Graduate Theses & Dissertations

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Phosphorus forms and response to changes in pH in acid-sensitive soils on the Precambrian Shield
Catchment soil acidification has been suggested as a possible mechanism for reducing phosphorus (P) loading to surface waters in North America and northern Europe, but much of the research that has been conducted regarding P immobilization in pH manipulated soils has been performed at high P concentrations (> 130 μM). This study investigated how soil acidity was related to P fractionation and P sorption at environmentally relevant P concentrations to evaluate the potential influence of long term changes in soil pH on P release to surface waters. Total phosphorus (TP) concentrations declined between 1980 and 2000 in many lakes and streams in central Ontario; over the same time period forest soils in this region became more acidic. Soils were collected from 18 soil pits at three forested catchments with similar bedrock geology but varying TP export loads. The soil pH at the 18 study soil pits spanned the historic soil pH range, allowing for `space for time' comparison of soil P factions. Soils were analysed by horizon for P fractions via Hedley P fractionation. Batch P sorption experiments were performed on selected B-horizon soils at varied solution pH. Soil P fractions varied by horizon but were comparable among the three catchments, with only apatite (PHCl) differing significantly across catchments. Contrary to expectation, both soluble and labile P showed negative relationships with pH in some horizons. Mineral soils were able to sorb almost all (> 90 %) of the P in solution at environmentally relevant P concentrations (4.5 - 45.2 μM). Phosphorus sorption at environmentally relevant P concentrations was unrelated to solution pH but at high P concentration there was a positive relationship between P sorption and solution pH, suggesting a P concentration dependant P sorption mechanism. Phosphorus budgets indicate that P is accumulating within catchments, suggesting that P is being immobilized in the terrestrial environment. An alternative hypothesis, which attempts to explain both the decline in stream TP export and terrestrial P accumulation, is discussed. The results from this study suggest that acidification induced P sorption in upland soils are not a contributing factor to decreases in stream TP concentration in the study catchments. Author Keywords: central Ontario, Hedley fractionation, phosphorus, podzols, soil acidification, sorption
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
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
Variation in the δ15N and δ13C composition of POM in the Lake Simcoe watershed
The purpose of this study was to quantify the variation of baseline carbon and nitrogen stable isotope signatures in the Lake Simcoe watershed and relate that variation to various physicochemical parameters. Particulate organic matter samples from 2009 and 2011 were used as representatives of baseline isotopic values. Temporal data from two offshore lake stations revealed that δ15N of POM was lowest mid-summer and highest after the fall turnover. POM δ13C was variable throughout the summer before declining after fall turnover. Spatial data from the lake and the tributaries revealed that POM stable isotope signatures were highly variable. Various physicochemical parameters indicative of phytoplankton biomass were significantly positively correlated with POM δ15N and significantly negatively correlated with POM δ13C. The correlations were mostly significant in the tributaries, not the lake. Moreover, many of the correlations involving δ15N of POM were driven by extreme values in Cook's Bay and its tributaries. In general, it's likely that different processes or combination of processes were affecting the δ15N and δ13C POM in the Lake Simcoe watershed as physicochemical parameters alone could not explain the variability. Measuring the δ15N of ammonium and nitrate, as well as the δ13C of DIC would help discern the dominant nitrogen and inorganic carbon cycling processes occurring in the Lake Simcoe watershed. Author Keywords: δ13C, δ15N, isotopic baseline, particulate organic matter, spatial variation, stable isotopes
Investigating the sources and fate of monomethylmercury and dimethylmercury in the Arctic marine boundary layer and waters
