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In electron-doped ferroelectrics, the free electrons can become concentrated along the domain walls which act like a conducting surface. We consider the impact of free electrons occupying the t2g orbitals on the domain walls of an electron-doped perovskite ferroelectric. We build an analytical model based on Landau-Ginzburg-Devonshire theory, and a trio of tight-binding Hamiltonians for free electrons. We self-consistently solve for the polarization, potential, and electron density using a finite-difference approximation. We find that the ferroelectric is effectively charge neutral. The free electrons are attracted to the positively-charged domain wall, leaving it with a small residual charge. As the electron density increases, the domain walls tilt to form zig-zag domain walls. Orbital selectivity of the t2g orbitals depends on the relative orientations of the orbital plane and the domain wall. This property influences the rate at which the domain wall tilts as a function of the electron density.

Author Keywords: Charged Domain Wall, Domain Wall, Ferroelectric, Landau-Ginzburg, Perovskite, Strontium Titanate

Recovery of forest soils from chronic acidification can be enhanced with the use of non-industrial wood ash (NIWA). Non-industrial wood ash is alkaline and contains high concentrations of macronutrients, but trace metal concentrations must be evaluated to limit risk of metal toxicity following application. Additionally, understanding how different forest ecosystem components respond to NIWA is essential to inform current policy regulating its use as a soil amendment. This study evaluated the response of sugar maple (Acer saccharum) sap yield and chemistry, the response of soils beneath maple, American beech (Fagus grandifolia) and mixed species canopies, and maple and beech fine roots, foliage, seedling abundance, and understory vegetation abundance and composition to an application of 6 Mg ha-1 NIWA. Eight 40 x 40 m plots were established in a hardwood stand in Bracebridge, Ontario and were sampled prior-to and up to two years following application of NIWA (n = 4). Non-industrial wood ash significantly increased organic horizon soil pH and macronutrient (Ca, Mg, and K) concentrations with increases in Mg and K extending to the mineral soils. Significantly higher concentrations of some trace metals (Al, Fe, Mn, Cd, Cu, Pb, Zn) were also observed, but these were restricted to the organic horizons. Sugar maple sap, pH, and sweetness were unaffected by NIWA application, and while increases were observed in nutrient and metal concentrations in sap, the differences were small and variable between years, and all concentrations were consistent with those commonly found in maple sap. Fine root biomass of maple and beech trees was not affected by NIWA application, but higher concentrations of K and Mg were observed in the roots of both species, consistent with higher concentrations observed in the mineral soil horizons beneath both species' canopies. Only significant increases were observed in K in sugar maple foliage. Both critical foliar concentrations and diagnosis and recommendation integrated system (DRIS) norms for sugar maple did not indicate mineral nutrient deficiencies at this site; although this site was acidic and nutrient-poor, this may account for the lack of differences observed, particularly between species. Changes observed in understory vegetation were driven by years rather than between treatments. These results suggest that moderate doses of NIWA can provide significant decreases in soil acidity and increase nutrient availability, with limited increases in metal concentrations that are primarily restricted to the organic horizons.

Author Keywords: American beech, metal toxicity, Non-industrial wood ash (NIWA), sap sweetness, sap yield, sugar maple

The significance of nursing retention in today's healthcare system is more prominent than ever before. The purpose of this study was to answer the question: What do Registered Nurses understand about their intention to stay at Ontario rural hospitals? A qualitative descriptive phenomenological approach was used to conduct this study. Ten Registered Nurses from rural hospitals were interviewed regarding their experiences working in rural hospitals. Seven themes were developed including: Sense of Community, Pride and Identity, Weight of Responsibility, Feeling Alone, Questioning Commitment, Rural Reality, and Feeling Misunderstood. Participants shared that their nursing co-workers were the reason they continued to stay working in their rural hospitals, with the essence of the themes being we are there for each other. The findings of this study can be used to influence nursing practice, nursing education, healthcare leaders, and areas of future research.

