Graduate Theses & Dissertations

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Assessing effects and fate of environmental contaminants in invasive, native, and endangered macrophytes
Macrophytes play an important role in aquatic ecosystems, and thus are integral to ecological risk assessments of environmental contaminants. In this dissertation, I address gaps in the assessments of contaminant fate and effects in macrophytes, with focus on glyphosate herbicide use for invasive plant control. First, I evaluated the suitability of Typha as future standard test species to represent emergent macrophytes in risk assessments. I concluded that Typha is ecologically relevant, straight-forward to grow, and its sensitivity can be assessed with various morphological and physiological endpoints. Second, I assessed effects from glyphosate (Roundup WeatherMAX® formulation) spray drift exposure on emergent non-target macrophytes. I performed toxicity tests with five taxa, Phragmites australis, Typha × glauca, Typha latifolia, Ammannia robusta, and Sida hermaphrodita, which in Canada collectively represent invasive, native, and endangered species. I found significant differences in glyphosate sensitivity among genera, and all species’ growth was adversely affected at concentrations as low as 0.1% (0.54 g/L), much below the currently used rate (5%, 27 g/L). Third, I assessed the potential for glyphosate accumulation in and release from treated plant tissues. I found that P. australis and T. × glauca accumulate glyphosate following spray treatment, and that accumulated glyphosate can leach out of treated plant tissues upon their submergence in water. Finally, I assessed effects of released glyphosate on non-target macrophytes. I found that P. australis and T. × glauca leachate containing glyphosate residues can stimulate the germination and seedling growth of T. latifolia, but can exert an inhibiting effect on A. robusta, although leachate without glyphosate caused similar responses in both plants. Additionally, I found no negative effects in A. robusta when exposed to glyphosate residues in surface water, or when grown with rhizosphere contact to an invasive plant that was wicked (touched) with glyphosate. My results show that non-target macrophytes can be at risk from glyphosate spray for invasive plant control, but risks can be mitigated through informed ecosystem management activities, such as targeted wick-applications or removing plant litter. Integrating contaminant fate and effect assessments with emergent macrophytes into ecological risk assessments can support the protection of diverse macrophyte communities. Author Keywords: Ecosystem management, Ecotoxicology, Glyphosate, Herbicide, Invasive plant, Species at risk
Automated Separation and Preconcentration of Ultra-Trace Levels of Radionuclides in Complex Matrices by Online Ion Exchange Chromatography Coupled with Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Radionuclides occur in the environment both naturally and artificially. Along with weapons testing and nuclear reactor operations, activities such as mining, fuel fabrication and fuel reprocessing are also major contributors to nuclear waste in the environment. In terms of nuclear safety, the concentration of radionuclides in nuclear waste must be monitored and reported before storage and/or discharge. Similarly, radionuclide waste from mining activities also contains radionuclides that need to be monitored. In addition, a knowledge of ongoing radionuclide concentrations is often required under certain ‘special’ conditions, for example in the area surrounding nuclear and mining operations, or when nuclear and other accidents occur. Thus, there is a huge demand for new methods that are suitable for continuously monitoring and rapidly analyzing radionuclide levels, especially in emergency situations. In this study, new automated analytical methods were successfully developed to measure ultra trace levels of single or multiple radionuclides in various environmental samples with the goal of faster analysis times and less analyst involvement while achieving detection limits suitable for typical environmental concentrations. Author Keywords: automation, ICP-MS, ion exchange, radionuclide
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
Using ultra high-resolution mass spectrometry to characterize the biosorbent Euglena gracilis and its application to dysprosium biosorption
Euglena gracilis is an enigmatic and adaptable organism that has great bioremediationpotential and is best known for its metabolic flexibility. The research done in this dissertation addresses (1) how growth conditions impact cellular composition, and (2) how chemometric approaches (such as statistical design of experiments and artificial neural networks) are viable alternatives to the conventional biosorption models for process optimization. Using high-resolution mass spectrometry for biosorbent characterization is a powerful way to assess the chemical characteristics of lyophilized and fractionated cells with high precision, especially to screen for compound classes that may have potentiality for rare earth element removal. Growth conditions impacted cellular composition and separated size fractions of cells yielded different molecular/chemical properties as described by compositional abundances, thus different biosorptive potential. Untargeted analysis demonstrated that exponential dark-grown cells with glucose supplementation were