Graduate Theses & Dissertations

Effect of Water Surface Simulated Rain Drop Impacts on Water to Air Chemical Transfers of Perfluorinated Carboxylic Acids (PFCAs)
Perfluorinated carboxylic acids (PFCAs) are anthropogenic environmentally ubiquitous surfactants that tend to concentrate on water surfaces. This investigation looked at the effect of simulated rain on the atmospheric concentration of a suite of PFCAs (C2 - C12) above the bulk water system. Increased air concentrations of all PFCAs were detected during simulated rain events. Long chain PFCAs (>C8) were found to be much more concentrated in the air above the bulk water system than their short chain counter parts (
Development and Use of Passive Samplers for Monitoring Dissolved and Nanoparticulate Silver in the Aquatic Environment
Silver nanoparticles (nAg) are the largest and fastest growing class of nanomaterials, and are a concern when released into aquatic environments even at low μg L-1+). Diffusive gradient in thin films (DGT) with a thiol-modified resin were used to detect labile silver and carbon nanotubes (CNT-sampler) were used to measure nAg. Laboratory uptake experiments in lake water provided an Ag+ DGT diffusion coefficient of 3.09 x 10 -7 cm2s-1 and CNT sampling rates of 24.73, 5.63, 7.31 mL day-1, for Ag+, citrate-nAg and PVP-nAg, respectively. The optimized passive samplers were deployed in mesocosms dosed with nAg. DGT samplers provided estimated Ag+ concentrations ranging from 0.15 to 0.98 μg L-1 and CNT-samplers provided nAg concentrations that closely matched measured concentrations in water filtered at 0.22 μm. Author Keywords: ICP-MS, mesocosms, nanoparticles, nanosilver, passive sampling
Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish
Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish Alena Kathryn Davidson Celsie A novel dynamic fugacity model is developed that simulates the uptake of chemicals in fish by respiration as applies in aquatic toxicity tests. A physiologically based toxicokinetic model was developed which calculates the time-course of chemical distribution in four tissue compartments in fish, including metabolic biotransformation in the liver. Toxic endpoints are defined by fugacity reaching a 50% mortality value. The model is tested against empirical data for the uptake of pentachloroethane in rainbow trout and from naphthalene and trichlorobenzene in fathead minnows. The model was able to predict bioconcentration and toxicity within a factor of 2 of empirical data. The sensitivity to partition coefficients of computed whole-body concentration was also investigated. In addition to this model development three methods for predicting partition coefficients were evaluated: lipid-fraction, COSMOtherm estimation, and using Abraham parameters. The lipid fraction method produced accurate tissue-water partitioning values consistently for all tissues tested and is recommended for estimating these values. Results also suggest that quantum chemical methods hold promise for predicting the aquatic toxicity of chemicals based only on molecular structure. Author Keywords: COSMOtherm, fish model, fugacity, Partition coefficient, tissue-water, toxicokinetics
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
Research and development of synthetic materials for presumptive testing in bloodstain pattern analysis
Chemical presumptive tests are used as the primary detection method for latent bloodstain evidence. This work focuses on developing a forensic blood substitute which mimics whole blood reactivity to a luminol solution commonly used in presumptive testing. Designing safe and accessible materials that mimic relevant properties of blood is a recognized research need in forensic science. Understanding the whole blood dynamics related to reactivity with presumptive testing chemicals is important for developing accurate analogues. Provided in this thesis is a quantitative and qualitative characterization of photoemission from the reaction of a luminol solution to ovine blood. Luminol reactivity of a horseradish peroxidase encapsulated sol-gel polymer was validated against this ovine blood standard. This material, the luminol-reactive forensic blood substitute, is a key deliverable of this research. An optimized protocol for implementing this technology as a reagent control test, and as a secondary school chemistry experiment are presented. This thesis outlines the research and development of a forensic blood substitute as it relates to presumptive testing in bloodstain pattern analysis. Author Keywords: bloodstain pattern analysis, forensic science, luminol, presumptive testing, secondary school education, sol-gel chemistry
Assessing limnological characteristics of subarctic Québec thaw ponds and mercury methylation and methylmercury demethylation within their sediments
Thawing permafrost due to increasingly warm temperatures in northern subarctic regions is releasing mercury. The consequent formation of thaw ponds in the peatland palsa valley of the Sasapimakwananisikw (SAS) river in Whapmagoostui-Kuujjuarapik, Québec may provide a pool for MMHg formation and a potential risk to aquatic and human life, if these ponds facilitate MMHg export through hydrological connections to nearby waterways. Hg methylation and MMHg demethylation activities were examined in thaw pond sediments using a Hg tracer isotope incubation experiment. Analysis by coupling gas chromatography cold-vapor atomic fluorescence spectrophotometry (GC-CVAFS) with inductively coupled mass spectrometry (ICP-MS) techniques showed that MMHg was produced at a higher rate and within the first 2 h of incubation for both summer and winter seasons. For thaw ponds