 25.6% of the variance. Average annual daily traffic was significantly related to Cr, Fe, Cu, Sb, Mn, Al, and Na. Road side monitoring shows consistently higher concentrations than active monitoring sites located further from the edge of the road, indicating a need for increased road side monitoring in Ontario, Canada. Author Keywords:
Assessing limnological characteristics of subarctic Québec thaw ponds and mercury methylation and methylmercury demethylation within their sediments
Thawing permafrost due to increasingly warm temperatures in northern subarctic regions is releasing mercury. The consequent formation of thaw ponds in the peatland palsa valley of the Sasapimakwananisikw (SAS) river in Whapmagoostui-Kuujjuarapik, Québec may provide a pool for MMHg formation and a potential risk to aquatic and human life, if these ponds facilitate MMHg export through hydrological connections to nearby waterways. Hg methylation and MMHg demethylation activities were examined in thaw pond sediments using a Hg tracer isotope incubation experiment. Analysis by coupling gas chromatography cold-vapor atomic fluorescence spectrophotometry (GC-CVAFS) with inductively coupled mass spectrometry (ICP-MS) techniques showed that MMHg was produced at a higher rate and within the first 2 h of incubation for both summer and winter seasons. For thaw ponds SAS1A, SAS1B and SAS2A, MMHg was formed at 0.0048 % h-1, 0.0012 % h-1, and 0.0008 % h-1, respectively during winter and at 0.0001 % h-1, 0.0016 % h-1, and 0.0010 % h-1, respectively during summer. Detection of MMHg losses were not as expected likely due to limitations of the combined tracer spike and overestimation of the in situ ambient mercury levels. Physical and chemical properties vary within ponds, among ponds and between winter and summer. SAS1B’s location nearby an organic carbon rich palsa may be ideal to study DOC – Hg interactions. Variability in pond characteristics including depth, surface area, age, pH, temperature, colour, oxygen concentration, total dissolved and suspended solids, conductivity, carbon, mercury, ammonium, calcium, magnesium, sulfate, total phosphorous, potassium, and sodium between seasons indicate the challenge of predicting future environmental impacts of climate change related thaw pond creation in the north. Author Keywords: demethylation, mercury, methylation, methylmercury, SAS, thaw ponds
Calcium Stress in Daphnia Pulicaria and Exposure to Predator-Derived Cues
In recent decades, declining calcium concentrations have been reported throughout lakes across the southern edge of the Canadian Shield. This raises concern as Daphnia populations have shown to be decreasing as they require calcium not only for survival but to mitigate predation risks. Therefore, the purpose of my thesis was to study the adaptability of Daphnia under calcium limitation and predation risk from Chaoborus. Firstly, I examined the effects of calcium limitation and Chaobours kairomones on daphniid life-history and population growth. I found that low calcium concentrations and Chaoborus kairomones affected Daphnia calcium content, life-history traits, and survival. Next, I focused on how calcium concentrations and Chaoborus abundance affected the calcium content and abundance of daphniids. During this study, I also examined the relationship between the abundance of Daphnia and a competitor Holopedium. I found that calcium concentrations and the abundance of Chaoborus affects daphniid abundance. Overall, results from this study show the importance of considering both predation risk and calcium declines to better determine daphniid losses. Author Keywords: anti-predator responses, Chaoborus, competition , Life-History traits, predator cues, Zooplankton
Study of Aerosols for use in Water Remediation of Pharmaceutical Pollutants
In this thesis, aerosolization was studied as a possible means of water remediation for several environmentally relevant pharmaceutical pollutants, known for their persistence in wastewater effluent and potable water sources. Seven different pharmaceutical compounds and a well-known plasticizer were all shown to decrease considerably in concentration in aerosol that was produced and subsequently collected within a short time span. Strong evidence is presented that an enhanced rate of partitioning into the gas phase at the air-water interface of water droplets exists for every compound tested relative to that occurring in bulk solution. UV photolysis in aerosols was also explored and shown for sulfamethoxazole to be at least an order of magnitude faster in aerosols then in bulk solution. The implications towards both the environmental fate, and removal of these compounds from water sources is discussed. Author Keywords: Aerosols, Air-water partitioning, Pharmaceuticals, Photolysis, Sulfamethoxazole
