Graduate Theses & Dissertations

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Anthropogenic microfibres in background natural environments in Ireland
Microfibres, which are threadlike particles < 5 mm, are the most common type of microplastic reported in the environment. However, few studies have focused on their abundance in background natural environments. This study assessed the abundance of microfibres in rainfall samples (from four precipitation monitoring stations) and across three headwater lake catchments that were in remote, undeveloped areas, away from anthropogenic disturbance and anthropogenic emission sources (i.e., sites were background natural environments). Anthropogenic microfibres were observed in all samples using visual identification methods, with Raman spectroscopy confirming the presence of polyester film and synthetic pigments, e.g., indigo and hostasol green. The estimated annual average atmospheric deposition of microfibres was ~28,800 mf m-2. Meteorological variables, e.g., rain, wind direction, and relative humidity were correlated with the abundance of microfibres. The average abundance of microfibres in headwater lake catchments was 24 mf g-1 in moss, 0.70 mf m-3 in surface trawl, 9,690 mf m-3 in subsurface, 910 mf kg-1 in lake sediment and 576 mf kg-1 in lakeshore sediment. Author Keywords: Atmospheric Deposition, Background Environments, Headwater Lake Catchments, Microfibres, Microplastics, Rainfall
Modelling Monthly Water Balance
Water balance models calculate water storage and movement within drainage basins, a primary concern for many hydrologists. A Thornthwaite water balance model (H2OBAAS) has shown poor accuracy in predicting low flows in the Petawawa River basin in Ontario, so lake storage and winter snow processes were investigated to improve the accuracy of the model. Lake storage coefficients, represented by the slopes of lake stage vs. lake runoff relationships, were estimated for 19 lakes in the Petawawa River basin and compared on a seasonal and inter-lake basis to determine the factors controlling lake runoff behaviour. Storage coefficients varied between seasons, with spring having the highest coefficients, summer and fall having equal magnitude, and winter having the lowest coefficients. Storage coefficients showed positive correlation with lake watershed area, and negative correlation with lake surface area during summer, fall, and winter. Lake storage was integrated into the H2OBAAS and improved model accuracy, especially in late summer, with large increases in LogNSE, a statistical measure sensitive to low flows. However, varying storage coefficients with respect to seasonal lake storage, watershed area, and surface area did not improve runoff predictions in the model. Modified precipitation partitioning and snowmelt methods using monthly minimum and maximum temperatures were incorporated into the H2OBAAS and compared to the original methods, which used only average temperatures. Methods using temperature extremes greatly improved simulations of winter runoff and snow water equivalent, with the precipitation partitioning threshold being the most important model parameter. This study provides methods for improving low flow accuracy in a monthly water balance model through the incorporation of simple snow processes and lake storages. Author Keywords: Lake Storage, Model Calibration, Monthly Water Balance, Petawawa River, Precipitation Partitioning, Snow Melt
Observation-based assessment of atmospheric sulphur surrounding a major aluminum smelter in British Columbia, Canada
Recent developments at an aluminum (Al) smelter in Kitimat, BC resulted in a permitted increase of 27 to 42 tonnes of sulphur dioxide (SO2) emissions per day. Gaseous SO2 is a pollutant known to contribute to acidic deposition through processes of wet and dry deposition and can additionally react in-atmosphere to form particulate sulphate (pSO42-). Between June 2017 to October 2018, an extensive network consisting of ion exchange resin (IER) column, passive-diffusive, and active filter-pack samplers was established to provide an estimate of total annual S deposition and pSO42- variation throughout the Kitimat Valley. Filter-pack sampling determined the relative concentration of pSO42- increased downwind of the smelter. Comparison of observation-based and modelled total annual deposition suggested CALPUFF was accurate in representing the spatial viability of S deposition (R2 = > 0.85). However, the model appeared to overpredict near-field deposition suggesting the potential of underestimation further downwind of the smelter. Author Keywords: aluminum smelter, atmospheric deposition, filter-pack sampler, ion-exchange column sampler, pSO42-, SO2
Soil Geochemistry and Normative Mineralogy across Canada
Soils play a crucial role in ecosystem functioning, for example, soil minerals provide important provisioning and regulate ecosystem services. This study used major soil oxides from the North American Soil Geochemical Landscapes Project (n=560) to assess elemental associations and infer soil minerals through exploratory data analysis and to determined quantitative soil mineralogy using a normative method, Analysis to Mineralogy (n=1170). Results showed elemental variability of oxides across the provinces of Canada and strong correlations occurred between elements indicative of soil mineral composition (e.g., Silicon and Aluminium). Principal component analysis inferred soil minerals from soil oxides trends on biplots and classified minerals, generally, as carbonates, silicates, and weathered secondary oxides. Spatial variability in minerals (quartz, plagioclase, potassium feldspar, chlorite, and muscovite) was related to the underlying bedrock geology. The use of Analysis to Mineralogy led to a reliable method of quantifying soil minerals at a large scale. Author Keywords: Analysis to Mineralogy, Exploratory data analysis, Normative procedures, North American Soil Geochemical Landscapes Project, Soil geochemistry, Soil mineralogy
