Graduate Theses & Dissertations


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)
Regional Assessment of Soil Calcium Weathering Rates and the Factors that Influence Lake Calcium in the Muskoka River Catchment, Central Ontario
(MRC) in central Ontario was carried out to determine the range and spatial distribution of soil Ca weathering rates, and investigate the relationships between lake Ca and soil and catchment attributes. The MRC is acid-sensitive, and has a long history of impacts from industrial emission sources in Ontario and the United States. Small headwater catchments were sampled for soil and landscape attributes (e.g. elevation, slope, catchment area) at 84 sites. Soil Ca weathering rates, estimated with the PROFILE model, were low throughout the region (average: 188 eq/(ha·yr)) compared to global averages, and lower than Ca deposition (average: 292 eq/(ha·yr)). Multiple linear regression models of lake Ca (n= 306) were dominated by landscape variables such as elevation, which suggests that on a regional scale, landscape variables are better predictors of lake Ca than catchment soil variables. Author Keywords: Calcium, Lakes, Regional assessment, Regression, Soils, Weathering
Impact of Wetland Disturbance on Phosphorus Loadings to Lakes
Total phosphorus (TP) concentrations have declined in many lakes and streams across south- central Ontario, Canada over the past three decades and changes have been most pronounced in wetland-dominated catchments. In this study, long-term (1980-2007) patterns in TP concentrations in streams were assessed at four wetland-dominated catchments that drain into Dickie Lake (DE) in south-central Ontario. Two of the sub-catchments (DE5 and DE6) have particularly large wetland components (31-34 % of catchment area), and wetlands are characterised by numerous standing dead trees and many young live trees (18 – 27 year old). These two streams exhibited large peaks in TP and potassium (K) export in the early 1980s. In contrast, TP and K export from DE8 and DE10 (wetland cover 19 – 20 %) were relatively flat over the entire record (1980-2007), and field surveys indicated negligible standing dead biomass in these wetlands, and a relatively healthy, mixed-age tree community. Furthermore, K:TP ratios in the DE5 and DE6 streams were around 5 in the early 1980s; very similar to the K:P ratio found in biomass, and as stream TP levels fell through the 1980s, K:TP ratios in DE5 and DE6 stream water increased. The coincidence of high TP and K concentrations in the DE5 and DE6 streams as well as evidence of a disturbance event in their wetlands during the early 1980s suggest that the two are related. The diameter of standing dead trees and allometric equations were used to estimate the amount of TP that would have been held in readily decomposed tree tissues in the DE5 wetland. The amount of P that would have been held in the bark, twig, root and foliage compartments of just the standing dead trees at DE5 was approximately half of the amount of excess stream TP export that occurred in the 1980s. This work suggests that disturbance events that lead to wetland tree mortality may contribute to patterns in surface water TP observed in this region. Author Keywords: Chemistry, Disurbance, Nutrients, Tree Death, Water, Wetland
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
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
Effects of road salt sodium on soil
While previous studies have focused on how road salt affects water quality and vegetation, limited research has characterized road salt distribution through soil and the resulting impacts. The potential for sodium (Na+) to be retained and impact soil physical and chemical properties is likely to vary depending on the soil’s parent material, and more specifically on the extent of base saturation on the cation exchange complex. This thesis contrasted Na+ retention, impacts, and mobility in roadside soils in two different parent materials within southern Ontario. Soils were sampled (pits and deep cores) during fall 2013 and spring 2014 from two sites along highways within base-poor, Precambrian Shield soil and base-rich soil, respectively. Batch experiments were subsequently performed to investigate the influence of parent material and the effect of co-applied Ca2+-enriched grit on the longevity of Na+ retention in soils. Less Na+ is adsorbed upon the co-application of Ca2+, suggesting grit has a protective effect on soil by increasing cation exchange competition. Positive correlations between Na+ and pH, and negative correlations between Na+ and soil organic matter, % clay and base cations within Shield soils suggest that they are more vulnerable to Na+ impacts than calcareous soils due to less cation exchange competition. However, Na+ is more readily released from calcareous roadside soils, suggesting there is greater potential for Na+ transfer to waterways in regions dominated by calcareous soils. Author Keywords: cation exchange, parent material, road salt, sodium retention, urban soil
Acidification of lakes in northern Saskatchewan
The emission of acid precursors by large point sources in Western Canada (such as the Athabasca Oil Sands Region) has prompted studies into the possible impact to downwind aquatic and terrestrial ecosystems. Sensitivity of catchments to acidic deposition was estimated for the total lake population of northern Saskatchewan (n=89,947) using regression kriging. Under the Steady State Water Chemistry model, a range of 12-15% of the total catchment population was predicted to be in exceedance of critical loads under 2006 deposition levels and 6% of catchments were estimated to be very sensitive (pH below 6 and acid neutralizing capacity, alkalinity, calcium below 50 eqL-1). Temporal changes in soil and water chemistry estimated for 18 Alberta and Saskatchewan catchments using the Very Simple Dynamic and PROFILE models showed that changes in soil base saturation and lake acid neutralizing capacity between 1850 and 2100 were slight, declining 0.8% and 0.9% by 2012, respectively. Author Keywords: acidification, critical loads, exceedance, PROFILE, regression kriging, VSD
