Metcalfe, Chris

The detection of ciguatoxins (CTXs) in biological samples is challenging due to their low concentrations, the presence of various congeners, and the absence of standardized methods. This study uses high resolution mass spectrometry (HRMS) with P-CTX-3B as a reference standard. The protonated molecules ([M+H]+) were most prevalent, especially when acetonitrile/water was utilized, providing enhanced sensitivity. Optimized collision energies of 15 eV for protonated molecules and flow rates of 10 µl/min enhance sensitivity and peak intensities, respectively. Acetonitrile/water (ACN/H2O) is recommended as the primary solvent for HRMS method, an aspect underexplored in existing literature. The detection of CTX-3B in fish tissue samples proved to be challenging, caused by variations in ion peak intensities and matrix effects, requiring a deeper exploration of the impact of complex matrices on CTX detection. The study emphasizes the need for a reliable internal standard to mitigate these effects and highlights the ongoing challenge of developing a rapid, simple, and sensitive detection method. The study's specific focus on the P-CTX-3B analogue significantly contributes to methodology development for this congener, serving as a foundational step in understanding and detecting CTX. Despite notable progress, the study acknowledges the absence of an ideal assay, outlining key challenges for future research on ciguatera analysis. It underscores the continuous necessity for method reevaluation, testing, and the broader goal of establishing a more clarified and rugged method for the identification of CTX in fish.

Author Keywords: Analytical Chemistry, Ciguatera Fish Poisoning, Ciguatoxin, High-Resolution Mass Spectrometry, Optimization, P-CTX-3B

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

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

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

Silver nanoparticles (AgNP) released into aquatic environments could threaten natural bacterial communities and ecosystem services they provide. We examined natural lake bacterioplankton communities' responses to different exposures (pulse vs chronic) and types (citrate and PVP) of AgNPs at realistic environmental conditions using a mesocosm study at the Experimental Lakes Area. An in situ bioassay examined interactions between AgNPs and phosphorus loading. Bacterial communities exposed to high AgNP concentrations regardless of exposure or capping agent type accumulated silver. We observed increases in community production during additions of polyvinylpyrrolidone (PVP) -capped AgNPs and that site and nutrient-specific conditions are important to AgNPs toxicology in aquatic systems. Toxicological effects of AgNP are attenuated in natural conditions and differ from results from laboratory studies of AgNP toxicity. Our results demonstrate more studies are needed to fully assess the risk posed by these novel chemicals to the environment. This work could be useful in forming risk assessment policies which are largely based on lab studies and typically demonstrate strong toxic effects.

Author Keywords: bacterial production, bacterioplankton communities, ecological stoichiometry, Experimental Lakes Area, mesocosms, silver nanoparticles

In this thesis, aerosolization was studied as a possible means of water remediation for several environmentally relevant pharmaceutical pollutants, known for their persistence in wastewater effluent and potable water sources. Seven different pharmaceutical compounds and a well-known plasticizer were all shown to decrease considerably in concentration in aerosol that was produced and subsequently collected within a short time span. Strong evidence is presented that an enhanced rate of partitioning into the gas phase at the air-water interface of water droplets exists for every compound tested relative to that occurring in bulk solution. UV photolysis in aerosols was also explored and shown for sulfamethoxazole to be at least an order of magnitude faster in aerosols then in bulk solution. The implications towards both the environmental fate, and removal of these compounds from water sources is discussed.

Author Keywords: Aerosols, Air-water partitioning, Pharmaceuticals, Photolysis, Sulfamethoxazole

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

Energy storage efficiency and sustainability require advanced technologies and novel materials. Recently, bio-based phase change materials (PCMs) have received significant attention for thermal energy storage (TES) uses. Vegetable oils are versatile renewable feedstocks that are well suited for the development of sustainable, functional PCMs. PCMs derived from vegetable oil, which compares favorably with paraffin waxes, the industry standard, are currently available. However, their melting points are typically below 80 °C preventing their wider integration in TES applications, particularly those requiring higher temperatures. The present work manipulated the structural building blocks of fatty acids to advantageously affect the intermolecular forces and increase the properties relevant to TES. The polar amide functional group was incorporated into fatty moieties to take advantage of the strong hydrogen bonds that it forms to increase intermolecular attractions and hence increase the phase change temperature and enthalpy as well as to improve thermal stability and thermal conductivity. A series of carefully designed lipid-derived monoamides and four series of lipid-derived diamides were synthesized via benign and simple amidation reactions. The purity of the amides and the intermolecular hydrogen bond strength were assessed using 1H NMR and FTIR. The properties relevant to TES such as thermal transition, crystal structure and polymorphism, thermal stability and thermal conductivity were measured using DSC, XRD, TGA and a thermal conductivity analyzer, respectively. The complex roles of the PCM's constituting molecular building blocks in the phase behavior were elucidated and correlations between structure, processing conditions and macroscopic physicochemical properties, never before elucidated, were assembled in predictive relationships, drawing a unified picture of the rules that generally govern the phase behavior of lipid-derived PCMs. Practically, the prepared amides demonstrated desirable TES properties with substantial performance improvement over current bio-based PCMs. They presented increased phase change temperatures (79 - 159 °C), enthalpies of fusion (155 - 220 J/g) and thermal stability (234 - 353 °C). More importantly, the predictive structure-function relationships established in this work will allow the straightforward engineering of lipid-derived amide PCM architectures with judicious selection of molecular building blocks to extend the range of organic PCMs and deliver thermal properties desirable for TES applications.

Author Keywords: LATENT HEAT THERMAL ENERGY STORAGE, LIPID-DERIVED AMIDES, PHASE CHANGE MATERIALS, RENEWABLE, SOLID LIQUID AMIDE PCMS, THERMAL PROPERTIES

In the Wabigoon/English River system, mercury concentrations downstream from Dryden, ON, where there was a former chlor-alkali plant, remain elevated in sediments and biota. Understanding the current extent and severity of mercury contamination downstream from the former chlor-alkali plant is of great interest in furthering the clean-up of mercury within the traditional territory of Asubpeeschoseewagong Netum (Grassy Narrows) First Nation. The objective of this study was to evaluate the current level and extent of mercury contamination within sediments, crayfish, Hexagenia mayflies, yellow perch, spottail shiner and walleye in the Wabigoon/English River system. An additional objective was to use mercury stable isotope analysis to distinguish between legacy mercury from the former chlor-alkali plant and mercury from geogenic sources. Mercury contamination within surface sediments and biota at locations as far as 178 kms downstream of the historical source of mercury contamination are elevated relative to the reference lake, Wabigoon Lake. Isotope ratios in young of the year fish and sediments collected from within the system were distinct from fish from the reference lake, Wabigoon Lake, indicating that anthropogenic mercury contamination is distinguishable from geogenic mercury.

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