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:
Hydrochemistry and critical loads of acidity for lakes and ponds in the Canadian Arctic
Threats such as climate change and increased anthropogenic activity such as shipping, are expected to negatively affect the Arctic. Lack of data on Arctic systems restricts our current understanding of these sensitive systems and limits our ability to predict future impacts. Lakes and ponds are a major feature of the Arctic landscape and are recognized as ‘sentinels of change’, as they integrate processes at a landscape scale. A total of 1300 aquatic sites were assessed for common chemical and physical characteristics. Geology type was found to be the greatest driver of water chemistry for Arctic lakes and ponds. Acid-sensitivity was assessed using the Steady State Water Chemistry model and a subset of 1138 sites from across the Canadian Arctic. A large portion of sites (40.0%, n = 455) were classified as highly sensitive to acidic deposition, which resulted in a median value of 35.8 meq·m―2·yr―1 for the Canadian Arctic. Under modelled sulphur deposition scenarios for the year 2010, exceedances associated with shipping is 12.5% (n = 142) and 12.0% (n = 136) for without shipping, suggesting that impacts of shipping are relatively small. Author Keywords: Acidic deposition, Arctic lakes, Critical loads, Shipping emissions, Steady-State Water Chemistry Model, Water chemistry
Moss Biomonitoring of Trace Element Deposition in Northwestern British Columbia, Canada
Atmospheric pollutant deposition poses a risk to ecosystem health; therefore, monitoring the spatial and temporal trends of deposition is integral to environmental sustainability. Although moss biomonitoring is a common method to monitor various pollutants in Europe, offering a cost-effective approach compared to traditional methods of monitoring, it is rarely used in Canada. The focus of this study was a spatial assessment of trace element deposition across a region with a known large-point source of emissions using the moss biomonitoring method. Moss tissues presented strong correlations with modelled deposition in the region, suggesting mosses are a valuable biomonitoring tool of trace element deposition, especially in regions dominated by large-point emission sources. Additionally, a moss species endemic to Canada was compared to commonly used moss species with results indicating this species (Isothecium stoloniferum) can be used reliably as a biomonitor. Moss biomonitoring is recommended as a compliment to fill in spatial gaps in current monitoring networks across the country. Author Keywords: biomonitoring, bryophytes, Hylocomium splendens, moss, Pleurozium schreberi, trace elements
Estimating mineral surface area and acid sensitivity of forest soils in Kitimat, British Columbia
In 2012, the Rio Tinto aluminum smelter in Kitimat, British Columbia increased sulphur dioxide (SO2) emissions from 27 to 42 tonnes/day. An initial study was conducted to investigate the effect of the increased sulphur (S) deposition on forest soils. A key uncertainty of the initial study was mineral surface area estimations that were applied to critical load calculations. The current study investigates the effect of organic matter (OM) removal techniques on mineral surface area and the ability to predict mineral surface area using pedotransfer functions (PTFs). Mineral surface area was measured on bulk soil samples using BET gas-adsorption. Organic matter was removed from soil samples prior to surface area measurements using a sodium hypochlorite treatment (NaOCl), loss on ignition (LOI) and no treatment. Removal techniques were found to affect surface area measurements; decreasing in the order of LOI> untreated> NaOCl. Particle-size based PTFs developed from other regions were not significantly correlated with measured surface area. A regionally-specific particle-size based function had stronger predictive value of surface area measurements (adjusted R2=0.82). The PTF that best reflected surface area measurements of bulk soil for the Kitimat area used particle-size data as well as kaolinite, the most abundant clay mineral in the region. Surface area values estimated using the particle-size PTF were applied to the PROFILE model to calculate weathering rates. Weathering rates were then input to critical load calculations using steady-state mass balance. These estimates predicted that none of the 24 measured sites are receiving SO2 deposition in exceedance of their critical load. Author Keywords: acid deposition, critical loads, mineral surface area, mineral weathering, pedotransfer functions, PROFILE
Calcium in the Muskoka River Watershed- Patterns, trends, the potential impact of forest harvesting and steps toward an ecosystem approach to mitigation
