The biogeochemical cycling of oceanic dissolved cadmium (dCd) has been an active area of research for the past ~40 years, due in part to the close correlation with phosphate (PO4). The global Cd:PO4 relationship has led to the use of microfossil Cd/Ca as a paleoproxy for ocean circulation and nutrient utilization; however considerable spatial and temporal variability in the relationship - particularly in surface waters - limits the utility of the proxy. Understanding the global biogeochemical cycling of Cd is an active area of research; however the Arctic Ocean is largely omitted from global models due to lack of data. This work presents depth profiles of dCd and Cd/PO4 ratios from 18 individual stations in the Canadian Arctic, collected during the Canadian GEOTRACES cruises GN02 and GN03, which connect the Arctic Ocean to the North Atlantic through the Canadian Arctic Archipelago (CAA). Salinity-driven water mass stratification exerts a primary control on the spatial distribution of Cd in the region, with elevated dCd and high Cd/PO4 ratios (~0.37 pM/μM) associated with waters of Pacific-origin. The elevated dCd and Cd/PO4 ratios are used as a tracer of Pacific-origin waters, identifying the presence of Pacific-origin water through the CAA and into Baffin Bay. High surface Cd/PO4 ratios were observed across the transect, consistent with a general global increase in surface water Cd/PO4 with increasing latitude. The analysis of Cd and other bioactive trace metals (Mn, Fe, Ni, Cu, Zn and Pb) still presents considerable analytical challenges due to the high-risks of contamination, low concentrations and complex matrices. I present a novel multi-element analytical method, which combines the commercially-available seaFAST pico preconcentration system with ICP-MS/MS analysis. In this work, we demonstrate that ICP-MS/MS, which combines two mass-selecting quadrupoles separated by an octopole collision/reaction cell, effectively removes common interferences (ArO+ on 56Fe and MoO+ on Cd) when pressurized with O2 gas. Accurate and precise measurements of iv the consensus references standards SAFe S and SAFe D and the certified reference material NASS-6 are presented as validation of the method. This thesis presents a novel method for the analysis of trace / Graduate

This research evaluates the decomposition of leaf litter while in litter traps. More specifically this study asks, ‘Does sugar maple (Acer saccharum Marsh.), American basswood (Tilia Americana L.) and American beech (Fagus grandifolia Ehrh.) leaf litter collected bi-weekly from litter traps undergo a loss of dry mass and nutrient content (C, N, P, K, Ca and Mg) in comparison to freshly abscised leaf litter?’The objective of the initial experiment was to determine if sugar maple, basswood and beech leaf litter collecting in litter traps, while exposed to in-situ conditions, experienced decomposition. Results indicated that sugar maple, basswood and beech leaf litter experienced early stages of decomposition and identified precipitation, freezing temperatures and microbial activity as possible mechanisms for the observed decomposition. It was found that the dry weight of sugar maple and basswood differed significantly (p < 0.05 and p < 0.10, respectively) post- 14-day experiment period as compared to the initial dry weight. Consequently, three experiments were completed to examine the aforementioned variables. Conclusions were based on measured changes in the mass and nutrient (C, N, P, K, Ca and Mg) content of freshly abscised sugar maple, basswood and beech leaf litter under ex-situ conditions. It was found that the dry weight sugar maple and basswood leaf litter exposed to 30 mm, 60 mm and 100 mm of precipitation differed significantly (p < 0.05) as compared to freshly abscised leaf litter. In general, this research affirmed that precipitation and freezing temperature contribute to a change in mass and nutrient content of leaf litter collecting in litter traps. Furthermore, through measurable production of CO2 and Community Level Physiological Profiling it was determined that microbes are present and active on the leaf surface and contribute to the decomposition of leaf litter in litter traps.