Author Keywords: Nurses, Retention, Rural

Agricultural and urban land uses have been linked to the recent resurgence of eutrophication and salinization issues in the lower Great Lakes. This thesis examined the relationship between watershed land use and stream nitrate-nitrogen (NO3-N), total phosphorus (TP), and chloride (Cl) concentrations across southern Ontario. Using a self-organizing map analysis, the watersheds were classified into eight distinct spatial clusters, representing four agricultural, two urban, and two natural clusters. Agricultural clusters under intensive row crop agriculture exhibited NO3-N and TP concentrations up to twelve and five times higher, respectively, than the most natural-dominated cluster. Urban clusters had Cl concentrations up to nine times greater than the natural-dominated clusters. Three agricultural land use practices, namely continuous corn-soybean rotation, synthetic fertilizer application, and tile drainage, were positively correlated with stream NO3-N concentrations, whereas Cl concentrations increased with urban area and human population density. This thesis also characterized sampling trends of the provincial stream water quality monitoring program and found that sampling frequency has declined since the mid-1990s, while current sites are monitored almost exclusively during the ice-free period. Sampling year-round is critical to capture seasonal variations in NO3-N and Cl, while sampling across a full range of flow conditions is important for describing TP. Exclusion of sampling sites in close proximity of downstream municipal wastewater treatment plants and greenhouses can help isolate and better understand water quality impacts of non-point sources. Although intensive agricultural watersheds in southwestern Ontario draining into Lake Erie remain a priority for research and management, regions experiencing row crop expansion such as along the northern shore of Lake Ontario as well as rapidly urbanizing areas require further attention as these land use shifts will likely increase stream NO3-N and Cl concentrations, placing further pressure on water resources in the lower Great Lakes.

Author Keywords: Chloride, Nitrogen, Phosphorus, Self-organizing map, Southern Ontario, Water quality

There is a `universal' picture of a charged domain wall (CDW) in theoretical work, often depicted as residing in an infinite thickness film, charge neutral, and with no bias voltage applied. However, in experiment CDWs are shown with none of these assumptions. CDWs are produced in thin or ultra-thin films, the CDW is not charge neutral, and a bias voltage is being applied. We look to go beyond these assumptions. It was shown that a positively charged domain wall (DW) moves against an external electric field which is not expected. The free electron density was also shown to determine the DW displacement amount. When the film thickness is lowered (ultra-thin film) we get a negatively charged DW which still moves against an external electric field, which agrees with experiment of a CDW in a ultra-thin film. This suggests the charge on the DW does not determine displacement direction.

Author Keywords: charged domain wall, displacement

Due to climate change and managed care, birds may face interacting effects of novel diets and environmental temperatures. I examined how captive zebra finches (Taeniopygia guttata) responded to a 6-month acclimation to either thermoneutral or cool temperatures when provided with saturated or unsaturated fatty acid enriched diets. Body mass was lower on the unsaturated fatty acid diet, but only in cool conditions. Individuals in cool temperatures and saturated fatty acid enriched diets had heavier organs, but pectoralis mass and metabolic rate did not display an effect of diet. While birds on each treatments illustrated similar initial increases in plasma fatty acid unsaturation, composition and concentration of constituent fatty acid varied based on their diet and temperature. Individuals on the unsaturated fatty acid enriched diet and cool treatments had lower survivorship. Collectively, my research will allow researchers to better predict how birds will be impacted by shifting or novel environments.

Author Keywords: chronic acclimation, fatty acids, metabolic rate, Taeniopygia guttata, temperature, unsaturation

Quantifying the impacts of environmental conditions on the abundance of wildlife populations is important for making informed management decisions in the face of increasing environmental threats. Managers require robust tools to estimate abundance and density of wildlife rapidly and with precision. Within the context of studying white-tailed deer, I evaluated the use of camera-traps and a recently developed spatial-mark resight model to estimate deer density and evaluate habitat and land use factors influencing deer density. The study was conducted in central Ontario, Canada on approximately 16 km2 of public land including the protected Peterborough Crown Game Preserve. Telemetry locations from 39 radio-collared deer were used and one hundred camera-traps were deployed for a total of 140 days from January 2022 to May 2022. Using telemetry locations and camera-trap photos I built a two-step spatial-mark resight model to estimate deer density. Deer density varied during the study as a portion of the population migrated to wintering areas outside of the study area. Despite fluctuations in precision, estimates improved towards the end of the study as more data became available and deer space use stabilized. The average deer density during the entire study was 3.0 deer/km2 (95% CI= 0.1, 5.8; SD= 1.7; CV= 55%; N= 238 deer). The lowest mean density was 0.2 deer/km2 (95% CI= 0.1, 0.4; SD= 0.1; CV= 50%; N= 15 deer) from February 26th to March 11th and the highest mean density was 4.8 deer/km2 (95% CI= 3.1, 6.2; SD= 0.8; CV= 17%; N= 378 deer) from May 7th to May 20th. When I incorporated spatial covariates into the model to estimate effects on deer density, higher proportions of mixed forest, deciduous forest, and road and trail density all had negative effects on deer density. While models contained some uncertainty, deer density appeared higher in the portion of the study area protected from licensed hunting. This thesis provides a framework for managers to use camera-traps and the spatial-mark resight model to monitor deer populations and link environmental covariates to spatial variation in density. As environmental threats such as habitat loss and infectious diseases increase in severity, monitoring wildlife population numbers will be vital for informed responses to these threats. The two-step spatial-mark resight model with environmental covariates provides managers with a long-term monitoring tool to evaluate management efforts and population health in forested areas.

