Graduate Theses & Dissertations

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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
THE LIFE HISTORY STRATEGY, GROWTH, BODY CONDITION, AND DIET OF STOCKED AMERICAN EEL (Anguilla rostrata) IN THE UPPER ST. LAWRENCE RIVER AND LAKE ONTARIO
My study was primarily focused on the comparison of life history traits between stocked American eel and their naturally recruited conspecifics in Lake Ontario and the upper St. Lawrence River (USLR/LO). I found that stocked eels experienced faster annual growth than their naturally recruited conspecifics and were comprised of a greater proportion of males. These findings indicate that the life history patterns of American eel may be genetically predisposed. Additionally, my study served to characterize the diets of stocked American eel and examine possible associations between eel and prey size. The eels consumed a number of macroinvertebrate prey orders as well as fishes and macrocrustaceans, with the latter prey items being more prevalent in the diets of larger eel specimens. A disparity in eel growth and body condition was observed between two primary stocking locations and were likely attributable to differences in available forage and habitat. Lastly, growth, body condition, and stocked eel diet were compared between lentic and lotic habitats. Eels from lotic streams experienced slower annual growth and had reduced body condition, and their diets were comprised of smaller prey items. The results of this study suggest that the current stocking methods employed in the USLR/LO are not suitable to restore the natural recruitment of individuals that will exhibit desired life history traits. Author Keywords:
Analysis and reactions of aqueous selenide and other reduced inorganic selenium compounds under anoxic conditions
Selenide is cited as a geochemically important selenium (Se) species, but it is unknown whether selenide is a stable aqueous ion in natural waters. The feasibility of using anoxic anion exchange chromatography (AEC) coupled to dynamic reaction cell-inductively coupled plasma-mass spectrometry to separate aqueous selenide was investigated with the goal of quantifying this anion to determine its importance in reducing waters. It was possible to qualitatively identify selenide using AEC, but much of the aqueous selenide oxidises to Se0 faster than the separation procedure could be completed. AEC analyses of solutions containing polyselenides produced peaks for unidentified Se compounds, which have been assigned tentative structures Se2O22-, Se2O32-, and Se2O62- based on close matches in retention time to stable S compounds. The results of this work show that aqueous selenide can be qualitatively observed in synthetic solutions using AEC, but it is unknown whether these conditions are relevant to natural waters. Author Keywords: anoxic speciation, polyselenides, selenide, selenium geochemistry, selenium speciation, selenoselenate
Influence of Habitat on Woodland Caribou Site Fidelity
Site fidelity is the behaviour of individuals to return to the same location; for female woodland caribou it may reflect reproductive success and depend on habitat quality. I investigated the influence of landscape and disturbance conditions on fidelity among three populations in Manitoba and Ontario, Canada. Habitat classifications were based on Forest Resource Inventory (FRI) and Landsat TM landcover maps. A total of 261 sites were ground-truthed to determine mapping accuracy. An amalgamated map incorporating FRI and Landsat TM data was estimated from field measurements to have an overall accuracy of 69.0%. Site fidelity was expressed as the distance between consecutive-year locations of individuals and was investigated during five week-long periods representing calving, early and late post-calving, winter, and breeding. Site fidelity was strongest during the post-calving seasons and weakest during the winter. Habitat had little influence on site fidelity in all seasons, excepting winter, even under highly disturbed conditions, suggesting maintenance of fidelity may be a maladaptive trait. Individual variation proved a strong predictor and cursory mapping indicated that caribou may return to sites visited two or more years earlier. Conservation management and policy should recognize that site fidelity may represent an ecological trap. Author Keywords: calving, disturbance, habitat, movement, Rangifer tarandus caribou, site fidelity
Tabanidae and Culicidae in the Northern Boreal Region of Ontario
I studied the abundance, distribution and diversity of horse fly and deer fly species (Diptera: Tabanidae) and mosquito species (Diptera: Culicidae) in the boreal forest region of northern Ontario in 2011 and 2012. I collected 19 mosquito species, including one species new for Ontario, Aedes pullatus (Coquillett). I documented 11 northern and one southern range extension. I also collected a total of 30 species of horse and deer flies, including one new species of horse fly for Ontario, Hybomitra osburni (Hine). Results were inconsistent with a hypothesis of colonization of dipteran species from west to east. I examined the trapping biases of Malaise and sweep sampling for horse and deer flies and found that Malaise traps collected fewer individuals than sweep netting (850 versus 1318) but more species (28 versus 22). Consequently, I determined that surveys of diversity benefit from the use of multiple trapping methods. I also examined how blood-feeding (anautogeny) requirements affect the distribution patterns of Tabanidae. Ultimately, there are likely multiple factors that affect the expression of anautogeny in Tabanidae. Author Keywords: Autogeny, Culicidae, Diversity, Hudson Bay Lowlands, Northern Ontario, Tabanidae
