Graduate Theses & Dissertations

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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
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
Effects of flooding on nutrient budgets and ecosystem services
Increases in flooding due to anthropogenic influences such as climate change and reservoir creation will undoubtedly impact aquatic ecosystems, affecting physical, chemical, and biological processes. We used two approaches to study these impacts: a whole-ecosystem reservoir flooding experiment and a systematic literature review. In the whole-ecosystem experiment, we analyzed the impact of flooding on nutrient release from stored organic matter in an upland forest. We found that flooded organic matter produced N (nitrogen) and P (phosphorus), but that more N was released relative to P, increasing the N:P ratio over time. In the systematic literature review, we linked small (<10 year recurrence interval) and extreme (>100 year recurrence interval) floods to changes in 10 aquatic ecosystem services. Generally, extreme floods negatively impacted aquatic ecosystem service provisioning, while small floods contributed positively. Overall, we found that flood impacts vary depending on ecosystem properties (organic matter content) and flood characteristics (magnitude). Author Keywords: ecosystem services, flooding, nutrients, reservoirs, rivers
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
Ostrich Eggshell from the Far Eastern Steppe
This study uses stable isotope analysis on both the organic and inorganic fractions of ostrich eggshell obtained from archaeological excavations in Mongolia, northern China, and southern Siberia. By establishing the δ13Corg, δ15N, δ13Cinorg, δ18O isotopic compositions of the eggshell of the Asian ostrich (Struthio asiaticus), this study provides insight into the maximum northern range of the species, which I suggest reached Lake Baikal, Siberia through the late Pleistocene, up to the Last Glacial Maximum. Through these isotopic data, the interactions between S. asiaticus and human forager groups are explored, specifically the trade of ostrich eggshell by hunter/gatherer populations in the early/middle Holocene. Because of deviations from the correlation between δ18O and latitude observed for other sites, the site of Shabarakh-usu may have been an aggregation point for ostrich eggshell from other locations. Movement of eggshell is observable from north to south but not from south to north on the basis of eggshell δ18O. Finally, I am able to develop a hypothesis regarding the drivers of species extinction. Specifically, I discuss trade in eggshell leading up to extinction as evidence for human pressure on S. asiaticus at a time when environmental shifts likely isolated populations in small regions of habitable landscape. I therefore implicate both changing environmental conditions and human pressure in my proposed explanation for the extinction of S. asiaticus. Author Keywords: Extinction, Holocene, ostrich, Pleistocene, Steppe, Struthio
influence of tree species litterfall on soil chemistry and implications for modelling soil recovery from acidification
Decades of acidic deposition have depleted base cation pools in soil over large parts of eastern north America, including the Muskoka-Haliburton region of central Ontario. This region has also experienced a shift in forest species composition over the past 200 years, favouring sugar maple (Acer saccharum Marsh.) at the expense of species such as white pine (Pinus strobus L.) and eastern hemlock (Tsuga canadensis (L.) Carr.). This shift in species composition may have changed soil chemistry over time due to differences in nutrient and metal inputs in litterfall. An analysis of litterfall and soil chemistry was conducted for five tree species commonly found across central Ontario. Stands were established in the Haliburton Forest & Wild Life Reserve and were dominated by one of balsam fir (Abies balsamea (L.) Mill.), eastern hemlock, white pine, sugar maple, or yellow birch (Betula alleghaniensis Britt.). Analysis of mineral soil oxides suggested that these stands were established on similar parent material. Deciduous dominated stands (maple and birch) had greater litterfall mass compared with conifer stands (fir, hemlock, and pine), generally leading to greater macronutrient inputs to the soil. Elemental cycling through the organic horizons was more rapid in deciduous stands, with base cations having the shortest residence times. This suggests that a change from greater conifer dominance to mixed hardwood forests may lead to more rapid elemental cycling and alter the distribution of elements in soil. Forests in the region are typically mixed and the resulting differences in soil chemistry may influence model predictions of soil recovery from acidification. Laboratory leaching tests indicated that both stand type and the acidity of simulated rainwater inputs influenced soil solution chemistry, with deciduous stands generally having a greater buffering capacity than sites dominated by coniferous species. Changes in soil chemistry were examined for each stand type using the Very Simple Dynamic (VSD) biogeochemical model. Simulations showed that soil base saturation began to increase following lows reached around the year 2000, and similar patterns were observed for all stands. When sulphur (S) and nitrogen (N) deposition were held constant at present rates, soil base saturation recovery (toward pre-1900 levels) was marginal by 2100. With additional deposition reductions, further increases in base saturation were minor at all sites. In conjunction with additional deposition reductions, the elimination of future forest harvesting allowed for the greatest potential for recovery in all stands. Overall, these results suggest that changes in forest cover may influence soil chemistry over time, most notably in the organic soil horizons. However, forecasted recovery from acidification is expected to follow similar patterns among stands, since differences in soil chemistry were less significant in the mineral soil horizons which compose a greater proportion of the soil profile. Author Keywords: base cation decline, forest harvesting, litterfall, mineral weathering, soil acidification, VSD model
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
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
Patterns of Vegetation Succession on Nickel-Copper Mine Tailings near Sudbury, Ontario
Natural establishment of vegetation on mine tailings is generally limited. Understanding the processes leading to vegetation germination and the survival mechanisms that vegetation species employ in these harsh environments is critical to future remediation efforts. As metalliferous mine tailings are generally nutrient-poor, high in harmful metals, and acidic, vegetation species require distinct mechanisms to germinate and survive in such harsh environments. In this study, edaphic and biotic factors linked to vegetation establishment and diversity were studied at two nickel-copper (Ni-Cu) tailings sites near Sudbury, Ontario. One site had experienced minimal treatment, and the second site was split into partial (hand-distribution of lime) and full (lime, fertilizer, seeding) treatment areas. Tailings were generally acidic, low in organic matter and “available” nutrients, and high in metals such as Al, Cu, Fe, and Ni, but these physical and chemical properties were extremely spatially variable. At both sites, vegetation was distributed in sparse patches, with the greatest diversity in treated areas. There was no clear link between metals and vegetation establishment/diversity at the sites. The primary limiting nutrients on the tailings were phosphorous (P) and potassium (K), and while there were areas of increased soil fertility at the sites, they were not clearly associated with increased vegetation diversity. Both traditional ecological succession and nucleation succession patterns were observed on the site, and the chief species associated with nucleation were primary colonizing trees such as B. papyrifera and P. tremuloides. The relationship between B. papyrifera nutrient retranslocation and tailings restoration was assessed and while B. papyrifera at the sites were deficient in P and K, the trees efficiently retranslocated both P and K during senescence. This research can provide insight into possibilities for future revegetation of similar tailings, enabling industry to make educated decisions when choosing where and how to revegetate, mimicking natural succession patterns. Author Keywords: Acid-mine drainage, Betula papyrifera, ecosystem health, metals, Sudbury, tailings
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
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
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

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