Graduate Theses & Dissertations

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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
In situ measurements of trace metal species in the Athabasca and Mackenzie Rivers using diffusive gradient in thin films (DGT) devices
This study assesses the bioavailable metal (Cu, Ni, Zn, Pb) species in the Athabasca-Mackenzie watersheds using diffusive gradient in thin films (DGT) devices. Metal toxicity is not only based on the concentration of metal in natural waters, but also on the nature of metal species. Four main forms in aquatic systems are: free ion, inorganic species, DOM bound (humic) species and metal colloidal species. The free ion and inorganic species and very small humic species are known as DGT-labile species and, are considered to be more bioavailable to micro-organisms due to the size and thus may be toxic to microorganisms. In this study, DGT devices were applied to (1) monitor the DGT-labile metal species in the lower Athabasca River and the Mackenzie River watershed and (2) assess the DGT-labile metal concentrations on temporal and spatial scales. In the lower Athabasca River, comparison between the DGT results and the Windermere Humic Acid Model (WHAM) calculation indicated good agreements for all metals when the precipitated iron(III) hydroxide was assumed as an active binding surface. No significant variations in labile species were found over 2003-2012 (RAMP database) despite the development of oil sands. In the Mackenzie River, no significant difference in DGT-labile metal concentrations and DOC concentrations was found in yearly basis 2012-2014. Only DOC was lower in August (6.98 and 3.85 ppm, respectively; p< 0.05) due to dilution from heavy rain events. Spatially, DGT-labile Cu and Ni in the downstream Mackenzie River were higher than upstream (1.79 and 0.58 ppb for Cu, 1.68 and 0.77 ppb for Ni, 4.06 and 6.91 ppm for DOC; p < 0.05). Overall the in situ measurements of metals constitute a benchmark for future studies in water quality and be helpful in environmental management in Alberta and the Northwest Territories in Canada. Author Keywords: Athabasca River, DGT, Mackenzie River, Speciation, Trace Metal, WHAM
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
ASSESSING THE IMPACT OF ATMOSPHERIC DEPOSITION AND HARVEST INTENSITY ON SOIL ACIDITY AND NUTRIENT POOLS IN PLANTATION FORESTS
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
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
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

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