Graduate Theses & Dissertations

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Equilibria and distribution models of ionizing organic chemical contaminants in environmental systems
Ionizing organic chemicals are recognized as constituting a large fraction of the organic chemicals of commerce. Many governments internationally are engaged in the time-consuming and expensive task of chemical risk assessment for the protection of human and environmental health. There are standard models that are consistently used to supplement experimental and monitoring data in such assessments of non-ionizing organics by both government regulators and industry stakeholders. No such standard models exist for ionizing organics. Equilibrium distribution models, the foundational equations within multimedia environmental fate models for non-ionizing organics, were developed for the standard series of biphasic systems: air-water, particle-water, air-particle and organic-aqueous phases within living tissue. Multiple chemical species due to the ionization reaction were considered for each system. It was confirmed that, under select conditions, the properties of the neutral parent are sufficient to predict the overall distribution of the organic chemical. Complications due to biotransformation and paucity of identifiable equilibrium distribution data for ionizing organics limited the development of the model for living tissues. However, the equilibrium distributions of ionizing organics within this biotic system were shown to correlate with the abiotic sediment-water system. This suggests that the model developed for particle-water systems should be adaptable to the biotic system as model input and test data become available. Observational data for soil- and sediment- water systems, i.e., particle-water systems, allowed the development of a primarily non-empirical distribution equation for mono-protic acids; this model was almost entirely theoretically derived. The theoretical approach to model development allowed a quantitative assessment of the role of the neutral ion pair, resulting from the complexation of the organic anion with metal cations. To demonstrate the model's potential usefulness in governmental screening risk assessments, it was applied to a broad range of mono-protic organics including drugs and pesticides using standard property estimation software and generic inputs. The order-of-magnitude agreement between prediction and observation typical of the existing models of non-ionizing organics was generally achieved for the chemicals tested. The model was sensitive to the octanol-water partition coefficient of the most populous species. No calibration set was used in the development of any of the models presented. Author Keywords: bioconcentration, chemical equilibrium, environmental modelling, ionizing organic, sorption
Fractionation of Mercury Isotopes in an Aqueous Environment
Fractionation of mercury isotopes in an aqueous environment: Chemical Oxidation Dimitri Stathopoulos The study of fractionation patterns for the stable isotopes of mercury is a growing field. The potential for stable isotopes to trace mercury through the environment from pollution sources to sinks make the subject interesting to geochemists and useful to a wider audience. The purpose of this study is to measure the fractionation of mercury as it is oxidized in an aqueous medium. Samples in this study are prepared by chemically oxidizing different proportions of elemental mercury using four different oxidants. The oxidized portion is then separated from the elemental portion and an analysis of the isotope ratios for both portions is performed using a multicollector inductively coupled plasma mass spectrometer MC-ICP/MS. These isotope ratios are measured against the preoxidation isotope ratio to determine what if any change has occurred. From the findings of this work, it is now known chemical oxidation causes both mass dependent and mass independent fractionation. Mass dependent fractionation causes an enrichment of the heavier isotopes in the oxidized portion while the opposite is true for the elemental portion. Mass independent fractionation occurred only in the odd isotopes and causes a depletion of odd isotopes in the oxidized portion and enrichment in the elemental portion. These trends were found to be true for all oxidants tested as the pattern of fractionation does not change with varying oxidants. Author Keywords: Isotope, Mass Dependent, Mass Independent, Mercury, Oxidation
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
Reintroducing species in the 21st century
