Gueguen, Celine

This study examined dissolved organic matter (DOM) and labile Mercury (from diffusive gradient in thin films (DGT)) in the Quesnel river, British and the Goose creek tributary of the Churchill river, Manitoba. DOM properties were measured with optical measurements of absorption coefficient (a254), spectral slopes (S275-295, SR) and fluorescence indices (HIX, BIX, FI). The DOC proxy measurements (a254) were almost 10 times higher at the Churchill site (Mean a254 116.77 cm-1) compared with the Quesnel river site (Mean a254 12.06 cm-1) during the study periods. While DGT labile Hg concentrations at the Quesnel site (2.17 to 98.97ppt) were almost 10 times more than the levels reported at the Churchill site (0.03 to 9.06 ppt). Fluorescence indices and the rise of labile Hg concentrations in spring indicated mostly terrestrial sources of DOM at both the sites. Spectral slopes and fluorescence indices substantiated that Churchill site had high molecular weight, complex and more humic DOM compared with Quesnel. DOM at both the sites was prone to temporal variation and affected by environmental conditions. Correlation between DGT labile-Hg and DOM parameters suggested that DGT collected Hg-organic complexes along with inorganic labile-Hg complexes.

Author Keywords: Churchill, Diffusive gradient in thin films, Dissolved organic matter, Labile Hg, Mercury, Quesnel

The rapid expansion of the worldwide population has caused an urgent need for the development of new, more environment-conscious, food sources. In this context, algae, such as Euglena, are of interest thanks to their capacity to naturally produce essential nutrients such as proteins and oils commonly found in animals and plant sources. While these processes are currently being investigated, underlying measures affecting growth of Euglena gracilis like hormonal influences and growth stress like nutrient deprivation are poorly understood. From this vantage point, this thesis seeks to understand the role of phytohormones cytokinin (CKs) and abscisic acid (ABA) in complex mechanisms underlying heterotrophic growth of Euglena gracilis under recycled, organic media conditions with no supplementation. Hormone profiles were quantified by HPLC-ESI-MS/MS and compared to culture growth dynamics of pH, weight accumulation, glucose content, cell count and morphology. It was expected that ABA acted as an inhibitory hormone and this was confirmed by its higher levels when CKs where low and vice versa. Contrastingly, it was expected that CKs stimulated growth, in which this was shown not to be the case. Interestingly, it was revealed that both hormone groups increase with increasing recycling. Other key findings include: E. gracilis synthesizes CKs via the tRNA-degradation pathway and is cZ and iP dominated, recycling E. gracilis medium is viable for growth, however, the percentage (25% or less) is crucial to cell viability and markedly no ABA was detected in E. gracilis pellet fractions from recycled media. Therefore, this data revealed that recycled media has a striking influence on physiological aspects of growth and illustrated unique changes in hormone profiles of which could be manipulated to help the food industry.

Author Keywords: cytokinin, endogenous hormones, Euglena gracilis, heterotrophic, large scale microalgae cultivation, recycled medium

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

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

The potential impacts of domestic wastewater (DWW) on the source of drinking water for the M'Chigeeng First Nation were monitored as part of the development of a Source Water Protection plan. During a period of continuous overflow of the Gaaming Wastewater Lagoon serving the community, the chemical tracers, caffeine and sucralose were tracked in West Bay with Passive Organic Chemical Integrative Samplers (POCIS). From the results, we speculated that DWI impacts could have been from three possible DWW sources. POCIS deployed above and below the thermocline indicated a higher mean sucralose concentration of 2.52 ± 1.83 ng/L in the hypolimnion of West Bay relative to mean epilimnetic sucralose concentrations of 0.56 ± 0.02 ng/L, suggesting possible wastewater percolation with an estimated time of travel of 61.5 days. Microbial loads of 200 CFU/100 ml E. coli from the lagoon overflow into Mill Creek decreased to 60 CFU/100 ml before entering West Bay. West Bay's wastewater assimilative capacity met Provincial Water Quality Objectives in the epilimnion and hypolimnion except for dissolved oxygen in the hypolimnion at 4.16 ± 1.86 mg/L, which is a threat to the onset of hypoxia for fish (i.e. <5 mg/L). Assimilative capacity results support a Fall lagoon discharge.

Author Keywords: caffeine, drinking water, Passive Organic Chemical Integrative Samplers (POCIS), sucralose, thermocline, wastewater

Threats such as climate change and increased anthropogenic activity such as shipping, are expected to negatively affect the Arctic. Lack of data on Arctic systems restricts our current understanding of these sensitive systems and limits our ability to predict future impacts. Lakes and ponds are a major feature of the Arctic landscape and are recognized as 'sentinels of change', as they integrate processes at a landscape scale. A total of 1300 aquatic sites were assessed for common chemical and physical characteristics. Geology type was found to be the greatest driver of water chemistry for Arctic lakes and ponds. Acid-sensitivity was assessed using the Steady State Water Chemistry model and a subset of 1138 sites from across the Canadian Arctic. A large portion of sites (40.0%, n = 455) were classified as highly sensitive to acidic deposition, which resulted in a median value of 35.8 meq·m―2·yr―1 for the Canadian Arctic. Under modelled sulphur deposition scenarios for the year 2010, exceedances associated with shipping is 12.5% (n = 142) and 12.0% (n = 136) for without shipping, suggesting that impacts of shipping are relatively small.

Author Keywords: Acidic deposition, Arctic lakes, Critical loads, Shipping emissions, Steady-State Water Chemistry Model, Water chemistry

In this thesis, water mass distribution of dissolved organic matter (DOM) characteristics (i.e. molecular weight, fluorescent components, thiols and humic substances concentration) was observed in the Arctic Ocean. For the first time, DOM molecular weight (MW) in Beaufort Sea was assessed using asymmetrical flow field-flow fractionation, as well as the first monitoring of thiols and humic substances (HS) using cathodic stripping voltammetry (CSV) in the Arctic Ocean. Based on fluorescence property, DOM characterization was carried out using parallel factor analysis – excitation-emission matrices. Pacific winter waters in the Canada Basin showed higher MW DOM associated with higher fluorescence intensity. High HS was associated with the Arctic outflow waters in top 300 m of the Canadian Arctic Archipelago. Interestingly, maximum thiol concentration was associated with the subsurface chlorophyll-a maximum at most sites, but not universal along the study area. Comparable distributions of CSV-based HS and humic-like fluorescent components suggest similar sources/ processes in the Arctic Ocean. The findings in this thesis suggested DOM characteristics could be used as fingerprints in tracing water masses in the Arctic Ocean.

Author Keywords: Asymmetrical flow field-flow fractionation, Cathodic stripping voltammetry, DOM, Metal-binding ligands, Molecular weight, PARAFAC-EEMs

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

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

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