Monomethylmercury (MMHg), the most bioavailable form of mercury (Hg) and a potent neurotoxin, is present at elevated concentrations in Arctic marine mammals posing serious health threats to the local populations relying on marine food for their subsistence living. The sources of MMHg in the Arctic Ocean surface water and the role of dimethylmercury (DMHg) as a source of MMHg remain unclear. The objective of this research was to determine the sources and fate of methylated Hg species (MMHg and DMHg) in the marine ecosystem by investigating processes controlling the presence of methylated Hg species in the Arctic Ocean marine boundary layer (MBL) and surface waters. A method based on solid phase adsorption on Bond Elut ENV was developed and successfully used for unprecedented measurement of methylated Hg species in the MBL in Hudson Bay (HB) and the Canadian Arctic Archipelago (CAA). MMHg and DMHg concentrations averaged 2.9 ± 3.6 (mean ± SD) and 3.8 ± 3.1 pg m-3, respectively, and varied significantly among sampling sites. MMHg in the MBL is suspected to be the product of marine DMHg degradation in the atmosphere. MMHg summer (June to September) atmospheric wet deposition rates were estimated to be 188 ± 117.5 ng m-2 and 37 ± 21.7 ng m-2 for HB and CAA, respectively, sustaining MMHg concentrations available for bio-magnification in the pelagic food web. The production and loss of methylated Hg species in surface waters was assessed using enriched stable isotope tracers. MMHg production in surface water was observed from methylation of inorganic Hg (Hg(II)) and, for the first time, from DMHg demethylation with experimentally derived rate constants of 0.92 ± 0.82 x 10-3 d-1 and 0.04 ± 0.02 d-1 respectively. DMHg demethyation rate constant (0.98 ± 0.51 d-1) was higher than that of MMHg (0.35 ± 0.25 d-1). Furthermore, relationships with environmental parameters suggest that methylated Hg species transformations in surface water are mainly biologically driven. We propose that in addition to Hg(II) methylation, the main processes controlling MMHg production in the Arctic Ocean surface waters are DMHg demethylation and deposition of atmospheric MMHg. These results are valuable for a better understanding of the cycle of methylated Hg in the Arctic marine environment. Author Keywords: Arctic Ocean, Atmosphere, Demethylation, Dimethylmercury, Methylation, Monomethylmercury
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
regional comparison of the structure and function of benthic macroinvertebrate communities within Precambrian Shield and St. Lawrence lowland lakes in south-central Ontario
Benthic macroinvertebrtes (BMI) are functionally important in aquatic ecosystems; as such, knowledge of their community structure and function is critical for understanding these systems. BMI were sampled from ten lakes in each of two regions of south-central Ontario to investigate which chemical and physical variables could be shaping their community structure and function. Ten Precambrian Shield lakes in the Muskoka-Haliburton region, and ten St Lawrence lowland lakes in the Kawartha lakes region were sampled. These lakes are geologically and chemically distinct, creating natural chemical and physical gradients within and between both regions. Community function was assessed using stable isotope analysis to elucidate carbon transfer dynamics (δ13C) and food web interactions (δ15N). It was predicted that the BMI from Shield lakes would have a δ13C signature indicative of allochthonous carbon subsidies, whereas the lowland lake BMI signatures would reflect autochthonous production. Additionally, it was predicted that the food web length (measured in δ15N units) would be different in Shield and lowland lakes. Both of these predictions were supported; however, the data indicate that δ13C signatures are more likely influenced by catchment geology (represented by bicarbonate concentration) than the extent of allochthony. The best predictor of food web length was found to be region. To assess BMI community structure, taxonomic richness, %EPT (% Ephemeroptera, Plecoptera, Trichoptera; a water quality index), and distribution of functional feeding groups were examined. Based on chemistry it was expected that the Shield lakes would be more speciose, and of greater water quality (relatively lower nutrient levels). These predictions were rejected; since there were no significant regional differences in taxonomic richness or biologically inferred water quality (%EPT). However, sediment size was found to best explain the variability in both metrics, with greater richness and %EPT found at sites with medium and small substrates than those with large substrates. Significant regional differences were found in the distribution of functional feeding groups. Most notably, there were significantly greater proportions of scrapers and shredders in the lowland and Shield lakes, respectively. Based on the feeding mechanisms of these invertebrates it can be inferred that allochthonous subsidies are likely of greater importance to Shield lake BMI communities than those of the lowland lakes; supporting the carbon transfer prediction. These findings provide insight about the structure and function of BMI communities from two dominant lake types in Ontario, and could be useful when determining how future chemical and physical changes will impact these communities. Author Keywords: benthic macroinvertebrates, community function, community structure, Precambrian Shield, stable isotopes, St. Lawrence lowlands
