Graduate Theses & Dissertations

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Novel Silica Sol-Gel Passive Sampler for Mercury Monitoring in Aqueous Systems
A novel passive sampler for mercury monitoring was prepared using organosilica sol-gel materials. It comprises a binding layer with thiol groups for mercury complexation and a porous diffusive layer through which mercury can diffuse and arrive at the binding layer. Our study demonstrated that this new sampler follows the principle of passive sampling. The mass of mercury accumulated in the binding layer depends linearly on the mercury concentration in solution, the sampling rate and the exposure time. A typical sol-gel sampler is characterized by a diffusive layer of 1.2 &mum, in which mercury ions diffuse with a coefficient of D = 0.09~10-6 cm2/s. The capacity for mercury uptake is approximately 0.64 &mug/cm2. Mercury diffusion and binding in the passive sampler are independent of the type of mercury-chloride complex. Its sampling rate increases with increasing water turbulence and decreases with increasing DOM amount. The field trial of sol-gel sampler in Miller Creek shows the concentration gained from the sol-gel passive sampler is slightly lower than that from the spot sampling. Author Keywords:
Ecological and morphological traits that affect the fitness and dispersal potential of Iberian pumpkinseed (Lepomis gibbosus)
The Pumpkinseed (Lepomis gibbosus) is a sunfish that is endemic to eastern portions of Canada and the United States. During the late 19th century, the species was introduced into Europe, and it is now present in over 28 countries. Previous attempts to determine the characteristics that can predict the spread of non-indigenous species have been largely unsuccessful, but new evidence suggests that phenotypic plasticity may help to explain the dispersal and range expansion of some organisms. Experimental comparisons on lower-order taxa have revealed that populations from areas outside of their native range are capable of exhibiting stronger levels of phenotypic plasticity than counterparts from their source of origin. Using Pumpkinseed, I conducted the first native/non- native comparison of phenotypic plasticity in a vertebrate. Progeny from adult Pumpkinseed collected in Ontario, Canada and the Iberian Peninsula (Spain) were reared under variable water velocities, habitat type and competitive pressures, three ecological factors that may affect the dispersal potential of fishes introduced into novel aquatic systems. Differences in phenotypic plasticity, assessed from a morphological perspective, were compared among populations using a traditional distance-based approach. All populations exhibited divergent morphological traits that appeared to be inherited over successive generations. In each experiment, all populations responded to environmental change by developing internal and external morphological forms that, in related taxa, enhance and facilitate foraging and navigation; however, non-native populations always exhibited an overall lower level of phenotypic plasticity. Pumpkinseed from non-native areas may have exhibited a reduction in phenotypic plasticity because of population-based differences. Nevertheless, all Pumpkinseed populations studied were capable of exhibiting phenotypic plasticity to novel environmental conditions, and develop morphological characteristics that may enhance fitness and dispersal in perturbed areas. Author Keywords: Invasive species, Morphology, Phenotypic plasticity, Pumpkinseed sunfish, Reaction norm
Scarring, sex assignment, and sex-specific sociality of Indo-Pacific humpback dolphins (Sousa chinensis) in the Pearl River Estuary and eastern Taiwan Strait
The Pearl River Estuary (PRE) and eastern Taiwan Strait (ETS) populations of Indo-Pacific humpback dolphins (Sousa chinensis) contain ~600 and 100 catalogued individuals, respectively. Population demography is important for conservation actions but few animals have been sexed by conventional methods. Longitudinal analysis of tooth-rake scars on dorsal fins showed scars disappear within 7 months; sexing adults by scarring is likely not impacted by juvenile scarring. Using dorsal fin photographs, sex assigned for 87% of catalogued PRE adults (n=300) and for 93% of ETS adults (n=60), using scars hypothesized from male-male competition, was in concordance with sex assigned by DNA, calf association, and ventral photographs. Scarring was higher in presumed males than females and in PRE females than ETS females. Female:male sex ratios were 3:2 (PRE) and 2:1 (ETS), though this likely results from biases in photo-identification methods. Social analysis with presumed sexes showed strong female-female associations in both populations but stronger female-male and male-male associations in PRE. These results support sex differentiation by scarring, which was a non-invasive approach, and sex assignment for many PRE and ETS individuals. Author Keywords: Indo-Pacific humpback dolphins, photo-identification, scarring, sex differentiation, sexes, social structure
Influence of nitrogen deposition on the vegetation community of Irish oak woodlands
In this study, the influence of N deposition on the vegetation community of semi-natural oak woodlands in Ireland was assessed through national and regional scale analysis of forest plot data. At both scales, Canonical Correspondence Analysis suggested that N deposition was a predictor of community composition, although site-specific soil characteristics were the strongest predictors of the species dataset. Threshold Indicator Taxon Analysis suggested that the vegetation community demonstrated the most change at 13.2 kg N ha-1 yr-1. While this change point falls within the current recommended critical load range for nutrient nitrogen for acidophilous oak dominated woodlands (10 to 15 kg N ha-1 yr-1), it is notable that 23% of species recorded had individual change points below this range, and could potentially be lost from this habitat if deposition increases. The results from this study suggest that, for acidophilous oak woodlands, habitat conservation policies should be unified with N emission reduction policies. Author Keywords: community composition, critical load, nitrogen depositioin, oak woodland, species richness, Taxon Indicator Threshold Analysis