abundant in polyphenolic- and carbohydrate-like compounds, molecular species highly involved in rare earth element binding. Light grown cells had more heterogeneity and the highest molecular weighted fractions from light grown cells (fraction D) had the most abundances of polyphenolic- and protein-like structures. Chemometric modeling used identified the best and worst conditions for iii dysprosium sorption and showed that pH had the most significant influence on bioremoval. Bioremoval ranged from 37% at pH 8 to 91% at pH 3 at Dy concentration ranging from 1 to 100 μg L-1. The work presented in the PhD dissertation will aid in understanding the chemical characteristics of biosorbents by using a Van krevelen analysis of elemental ratios whether algal cells are grown in different environmental growth conditions, or when algal cell are size fractionated. This is especially applied for the screening for metal binding potentiality to Dysprosium. Chemometric methods provide an alternative method for the investigating factors for bioremoval, and applications for process optimization and for real-world applications. This dissertation will aid in understanding chemical characteristics when a biosorbent is grown in a given condition and which factors are important for rare earth element (REE) bioremoval. The significance of this work aims to look for alternate ways to screen biosorbents and using a more efficient experimental design for REE bioremoval. Author Keywords: bioremoval, biosorption, chemometrics, dysprosium, euglena, mass spectrometry
Composition and Transformation of Dissolved Organic Matter in Hudson Bay, Canada
The Hudson Bay region is a sensitive environment, where anthropogenic (e.g., dams, diversions, and/or reservoirs) impacts have increased in recent decades, potentially influencing the functioning of the ecosystem. Dissolved organic matter (DOM) entering Hudson Bay comes from both terrestrial (allochthonous) and aquatic (autochthonous) sources. The chemical composition of DOM is important, as it controls carbon biogeochemistry, nutrient cycling, and heat exchange. In rivers, estuaries, and oceans, photochemical processes and microbial degradation play a significant role in the chemical composition of DOM. Yet, our knowledge is scarce into how photochemical and microbial processes effect DOM composition specifically in Arctic aquatic systems making it difficult to predict how the carbon cycle will respond to a changing environment. This Ph.D. thesis addresses: (1) the composition of photochemically altered autochthonous and allochthonous DOM; (2) the photochemical transformations of DOM in surface waters of Hudson Bay; and (3) the microbial transformations of DOM in Hudson Bay surface waters. Using multiple analytical techniques, this work demonstrated that photochemical and microbial effects were different for light absorbing DOM compounds and ionisable DOM analyzed by Fourier transform-ion cyclotron-resonance-mass spectrometry (FT-ICR-MS). Based on FT-ICR-MS analysis, microbial processes had a greater impact on the molecular composition of allochthonous DOM originating from riverine sources and estuary whereas photochemical processes were the dominant mechanism for degradation of autochthonous DOM in Hudson Bay. Photochemical processes significantly decreased colored dissolved organic matter (CDOM) and fluorescence dissolved organic matter (FDOM) loss whereas microbial degradation was minimal in Hudson Bay river, estuary, and coastal waters. The results of this thesis highlight the importance of photochemical and microbial alteration of DOM in Arctic regions, two processes that are expected to be enhanced under climate change conditions. Author Keywords: Carbon cycle, Field flow fractionation, Microbial transformation, Optical properties, Photochemical degradation
Assessing Measured and Perceived Risks to Drinking Water Sources
Microcontaminants originating from wastewater effluent and run-off from agricultural lands may be present in the sources of drinking water for rural and Indigenous communities in mixed-use watersheds. In this study, a convergent parallel mixed-methods design was applied to assess measured and perceived risks of contamination in the sources of drinking water for two communities; the Six Nations of the Grand River community in Ontario and the community of Soufriere in St. Lucia, West Indies. The overall goal of the project was to assess how measured and perceived risks of exposure to chemical and biological contaminants in drinking water sources could inform water management strategies for the communities. Quantitative data obtained from the analysis of water samples collected indicated that the highest levels and occurrence of fecal bacteria were found in the Soufriere watershed while the highest concentrations and occurrence of pesticides were found in the Grand River watershed. In the Grand River watershed, conventional treatment of water followed by activated carbon filtration and UV disinfection removed fecal bacteria and also removed many chemical microcontaminants with efficiencies as high as 98%. Data from both watersheds indicated that there was a strong positive correlation between the levels of caffeine and sucralose (i.e. indicators of wastewater contamination) in water samples and the levels of either Total Coliforms or fecal bacteria of human origin. Human health risk assessments of individual pesticides and pesticide mixtures performed by applying a hazard quotient (HQ) and hazard index (HI) model, respectively indicated that there were no apparent risks to human health from those microcontaminants. Qualitative data obtained from face-to-face interviews with water managers and health professionals working in the two communities, which were collected and analysed concurrently but independently, illustrated that there were cross-cultural similarities and differences in factors influencing the perceptions of risks associated with the sources of drinking water. These perceptions of risks were mainly influenced by factors such as heuristics or informal and informal reasoning, cognitive-affective factors, social-political institutions and cultural factors. These factors may have also influenced water managers and health professionals, as they often recommended more “soft” strategies for managing water resources in the communities. Key words: pesticides, fecal bacteria, microcontaminants, POCIS, measured risks, perceived risks, water management, First Nations, Grand River, Soufriere, St. Lucia Author Keywords: fecal bacteria, measured risks, microcontaminants, perceived risks, POCIS, water management
An Investigation of Rare Earth Element Patterns and an Application of Using Zn and Cd Isotope Ratios in Oysters to Identify Contamination Sources in an Estuary in Southern China
Environmental monitoring and investigation of metal biogeochemical cycling has been carried out in the Pearl River Estuary (PRE), an important and complex system in Southern China. In this study, rare earth element (REE) patterns as well as isotope ratios (i.e., Zn and Cd) were evaluated as tools to identify contamination sources in environmental compartments (i.e., water and suspended particles (SP)) as well as in oysters collected from estuarine sites. Results show elevated concentrations (also called anomalies) of Pr, Nd, Dy and Ho, relative to other REE elements, in water samples, potentially from REE recycling and other industrialized activities in this area. Unlike water samples, no REE anomalies were found in SP or oysters, suggesting that the dominate REE uptake pathway in oysters is from particles. Secondly, site to site variations in Zn isotope ratios were found in water and SP, showing the complexity of the source inputs in this area. Also, in estuarine locations, larger spatially differences in Zn isotope ratios were found in water collected in wet season than those in dry season, which may due to mixing of different source inputs under the water circulations in different seasons. A series of laboratory experiments were conducted during which changes in Zn isotope ratios were measured during uptake under varying salinity and Zn concentrations and during depuration. Neither in vivo Zn transportation among the various tissues within the oysters nor water exposure conditions (i.e., different salinities or Zn concentrations) caused Zn isotopic fractionation in the oysters. Cd and Zn isotope ratios were also determined in oysters obtained from the PRE. Large variations in Cd and Zn isotope ratios suggest that oysters were receiving contaminants from different input sources within the PRE. A consistent difference (approximately 0.67‰) was observed for Zn isotope ratios in oysters collected from the east side of the PRE compared to those from sampling locations on the western side of the PRE, suggesting different Zn sources in these two areas. Ultimately, by combining biogeochemistry with physiology, this study represents a first attempt to assess pollution status, monitor contaminants using oysters and model/identify contamination sources using both REEs and metal isotope ratios. Author Keywords:
Characterization of Synthetic and Natural Se8 and Related SenSm Compounds by Gas Chromatography-Mass Spectrometry
Elemental selenium has been extensively quantitatively measured in sediments; however, its physical composition is largely unknown, despite it being the dominant selenium species in some reducing environments. Here, for the first time, it is shown that small, cyclic selenium compounds can account for a quantitatively-relevant fraction of the total elemental selenium present. A new method was developed to analyze for cyclooctaselenium (Se8) in both synthetic samples and selenium-impacted sediments. Despite some analytical limitations, this gas chromatography-mass spectrometry (GC-MS) method is the first GC-MS method developed to identify and quantify Se8 in sediments. Once this method was established, it was then applied to more complex systems: first, the identification of compounds in mixed selenium-sulfur melt solutions, and then the determination of SenSm in selenium-impacted sediments. Despite complications arising from pronounced fragmentation in the ion source, assignment of definitive molecular formulae to chromatographically-resolved peaks was possible for five compounds. Developing a fully quantitative method to obtain elemental ratio information can aid in the assignment of molecular formulae to chromatographically-resolved SeS-containing chromatographic peaks. Coupling the existing gas chromatography method to an inductively coupled plasma-mass spectrometer (ICP-MS) system should accomplish this. However, due to a number of complications, this was not completed successfully during the duration of this thesis project. High detection limits for sulfur, retention time discrepancies, and inconsistent injection results between the GC-MS and GC-ICP-MS system led to difficulties in comparing results between both analytical methods. Despite these limitations, GC-ICP-MS remains the most promising method for the identification and quantification of SenSm compounds in synthetic melt mixtures and selenium impacted sediments. Author Keywords: gas chromatography-mass spectrometry, sediments, selenium
