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
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
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
Phosphorus deposition in forested watersheds
Phosphorus (P) is an essential macronutrient. In south-central Ontario, foliar P concentrations are low and studies have suggested that P may be limiting forest productivity. Current catchment mass balance estimates however, indicate that P is being retained suggesting that P should not be limiting to tree growth. Phosphorus deposition is measured using bulk deposition collectors, which are continuously open and therefore are subject to contamination by pollen and other biotic material with high P and potassium (K) concentrations and may therefore overestimate net P inputs to forested catchments. Average annual TP and K deposition at three long-term (1984 – 2013) monitoring sites near Dorset, Ontario ranged from 15 to 20 mg·m-2y-1 and 63 to 85 mg·m-2y-1, respectively, and was higher at Paint Lake compared with Plastic Lake and Heney Lake. Phosphorus and K in bulk precipitation were strongly positively correlated, but deposition patterns varied spatially and temporally among the three sites. Total phosphorus and K deposition increased significantly at Plastic Lake and decreased significantly at Paint Lake, but there was no significant trend in TP or K deposition at Heney Lake over the 30 year period. All sites, but especially Paint Lake, exhibited considerable inter-annual variation in TP and K deposition. To quantify the contribution of pollen, which represents an internal source of atmospheric P deposition, Durham pollen collectors during the spring and summer of 2014 were used. The three sites, Paint Lake, Heney Lake, and Plastic Lake had pollen deposition amounts of 5202 grains·cm-2, 7415 grains·cm-2, and 12 250 grains·cm-2, respectively in 2014. Approximately 83% of pollen deposition can be attributed to white pine and red pine that has a concentration of 3 mg·g-1 of P. It was estimated that pollen alone could account for up to one-third of annual bulk P deposition. Extrapolating winter P deposition values to exclude all potential biotic influences (insects, bird feces, leaves), indicates that bulk deposition estimates may double actual net P to forests, which has implications for long-term P availability, especially in harvested sites. Author Keywords: Atmospheric Deposition, Phosphorus, Pine, Pollen, Potassium, South-Central Ontario
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
Early Responses of Understory Vegetation to Above Canopy Nitrogen Additions in a Jack Pine Stand in Northern Alberta
Abstract Early Responses of Understory Vegetation After One Year of Above Canopy Nitrogen Additions in a Jack Pine Stand in Northern Alberta Nicole Melong Nitrogen (N) emissions are expected to increase in western Canada due to oil and gas extraction operations. An increase in N exposure could potentially impact the surrounding boreal forest, which has adapted and thrived under traditionally low N deposition. The majority of N addition studies on forest ecosystems apply N to the forest floor and often exclude the important interaction of the tree canopy. This research consisted of aerial NH4NO3 spray applications (5, 10, 15, 20, 25 kg N ha-1yr-1) by helicopter to a jack pine (Pinus banksiana Lamb.) stand in the Athabasca Oil Sands Region (AOSR) in northern Alberta, Canada. The main objective was to assess the impacts of elevated N after one year of treatment on the chemistry of understory vegetation, which included vascular plants, terricolous lichens, epiphytic lichens and a terricolous moss species. Changes in vegetation chemistry are expected to be early signs of stress and possible N saturation. Increased N availability is also thought to decrease plant secondary compound production because of a tradeoff that exists between growth and plant defense compounds when resources become available. Approximately 60% of applied N reached the ground vegetation in throughfall (TF) and stemflow (SF). Nitrate was the dominant form of N in TF in all treated plots and organic N (ON) was the dominant form of N in SF in all plots. The terricolous non-vascular species were the only understory vegetation that responded to the N treatments as N concentration increased with increased treatment. Foliar chemistry of the measured epiphytic lichens, vascular species, and jack pine was unaffected by the N treatments. Based on biomass measurements and N concentration increases, the non-vascular terricolous species appear to be assimilating the majority of TF N after one year. Vegetation from the high treatment plot (25 kg N ha-1yr-1) was compared to a jack pine forest receiving ambient high levels of N (21 kg N ha-1yr-1) due to its proximity to Syncrude mining activities. Nitrogen concentrations in plant tissues did not differ between the two sites; however, other elements and compounds differed significantly (Ca, Mg, Al, Fe). After one year of experimental N application, there were no environmental impacts consistent with the original N saturation hypothesis. Author Keywords: Athabasca Oil Sands Region, Canopy Interactions, Jack Pine, Nitrogen, Secondary Chemistry, Understory Vegetation
Hydroclimatic and spatial controls on stream nutrient export from forested catchments
Winter nutrient export from forested catchments is extremely variable from year-to-year and across the landscape of south-central Ontario. Understanding the controls on this variability is critical, as what happens during the winter sets up the timing and nature of the spring snowmelt, the major period of export for water and nutrients from seasonally snow-covered forests. Furthermore, winter processes are especially vulnerable to changes in climate, particularly to shifts in precipitation from snow to rain as air temperatures rise. The objective of this thesis was to assess climatic and topographic controls on variability in stream nutrient export from a series of forested catchments in south-central Ontario. The impacts of climate on the timing and magnitude of winter stream nutrient export, with particular focus on the impact of winter rain-on-snow (ROS) events was investigated through a) analysis of long-term hydrological, chemical and meteorological records and b) high frequency chemical and isotopic measurements of