Graduate Theses & Dissertations

Pages

Analysis and reactions of aqueous selenide and other reduced inorganic selenium compounds under anoxic conditions
Selenide is cited as a geochemically important selenium (Se) species, but it is unknown whether selenide is a stable aqueous ion in natural waters. The feasibility of using anoxic anion exchange chromatography (AEC) coupled to dynamic reaction cell-inductively coupled plasma-mass spectrometry to separate aqueous selenide was investigated with the goal of quantifying this anion to determine its importance in reducing waters. It was possible to qualitatively identify selenide using AEC, but much of the aqueous selenide oxidises to Se0 faster than the separation procedure could be completed. AEC analyses of solutions containing polyselenides produced peaks for unidentified Se compounds, which have been assigned tentative structures Se2O22-, Se2O32-, and Se2O62- based on close matches in retention time to stable S compounds. The results of this work show that aqueous selenide can be qualitatively observed in synthetic solutions using AEC, but it is unknown whether these conditions are relevant to natural waters. Author Keywords: anoxic speciation, polyselenides, selenide, selenium geochemistry, selenium speciation, selenoselenate
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
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
Electrochemical versus Chemical Oxidation of Bulky Phenols
Phenolic compounds are used in industry, such as agriculture and biotechnology, and inevitably end up in our environment. These compounds may serve as a phenolic precursor to produce raw materials for a wide range of applications. Chemical oxidation has been the common synthetic pathway to oxidize phenols and related compounds. However, traditional chemical approaches suffer from use of harsh chemicals, waste generation, and lack of reaction selectivity. Electrochemical synthesis has emerged as an alternative method to mitigate common challenges associated with organic synthesis. Herein, electrochemical oxidation of 2,6-diphenylphenol (DPP) and 2,2-dihydroxybiphenol (DHBP) was carried out and compared to traditional chemical oxidation. Contrasted with chemical oxidation, cyclic voltammetry of DPP resulted in a range of products based on the specific potential ranges used, whereas chemical oxidation of DHBP yield a dark-coloured polymeric product. The electrooxidation and chemical oxidation of DPP and DHBP resulted in a solution colour change, indicative of the formation of new, but different products monitored by UV-vis, and characterized by nuclear magnetic spectroscopy (NMR), X-ray single crystal diffraction, IR spectroscopy, transmission electron microscopy (TEM), and gas chromatography-mass spectrometry (GC-MS). The data indicate that the synthetic outcomes are dependent on the synthetic methodology employed, and that electrooxidation and chemical oxidation can form products unique to the pathway utilized. Author Keywords: chemoselectivity, electrochemistry, phenols, radical, synthesis
Identification and Quantification of Organic Selenium Species Produced by Microbiological Activity in Freshwater Environments
Despite being an essential nutrient at trace levels, selenium can be devastating to aquatic environments when present in excess. There is no apparent correlation between total aqueous selenium concentrations and observed toxic effects because bioaccumulation varies over several orders of magnitude depending on the chemical species of selenium and the biological species present in the lowest trophic level of the aquatic food chain. Despite being used in toxicity models due to its high bioavailability, free selenomethionine had not been found previously in the environment outside of a biological entity. Here, it is confirmed that selenomethionine is produced during the biological treatment of selenium-contaminated wastewater, and released in the effluent along with other discrete organic selenium species, including selenomethionine oxide. This identification followed the development of a rigorous preconcentration and cleanup procedure, allowing for the analysis of these organic selenium species in high-ionic strength matrices. A newly optimized anion-exchange chromatographic separation was coupled to inductively-coupled plasma mass spectrometry for the simultaneous quantification of these organic selenium species along with the more ubiquitous selenium oxyanions, selenite and selenate. This separation method was also coupled to electrospray tandem mass spectrometry for structural confirmation of selenomethionine and selenomethionine oxide. High resolution orbitrap mass spectrometry was used to identify another oxidation product of selenomethionine – a cyclic species which was tentatively identified, by coelution, in a selenium-contaminated river water sample. The production and release of selenomethionine, selenomethionine oxide, Se-(methyl) selenocysteine, and methyl