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Graduate Theses & Dissertations
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- Predictive Digital Mapping of Soils in Kitimat, British Columbia
- Soil is an essential natural resource that supports provisioning services such as agriculture, silviculture, and mining. However, there is limited knowledge on forest soil properties across Canada. Digital soil mapping may be used to fill these data gaps, as it can predict soil properties in areas with limited observations. The focus of this study was to develop predictive maps of select soil physicochemical properties for the Kitimat Valley, British Columbia, and apply these maps to assess the potential impacts of sulphur dioxide emissions from an aluminum smelter, on soil properties in the Valley. Exchangeable [Ex.] magnesium, organic matter, pH, coarse fragment, Ex. potassium, bulk density, Ex. calcium, Ex. acidity, and Ex. sodium were all mapped with acceptable confidence. Time to depletion of base cation pools showed that ~240 km2 of the study area had a depletion time of 50 years or less. However, sources of base cations such as atmospheric deposition and mineral weathering were not considered. Author Keywords: acidification, buffering capacity, Digital soil mapping, predictive mapping, regression kriging, soil properties
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- Organic Matter and Total Mercury in Acid-Sensitive Lakes in Ireland
- The following study measured dissolved organic carbon (DOC) and total mercury (THg) concentrations in acid sensitive lakes in the Republic of Ireland. Sixty-eight upland lakes and 48 lowland lakes were sampled for DOC; the upland lakes were additionally sampled for THg. Spatial variability of DOC was explained by regional precipitation and soil organic matter. A subset of lakes was tested for long-term trends and in contrast to reports of rising DOC in European surface waters, changes in DOC were minor. Spatial variability in THg was explained by DOC and organic matter aromaticity. Long-term THg concentrations increased, likely caused by inputs of terrestrial THg. A subset of lakes was sampled for sediment and soil and the results suggested soils drove THg variation in lake water and sediment. Lake water and sediment THg was low and consistent with background regions, while soil THg was relatively high due to high organic content. Author Keywords: Dissolved Organic Carbon, Lakes, Organic Matter, Soil, Total Mercury, Water
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- Effects of Agricultural Land Use Change on Nitrogen and Phosphorus in North Shore Lake Ontario Tributaries
- Row crop agriculture and associated land use practices including tile drainage and conservation tillage have been cited as a probable cause of re-emerging eutrophication in the lower Great Lakes. In this thesis, I sought to quantify and evaluate the effect of agricultural land cover and land use changes on total phosphorus (TP) and nitrate-nitrogen (NO3-N) concentrations and export in north shore Lake Ontario tributaries. This included (a) a long-term data analyses at 12 large watersheds (47 to 278 km²) using historical land cover and water quality data (1971-2010), and (b) a space-for-time study examining 12 small sub-catchments (< 8 km²) with majority (> 50%) row crop, pasture, or forest cover. Concentrations of TP were greatest in urbanized watersheds and declined particularly during the first decades of the study period, while NO3-N concentrations were greatest and steadily increased in agricultural catchments with increasing row crop cover. The space-for-time approach revealed that TP concentrations were similar across agricultural land uses and that export was most dependent on runoff. Meanwhile, NO3-N concentrations and export were greatest in row crop catchments and were positively related to row crop area. These results suggest that increases in row crop cover and associated agricultural practices including increased nutrient amendments and tile drainage may be responsible for increased NO3-N concentrations and export in northern Lake Ontario tributaries. Author Keywords: agriculture, Lake Ontario, nitrogen, phosphorus, streams, Water quality
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- Identification and Quantification of Organic Selenium Species Produced by Microbiological Activity in Freshwater Environments