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
Influence of nitrogen deposition on the vegetation community of Irish oak woodlands
In this study, the influence of N deposition on the vegetation community of semi-natural oak woodlands in Ireland was assessed through national and regional scale analysis of forest plot data. At both scales, Canonical Correspondence Analysis suggested that N deposition was a predictor of community composition, although site-specific soil characteristics were the strongest predictors of the species dataset. Threshold Indicator Taxon Analysis suggested that the vegetation community demonstrated the most change at 13.2 kg N ha-1 yr-1. While this change point falls within the current recommended critical load range for nutrient nitrogen for acidophilous oak dominated woodlands (10 to 15 kg N ha-1 yr-1), it is notable that 23% of species recorded had individual change points below this range, and could potentially be lost from this habitat if deposition increases. The results from this study suggest that, for acidophilous oak woodlands, habitat conservation policies should be unified with N emission reduction policies. Author Keywords: community composition, critical load, nitrogen depositioin, oak woodland, species richness, Taxon Indicator Threshold Analysis
Spatial and Temporal Variation in Peatland Geochemistry in Sudbury, Ontario, Canada
The damage to Sudbury's landscape from over a century of smelter and logging activity has been severe and impacts well documented. However, despite their abundance in the region, wetlands have received little attention. Recent studies have identified that nutrient limitation is as much a problem as metal toxicity and highlighted not only the importance of wetlands but also the need for more detailed studies examining the role of wetlands in the recovery of lakes. The objective of this work is to characterize the spatial and temporal variability in the geochemistry of 18 wetlands (poor fens) surrounding Sudbury, Ontario. Peat and water chemistry in the wetlands exhibited large spatial and temporal variability. Copper and Ni concentrations in surface peat decreased with distance from the largest smelter in the area, but water chemistry was also strongly influenced by natural factors such as climate, groundwater and peat carbon content. Redox processes contribute greatly to temporal variation in pore-water chemistry: the August and October campaigns were characterized by higher SO4, lower pH and higher concentrations of metals such as Ni, Cu and Mn compared with the May campaign. Other factors contributing to the temporal variability in pore water chemistry include DOC production, senescence and water source. Despite the large variability, soil-solution partitioning can be explained by pH alone for some metals. Modeling is significantly improved with the addition of other variables representing dissolved organic matter quality and quantity, sulphate concentration and hydrology. Author Keywords: metal contamination, metal mobility, organic matter quality, peatland geochemistry
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
The objective of this thesis was to assess the influence of anthropogenic sulphur (S) and nitrogen (N) deposition, and harvesting on soil acidity and calcium (Ca2+), magnesium (Mg2+), potassium (K+) and N soil pools in plantation forest soils in Ireland. The response to reductions in anthropogenic S deposition was assessed using temporal trends in soil solution chemistry at two long-term monitoring plots--one on a blanket peat, the other on a peaty podzol. At the peat site, there was little evidence of a response to reductions in throughfall non marine sulphate (nmSO42-) and acidity; soil water acidity was determined by organic acids. In addition, temporal variation in soil water did not respond to that in throughfall. In the podzol, reductions in anthropogenic S and H+ deposition led to a significant improvement in soil water chemistry at 75 cm; pH increased and total aluminum (Altot) concentrations declined. The impact of harvest scenarios on exchangeable Ca2+, Mg2+ and K+ pools was assessed using input-output budgets at 40 sites (30 spruce, 10 pine). Harvest scenarios were stem-only harvest (SOH), stem plus branch harvest (SBH) and stem, branch and needle harvest (whole-tree harvesting; WTH). Average K+ and Mg2+ budgets were positive under these scenarios. However, exchangeable K+ pools were small and due to uncertainty in K+ budgets, could be depleted within one rotation. Average Ca2+ budgets for spruce were balanced under SOH, but negative under SBH and WTH. Nitrogen deposition was high, between 5 and 19 kg N ha-1 yr-1, but was balanced by N removal in SOH. However, N budgets were under SBH and WTH, indicating that these harvesting methods would lead to depletion of soil N over the long-term. Finally, monitoring of N cycling at a spruce plot indicated that N deposition was contributing to large NO3- leaching, and as such the site was N saturated. However, N cycling did not fit the criteria of the N saturation hypothesis; instead leaching was directly related to N deposition and supported the model of kinetic N saturation. Author Keywords: acidic deposition, base cations, input-output budgets, Ireland, nitrogen, whole-tree harvesting


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