Decreasing lake calcium (Ca) concentration, in lakes located in base poor catchments of the Muskoka River Watershed (MRW) in south-central Ontario, is a well- established acid-rain driven legacy effect threatening the health and integrity of aquatic ecosystems that can be compounded by additional Ca removals through forest harvesting. The objectives of this thesis were to assess patterns and temporal trends in key water chemistry parameters for a set of lakes in forested catchments in the MRW in south- central Ontario, to predict the pre-industrial steady state lake Ca concentration and the potential impact of harvesting on lake Ca levels in lakes located in managed MRW Crown forests, and to assess potential effects of various mitigation strategies in Ca depleted managed forests. Mean lake Ca (mg L-1) in 104 lakes across the MRW have decreased by 30% since the 1980's with the rate of decrease slowing over time. Mean Lake SO4 (mg L-1), and Mg (mg L-1) concentration also decreased significantly with time (37% and 29%, respectively) again with a declining rate of decrease, while mean lake pH and DOC increased significantly between the 1980's and the 1990's (16% and 12%, respectively) but exhibited no significant pattern after that. Principal components and GIS spatial analyses of 75 lakes with data from 2011 or 2012 water seasons suggested that smaller lakes, at higher elevation in smaller catchments with higher runoff and minimally impacted by the influence of roads and agriculture are associated with lower Ca concentrations and thus are the lakes at risk of amplified Ca depletion from forest harvesting. Spatial analyses of harvested catchments indicated that, under the proposed 10 year land forest management cut volumes, 38% of 364 lakes in the MRW will fall below the critical 1 mg L-1 Ca threshold compared with 8% in the absence of future harvesting. With respect to potential mitigation measures, soil pH and foliar Ca were indicated by meta-analysis to be more responsive to lime addition studies while soil base saturation and tree growth appeared more responsive to wood-ash addition. Future research should address the spatial extent of lakes at risk and identify when critical levels will be reached under harvesting regimes. Further investigation into the use of Ca-addition as a tool for managing the cumulative effects of past, present and future stressors is recommended. Author Keywords: calcium, harvesting, lakes, lime, Muskoka River Watershed, wood-ash
Passive sampling of indoor and outdoor atmospheric nitrogen dioxide in the greater Toronto area
The reliability and performance of four passive sampler membrane coatings specific to nitrogen dioxide (NO2) were evaluated through co-exposure at multiple Ontario Ministry of Environment and Climate Change (OMOECC) active monitoring stations. All four coatings performed relatively similar under a wide range of meteorological conditions, notably showing exposure-specific atmospheric uptake rates. Further, indoor and outdoor atmospheric concentrations of NO2 (a marker of traffic-related air pollution) were evaluated at multiple elementary schools in a high-density traffic region of Toronto, Ontario, using a Triethanolamine based passive sampler membrane coating. Samplers were also co-exposed at OMOECC active monitoring stations to facilitate calibration of exposure-specific atmospheric uptake rates. Indoor NO2 atmospheric concentrations were 40 to 50% lower than outdoor concentrations during the spring−summer and autumn−winter periods, respectively. In large cities such as Toronto (Population 2,700,000), the influence of a single major road on outdoor and indoor NO2 concentrations is predominantly masked by spatially-extensive high-density traffic. Author Keywords: active sampler, membrane coating type, nitrogen dioxide, passive sampler, Toronto, traffic density
Mercury and Persistent Organic Pollutants in Remote Acid Sensitive Irish Lake Catchments
A catchment-based study was carried out at three remote acid sensitive Irish lakes to determine concentrations of Hg and POPs and to investigate the factors governing the partitioning of these pollutants in various environmental matrices. Both Hg and POPs are an environmental concern due to their ability to travel long distances via atmospheric transport and their tendency to accumulate in biota and in various environmental compartments. Concentrations of POPs and Hg measured in this study were relatively low and consistent with concentrations measured at background levels around the world. Mercury concentrations appeared to be influenced by various site characteristics, specifically organic matter. Many of the POPs examined in this study appeared to be present as a result of long-range transport and more specifically; the physico-chemical properties of POPs appeared to dictate their distribution within soils, moss and sediment at each of the study catchments. Author Keywords:
Regional Assessment of Soil Calcium Weathering Rates and the Factors that Influence Lake Calcium in the Muskoka River Catchment, Central Ontario
(MRC) in central Ontario was carried out to determine the range and spatial distribution of soil Ca weathering rates, and investigate the relationships between lake Ca and soil and catchment attributes. The MRC is acid-sensitive, and has a long history of impacts from industrial emission sources in Ontario and the United States. Small headwater catchments were sampled for soil and landscape attributes (e.g. elevation, slope, catchment area) at 84 sites. Soil Ca weathering rates, estimated with the PROFILE model, were low throughout the region (average: 188 eq/(ha·yr)) compared to global averages, and lower than Ca deposition (average: 292 eq/(ha·yr)). Multiple linear regression models of lake Ca (n= 306) were dominated by landscape variables such as elevation, which suggests that on a regional scale, landscape variables are better predictors of lake Ca than catchment soil variables. Author Keywords: Calcium, Lakes, Regional assessment, Regression, Soils, Weathering

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