- Despite being an essential nutrient at trace levels, selenium can be devastating to aquatic environments when present in excess. There is no apparent correlation between total aqueous selenium concentrations and observed toxic effects because bioaccumulation varies over several orders of magnitude depending on the chemical species of selenium and the biological species present in the lowest trophic level of the aquatic food chain. Despite being used in toxicity models due to its high bioavailability, free selenomethionine had not been found previously in the environment outside of a biological entity. Here, it is confirmed that selenomethionine is produced during the biological treatment of selenium-contaminated wastewater, and released in the effluent along with other discrete organic selenium species, including selenomethionine oxide. This identification followed the development of a rigorous preconcentration and cleanup procedure, allowing for the analysis of these organic selenium species in high-ionic strength matrices. A newly optimized anion-exchange chromatographic separation was coupled to inductively-coupled plasma mass spectrometry for the simultaneous quantification of these organic selenium species along with the more ubiquitous selenium oxyanions, selenite and selenate. This separation method was also coupled to electrospray tandem mass spectrometry for structural confirmation of selenomethionine and selenomethionine oxide. High resolution orbitrap mass spectrometry was used to identify another oxidation product of selenomethionine – a cyclic species which was tentatively identified, by coelution, in a selenium-contaminated river water sample. The production and release of selenomethionine, selenomethionine oxide, Se-(methyl) selenocysteine, and methyl selenic acid were observed for various laboratory algal cultures. Once the presence of free selenomethionine in a water system was confirmed, factors affecting its uptake into algal cultures were examined. The uptake of selenomethionine into Scenedesmus obliquus was noted to be significantly higher under low nitrate conditions, where it was incorporated into selenium-containing proteins more readily than at higher nitrate conditions where other metabolites were produced. With the increasing popularity of biological treatment systems for the remediation of selenium-contaminated waters, these observations, combined with existing knowledge, could be used to make predictions regarding the potential toxicity of selenium in various environmental scenarios. Author Keywords: bioremediation, electrospray mass spectrometry, inductively-coupled plasma mass spectrometry, selenium, selenoamino acids, selenomethionine
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- Impact of Invasive Earthworms on Soil Respiration and Soil Carbon within Temperate Hardwood Forests
- Improving current understanding of the factors that control soil carbon (C) dynamics in forest ecosystems remains an important topic of research as it plays an integral role in the fertility of forest soils and the global carbon cycle. Invasive earthworms have the potential to alter soil C dynamics, though mechanisms and effects remain poorly understood. To investigate potential effects of invasive earthworms on forest C the forest floor, mineral soil, fine root biomass, litterfall and litter decomposition rates and total soil respiration (TSR) over a full year were measured at two invaded and one uninvaded deciduous forest sites in southern Ontario. The uninvaded site was approximately 300m from one of the invaded sites and a distinct invasion front between the sites was present. Along the invasion front, the biomass of the forest floor was negatively correlated with earthworm abundance and biomass. There was no significant difference between litterfall, litter decomposition and TSR between the invaded and uninvaded sites, but fine root biomass was approximately 30% lower at the invaded site. There was no significant difference in soil C pools between the invaded and uninvaded sites. Despite profound impacts on forest floor soil C pools, earthworm invasion does not significantly increase TSR, most likely because increased heterotrophic respiration associated with earthworms is largely offset by a decrease in autotrophic respiration caused by lower fine root biomass. Author Keywords: Biological Invasions, Carbon, Earthworms, Forest Ecosystems, Forest Floor, Soil Respiration
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- An Assessment of Spatial Trends in the Accumulation of Oil Sands Related Metals in the Clearwater River Valley and Temporal Trends in Six Northern Saskatchewan Lakes