Climate change has had numerous impacts on species' distributions by shifting suitable habitat to higher latitudes and elevations. These shifts pose new challenges to biodiversity management, in particular translocations, where suitable habitat is considered crucial for the reintroduced population. De-extinction is a new conservation tool, similar to reintroduction, except that the proposed candidates are extinct. However, this novel tool will be faced with similar problems from anthropogenic change, as are typical translocation efforts. Using ecological niche modelling, I measured suitability changes at translocation sites for several Holarctic mammal species under various climate change scenarios, and compared changes between release sites located in the southern, core, and northern regions of the species' historic range. I demonstrate that past translocations located in the southern regions of species' ranges will have a substantial decline in environmental suitability, whereas core and northern sites exhibited the reverse trend. In addition, lower percentages (< 50% in certain scenarios) of southern sites fall above the minimal suitability threshold for current and long-term species occurrence. Furthermore, I demonstrate that three popular de-extinction candidate species have experienced changes in habitat suitability in their historic range, owing to climate change and increased land conversion. Additionally, substantial increase in potentially suitable space is projected beyond the range-limits for all three species, which could raise concerns for native wildlife if de-extinct species are successfully established. In general, this thesis provides insight for how the selection of translocation sites can be more adaptable to continued climate change, and marks perhaps the first rigorous attempt to assess the potential for species de-extinction given contemporary and predicted changes in land use and climate. Author Keywords: climate change, de-extinction, ecological niche models, MaxEnt, reintroduction, translocation
ADAPT
This thesis focuses on the design of a modelling framework consisting of loose-coupling of a sequence of spatial and process models and procedures necessary to predict future flood events for the years 2030 and 2050 in Tabasco Mexico. Temperature and precipitation data from the Hadley Centers Coupled Model (HadCM3), for those future years were downscaled using the Statistical Downscaling Model (SDSM4.2.9). These data were then used along with a variety of digital spatial data and models (current land use, soil characteristics, surface elevation and rivers) to parameterize the Soil Water Assessment Tool (SWAT) model and predict flows. Flow data were then input into the Hydrological Engineering Centers-River Analysis System (HEC-RAS) model. This model mapped the areas that are expected to be flooded based on the predicted flow values. Results from this modelling sequence generate images of flood extents, which are then ported to an online tool (ADAPT) for display. The results of this thesis indicate that with current prediction of climate change the city of Villahermosa, Tabasco, Mexico, and the surrounding area will experience a substantial amount of flooding. Therefore there is a need for adaptation planning to begin immediately. Author Keywords: Adaptation Planning, Climate Change, Extreme Weather Events, Flood Planning, Simulation Modelling
Nutritional stoichiometry and growth of filamentous green algae (Family Zygnemataceae) in response to variable nutrient supply
In this study, I investigate the effects of nitrogen (N) and phosphorus (P) on the nutritional stoichiometry and growth of filamentous green algae of the family Zygnemataceae in situ and ex situ. I found a mean of Carbon (C):N:P ratio of 1308:66:1 for populations growing in the Kawartha Lakes of southern Ontario during the summer of 2012. FGA stoichiometry was variable, with much of the variation in algal P related to sediment P (p < 0.005, R2 = 0.58). Despite large variability in their cellular nutrient stoichiometry, laboratory analysis revealed that Mougeotia growth rates remained relatively consistent around 0.28 day-1. In addition, Mougeotia was found to be weakly homeostatic with respect to TDN:TDP supply (1/HNP = 0.32). These results suggest that FGA stoichiometry and growth rates are affected by sediment and water N and P. However, they will likely continue to grow slowly throughout the summer despite variable nutrient supply. Author Keywords: Chlorophyll concentration, Filamentous algae, Growth rate, Homeostatic regulation, Nutritional stoichiometry
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
Longitudinal trends of benthic invertebrates in regulated rivers
The Serial Discontinuity Concept describes the downstream recovery of key biophysical variables below an impoundment. With the proliferation of hydropower dams to meet increasing societal demands, further refinement and understanding of the Serial Discontinuity Concept is needed to accurately predict downstream impacts and ensure the proper management of rivers. In this study, I examine SDC predictions on physical, chemical and biological recovery in regulated rivers providing evidence from 1) a comprehensive literature review and 2) a formal test using two regulated rivers in Northern Ontario. I specifically address how these changes are reflected in benthic invertebrate abundance, diversity, and community composition. The literature review and case studies support the predicted recovery of temperature, periphyton, substrate, and drift. In addition, the study suggests that two recovery gradients exist in regulated rivers: 1) a longer, thermal gradient taking up to hundreds of kilometres downstream; and 2) a shorter, resource