Effects of Silver Nanoparticles on Lower Trophic Levels in Aquatic Ecosystems
Due to their effective antibacterial and antifungal properties, silver nanoparticles (AgNPs) have quickly become the most commonly used nanomaterial, with applications in industry, medicine and consumer products. This increased use of AgNPs over the past decade will inevitably result in an elevated release of nanoparticles into the environment, highlighting the importance of assessing the environmental impacts of these nanomaterials on aquatic ecosystems. Although numerous laboratory studies have already reported on the negative effects of AgNPs to freshwater organisms, only a handful of studies have investigated the impacts of environmentally relevant levels of AgNPs on whole communities under natural conditions. This thesis examines the effects of chronic AgNP exposure on natural freshwater littoral microcrustacean, benthic macroinvertebrate and pelagic zooplankton communities. To assess the responses of these communities to AgNPs, I focused on a solely field-based approach, combining a six-week mesocosm study with a three-year whole lake experiment at the IISD – Experimental Lakes Area (Ontario, Canada). Our mesocosm study tested the effects of AgNP concentration (low, medium and high dose), surface coating (citrate- and polyvinylpyrrolidone [PVP]-coated AgNPs), and type of exposure (chronic and pulsed addition) on benthic macroinvertebrates in fine and stony sediments. Relative abundances of metal-tolerant Chironomidae in fine sediments were highest in high dose PVP-AgNP treatments; however, no negative effects of AgNP exposure were seen on biodiversity metrics or overall community structure throughout the study. I observed similar results within the whole lake study that incorporated a long-term addition of low levels of AgNPs to an experimental lake. Mixed-effects models and multivariate methods revealed a decline in all species of the littoral microcrustacean family Chydoridae in the final year of the study within our experimental lake, suggesting that this taxon may be sensitive to AgNP exposure; however, these effects were fairly subtle and were not reflected in the overall composition of littoral communities. No other negative effects of AgNPs were observed on the pelagic zooplankton or benthic macroinvertebrate communities. My results demonstrate that environmentally relevant levels of AgNPs have little impact on natural freshwater microcrustacean and benthic macroinvertebrate communities. Instead, biodiversity metrics and community structure are primarily influenced by seasonal dynamics and nutrient concentrations across both lakes. This thesis highlights the importance of incorporating environmental conditions and the natural variability of communities when examining the potential risks posed by the release of AgNPs into the environment, as simplistic laboratory bioassays may not provide an adequate assessment of the long-term impacts of AgNPs on freshwater systems. Author Keywords: Benthic macroinvertebrates, IISD - Experimental Lakes Area, Littoral microcrustaceans, Silver nanoparticles, Whole lake experiment, Zooplankton
Effect Assessment of Binary Metal Mixtures of Ni, Cu, Zn, and Cd to Daphnia magna
Mixtures of metals occur in surface waters, toxicity of which has drawn world-wide attention due to their crucial role in both ecotoxicology and regulations. The present research was undertaken to study the acute toxicity of binary mixtures of Ni, Cu, Zn, and Cd to the freshwater organism, Daphnia magna. The experimental approach included single and binary metal toxicity tests based on the 48h acute toxicity bioassay of Environment Canada. The acute toxicity of single metals followed the order of Cd > Cu > Zn > Ni. Based on the calculated 48h EC50 value of single metals, a toxic unit (TU) approach was used to combine two metals in a binary mixture, in which 1TU was equal to the 48h EC50 value of a metal in single exposure. The toxicity of binary metal mixtures to D. magna followed the order of Cu-Cd > Cu-Zn > Zn-Cd > Cu-Ni > Zn-Ni > Cd-Ni, which demonstrated three types of toxicity (i.e., less than additive, additive, and greater additive). Predictions from additivity models (including concentration addition (CA) and independent action (IA) models), a generalized linear model (GLM), and a biotic-ligand-like model (BLM-like) were compared to the bioassay results. The CA and the RA models also predicted three types of toxicity of the binary metal mixtures (i.e., less than additive, additive, and greater than additive). However, the CA model mostly overestimated the toxicity of binary mixtures. Predictions from the GLM supported the inclusion of the interaction between two metals in a mixture to predict the toxicity of binary metal mixtures. The binary metal toxicity was also predicted using a BLM-like model based on the calculated concentrations of free ionic forms of the metals, affinity constants, and toxic potency of each metal. In this model, it was hypothesized that the toxicity of metal mixture is the result of competition of metals with Ca2+ at biotic ligands, which can lead to whole-body deficiency of Ca2+ in D. magna. The BLM-like model provided the toxic potency of single metals with the following order, Cu > Cd > Zn > Ni. Although the prediction of the BLM-like model was not in good agreement with the observed toxicity of binary metal mixtures, an overestimation of risk of mixture toxicity was obtained using this model, which could be promising for use in environmental risk assessment. Author Keywords: biotic ligand model, concentration addition, Daphnia magna, independent action, metal toxicity, modeling