Equilibria and distribution models of ionizing organic chemical contaminants in environmental systems
Ionizing organic chemicals are recognized as constituting a large fraction of the organic chemicals of commerce. Many governments internationally are engaged in the time-consuming and expensive task of chemical risk assessment for the protection of human and environmental health. There are standard models that are consistently used to supplement experimental and monitoring data in such assessments of non-ionizing organics by both government regulators and industry stakeholders. No such standard models exist for ionizing organics. Equilibrium distribution models, the foundational equations within multimedia environmental fate models for non-ionizing organics, were developed for the standard series of biphasic systems: air-water, particle-water, air-particle and organic-aqueous phases within living tissue. Multiple chemical species due to the ionization reaction were considered for each system. It was confirmed that, under select conditions, the properties of the neutral parent are sufficient to predict the overall distribution of the organic chemical. Complications due to biotransformation and paucity of identifiable equilibrium distribution data for ionizing organics limited the development of the model for living tissues. However, the equilibrium distributions of ionizing organics within this biotic system were shown to correlate with the abiotic sediment-water system. This suggests that the model developed for particle-water systems should be adaptable to the biotic system as model input and test data become available. Observational data for soil- and sediment- water systems, i.e., particle-water systems, allowed the development of a primarily non-empirical distribution equation for mono-protic acids; this model was almost entirely theoretically derived. The theoretical approach to model development allowed a quantitative assessment of the role of the neutral ion pair, resulting from the complexation of the organic anion with metal cations. To demonstrate the model's potential usefulness in governmental screening risk assessments, it was applied to a broad range of mono-protic organics including drugs and pesticides using standard property estimation software and generic inputs. The order-of-magnitude agreement between prediction and observation typical of the existing models of non-ionizing organics was generally achieved for the chemicals tested. The model was sensitive to the octanol-water partition coefficient of the most populous species. No calibration set was used in the development of any of the models presented. Author Keywords: bioconcentration, chemical equilibrium, environmental modelling, ionizing organic, sorption
Heavy Rydberg Photo-dissociation Cross-section Calculations and Experimental Progress Towards Cold Collisions in Lithium
This thesis is divided into two parts, each of which supports constructing and using a lithium magneto-optical trap for cold collision studies: Part I One outgoing channel of interest from cold collisions is the production of ion pairs. We describe an effective method for calculating bound-to-continuum cross-sections for charged binary systems by examining transitions to states above the binding energy that become bound when the system is placed within an infinite spherical well. This approach is verified for ionization of a hydrogen atom, and is then applied to the heavy Rydberg system Li+...I-. Part II A wavemeter previously built in the lab is redesigned for increased reliability and ease of use by replacing the optical hardware with a rocker system, which can be aligned in mere minutes rather than half a day as was previously the case. The new wavemeter has been tested through saturated absorption spectroscopy of lithium. Author Keywords: cross-section, dissociation, lithium, magneto-optical trap, Michelson, wavemeter
HABITAT SELECTION AND LIFE-HISTORY TRAITS OF BREEDING BIRDS IN THE BOREAL-TUNDRA ECOTONE, WITH SPECIAL ATTENTION TO THE AMERICAN ROBIN (TURDUS MIGRATORIUS)
I investigated biodiversity of birds and vegetation associations along the boreal-tundra ecotone in Ivvavik National Park, Yukon Territory, and breeding adaptations used by American Robins (Turdus migratorius) at high latitudes. Twenty bird species were detected over three years using point-count surveys. Densities of American Robin, Dark-eyed Juncos (Junco hyemalis), and Yellow-rumped Warbler (Dendroica coronata) had positive relationships with tree and shrub density, whereas density of White-crowned Sparrows (Zonotrichia leucophrys) was negatively related to tree density. American Robins at this latitude raised only one brood, but females laid slightly larger clutches, the young fledged earlier, and pairs experienced higher nest-success than American Robins at more southerly latitudes. American Robins selected nest sites with high vegetation volume, at both the nest-site, and the nest-patch. This study is important for the first description of the bird community at this high latitude location, and describing how a species at the northern limit of the boreal forest has adapted to living with short-breeding seasons. Author Keywords: American Robin, Ivvavik National Park, Life History, Nest-stie selection, Northern limit
Gaagnig Pane Chiyaayong: Forever, We Will Remain, Reflections and Memories