TWO-DIMENSIONAL CONDUCTIVITY AT LaAlO3/SrTiO3 INTERFACES
Experiments have observed a two-dimensional electron gas at the interface of two insulating oxides: strontium titanate (SrTiO3) and lanthanum aluminate (LaAlO3). These interfaces exhibit metallic, superconducting, and magnetic behaviours, which are strongly affected by impurities. Motivated by experiments, we introduce a simple model in which impurities lie at the interface. We treat the LaAlO3 as an insulator and model the SrTiO3 film. By solving a set of self-consistent Hartree equations for the charge density, we obtain the band structure of the SrTiO3 film. We then study the relative contributions made by the occupied bands to the two-dimensional conductivity of the LaAlO3/SrTiO3 interface. We find that the fractional conductivity of each band depends on several parameters: the mass anisotropy, the filling, and the impurity potential. Author Keywords: conductivity, impurities, insulating oxides, Two-dimensional electron gases
ECTOPARASITIC INFLUENCES OF DIPTERA ON THE ACTIVITY AND BEHAVIOUR OF WOODLAND CARIBOU (RANGIFER TARANDUS) IN A MANAGED BOREAL FOREST LANDSCAPE IN NORTHERN ONTARIO
Caribou experience direct and indirect negative effects of harassment from biting flies, influencing behavior and activity on several spatial and temporal scales. I used systematic insect collection surveys during the summers of 2011 and 2012 to examine the spatial and temporal distributions of black flies (Simuliidae), mosquitoes (Culicidae), and deer flies and horse flies (Tabanidae) in a managed boreal forest in northern Ontario. Mosquitoes had a positive association with densely treed habitats, whereas black flies more often occurred in open areas, and tabanids had a strong presence in all habitat types. Habitats in proximity to large bodies of water had fewer biting flies than inland areas. Young stands supported higher abundances of tabanids despite vegetation community type. Next, I tested for seasonal effects of biting fly abundance on caribou activity by modelling the seasonal trend in abundance for each fly family for each year and compared this to an index of daily activity for 20 radio-collared female caribou in 2011 and 10 females in 2012. I modeled this index of caribou activity for each animal in each year and extracted the set of partial correlation coefficients from multiple regressions to test for effects of biting fly abundances on caribou activity. Caribou reduced their daily activity when tabanids were more numerous, and increased activity when mosquitoes were numerous. This divergent response may reflect a difference in the efficacy of moving to reduce harassment, owing to the stronger flight capabilities of tabanids. Author Keywords: Activity, Anthropogenic Disturbance, Behaviour, Insect harassment, Temporal distribution, Woodland Caribou
Home range use, habitat selection, and stress physiology of eastern whip-poor-wills (Antrostomus vociferus) at the northern edge of their range
The distribution of animals is rarely random and is affected by various environmental factors. We examined space-use patterns, habitat selection and stress responses of whip-poor-wills to mining exploration activity.To the best of my knowledge, fine scale patterns such as the habitat composition within known home ranges or territories of eastern whip-poor-wills have not been investigated. Using a population at the northern edge of the distribution in an area surrounding a mining exploration site, we tested whether variations in habitat and anthropogenic disturbances influence the stress physiology of individuals. We found no effect of increased mining activity on the stress physiology of birds but found a significant scale-dependent effect of habitat on their baseline and stress-induced corticosterone levels, and we suggest that these are the result of variations in habitat quality. The importance of other factors associated with those habitat differences (e.g., insect availability, predator abundance, and microhabitat features) warrants further research. Author Keywords: anthropogenic disturbances, Antrostomus vociferus, corticosterone, eastern whip-poor-will, habitat selection, radio-­telemetry
Productive Capacity of Semi-Alluvial Streams in Ontario
Changes in climate and land-use practices are leading to higher peak flows and increased transport capacity of channel substrate. Semi-alluvial streams underlain by bedrock or clay were examined to understand the potential impacts of alluvium loss on the biological community and overall productive capacity of semi-alluvial rivers. More specifically, this research investigates the productivity of gravels, bedrock, and consolidated clay, through the biomass and density of periphyton, coarse particulate organic matter, benthic invertebrates, and fish. The ecological approach undertaken demonstrates the relationships among each trophic level and linkages to productive capacity between different substrate types. Significant results were detected at the stream type level and substrate level. Bedrock-based streams were overall more productive in terms of CPOM, biomass and density