Investigation of fugitive dust emissions from nepheline syenite mine tailings near Nephton, Ontario
A set of experiments was designed to investigate the factors—atmospheric and surficial—controlling fugitive dust emissions from the tailings ponds of UNIMIN Canada, a mining company that extracts and produces nepheline syenite (feldspar) at two adjacent sites (Nephton and Blue Mountain) located north of Havelock, Ontario. Using wind tunnel measurements, the combined influence of relative humidity and temperature (represented by the absolute matric potential, |Ψ|) on dust emission was quantified and modelled. About 300 experimental runs were conducted under various conditions of wind speed (4.5-6.25 ms-1), temperature (0-30oC) and relative humidity (10-70%). Generally, dust flux decreased as a logarithmic function of matric potential, with dust emission strongly suppressed for RH > 60% or |Ψ|<70 MPa. Field measurements also confirmed the role of relative humidity in suppressing dust emission. Irrigation, which is widely used by mines to control dust emissions, reduced ambient dust concentration at the study site only about 60% of the time, with the highest mitigation efficiencies (average of 90%) occurring when the total depth of water applied intermittently over a few hours was greater than 10 mm. In the absence of emergent vegetation, the terrestrial laser scanning (TLS) technique proved to be a promising method for detecting and estimating both spatial and temporal moisture content changes in the field environment, particularly for the very thin surface layer, which is the most important layer for dust emission. It is hoped that the results from this study will help mines to optimize their dust management programs for the range of climate and topographic conditions found at their sites, and also serve as a source of useful information and input data for atmospheric dispersion models, such as AERMOD and CALPUFF, whose accuracy depends on the quality of the input data such as the emission rate. Author Keywords: dust mitigation efficiency, Fugitive dust, nepheline syenite, relative humidity, tailings, terrestrial laser scanning
effects of Dissolved Organic Matter (DOM) sources on Pb2+, Zn2+ and Cd2+ binding
Metal binding to dissolved organic matter (DOM) determines metal speciation and strongly influences potential toxicity. The understanding of this process, however, is challenged by DOM source variation, which is not always considered by most existing metal speciation models. Source determines the molecular structure of DOM, including metal binding functional groups. This study has experimentally showed that the allochthonous-dominant DOM (i.e. more aromatic and humic) consistently has higher level of Pb binding than the autochthonous-dominant DOM (i.e. more aliphatic and proteinaceous) by more than two orders of magnitude. This source-discrimination, however, is less noticeable for Zn and Cd, although variation still exceeds a factor of four for both metals. The results indicate that metal binding is source-dependent, but the dependency is metal-specific. Accordingly, metal speciation models, such as the Windermere Humic Aqueous Model (WHAM), needs to consider DOM source variations. The WHAM input of active fraction of DOM participating in metal binding (f) is sensitive to DOM source. The commonly-used f = 0.65 substantially overestimated the Pb and Zn binding to autochthonous-dominant DOM, indicating f needs to be adjusted specifically. The optimal f value (fopt) linearly correlates with optical indexes, showing a potential to estimate fopt using simple absorbance and/or fluorescence measurements. Other DOM properties not optically-characterized may be also important to determine fopt, such as thiol, which shows strong affinity to most toxic metals and whose concentrations are appreciably high in natural waters (< 0.1 to 400 nmol L-1). Other analytical techniques rather than Cathodic Stripping Voltammetry (CSV) are required to accurately quantify thiol concentration for DOM with concentration > 1 mg L-1. To better explain the DOM-source effects, the conditional affinity spectrum (CAS) was calculated using a Fully Optimized ContinUous Spectrum (FOCUS) method. This method not only provides satisfactory goodness-of-fit, but also unique CAS solution. The allochthonous-dominant DOM consistently shows higher Pb affinity than autochthonous-dominant DOM. This source-discrimination is not clearly observed for Zn and Cd. Neither the variability of affinity nor capacity can be fully explained by the variability of individual DOM properties, indicating multiple properties may involve simultaneously. Together, the results help improve WHAM prediction of metal speciation, and consequently, benefit geochemical modelling of metal speciation, such as Biotic Ligand Model for predicting metal toxicity. Author Keywords: Dissolved organic matter, Metal binding, Source, Windermere Humic Aqueous Model

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