Graduate Theses & Dissertations


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
effects of environmental variables and dissolved organic matter characteristics on the diffusion coefficient of dissolved organic matter using diffusive gradients in thin films
The efficacy of the diffusive gradients in thin films (DGT) passive samplers to provide accurate measurements of free metal ions and those complexed with dissolved organic matter (DOM) was investigated. DOM controls the diffusive properties of DOM-complexed metal species in natural systems. Knowing the diffusion coeiffiecent (D) for DOM of different molecular weights (MW) and the major environmental variables influencing D is critical in developing the use of DGT passive samplers and understanding labile species. D and MW were determined for natural and standard DOM. No noticeable changes in DOM MW were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. Data analysis revealed that MW had the greatest influence on D, with a negative relationship between D and MW, except in tidal areas where ionic strength influence on D was significant. This study provides further characterization of the variables influencing D using the DGT technique. Author Keywords: Diffusion coefficient, Diffusive gradients in thin films, Dissolved organic matter, Flow field-flow fractionation, Principal Component Analysis, UV-Vis Spectroscopy
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
Acidification of lakes in northern Saskatchewan
The emission of acid precursors by large point sources in Western Canada (such as the Athabasca Oil Sands Region) has prompted studies into the possible impact to downwind aquatic and terrestrial ecosystems. Sensitivity of catchments to acidic deposition was estimated for the total lake population of northern Saskatchewan (n=89,947) using regression kriging. Under the Steady State Water Chemistry model, a range of 12-15% of the total catchment population was predicted to be in exceedance of critical loads under 2006 deposition levels and 6% of catchments were estimated to be very sensitive (pH below 6 and acid neutralizing capacity, alkalinity, calcium below 50 eqL-1). Temporal changes in soil and water chemistry estimated for 18 Alberta and Saskatchewan catchments using the Very Simple Dynamic and PROFILE models showed that changes in soil base saturation and lake acid neutralizing capacity between 1850 and 2100 were slight, declining 0.8% and 0.9% by 2012, respectively. Author Keywords: acidification, critical loads, exceedance, PROFILE, regression kriging, VSD
Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish
Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish Alena Kathryn Davidson Celsie A novel dynamic fugacity model is developed that simulates the uptake of chemicals in fish by respiration as applies in aquatic toxicity tests. A physiologically based toxicokinetic model was developed which calculates the time-course of chemical distribution in four tissue compartments in fish, including metabolic biotransformation in the liver. Toxic endpoints are defined by fugacity reaching a 50% mortality value. The model is tested against empirical data for the uptake of pentachloroethane in rainbow trout and from naphthalene and trichlorobenzene in fathead minnows. The model was able to predict bioconcentration and toxicity within a factor of 2 of empirical data. The sensitivity to partition coefficients of computed whole-body concentration was also investigated. In addition to this model development three methods for predicting partition coefficients were evaluated: lipid-fraction, COSMOtherm estimation, and using Abraham parameters. The lipid fraction method produced accurate tissue-water partitioning values consistently for all tissues tested and is recommended for estimating these values. Results also suggest that quantum chemical methods hold promise for predicting the aquatic toxicity of chemicals based only on molecular structure. Author Keywords: COSMOtherm, fish model, fugacity, Partition coefficient, tissue-water, toxicokinetics
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
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
The objective of this thesis was to assess the influence of anthropogenic sulphur (S) and nitrogen (N) deposition, and harvesting on soil acidity and calcium (Ca2+), magnesium (Mg2+), potassium (K+) and N soil pools in plantation forest soils in Ireland. The response to reductions in anthropogenic S deposition was assessed using temporal trends in soil solution chemistry at two long-term monitoring plots--one on a blanket peat, the other on a peaty podzol. At the peat site, there was little evidence of a response to reductions in throughfall non marine sulphate (nmSO42-) and acidity; soil water acidity was determined by organic acids. In addition, temporal variation in soil water did not respond to that in throughfall. In the podzol, reductions in anthropogenic S and H+ deposition led to a significant improvement in soil water chemistry at 75 cm; pH increased and total aluminum (Altot) concentrations declined. The impact of harvest scenarios on exchangeable Ca2+, Mg2+ and K+ pools was assessed using input-output budgets at 40 sites (30 spruce, 10 pine). Harvest scenarios were stem-only harvest (SOH), stem plus branch harvest (SBH) and stem, branch and needle harvest (whole-tree harvesting; WTH). Average K+ and Mg2+ budgets were positive under these scenarios. However, exchangeable K+ pools were small and due to uncertainty in K+ budgets, could be depleted within one rotation. Average Ca2+ budgets for spruce were balanced under SOH, but negative under SBH and WTH. Nitrogen deposition was high, between 5 and 19 kg N ha-1 yr-1, but was balanced by N removal in SOH. However, N budgets were under SBH and WTH, indicating that these harvesting methods would lead to depletion of soil N over the long-term. Finally, monitoring of N cycling at a spruce plot indicated that N deposition was contributing to large NO3- leaching, and as such the site was N saturated. However, N cycling did not fit the criteria of the N saturation hypothesis; instead leaching was directly related to N deposition and supported the model of kinetic N saturation. Author Keywords: acidic deposition, base cations, input-output budgets, Ireland, nitrogen, whole-tree harvesting
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
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
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
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:


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