SAS1A, SAS1B and SAS2A, MMHg was formed at 0.0048 % h-1, 0.0012 % h-1, and 0.0008 % h-1, respectively during winter and at 0.0001 % h-1, 0.0016 % h-1, and 0.0010 % h-1, respectively during summer. Detection of MMHg losses were not as expected likely due to limitations of the combined tracer spike and overestimation of the in situ ambient mercury levels. Physical and chemical properties vary within ponds, among ponds and between winter and summer. SAS1B’s location nearby an organic carbon rich palsa may be ideal to study DOC – Hg interactions. Variability in pond characteristics including depth, surface area, age, pH, temperature, colour, oxygen concentration, total dissolved and suspended solids, conductivity, carbon, mercury, ammonium, calcium, magnesium, sulfate, total phosphorous, potassium, and sodium between seasons indicate the challenge of predicting future environmental impacts of climate change related thaw pond creation in the north. Author Keywords: demethylation, mercury, methylation, methylmercury, SAS, thaw ponds
Relationships between Dissolved Organic Matter and Vanadium Speciation in the Churchill River, MB and the Mackenzie River Basin, NWT using diffusive gradients in thin films (DGT)
This study examines the influence of dissolved organic matter (DOM) on dissolved vanadium (V) speciation in the Churchill River and Great Slave Lake using diffusive gradients in thin film (DGT). Vanadium is commonly found in natural environments such as rivers, lakes and oceans. It regulates normal cell growth, but in excessive amounts, it can have toxic effects on human and aquatic organisms. The use of in situ, time integrated DGT devices allows to better (1) monitor the most bioavailable fraction of V, the DGT-labile V, in Arctic Rivers and (2) assess the influence of DOM on dissolved V speciation. Higher DGT-labile V was found in the the central regions of the Mackenzie River (MR), with an average of 7.7 ± 2.3 nM, likely due to sediment leaching and permafrost thawing. The Churchill River and Great Slave Lake (GSL) showed lower DGT-labile V levels (2.2 ± 1.6 nM and 3.6 ± 2.7 nM, respectively), compared to central regions in MR. The CR DGT-labile V concentrations was positively correlated to protein-like DOM concentration and abundance (r = 0.3, p < 0.05). The data collected from this study will help in developing new strategies regarding environmental health and impact assessments of environmentally hazardous waste that consist of potentially high levels of toxic vanadium species. Developments in the use of DGT devices as a sampling method will also aid in future studies involved in analyzing environmental health and specifically dissolved V species in natural waters. Author Keywords: diffusive gradients in thin-films, dissolved organic matter, fluorescence, mass spectrometry, UV-Vis, vanadium
origin and ecological function of an ion inducing anti-predator behaviour in Lithobates tadpoles
Chemical cues are used commonly by prey to identify predation risk in aquatic environments. Previous work has indicated that negatively-charged ions of m/z 501 are possibly a kairomone that induces anti-predator responses in tadpoles. This thesis found that this ion species: (i) is produced by injured tadpoles; (ii) exhibits increased spectral intensity with higher tadpole biomass; and (iii) is not produced by starved predators. These results refute the hypothesis that the ion is a kairomone, and rather support its role as an alarm cue released from tadpoles. High resolution mass spectrometry (HR-MS) revealed a unique elemental composition for [M-H]-, m/z 501.2886, of C26H45O7S-. Collision induced dissociation (CID) of ion m/z 501 formed product ions of m/z 97 and m/z 80, HSO4- and SO3-, respectively, indicating the presence of sulfate. Green frog (Lithobates clamitans) tadpoles exposed to m/z 501, and an industrial analogue, sodium dodecyl sulphate (NaC12H25O4S), exhibited similar anti-predator responses, thereby suggesting the potential role of organic sulfate as a tadpole behavioural alterant. Author Keywords: Alarm cue, Amphibian, Chemical Ecology, Mass spectrometry, Predator-prey interactions
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
Detecting anti-estrogens and anti-androgens in surface waters impacted by municipal wastewater discharges and agricultural runoff
This study focused on detecting 22 target anti-estrogenic and anti-androgenic compounds in surface waters influenced by both discharges of municipal wastewater and agricultural runoff in Canada and Argentina. Polar organic chemical integrative samplers (POCIS) were used to monitor the target compounds in surface waters. The removals of the target compounds in a municipal wastewater treatment plant (WWTP) in Canada were also evaluated. In both Canada and Argentina pesticides with potential anti-estrogenic and anti-androgenic activities were detected in the surface waters. The highest concentrations were found in Argentina (up to 1010 ng L-1) in areas impacted by heavy agricultural practices. Cyproterone acetate and bicalutamide were the only two anti-cancer drugs detected only at the Canadian study site, the Speed River, ON. In the Guelph WWTP, that discharges into the Speed River, these target compounds were not all efficiently removed (>70%) during treatment. Overall, this study provides insight to possible anti-estrogenic and anti-androgenic compounds that may be contributing to endocrine disrupting activities in surface waters. Author Keywords: Anti-androgens, Anti-estrogens, Cancer Therapy Drugs, Current use pesticides, Pharmaceuticals and Personal Care Products, Polar Organic Chemical Integrative Samplers

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