ABSTRACT Gaagnig Pane Chiyaayong: Forever, We Will Remain Reflections and Memories: `Resiliency' Concerning the Walpole Island Residential School Survivors Group Theresa Turmel From 1830 to 1996, Canada pursued a policy of removing Indigenous children from their families and educating them in residential schools. In coming to terms with the harsh and abusive treatment they endured, many survivors from residential schools have formed organizations to support each other and to make their experiences known. This project is a result of a participatory, community-based partnership with one such group in southwestern Ontario, the Walpole Island Residential School Survivors Group (WIRSSG), many of whom attended Shingwauk Indian Residential School. Like most of the survivors of the WIRSSG, I am Anishinaabe but did not attend residential school. The survivors invited me to deeply listen to their life experiences in order to learn about their resiliency. Guided by traditional Anishinaabe teachings and using an Anishinaabe methodology, I interviewed thirteen survivors and considered their life stories within the context of the traditional Anishinaabe life cycle. In their descriptions of resiliency, what became clear to me was that they were describing life force energy. This life force energy is innate and holistic, and can be found within each of us. It manifests within all of our relations: land, animals, plants, ancestors and other people. The life force energy cannot be extinguished but can be severely dampened as was evident in the attempt to assimilate residential school students. From their accounts, we learn that students found ways to nurture their life force energy through relationships and acts of resistance. As they have continued on their life path, they have reclaimed their spirit and today, they are telling their stories and keeping this history alive for the benefit of future generations. Key words: Anishinaabe; Anishinaabe Mino-bimaadiziwin; Residential Schools; Aboriginal Residential School survivors; Indian Residential Schools; Indian Residential School survivors; life force energy; resilience; resiliency; resiliency theory; Walpole Island Residential School Survivors Group; Shingwauk; Shingwauk Indian Residential School Author Keywords: life force energy, residential school survivors, resiliency
War and Peace
The relationship between siblings is unique in both its history and duration across the lifespan. Previous relationship researchers have examined siblings in childhood, but few have explored this distinctive relationship in adulthood. In this study, the adult sibling relationship was explored from an attachment perspective to determine the effect of an individual's attachment on conflict and collaboration with siblings. As expected, secure attachment predicted negative associations with conflict and positive associations with collaboration whereas insecure attachment (fearful, preoccupied, and dismissing) predicted opposite patterns. Results were compared to the abundance of literature on romantic relationships and findings from this study provided support for the theory that siblings function as attachment figures in adulthood. Author Keywords: Attachment, Collaboration, Conflict, Relationships, Romantic partners, Siblings
"Multimodal Contrast" from the Multivariate Analysis of Hyperspectral CARS Images
The typical contrast mechanism employed in multimodal CARS microscopy involves the use of other nonlinear imaging modalities such as two-photon excitation fluorescence (TPEF) microscopy and second harmonic generation (SHG) microscopy to produce a molecule-specific pseudocolor image. In this work, I explore the use of unsupervised multivariate statistical analysis tools such as Principal Component Analysis (PCA) and Vertex Component Analysis (VCA) to provide better contrast using the hyperspectral CARS data alone. Using simulated CARS images, I investigate the effects of the quadratic dependence of CARS signal on concentration on the pixel clustering and classification and I find that a normalization step is necessary to improve pixel color assignment. Using an atherosclerotic rabbit aorta test image, I show that the VCA algorithm provides pseudocolor contrast that is comparable to multimodal imaging, thus showing that much of the information gleaned from a multimodal approach can be sufficiently extracted from the CARS hyperspectral stack itself. Author Keywords: Coherent Anti-Stokes Raman Scattering Microscopy, Hyperspectral Imaging, Multimodal Imaging, Multivariate Analysis, Principal Component Analysis, Vertex Component Analysis
Identifying non-local individuals at the ancient Maya centre of Minanha, Belize through the use of strontium isotope analysis
Strontium isotope analysis has become an important tool in identifying non-local individuals at archaeological sites. For this study, tooth enamel samples were collected from 20 individuals from the ancient Maya centre of Minanha, Belize. These individuals date to periods spanning the formative occupation of the centre, as well as its fluorescence and protracted decline. The goal of this research was to investigate if non-local individuals played a role in Minanha's formation and fluorescence. The study utilised published strontium isotope maps from Belize and the Yucatán in order to establish local 87Sr/86Sr values. The values of the Minanha enamel samples (n = 20) fell predominantly outside of the expected strontium isotope range; this result seemed implausible and an alternative method was utilised to establish the local 87Sr/86Sr values. The outlier method identified 5/20 (25%) non-local individuals. All of the non-local individuals had 87Sr/86Sr values that coincided with published 87Sr/86Sr values reported from within 10 - 20 km of Minanha. However, some strontium isotope values also corresponded with 87Sr/86Sr values reported from regions >50 km away. The percentage of non-locals at Minanha is consistent with other Mesoamerican centres. This study emphasises the importance of collecting local baseline 87Sr/86Sr values from sites themselves, as 87Sr/86Sr values from neighbouring regions might not reflect local strontium isotope values. Author Keywords: Ancient Maya, bioarchaeology, migration, mobility, Vaca Plateau
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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Format: 2024/04/23