selenic acid were observed for various laboratory algal cultures. Once the presence of free selenomethionine in a water system was confirmed, factors affecting its uptake into algal cultures were examined. The uptake of selenomethionine into Scenedesmus obliquus was noted to be significantly higher under low nitrate conditions, where it was incorporated into selenium-containing proteins more readily than at higher nitrate conditions where other metabolites were produced. With the increasing popularity of biological treatment systems for the remediation of selenium-contaminated waters, these observations, combined with existing knowledge, could be used to make predictions regarding the potential toxicity of selenium in various environmental scenarios. Author Keywords: bioremediation, electrospray mass spectrometry, inductively-coupled plasma mass spectrometry, selenium, selenoamino acids, selenomethionine
Investigating the sources and fate of monomethylmercury and dimethylmercury in the Arctic marine boundary layer and waters
Monomethylmercury (MMHg), the most bioavailable form of mercury (Hg) and a potent neurotoxin, is present at elevated concentrations in Arctic marine mammals posing serious health threats to the local populations relying on marine food for their subsistence living. The sources of MMHg in the Arctic Ocean surface water and the role of dimethylmercury (DMHg) as a source of MMHg remain unclear. The objective of this research was to determine the sources and fate of methylated Hg species (MMHg and DMHg) in the marine ecosystem by investigating processes controlling the presence of methylated Hg species in the Arctic Ocean marine boundary layer (MBL) and surface waters. A method based on solid phase adsorption on Bond Elut ENV was developed and successfully used for unprecedented measurement of methylated Hg species in the MBL in Hudson Bay (HB) and the Canadian Arctic Archipelago (CAA). MMHg and DMHg concentrations averaged 2.9 ± 3.6 (mean ± SD) and 3.8 ± 3.1 pg m-3, respectively, and varied significantly among sampling sites. MMHg in the MBL is suspected to be the product of marine DMHg degradation in the atmosphere. MMHg summer (June to September) atmospheric wet deposition rates were estimated to be 188 ± 117.5 ng m-2 and 37 ± 21.7 ng m-2 for HB and CAA, respectively, sustaining MMHg concentrations available for bio-magnification in the pelagic food web. The production and loss of methylated Hg species in surface waters was assessed using enriched stable isotope tracers. MMHg production in surface water was observed from methylation of inorganic Hg (Hg(II)) and, for the first time, from DMHg demethylation with experimentally derived rate constants of 0.92 ± 0.82 x 10-3 d-1 and 0.04 ± 0.02 d-1 respectively. DMHg demethyation rate constant (0.98 ± 0.51 d-1) was higher than that of MMHg (0.35 ± 0.25 d-1). Furthermore, relationships with environmental parameters suggest that methylated Hg species transformations in surface water are mainly biologically driven. We propose that in addition to Hg(II) methylation, the main processes controlling MMHg production in the Arctic Ocean surface waters are DMHg demethylation and deposition of atmospheric MMHg. These results are valuable for a better understanding of the cycle of methylated Hg in the Arctic marine environment. Author Keywords: Arctic Ocean, Atmosphere, Demethylation, Dimethylmercury, Methylation, Monomethylmercury
Molecular Composition of Dissolved Organic Matter Controls Metal Speciation and Microbial Uptake
Aquatic contaminant mobility and biological availability is strongly governed by the complexation of organic and inorganic ligands. Dissolved organic matter (DOM) is a complex, heterogeneous mixture of organic acids, amino acids, lipids, carbohydrates and polyphenols that vary in composition and can complex to dissolved metals thereby altering their fate in aquatic systems. The research conducted in this doctoral dissertation addresses 1) how DOM composition differs between phytoplankton taxa and 2) how DOM composition affects metal speciation and its subsequent microbial bioavailability in laboratory and field conditions. To accomplish this, a series of analytical methods were developed and applied to quantify thiols, sulphur containing DOM moieties, and the molecular composition of DOM. The works presented in this thesis represents one of the first comprehensive and multipronged analyses of the impact of phytoplankton metabolite exudates on microbial metal bioavailability. This dissertation demonstrated the analytical versatility of high-resolution mass spectrometry as a tool for compound specific information, as well as having the capabilities to obtain speciation information of organometallic complexes. The work presented in this PhD strengthens the understanding compositional differences of both autochthonous and allochthonous DOM and their effects on metal biogeochemistry. Author Keywords: Dissolved Organic Matter, Mercury, Metal Accumulation, Phytoplankton, Spring Melts, Thiol