of benthos in comparison to clay-based streams. Stream reaches with small to large areas of exposed bedrock or clay at the site level did not differ to areas with 100% gravel coverage in the comparison of any variable, including stream fishes. At the substrate level, gravels demonstrated the highest productive capacity in comparison to bedrock and clay substrates. CPOM biomass in gravels compared to bedrock and clay at a ratio of 30:14:1, respectively. Biomass of benthic invertebrates also demonstrated a higher productivity on gravels with a ratio of 59:19:1 in comparison to bedrock and clay, respectively. Positive relationships between CPOM and benthic invertebrate biomass were detected in both stream types. Relationships were also detected between fish biomass and benthic invertebrate biomass. Examination of benthic fishes also demonstrated positive relationships with benthic invertebrate biomass and density. Clay substrate on all accounts supported little biota. Results indicate alluvium loss in clay bed streams could reduce productive capacity. Understanding and integration of the potential impacts of alluvium loss would aid management and No Net Loss compensation plans to protect fisheries resources in semi-alluvial streams. Author Keywords:
An Investigation of Load Balancing in a Distributed Web Caching System
With the exponential growth of the Internet, performance is an issue as bandwidth is often limited. A scalable solution to reduce the amount of bandwidth required is Web caching. Web caching (especially at the proxy-level) has been shown to be quite successful at addressing this issue. However as the number and needs of the clients grow, it becomes infeasible and inefficient to have just a single Web cache. To address this concern, the Web caching system can be set up in a distributed manner, allowing multiple machines to work together to meet the needs of the clients. Furthermore, it is also possible that further efficiency could be achieved by balancing the workload across all the Web caches in the system. This thesis investigates the benefits of load balancing in a distributed Web caching environment in order to improve the response times and help reduce bandwidth. Author Keywords: adaptive load sharing, Distributed systems, Load Balancing, Simulation, Web Caching
Demography of a Breeding Population of Whimbrel (Numenius phaeopus) Near Churchill, Manitoba, Canada
I used a GIS raster layer of an area in the Churchill, Manitoba region to investigate the effect of breeding habitat on demography and density of Whimbrel from 2010 through 2013. Program MARK was used to quantify adult and daily nest survival. Apparent annual survival of 0.73 ± 0.06 SE (95% CI = 0.60-0.83) did not significantly differ between sexes or habitats and was lower than expected based on longevity records and estimates for other large-bodied shorebirds. Nest success, corrected for exposure days, was highly variable, ranging from a low of 3% (95% CI = 0-12%) in 2011 to a high of 71% (95% CI = 54-83%) in 2013. The highest rate of nest survival occurred in the spring with the warmest mean temperature. I developed a generalized linear model (GLM) with a negative-binomial distribution from random plots that were surveyed for abundance to extrapolate a local breeding population size of 410 ± 230 SE and density of 3.2 birds per square km ± 1.8 SE. The result of my study suggests that other aspects of habitat not captured by the land cover categories may be more important to population dynamics. Author Keywords: abundance, apparent survival, curlew, land cover map, nest-site fidelity, nest success
Spatial and Temporal Variation in Peatland Geochemistry in Sudbury, Ontario, Canada
The damage to Sudbury's landscape from over a century of smelter and logging activity has been severe and impacts well documented. However, despite their abundance in the region, wetlands have received little attention. Recent studies have identified that nutrient limitation is as much a problem as metal toxicity and highlighted not only the importance of wetlands but also the need for more detailed studies examining the role of wetlands in the recovery of lakes. The objective of this work is to characterize the spatial and temporal variability in the geochemistry of 18 wetlands (poor fens) surrounding Sudbury, Ontario. Peat and water chemistry in the wetlands exhibited large spatial and temporal variability. Copper and Ni concentrations in surface peat decreased with distance from the largest smelter in the area, but water chemistry was also strongly influenced by natural factors such as climate, groundwater and peat carbon content. Redox processes contribute greatly to temporal variation in pore-water chemistry: the August and October campaigns were characterized by higher SO4, lower pH and higher concentrations of metals such as Ni, Cu and Mn compared with the May campaign. Other factors contributing to the temporal variability in pore water chemistry include DOC production, senescence and water source. Despite the large variability, soil-solution partitioning can be explained by pH alone for some metals. Modeling is significantly improved with the addition of other variables representing dissolved organic matter quality and quantity, sulphate concentration and hydrology. Author Keywords: metal contamination, metal mobility, organic matter quality, peatland geochemistry

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