- The objective of this thesis was to assess current spatial trends and historic trends in the accumulation of trace metals related to the Athabasca Oil Sands Region (AOSR). The AOSR hosts some of the largest industrial developments in Canada, yet relatively little is known about the transport and fate of trace metal emissions from the region – particularly in the relatively remote areas to the east of the AOSR. Lichens are widely used as biomonitors and are employed in this thesis to assess the range of metals deposition within the Clearwater River and Athabasca River Valleys. Lake sediment cores can retain a historical record of the long-range transport and deposition of metals but can also respond to large regional metal emissions sources. This thesis used lake sediment cores to assess temporal trends in metals accumulation in six road accessible lakes in NW Saskatchewan that are likely to be used by local residents. Results show that metal concentrations (V, Co, Cu, Ni, Pb, Zn, Zr and Cd ) in lichen decline exponentially with distance from the AOSR and approach background levels within a few kilometers . Results from lake sediment cores show that there was no evidence that metal concentrations had increased due to industrial activities in the AOSR. Author Keywords: Air Emissions, Lakes, Lichens, Oil Sands, Saskatchewan, Trace Metals
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- Effects of biodiversity and lake environment on the decomposition rates of aquatic macrophytes in the Kawartha Lakes, Ontario
- Decomposition of aquatic macrophytes has an important role in defining lake carbon (C) storage and nutrient dynamics. To test how diversity impacts decomposition dynamics and site-quality effects, I first examined whether the decomposition rate of aquatic macrophytes varies with species richness. Generally, I found neutral effects of mixing, with initial stoichiometry of component species driving decomposition rates. Additionally, external lake conditions can also influence decomposition dynamics. Therefore, I assessed how the decomposition rate of a submersed macrophyte varies across a nutrient gradient in nine lakes. I found decomposition rates varied among lakes. Across all lakes, I found Myriophyllum decomposition rates and changes in stoichiometry to be related to both nutrients and water chemistry. During the incubation changes in detrital stoichiometry were related to lake P and decomposition rates. Aquatic plant community composition and stoichiometry could alter decomposition dynamics in moderately nutrient enriched lakes. Author Keywords: Aquatic Plants, Decomposition, Diversity, Littoral, Macrophytes, Nutrients
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- Geochemistry and Toxicity of a Large Slag Pile and its Drainage Complex in Sudbury, Ontario
- This study was designed to determine the geochemistry and potential toxicity of water draining a large slag pile in Sudbury, Ontario, which runs through a pond complex prior to entering Alice Lake. Slag leaching experiments confirmed slag is a source of sulphate, heavy metals (including Fe, Al, Ni, Co, Cu, Zn, Pb, Cr, Mn) and base cations (Ca, K, Mg, Na). Concentrations of most metals draining through slag in column experiments were similar to metal concentrations measured at the base of the slag pile, although base cations, S and pH were much higher, possibly because of water inputs interacting with the surrounding basic glaciolacustrine landscape. The increase in pH rapidly precipitates metals leading to high accumulation in the surface sediments. Away from the base of the pile, an increase in vegetation cover leads to an increase in DOC and nutrients and transport of metals with strong binding affinities (Cu). Total metal concentration in water and sediment exceed provincial water quality guidelines, particularly near the slag pile, however WHAM7 modeling indicated that the free metal ion concentration in water is very low. Nevertheless, toxicity experiments showed that water with greater concentrations of solutes collected close to the slag pile negatively impacts D. magna suggesting that water draining the slag pile can adversely impact biota in nearby drainage areas. Author Keywords: geochemistry, heavy metals, leaching, non-ferrous slag, precipitation, toxicity
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- Size and fluorescence properties of allochthonous dissolved organic matter
- Dissolved organic matter (DOM) is a mixture of molecules with dynamic structure and composition that are ubiquitous in aquatic systems. DOM has several important functions in both natural and engineered systems, such as supporting microorganisms, governing the toxicity of metals and other pollutants, and controlling the fate of dissolved carbon. The structure and composition of DOM determine its reactivity, and hence its effectiveness in these ecosystem functions. While the structure, composition, and reactivity of riverine and marine DOM have been previously investigated, those of allochthonous DOM collected prior to exposure to microbes and sunlight have received scant attention. The following dissertation constitutes the first in-depth study of the structure, composition, and reactivity of allochthonous DOM at its point of origin (i.e. leaf leachates, LLDOM), as detected