subsidy gradient recovering within 1-4 km downstream of an impoundment. Total benthic invertebrate abundance varies considerably and depends on the degree of flow alteration and resource subsidies from the upstream reservoir. In contrast, benthic diversity is reduced below dams irrespective of dam location and operation with little recovery observed downstream. Contrary to SDC predictions, the longitudinal gradient in regulated rivers is not a compaction of functional changes seen over several stream orders in natural rivers but a response to dam design and reservoir conditions. Stoneflies and dragonflies are particularly sensitive to regulation while filter feeding invertebrates are enhanced. Ward and Stanford's (1983) Serial Discontinuity Concept is still a useful framework for testing hypotheses. Future studies should further expand the SDC through empirical estimation within the context of the landscape to gain a better scientific understanding of regulated river ecology. Author Keywords: benthic invertebrates, dams, longitudinal, recovery, River Continuum Concept, Serial Discontinuity Concept
Speciation of Aluminum and Zinc in Three Streams of a Forested Catchment of the Boreal Zone
This study presents a detailed assessment of the chemical speciation of aluminum and zinc in three streams of a small, acid-sensitive forested catchment on the southern edge of the Precambrian Shield. Speciation analysis was achieved using an in-situ analytical technique known as Diffusive Gradient in Thin film (DGT) which measures labile metals, and a predictive computer algorithm (WHAM VI) which calculates metal species concentrations. Three types of DGT with different metal scavenging capabilities were used and a total of 11 deployments performed across four seasons. WHAM VI predictions showed that the organic fraction of aluminum was the main contributor to the dissolved concentrations in the main inflow stream (PC1) (~ 80 %) and the lake's outflow (PCO) (~ 75%); in the upland stream (PC1-08) the inorganic fraction contributed ~ 75%. For zinc the free ion was the single most important contributor to the dissolved concentration (< 90%) in all three streams. A comparative study of the DGT and WHAM methods showed an agreement between their inorganic concentrations during the spring season. Both methods indicate the greatest environmental impact for Al takes place during snow melt period in PCO and PC1-08 and in the summer for PC1. The greatest environmental impact for Zn predicted with WHAM VI, occurs during the spring in all three streams. Author Keywords: Aluminum, DGT, Metal speciation, WHAM, Zinc
ASSESSING THE IMPACT OF ATMOSPHERIC DEPOSITION AND HARVEST INTENSITY ON SOIL ACIDITY AND NUTRIENT POOLS IN PLANTATION FORESTS
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
Carbon and Nitrogen Isotope Changes in Streams along an Agricultural Gradient
Nitrogen is a major constituent of agricultural fertilizers, and nitrogen inputs to stream water via runoff and groundwater lead to a variety of negative environmental impacts. In order to quantify the movement of nitrogen through aquatic food webs, fourteen streams with varying land uses across South-Central Ontario were sampled for two species of fish, freshwater mussels, and water for measurement of isotope ratios of δ15N and δ13C. I found that nitrogen isotopes in fish, water, and mussels were related to the percentage of riparian monoculture, and that carbon isotopes were unrelated to monoculture. Though all species were enriched as monoculture increased, the rate of δ15N enrichment as monoculture increased did not vary between species. This study has improved our understanding of how monoculture affects nutrient enrichment in stream food webs, and assesses the validity of using nitrogen isotopes to measure trophic positions of aquatic organisms across an environmental gradient. Author Keywords: agriculture, fish, food webs, nitrogen, stable isotopes, streams
Fate of Silver Nanoparticles in Lake Mesocosms
The fate of silver nanoparticles (AgNPs) in surface waters determines the ecological risk of this emerging contaminant. In this research, the fate of AgNPs in lake mesocosms was studied using both a continuous (i.e. drip) and one-time (i.e. plug) dosing regime. AgNPs were persistent in the tested lake environment as there was accumulation in the water column over time in drip mesocosms and slow dissipation from the water column (half life of 20 days) in plug mesocosms. In drip mesocosms, AgNPs were found to accumulate in the water column, periphtyon, and sediment according to loading rate; and, AgNP coating (PVP vs. CT) had no effect on agglomeration and dissolution based on filtration analysis. In plug mesocosms, cloud point extraction (CPE), single-particle-inductively coupled mass spectroscopy (spICP-MS), and asymmetrical flow field-flow fractionation (AF4-ICP-MS) confirmed the temporal dissolution of AgNPs into Ag+ over time; however, complexation is expected to reduce the toxicity of Ag+ in natural waters. Author Keywords: AF4-ICP-MS, cloud point extraction, fate, mesocosms, silver nanoparticles, SP-ICP-MS

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