stream and snow samples over two winters. The relationship between topography and variability in stream chemistry among catchments was investigated through a) a series of field and laboratory incubations to measure rates and discern controls on nitrogen mineralization and nitrification and b) analysis of high resolution spatial data to assess relationships between topographic metrics and seasonal stream chemistry. Warmer winters with more ROS events were shown to shift the bulk of nitrate (NO3-N) export earlier in the winter at the expense of spring export; this pattern was not observed in other nutrients [i.e. dissolved organic carbon (DOC), total phosphorus (TP), sulphate (SO4), calcium (Ca)]. Hydrograph separation revealed the majority of ROS flow came from baseflow, but the NO3-N concentrations in rainfall and melting snow were so high that the majority of NO3-N export was due to these two sources. Other nutrient concentrations did not show such a great separation between sources, and thus event export of these nutrients was not as great. Proportionally, catchments with varying topography responded similarly to ROS events, but the absolute magnitude of export varied substantially, due to differences in baseflow NO3-N concentrations. Field and laboratory incubations revealed differences in rates of net NO3-N production between wetland soils and upland soils, suggesting that topographic differences amongst catchments may be responsible for differences in baseflow NO3-N. Spatial analysis of digital elevation models revealed strong relationships between wetland coverage and DOC and dissolved organic nitrogen (DON) concentrations in all seasons, but relationships between topography and NO3-N were often improved by considering only the area within 50 or 100m of the stream channel. This suggests nutrient cycling processes occurring near the stream channel may exert a stronger control over NO3-N stream outflow chemistry. Overall, topography and climate exert strong controls over spatial and temporal variability in stream chemistry at forested catchments; it is important to consider the interaction of these two factors when predicting the effects of future changes in climate or deposition. Author Keywords: biogeochemistry, forest, nitrate, south-central Ontario, stream chemistry, winter
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)
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
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
Molecular Composition of Dissolved Organic Matter Controls Metal Speciation and Microbial Uptake
Aquatic contaminant mobility and biological availability is strongly governed by the complexation of organic and inorganic ligands. Dissolved organic matter (DOM) is a complex, heterogeneous mixture of organic acids, amino acids, lipids, carbohydrates and polyphenols that vary in composition and can complex to dissolved metals thereby altering their fate in aquatic systems. The research conducted in this doctoral dissertation addresses 1) how DOM composition differs between phytoplankton taxa and 2) how DOM composition affects metal speciation and its subsequent microbial bioavailability in laboratory and field conditions. To accomplish this, a series of analytical methods were developed and applied to quantify thiols, sulphur containing DOM moieties, and the molecular composition of DOM. The works presented in this thesis represents one of the first comprehensive and multipronged analyses of the impact of phytoplankton metabolite exudates on microbial metal bioavailability. This dissertation demonstrated the analytical versatility of high-resolution mass spectrometry as a tool for compound specific information, as well as having the capabilities to obtain speciation information of organometallic complexes. The work presented in this PhD strengthens the understanding compositional differences of both autochthonous and allochthonous DOM and their effects on metal biogeochemistry. Author Keywords: Dissolved Organic Matter, Mercury, Metal Accumulation, Phytoplankton, Spring Melts, Thiol
Nitrogen Retention of Terricolous Lichens in a Jack Pine Forest in Northern Alberta
The Athabasca Oil Sands in Alberta, Canada is one of the largest point sources emitters of NOx in Canada and there are concerns that elevated nitrogen (N) deposition will lead to widespread eutrophication impacts, including altered species composition, similar to what has occurred in several parts of Europe. Atmospheric deposition rates as high as 25 kg N ha-1 yr-1 have been measured close to the industrial center. The role of the forest floor in regulating these potential eutrophication effects was investigated following a 5-year enrichment study in which N was applied as NH4NO3 above the canopy of a jack pine (Pinus banksiana Lamb) stand in northern Alberta close to Fort McMurray at dosages ranging from 5 – 25 kg N ha-1 yr-1 in addition to background deposition of 2 kg N ha-1 yr-1. Chemical analysis of lichen mats revealed that apical (upper) lichen tissue N concentration increased with treatment, as did the necrotic tissue. When expressed as a pool, the fibric-humic (FH) material held the largest quantity of N across all treatments due to its relatively large mass. Soil net N mineralization and net nitrification rates did not differ among N inputs after five years of application. A 15N tracer applied to the forest floor showed that N is initially absorbed by the apical lichen, FH material, and the foliage of the vascular plant Vaccinium myrtilloides in particular. After 2 years, the FH 15N pool size was elevated and all other measured pools were depleted, indicating a slow transfer of N to the FH material. Applied 15N was not detectable in mineral soil. The microbial functional gene ammonia monooxygenase (amoA) was undetectable using PCR screening of mineral soil microbial communities in all treatments, and broad fungal/bacterial qPCR assays revealed a weak treatment effect on fungal/bacterial ratios in mineral soil. This work suggests that terricolous lichen mats, which form the majority of ground cover in upland jack pine systems, have a large capacity to effectively retain elevated N deposition via the formation of stable humus. Author Keywords: Biogeochemistry, Boreal Ecology, Lichen, Nitrogen Enrichment, Oil Sands

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