by measuring its size and optical properties. Concomitantly, novel chemometric methods were developed to interpret size-resolved data obtained using asymmetrical flow field-flow fractionation, including spectral deconvolution and the application of machine learning algorithms such as self-organizing maps to fluorescence data using a dataset of more than 1000 fluorescence excitation-emission matrices. The size and fluorescence properties of LLDOM are highly distinct. Indeed, LLDOM was correctly classified as one of 13 species/sources with 92.5% accuracy based on its fluorescence composition, and LLDOM was distinguished from riverine DOM sampled from eight different rivers with 98.3% accuracy. Additionally, both fluorescence and size properties were effective conservative tracers of DOC contribution in pH-controlled mixtures of leaf leachates and riverine DOM over two weeks. However, the structure of LLDOM responded differently to pH changes for leaves/needles from different tree species, and for older needles. Structural changes were non-reversible. Copper-binding strength (log K) differed for the different fluorescent components of DOM in a single allochthonous source by more than an order of magnitude (4.73 compared to 6.11). Biotransformation preferentially removed protein/polyphenol-like fluorescence and altered copper-binding parameters: log K increased from 4.7 to 5.5 for one fluorescent component measured by fluorescence quenching, but decreased from 7.2 to 5.8 for the overall DOM, as measured using voltammetry. The complexing capacity of DOM increased in response to biotransformation for both fluorescent and total DOM. The relationship between fluorescence and size properties was consistent for fresh allochthonous DOM, but differed in aged material. Since the size and fluorescence properties of LLDOM are strikingly different from those of riverine DOM, deeper investigation into transformative pathways and mixing processes is required to elucidate the contribution of riparian plant species to DOM signatures in rivers. Author Keywords: Analytical chemistry, Chemometrics, Dissolved organic matter (DOM), Field-flow fractionation, Fluorescence spectroscopy, Parallel factor analysis (PARAFAC)
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- Nutrient Metabolism of an Aquatic Invertebrate and its Importance to Ecology
- Aquatic consumers frequently face nutritional limitation, caused in part, by imbalances between the nutrients supplied by primary producers and the metabolic demands of the consumers. These nutritional imbalances alter many ecological processes including consumer life-history traits, population dynamics, and food web properties. Given the important ecological role of organismal nutrition, there is a need to have precise and specific indicators of nutritional stress in animals. Despite this need, current methods used to study nutrition are unable to distinguish between different types of nutritional limitation. Here I studied nutritional metabolism in the freshwater zooplankter, Daphnia. A greater understanding of nutritional metabolism would allow for the development of dietary bio-indicators that could improve the study of the nutritional ecology of animal consumers. Specifically, I addressed the question: What affects the biochemical composition of a generalist aquatic consumer? My overall hypothesis was that the quantity and quality of the diet affects the biochemical composition in a nutrient specific manner. To test this hypothesis, I examined various response variables involved in nutrient metabolism such as alkaline phosphatase activity, whole metabolome, and free amino acid composition. For each response variable, I grew Daphnia under various nutritional stressors and determined if responses are nutrient specific or are a general stress response. I found the current method of measuring alkaline phosphatase was not a phosphorus specific indicator, as activity increased in all nutrient stressed treatments. Analyzing the whole metabolome resulted in nutritional stressors being separated in multivariate space, with many identified metabolites being significantly different from nutrient rich Daphnia. Upon further examination the daphnids free amino acids profiles are caused by differences between the supply of amino acids from the algae and the demand within the Daphnia. These differences in supply and demand resulted in the ability to classify the nutritional status of Daphnia with the use of discriminant analysis, a classification multivariate model. In addition to a deeper understanding and advanced knowledge of the physiological changes caused by nutrient limitation, this research has provided strong evidence for the application of nutritional biomarkers/profiles to identified the nutritional status of Daphnia. Author Keywords: Bio-indictor, Ecological stoichiometry, Metabolism, Nutritional limitation, Nutritional status