Temporal variation of dissolved organic matter and diffusive gradient in thin films-labile mercury in the Quesnel river, BC, and the Goose Creek tributary of Churchill river, MB
This study examined dissolved organic matter (DOM) and labile Mercury (from diffusive gradient in thin films (DGT)) in the Quesnel river, British and the Goose creek tributary of the Churchill river, Manitoba. DOM properties were measured with optical measurements of absorption coefficient (a254), spectral slopes (S275-295, SR) and fluorescence indices (HIX, BIX, FI). The DOC proxy measurements (a254) were almost 10 times higher at the Churchill site (Mean a254 116.77 cm-1) compared with the Quesnel river site (Mean a254 12.06 cm-1) during the study periods. While DGT labile Hg concentrations at the Quesnel site (2.17 to 98.97ppt) were almost 10 times more than the levels reported at the Churchill site (0.03 to 9.06 ppt). Fluorescence indices and the rise of labile Hg concentrations in spring indicated mostly terrestrial sources of DOM at both the sites. Spectral slopes and fluorescence indices substantiated that Churchill site had high molecular weight, complex and more humic DOM compared with Quesnel. DOM at both the sites was prone to temporal variation and affected by environmental conditions. Correlation between DGT labile-Hg and DOM parameters suggested that DGT collected Hg-organic complexes along with inorganic labile-Hg complexes. Author Keywords: Churchill, Diffusive gradient in thin films, Dissolved organic matter, Labile Hg, Mercury, Quesnel
Relationships between Dissolved Organic Matter and Vanadium Speciation in the Churchill River, MB and the Mackenzie River Basin, NWT using diffusive gradients in thin films (DGT)
This study examines the influence of dissolved organic matter (DOM) on dissolved vanadium (V) speciation in the Churchill River and Great Slave Lake using diffusive gradients in thin film (DGT). Vanadium is commonly found in natural environments such as rivers, lakes and oceans. It regulates normal cell growth, but in excessive amounts, it can have toxic effects on human and aquatic organisms. The use of in situ, time integrated DGT devices allows to better (1) monitor the most bioavailable fraction of V, the DGT-labile V, in Arctic Rivers and (2) assess the influence of DOM on dissolved V speciation. Higher DGT-labile V was found in the the central regions of the Mackenzie River (MR), with an average of 7.7 ± 2.3 nM, likely due to sediment leaching and permafrost thawing. The Churchill River and Great Slave Lake (GSL) showed lower DGT-labile V levels (2.2 ± 1.6 nM and 3.6 ± 2.7 nM, respectively), compared to central regions in MR. The CR DGT-labile V concentrations was positively correlated to protein-like DOM concentration and abundance (r = 0.3, p < 0.05). The data collected from this study will help in developing new strategies regarding environmental health and impact assessments of environmentally hazardous waste that consist of potentially high levels of toxic vanadium species. Developments in the use of DGT devices as a sampling method will also aid in future studies involved in analyzing environmental health and specifically dissolved V species in natural waters. Author Keywords: diffusive gradients in thin-films, dissolved organic matter, fluorescence, mass spectrometry, UV-Vis, vanadium
Changes in Forms of Uranium in Anoxic Lake Sediments and Porewaters Near an Abandoned Uranium Mine, Bancroft, Ontario
Soluble uranium (U) has been observed continuously in the porewaters of Bentley Lake, a lake with semi-permanent anoxic sediments, despite the fact that reduced U(IV) is known to be insoluble. To be able to predict the fate and mobility of U that has been deposited in lake sediments, it is very important to understand the factors that determine soluble uranium in anoxic environments. Understanding soluble U species is crucial for predicting its behavior in natural systems as well as for the development of U remediation schemes. To explore the factors affecting soluble U in natural environments, anoxic lake sediments and porewaters were tested using two analytic methods, ICP-MS and ESI-HR-MS. Reduced uranium (U(IV)) can be precipitated as U(IV)-NdF3. Using this method revealed that most of the uranium in porewater is not able to be co-precipitated with NdF3. In addition, UO2+ was found using ESI-HR-MS, showing uranyl ions exist in reduced porewater. However, the UO2+ might be attached to some organic groups rather than present as free ions. Seasonal variation and air exposure experiments on the mobility of U between sediments and porewater were observed to test for changes of the redox state of U as a function of sample collection and storage. The results of this study will contribute to better remediation strategies for U tailings and will help U mining operations in the future. Author Keywords:
