Graduate Theses & Dissertations

Chemical characterization of dissolved organic matter in relation with hydrography in the Arctic Ocean
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
Regional Assessment of Soil Calcium Weathering Rates and the Factors that Influence Lake Calcium in the Muskoka River Catchment, Central Ontario
(MRC) in central Ontario was carried out to determine the range and spatial distribution of soil Ca weathering rates, and investigate the relationships between lake Ca and soil and catchment attributes. The MRC is acid-sensitive, and has a long history of impacts from industrial emission sources in Ontario and the United States. Small headwater catchments were sampled for soil and landscape attributes (e.g. elevation, slope, catchment area) at 84 sites. Soil Ca weathering rates, estimated with the PROFILE model, were low throughout the region (average: 188 eq/(ha·yr)) compared to global averages, and lower than Ca deposition (average: 292 eq/(ha·yr)). Multiple linear regression models of lake Ca (n= 306) were dominated by landscape variables such as elevation, which suggests that on a regional scale, landscape variables are better predictors of lake Ca than catchment soil variables. Author Keywords: Calcium, Lakes, Regional assessment, Regression, Soils, Weathering
Impact of Wetland Disturbance on Phosphorus Loadings to Lakes
Total phosphorus (TP) concentrations have declined in many lakes and streams across south- central Ontario, Canada over the past three decades and changes have been most pronounced in wetland-dominated catchments. In this study, long-term (1980-2007) patterns in TP concentrations in streams were assessed at four wetland-dominated catchments that drain into Dickie Lake (DE) in south-central Ontario. Two of the sub-catchments (DE5 and DE6) have particularly large wetland components (31-34 % of catchment area), and wetlands are characterised by numerous standing dead trees and many young live trees (18 – 27 year old). These two streams exhibited large peaks in TP and potassium (K) export in the early 1980s. In contrast, TP and K export from DE8 and DE10 (wetland cover 19 – 20 %) were relatively flat over the entire record (1980-2007), and field surveys indicated negligible standing dead biomass in these wetlands, and a relatively healthy, mixed-age tree community. Furthermore, K:TP ratios in the DE5 and DE6 streams were around 5 in the early 1980s; very similar to the K:P ratio found in biomass, and as stream TP levels fell through the 1980s, K:TP ratios in DE5 and DE6 stream water increased. The coincidence of high TP and K concentrations in the DE5 and DE6 streams as well as evidence of a disturbance event in their wetlands during the early 1980s suggest that the two are related. The diameter of standing dead trees and allometric equations were used to estimate the amount of TP that would have been held in readily decomposed tree tissues in the DE5 wetland. The amount of P that would have been held in the bark, twig, root and foliage compartments of just the standing dead trees at DE5 was approximately half of the amount of excess stream TP export that occurred in the 1980s. This work suggests that disturbance events that lead to wetland tree mortality may contribute to patterns in surface water TP observed in this region. Author Keywords: Chemistry, Disurbance, Nutrients, Tree Death, Water, Wetland
Fractionation of Mercury Isotopes in an Aqueous Environment
Fractionation of mercury isotopes in an aqueous environment: Chemical Oxidation Dimitri Stathopoulos The study of fractionation patterns for the stable isotopes of mercury is a growing field. The potential for stable isotopes to trace mercury through the environment from pollution sources to sinks make the subject interesting to geochemists and useful to a wider audience. The purpose of this study is to measure the fractionation of mercury as it is oxidized in an aqueous medium. Samples in this study are prepared by chemically oxidizing different proportions of elemental mercury using four different oxidants. The oxidized portion is then separated from the elemental portion and an analysis of the isotope ratios for both portions is performed using a multicollector inductively coupled plasma mass spectrometer MC-ICP/MS. These isotope ratios are measured against the preoxidation isotope ratio to determine what if any change has occurred. From the findings of this work, it is now known chemical oxidation causes both mass dependent and mass independent fractionation. Mass dependent fractionation causes an enrichment of the heavier isotopes in the oxidized portion while the opposite is true for the elemental portion. Mass independent fractionation occurred only in the odd isotopes and causes a depletion of odd isotopes in the oxidized portion and enrichment in the elemental portion. These trends were found to be true for all oxidants tested as the pattern of fractionation does not change with varying oxidants. Author Keywords: Isotope, Mass Dependent, Mass Independent, Mercury, Oxidation

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