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- Ecosystem Response to Above Canopy Nitrogen Addition in a Jack Pine (Pinus banksiana) Forest in the Athabasca Bituminous Sands Region of Northeastern Alberta, Canada
- In this study we seek to better understand the potential effects of short-term (5-year) N fertilization on jack pine forest biogeochemistry, vascular plant community composition and to project a temporal endpoint of nitrogen leaching below the major rooting zone. Aqueous ammonium nitrate (NH4NO3) was applied above the forest canopy across five treatment plots (20 x 80 m) four times annually. The experimental deposition gradient followed those known for localized areas around the major open pit operations at 0, 5, 10, 15, 20 and 25 kg N ha-1 yr-1 over a five-year period (2011 – 2015). Nitrate recovery in throughfall was significantly higher than NH4+ (p < 0.05), indicating canopy NH4+ immobilization. There was a strong treatment effect (p < 0.05) of N on the epiphytic lichen thalli concentrations of Hypogymnia physodes and Evernia mesomorpha after five years. The canopy appeared to approach saturation at the highest deposition load (25 kg N ha-1 yr-1) during the fifth year of N additions as most N added above the canopy was accounted for in throughfall and stemflow. The non-vascular (lichen and moss) vegetation pool above the forest floor was the largest receptor of N as cryptogam foliar and thalli N concentrations showed a significant treatment effect (p < 0.05). Nitrogen in decomposing litter (25 kg N ha-1 yr-1) remained immobilized after five years, while treatments ≤ 20 kg N ha-1 yr-1 started to mobilize. Understory vascular plant cover expansion was muted when deposition was ≥ 10 kg N ha-1 yr-1. Finally, modeling suggests the forest may not leach N below the rooting zone until around 50 years after chronic addition begin (25 kg N ha-1 yr-1). The modeling results are consistent with empirical data from a high exposure (~20 - 25 kg N ha-1 yr-1) jack pine site approximately 12 km west of the experimental site that has not yet experienced N leaching. Author Keywords: Biogeochemistry, Canopy, Deposition, Jack Pine, Nitrogen, Understory
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- Phosphorus delivery in the Rainy-River Lake of the Woods Watershed
- Lake of the Woods (LOW) is a large international waterbody which suffers from frequent and widespread algae blooms. Previous studies have highlighted the importance of the lake's largest tributary, the Rainy River (RR) and its significance in total phosphorus (TP) delivery to the LOW. Unfortunately, little is known about TP contributions from the RR and its tributaries within the Canadian portion of the watershed. This thesis examines patterns and sources of TP from four tributaries on the Canadian side of the lower RR region, two of which are predominantly natural, and two that are predominantly agricultural. Relationships between water quality parameters, land use and geologic characteristics were observed over a complete hydrologic year (Oct 1, 2018 - Sept 31, 2019), and through an intensive sampling campaign using a nested watershed approach during the spring high flow and summer low flow periods. Results revealed that TP and total suspended sediment (TSS) concentrations (>100 µg/L and >20 mg/L respectively), and loads (>20 kg/km2 and >3500 kg/km2, respectively), were greater at agricultural sites compared with natural sites (<65 µg/L TP and <15 mg/L TSS concentration, and <20 kg/km2 TP and <4000 kg/km2 TSS export). Total P, TSS, Fe, and Al were significantly positively correlated (R2= 0.26-0.59; p<0.05) and intensive sampling revealed that these relationships were strongest during the spring and at the agricultural sites (R2= 0.73-0.98; p<0.05). In contrast, the summer intensive sampling revealed that TP and redox sensitive Fe were significantly correlated (R2= 0.72; p<0.005), whereas redox insensitive Al and TSS were not, suggesting TP may be sourced via redox processes in the summer due to favourable hydrologic conditions. This was observed not only at sites with high wetland influence, but also at sites with more agricultural presence suggesting that redox sourced TP may also originate from mineral stream bed sediment during low flow periods. This research suggested two primary TP sources in the lower RR region: erosion in the spring, and redox processes (internal release) in the summer. It is recommended that intensive monitoring continue in Canada, and further research be conducted to fully understand the significance of internal P release in the tributaries. Author Keywords: erosion, land use, nutrients, particulates, redox, water quality