Augmented Reality Sandbox (Aeolian Box)
The AeolianBox is an educational and presentation tool extended in this thesis to represent the atmospheric boundary layer (ABL) flow over a deformable surface in the sandbox. It is a hybrid hardware cum mathematical model which helps users to visually, interactively and spatially fathom the natural laws governing ABL airflow. The AeolianBox uses a Kinect V1 camera and a short focal length projector to capture the Digital Elevation Model (DEM) of the topography within the sandbox. The captured DEM is used to generate a Computational Fluid Dynamics (CFD) model and project the ABL flow back onto the surface topography within the sandbox. AeolianBox is designed to be used in a classroom setting. This requires a low time cost for the ABL flow simulation to keep the students engaged in the classroom. Thus, the process of DEM capture and CFD modelling were investigated to lower the time cost while maintaining key features of the ABL flow structure. A mesh-time sensitivity analysis was also conducted to investigate the tradeoff between the number of cells inside the mesh and time cost for both meshing process and CFD modelling. This allows the user to make an informed decision regarding the level of detail desired in the ABL flow structure by changing the number of cells in the mesh. There are infinite possible surface topographies which can be created by molding sand inside the sandbox. Therefore, in addition to keeping the time cost low while maintaining key features of the ABL flow structure, the meshing process and CFD modelling are required to be robust to variety of different surface topographies. To achieve these research objectives, in this thesis, parametrization is done for meshing process and CFD modelling. The accuracy of the CFD model for ABL flow used in the AeolianBox was qualitatively validated with airflow profiles captured in the Trent Environmental Wind Tunnel (TEWT) at Trent University using the Laser Doppler Anemometer (LDA). Three simple geometries namely a hemisphere, cube and a ridge were selected since they are well studied in academia. The CFD model was scaled to the dimensions of the grid where the airflow was captured in TEWT. The boundary conditions were also kept the same as the model used in the AeolianBox. The ABL flow is simulated by using software like OpenFoam and Paraview to build and visualize a CFD model. The AeolianBox is interactive and capable of detecting hands using the Kinect camera which allows a user to interact and change the topography of the sandbox in real time. The AeolianBox’s software built for this thesis uses only opensource tools and is accessible to anyone with an existing hardware model of its predecessors. Author Keywords: Augmented Reality, Computational Fluid Dynamics, Kinect Projector Calibration, OpenFoam, Paraview
Assessing habitat suitability and connectivity for an endangered salamander complex
Habitat loss and fragmentation have significantly contributed to amphibian population declines, globally. Evaluating the state of remaining habitat patches can prove to be beneficial in identifying areas to prioritize in conservation efforts. Pelee Island, Ontario is home to a complex of salamanders including small-mouthed salamanders (Ambystoma texanum), blue-spotted salamanders (A. laterale) and unisexual Ambystoma (small-mouthed salamander dependent population). These populations have declined from intense landscape changes since the late 1800s, particularly from the historical drainage of wetlands. In this thesis, I evaluated the suitability and connectivity of habitat patches occupied by these salamanders to assess the size of, and dispersal capabilities between, remaining habitat patches. I found that there was a low amount of suitable terrestrial habitat available for this complex of salamanders, and existing habitat patches were small and isolated. Forested areas and non-breeding wetlands were considered to be suitable habitat when adjacent to existing breeding locations, suggesting that these habitats should be a focus for conservation efforts. Notably, intervention may be necessary to maintain this amphibian complex as many assemblages are isolated from one another and potential corridors currently consist of primarily unsuitable habitat. Given that much of the salamander complex is reliant on one species for reproduction, the long-term viability of this population of Ambystoma salamanders may rely on the enhancement of suitable habitat near current breeding sites by conservation organizations and local stakeholders. Ultimately, the approach used in this thesis emphasizes the value of evaluating habitat within a fragmented landscape to focus conservation efforts on imperilled species. Author Keywords: amphibians, connectivity, habitat suitability, landscape fragmentation, landscape resistance, unisexual