Novel Silica Sol-Gel Passive Sampler for Mercury Monitoring in Aqueous Systems
A novel passive sampler for mercury monitoring was prepared using organosilica sol-gel materials. It comprises a binding layer with thiol groups for mercury complexation and a porous diffusive layer through which mercury can diffuse and arrive at the binding layer. Our study demonstrated that this new sampler follows the principle of passive sampling. The mass of mercury accumulated in the binding layer depends linearly on the mercury concentration in solution, the sampling rate and the exposure time. A typical sol-gel sampler is characterized by a diffusive layer of 1.2 &mum, in which mercury ions diffuse with a coefficient of D = 0.09~10-6 cm2/s. The capacity for mercury uptake is approximately 0.64 &mug/cm2. Mercury diffusion and binding in the passive sampler are independent of the type of mercury-chloride complex. Its sampling rate increases with increasing water turbulence and decreases with increasing DOM amount. The field trial of sol-gel sampler in Miller Creek shows the concentration gained from the sol-gel passive sampler is slightly lower than that from the spot sampling. Author Keywords:
Purification and Identification of Selenium-containing C-phycocyanin from Spirulina
Selenium is an essential trace nutrient to many organisms, yet in high concentrations it is toxic. Organic selenium is more bioavailable to aquatic biota than inorganic selenium, but is usually found in much lower concentrations. Algae are known to biotransform inorganic selenium into several organo-selenium compounds, but it is unknown whether any of these bioaccumulate in the food chain. In this study, selenium was incorporated into the methionine residues of an algal photosynthetic protein, c-phycocyanin from Spirulina spp. The extent of selenium incorporation was quantified by inductively coupled plasma-mass spectrometry (ICP-MS), and the protein was identified using electrospray mass spectrometry (ES-MS). C-phycocyanin was isolated and purified from Spirulina with a final recovery of 20-30 % of the total c-phycocyanin present. Selenomethionine replaced 92.8% ± 1.22 of the methionine residues in c-phycocyanin when grown in 2.5 ppm sodium selenite. ES-MS was used to obtain protein spectra, and pure c-phycocyanin was identified. Data of full scans provided estimated masses of both protein subunits--α-chain measured at 18,036 Da; β-chain measured at 19,250 Da--close to the theoretical masses. Protein fragmentation by collision-induced dissociation and electron capture dissociation provided approximately 52 % amino acid sequence match with c-phycocyanin from Spirulina platensis. This study demonstrates the incorporation of selenium into an algal protein, and the identification of c-phycocyanin using electrospray ionization-mass spectrometry. Author Keywords:
SARS-CoV-2 Protein-based Detection Using Localized Surface Plasmon Resonance
During the COVID-19 pandemic, nucleic acid and antibody-based testing methods were heavily relied upon, but can be costly, time-consuming and exhibit high false -negative and -positive rates. Thus, alternative strategies are needed. Viral antigens such as the SARS-CoV-2 spike (S) glycoprotein are critical in the function of the virus and useful as diagnostic biomarkers for viral infections. For biosensing applications, aptamers are suitable high-affinity and cost-effective binding partners for their specific targets. Using localized surface plasmon resonance (LSPR), real-time, rapid acquisition of results can be achieved, essential for improving the efficacy of a sensor. Herein, LSPR aptamer sensors were fabricated for the detection of the SARS-CoV-2 protein. Data indicate that the best performing aptasensor was the streptavidin-biotin sensor, while the current gold aptasensor exhibited lower sensitivity and the fabrication of the carboxyl aptasensor was unsuccessful. The S1 aptamer selectively bound the S1 protein with high binding affinity. Excellent shelf-life stability, reusability, and high recovery in complex matrices was also maintained. Additionally, a receptor binding domain (RBD) functionalized sensor was fabricated to examine the interactions with angiotensin converting enzyme 2 (ACE2), for future assessment of inhibitors used in drug therapies. Overall, LSPR has been demonstrated as a viable tool for measuring SARS-CoV-2 related aptamer-protein and protein-protein interactions, and this strategy may be applied to other viral or non-viral antigen targets. Author Keywords: Antigen-based Detection, Coronavirus, COVID-19, Inhibition, Localized Surface Plasmon Resonance, SARS-CoV-2
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)
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

Pages

Search Our Digital Collections

Query

Enabled Filters

  • (-) ≠ Materials Science
  • (-) ≠ Southeast Asian studies
  • (-) = Environmental and Life Sciences
  • (-) = Analytical chemistry