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)
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
Effects of wood ash addition on soil chemical properties and sugar maple (Acer saccharum, Marsh.) seedling growth in two northern hardwood forest sites in central Ontario
One possible solution to acidification and losses of base cations in central Ontario forest soils may be the application of wood ash. Wood ash is generally high in pH and contains large amounts of calcium (Ca) and other nutrients essential for ecosystem health, however it also contains trace metals. Understanding the chemistry of soils following ash application to forests is crucial for future policy recommendations and remediation efforts. In this study, soil and soil water chemistry was measured at two acidic forest sites in central Ontario. Sugar maple (Acer saccharum, Marsh.) seedling growth and chemistry, as well as understory vegetation composition, were also measured. At site one, plots (2 m x 2 m) were established with sugar maple, white pine (Pinus strobus L.) and yellow birch (Betula alleghaniensis Britt.) residential wood ash treatments and applied at rates of 0 and 6 Mg ha-1. The effects of residential wood ash on soil and understory vegetation were measured three- and 12-months following ash addition. At site two, plots (5 m x 5 m) were established with both fly and bottom industrial grade bark ash treatments of 0, 4 and 8 Mg ha-1 (n=4), and tension lysimeters were positioned in each plot at 30, 50, and 100 cm depths. The effects of industrial grade wood ash on soil, soil water and understory vegetation were measured four years following ash addition. Metal concentrations in the ashes were generally low but were higher in the fly ash and yellow birch ash types. At site one, significant increase in soil pH, and Ca and magnesium (Mg) concentrations were observed after three months, however changes varied by treatment. Some metal concentrations increased in the upper organic horizons, but metals were likely immobilized in the soil due to increases in soil pH, electrical conductivity (EC) and high organic matter content of the soil. After one year, changes to metal concentrations in soils could be seen in mineral horizons, and a few metals (aluminum (Al), zinc (Zn), copper (Cu), chromium (Cr), strontium (Sr)) increased in treatment plots. At site two, the effects of industrial-grade bark ashes on soil pH could still be seen after four years and soil water metal concentrations were not elevated relative to controls. Changes to understory vegetation composition following ash application were observed, but ash addition had no significant effect on sugar maple seedling growth (root:shoot ratio) and did not lead to significant increases in foliar metal concentrations. There were significant differences in root chemistry, suggesting metal translocation and uptake could be restricted. Mass balance estimates indicate that the organic horizon is a sink for all metals and simulated drought in this horizon led to a decrease in soil pH and increase in soil water metal concentration, but this occurred in all treatments including control. These results suggest that application of industrial and residential wood ash in moderate doses with trace metal concentrations below or near regulatory limits will increase soil pH and base cation concentrations, as well as increase seedling tissue nutrient concentrations in northern hardwood forest soils. However, depending on the parent material of the ash, increased metal availability can also occur. Author Keywords: Acer saccharum, calcium decline, forest soil amendment, Haliburton Forest and Wildlife Reserve, heavy metal, wood ash
Fingerprinting of dissolved organic matter and copper ligands in the Canadian Arctic and North Pacific Ocean
Dissolved organic matter (DOM) in oceans provides nutrients and ultraviolet radiation protection to microbes. Some DOM compounds can chelate with metals, including copper, controlling their transport and bioavailability in marine systems. As copper functions as both a nutrient and toxicant, studies into the chemical structures of Cu-ligands is important, however currently limited. In this thesis, the chemical composition of total and Cu-binding DOM is investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in the Canadian Arctic and North Pacific. Chapter 2 reveals chemical differences in DOM composition between the southern and northern Canada Basin, revealing the influence of terrestrial and biological sources. Chapter 3 shows the uniqueness of Cu-binding ligands found in the Canadian Arctic and North Pacific Ocean. Studying the composition of DOM gives insight into the chemical diversity of marine DOM, helping to predict the effects of a changing climate on marine ecosystems. Author Keywords: biological, dissolved organic matter, fluorescence, immobilized metal-ion affinity chromatography, mass spectrometry, terrestrial

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