Geochemistry and Toxicity of a Large Slag Pile and its Drainage Complex in Sudbury, Ontario
This study was designed to determine the geochemistry and potential toxicity of water draining a large slag pile in Sudbury, Ontario, which runs through a pond complex prior to entering Alice Lake. Slag leaching experiments confirmed slag is a source of sulphate, heavy metals (including Fe, Al, Ni, Co, Cu, Zn, Pb, Cr, Mn) and base cations (Ca, K, Mg, Na). Concentrations of most metals draining through slag in column experiments were similar to metal concentrations measured at the base of the slag pile, although base cations, S and pH were much higher, possibly because of water inputs interacting with the surrounding basic glaciolacustrine landscape. The increase in pH rapidly precipitates metals leading to high accumulation in the surface sediments. Away from the base of the pile, an increase in vegetation cover leads to an increase in DOC and nutrients and transport of metals with strong binding affinities (Cu). Total metal concentration in water and sediment exceed provincial water quality guidelines, particularly near the slag pile, however WHAM7 modeling indicated that the free metal ion concentration in water is very low. Nevertheless, toxicity experiments showed that water with greater concentrations of solutes collected close to the slag pile negatively impacts D. magna suggesting that water draining the slag pile can adversely impact biota in nearby drainage areas. Author Keywords: geochemistry, heavy metals, leaching, non-ferrous slag, precipitation, toxicity
Daphnia pulicaria responses to temperature and nutrients stress
Warming climates have had various consequences on terrestrial and aquatic food webs that are expected to persist. There is evidence suggesting that certain organisms are better equipped to handle changing climates compared to others. Therefore, the purpose of my thesis was to study the adaptability of Daphnia under temperature stress and nutrient limitation. First, to examine the effects of dietary phosphorus limitation and temperature on daphniid life-history and population growth, a series of experiments were conducted in the laboratory. In general, I found that Daphnia body growth rates and life-history traits to food carbon to phosphorus (C:P) ratios change with temperature. Next, I identified a protocol to limit the genomic DNA (gDNA) from ribonucleic acid (RNA) extractions. I found that using a modified phenol-chloroform extraction protocol was the most effective way to remove gDNA from extracted Daphnia RNA samples. Overall, results from this study show that temperature and food quality interactions are more complicated than previously thought. Furthermore, the RNA extraction protocol developed will be useful in future studies examining gene expression responses in Daphnia. Author Keywords: ecological stoichiometry, gene expression, life-history, nutrient limitation, RNA puritiy, temperature
Fractionation of Mercury Isotopes in an Aqueous Environment
Fractionation of mercury isotopes in an aqueous environment: Chemical Oxidation Dimitri Stathopoulos The study of fractionation patterns for the stable isotopes of mercury is a growing field. The potential for stable isotopes to trace mercury through the environment from pollution sources to sinks make the subject interesting to geochemists and useful to a wider audience. The purpose of this study is to measure the fractionation of mercury as it is oxidized in an aqueous medium. Samples in this study are prepared by chemically oxidizing different proportions of elemental mercury using four different oxidants. The oxidized portion is then separated from the elemental portion and an analysis of the isotope ratios for both portions is performed using a multicollector inductively coupled plasma mass spectrometer MC-ICP/MS. These isotope ratios are measured against the preoxidation isotope ratio to determine what if any change has occurred. From the findings of this work, it is now known chemical oxidation causes both mass dependent and mass independent fractionation. Mass dependent fractionation causes an enrichment of the heavier isotopes in the oxidized portion while the opposite is true for the elemental portion. Mass independent fractionation occurred only in the odd isotopes and causes a depletion of odd isotopes in the oxidized portion and enrichment in the elemental portion. These trends were found to be true for all oxidants tested as the pattern of fractionation does not change with varying oxidants. Author Keywords: Isotope, Mass Dependent, Mass Independent, Mercury, Oxidation

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