Author Keywords: camera-trap, chronic wasting disease, landscape ecology, spatial-capture recapture, white-tailed deer, wildlife management

I used 31 years of Semipalmated Plover (Charadrius semipalmatus) population data to assess the effects of vital rates on a local breeding population of plovers in Churchill, Manitoba, Canada. I used three similar Bayesian Integrated Population Models (IPMs), with the last a coupled IPM population viability analysis (PVA) approach to predict the impact of changing spring temperatures on future population size. I estimated adult and juvenile apparent survival, fecundity, immigration rate, and yearly population size estimates, and I found that population growth rate was most highly correlated with immigration and adult apparent survival. Moreover, I found that the population remained relatively stationary with a slight decline in recent years. I also found a significant positive effect of spring average daily minimum temperature on juvenile apparent survival. I used this effect to inform my PVA and to evaluate the risk of quasi-extinction for 20 years after the end of the study. I found a low quasi-extinction risk and a greater probability of the population increasing in the next twenty years when informed by predicted spring temperatures from global climate models. My findings suggest some resilience of this species to one effect of climate change and emphasize the importance of continued monitoring to assess if declines in this species will change as multiple threats to their existence in the sub-arctic progress.

Author Keywords: Bayesian, Climate change, Integrated population model, Population dynamics, Population viability, Semipalmated Plover

In this study, twenty lake catchments surrounding Iqaluit, Baffin Island, were assessed for trace element concentrations (Al, As, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Se, THg, V, Zn) in lake water, catchment soil, lake sediment, and moss (Hylocomium splendens). Additionally, the sources of each trace element were determined through the positive matrix factorization (PMF) model and enrichment factors (only in moss). Geogenic trace elements had the highest median concentrations (Fe>Al>Mn) throughout the study media and across the study catchments. Anthropogenic trace elements had the lowest median concentrations (Pb>As>Cd>THg) across the lake catchments, which were generally several orders of magnitude lower compared to geogenic elements. The PMF model identified trace elements associated with geogenic or anthropogenic sources, i.e., THg (47%), Cd (40%), Zn (34%), and Al (27%) were identified as originating from industrial emission sources deposited onto lakes because they accounted for a large proportion within the model.

Author Keywords: Arctic lake catchments, Biomonitoring, Enrichment factors, Positive matrix factorization model, Trace elements, Water chemistry

The synthesis of biaryls through transition metal catalyzed cross-coupling reactions has been instrumental for synthetic organic chemists. The Hiyama reaction, which features organosilicon derived cross-coupling partners with aryl chlorides, remains relatively underdeveloped compared to other cross-coupling reactions. In this thesis, it is demonstrated that bench stable Palladium N-Heterocyclic Carbene (NHC) precatalysts of the general type [(NHC)Pd(allyl)Cl] are highly active in the Hiyama cross-coupling of activated aryl chlorides with low catalyst loading. Notably, this research demonstrates that catalysts featuring sterically less demanding NHCs display higher activity in this reaction, which contrasts with other cross-coupling reactions. Preliminary mechanistic investigations including in situ reaction monitoring by 19F NMR spectroscopy have uncovered side reactions. These side reactions may explain the low catalytic performance observed with unactivated substrates. These studies could help to further develop this reaction and improve catalytic performance. Additional investigations have also been made into ligand development by altering the electronics of sterically hindered NHC ligands for use in other cross-coupling reactions.

Author Keywords: Catalysis, Cross-coupling, Organic Chemistry, Organometallics, Side Reactions, Synthesis