Geochemistry

Mineral feedstocks, including alkaline mine wastes, can sequester CO2 as a dissolved phase (e.g., HCO3-) or a solid carbonate via enhanced rock weathering (ERW). For this thesis, the release of easily accessible Ca and Mg from non-carbonate sources was determined for kimberlite residues from several diamond mines and commonly proposed ERW rock types, including wollastonite and olivine. Batch leaches determined the CO2 sequestration potentials of kimberlites to be in the range of 3–12 kg CO2/t, which was exceeded by most ERW feedstocks. Leaches also assessed the release of Ni and Cr, elements of concern in ERW settings, and P and K, which benefit agricultural soils. Year-long leaching columns were deployed using kimberlite from the Gahcho Kué and Venetia diamond mines, wollastonite skarn, and olivine sand from the initial assessment. The kimberlite residues sequestered 0.03 kg CO2/t as dissolved inorganic carbon and 0.6 kg CO2/t as solid total inorganic carbon. Weathering of wollastonite skarn resulted in CO2 removal rates via mineral trapping of CO2 of 6.31 kg CO2/t, while the olivine sand yielded rates of 0.5 kg CO2/t via solubility trapping. Both methodologies used in this study demonstrated value in the prediction and monitoring of drainage chemistry as it relates to ERW and CO2 mineralization. Implementation of these strategies can progress ERW efforts by providing confidence in feedstock selection and the verification of carbon offsets.

Author Keywords: CO2 mineralization, Drainage chemistry, Enhanced weathering, Mine wastes, Mineral trapping, Solubility trapping

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

Maximum permitted SO2 emissions from an aluminum smelter in Kitimat, B.C., increased after modernization in 2015. An increase in acidic deposition can potentially acidify forest soils. Monitoring was conducted at two long-term soil monitoring plots at near (7 km) and far (41 km) sites downwind from the smelter. Change in soil properties was assessed between 2015 and 2018: for the near plot, there was significant decrease in pH and exchange acidity; far plot soils exhibited significant decrease of base cations and exchange acidity in the 0–5 cm layer only. The average total SO42- deposition at near and far plots were estimated to be between 8.2–12.1 and 6.7–7.4 kg/ha/yr, respectively. It was concluded no soil acidification was detected. Observed changes were attributed to measured differences in organic matter, likely influenced by sampling difficulty and measurement process discrepancies. Estimated SO42- deposition levels pose no risk to soil base cation depletion.

Author Keywords: acid forest soils, acidic deposition, aluminum smelter, exchangeable base cations, long-term monitoring, minimum detectable change

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

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

(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

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

A bedrock fracture hosting arsenic (As) contaminated groundwater was suspected to be transported to Ramsey Lake, a drinking water resource for more than 50,000 residents of Sudbury, Ontario. A high resolution, spatial, water quality mapping technique using an underwater towed vehicle (UTV) was used to identify sources of upwelling groundwater into lake water and localize the upwelling As contaminated groundwater vent site. The top 7 cm of lake sediments (in-situ) at this vent site were observed to adsorb 93 % of the dissolved As, thus inhibiting lake water quality degradation from this contaminant source. Sediment samples from this location were used in laboratory experiments to assess the potential for this system to become a source of As contamination to Ramsey Lake water quality and elucidate As(III) fractionation, transformation and redistribution rates and processes during aging. Arsenic speciation is important because As(III) has been shown to be more toxic than As(V). To accomplish this a sequential extraction procedure (SEP) that maintains As(III) and As(V) speciation in (sub)oxic sediments and soils was validated for the operationally defined fractions: easily exchangeable, strongly sorbed, amorphous Fe oxide bound, crystalline Fe oxide bound, and the residual fraction for total As because the characteristics of the reagents required to extract the final fraction do not maintain As species.

Batch reaction experiments using sediment spiked with As(III) or As(V) and aged for up to 32 d were sequentially extracted and analysed for As(III) and As(V). Consecutive reaction models illustrate As(III) is first adsorbed to the sediment then oxidized to As(V). Fractionation analyses show As(III) most rapidly adsorbs to the easily exchangeable fraction where it is oxidized and redistributes to the strongly sorbed and amorphous Fe oxide bound fractions. Oxidation of As(III) adsorbed to the amorphous and crystalline Fe oxide bound fractions is less efficient and possibly inhibited. Select samples amended with goethite provide evidence supporting Mn(II) oxidation is catalyzed by the goethite surface, thus increasing As(III) oxidation by Mn(III/IV) complexed with the strongly sorbed fraction. Although As immobilization through groundwater sediment interactions may be inhibited by increased ion activity, particularly phosphate or lake eutrophication, this threat in Ramsey Lake is likely low.

Author Keywords: arsenic, fractionation, modelling, redistribution, speciation, water quality mapping