This research evaluates the decomposition of leaf litter while in litter traps. More specifically this study asks, ‘Does sugar maple (Acer saccharum Marsh.), American basswood (Tilia Americana L.) and American beech (Fagus grandifolia Ehrh.) leaf litter collected bi-weekly from litter traps undergo a loss of dry mass and nutrient content (C, N, P, K, Ca and Mg) in comparison to freshly abscised leaf litter?’The objective of the initial experiment was to determine if sugar maple, basswood and beech leaf litter collecting in litter traps, while exposed to in-situ conditions, experienced decomposition. Results indicated that sugar maple, basswood and beech leaf litter experienced early stages of decomposition and identified precipitation, freezing temperatures and microbial activity as possible mechanisms for the observed decomposition. It was found that the dry weight of sugar maple and basswood differed significantly (p < 0.05 and p < 0.10, respectively) post- 14-day experiment period as compared to the initial dry weight. Consequently, three experiments were completed to examine the aforementioned variables. Conclusions were based on measured changes in the mass and nutrient (C, N, P, K, Ca and Mg) content of freshly abscised sugar maple, basswood and beech leaf litter under ex-situ conditions. It was found that the dry weight sugar maple and basswood leaf litter exposed to 30 mm, 60 mm and 100 mm of precipitation differed significantly (p < 0.05) as compared to freshly abscised leaf litter. In general, this research affirmed that precipitation and freezing temperature contribute to a change in mass and nutrient content of leaf litter collecting in litter traps. Furthermore, through measurable production of CO2 and Community Level Physiological Profiling it was determined that microbes are present and active on the leaf surface and contribute to the decomposition of leaf litter in litter traps.

Evidence of three glaciations in Paleoproterozoic successions of North America and at least one on three other continents, suggests that these glaciations were of global extent. In common with the Neoproterozoic record, carbonates cap the glacials. However, the relationship between biogeochemical cycling of carbon and ice ages has not been fully appreciated. This research involved the sedimentology and isotope stratigraphy of carbonates and shales in Paleoproterozoic glacially-influenced successions of Wyoming and South Africa. Carbonates of the Vagner Formation cap the middle of three diamictites in the Snowy Pass Supergroup, Medicine Bow Mountains, WY. The Duitschland Formation occurs between two glacial horizons in South Africa. Limestones retain negative d13C values for over 60 m in the Vagner Formation, and for over 100 m in the lower part of the Duitschland Formation. Isotope compositions of TOC from the lower part of the Duitschland Formation reveal pronounced enrichment resulting in significantly lower fractionation between organic and inorganic carbon. This is similar to enrichment noted in Neoproterozoic cap carbonates. Combined with strongly positive carbon isotope compositions in upper Duitschland carbonates, the data from the Vagner Formation underscores strongly positive-to-negative carbon isotope trends bracketing Paleoproterozoic glaciations. These trends mimic those noted in Neoproterozoic glacial successions and possibly indicate a recurrence of global glaciations. The Slaughterhouse and Nash Fork formations significantly postdate the glacial epoch. Both the lower part of the Nash Fork Formation, Medicine Bow Mountains and the Slaughterhouse Formation, Sierra Madre contains carbonates with 13C-enrichment >+6â ° and locally up to +28%, whereas carbonates higher in the Nash Fork Formation have d13C values between 0 and 2.5%. This dramatic change in the composition of the Paleoproterozoic ocean is constrained at ca. 2.1 Ga (Karhu, 1993). Carbonates in the Rawhide Canyon section of the Whalen Group in the Hartville Uplift (the easternmost exposure of the Wyoming Craton) display δ13C values up to +8.2% suggesting correlation with the Slaughterhouse and Nash Fork formations and their deposition on continuous carbonate platform along the margin of the Wyoming Craton. These data support an open-marine, and therefore a global origin for the ca. 2.2-2.1 Ga carbon isotope excursion. / Ph. D.

Indiana University-Purdue University Indianapolis (IUPUI) / The evolution of land plant root systems occurred stepwise throughout the Devonian, with the first evidence of complex root systems appearing in the mid-Givetian. This biological innovation provided an enhanced pathway for the transfer of terrestrial phosphorus (P) to the marine system via weathering and erosion. This enhancement is consistent with paleosol records and has led to hypotheses about the causes of marine eutrophication and mass extinctions during the Devonian. To gain insight into the transport of P between terrestrial and marine domains, presented here are geochemical records from a survey of Middle and Late Devonian lacustrine and near lacustrine sequences that span some of these key marine extinction intervals. Root innovation is hypothesized to have enhanced P delivery and results from multiple Devonian sequences from Euramerica show evidence of a net loss of P from terrestrial sources coincident with the appearance of early progymnosperms. Evidence from multiple Middle to Late Devonian sites (from Greenland and northern Scotland/Orkney), reveal a near-identical net loss of P. Nitrogen and Carbon isotopes from a subset of these lakes confirm elevated input of terrestrial plant material concurrent with P perturbations. Terrestrial P input appears to be episodic in nature, suggesting land plant expansion was driven by an external catalyst in the study region. All sites analyzed are temporally proximal to significant marine extinctions, including precise correlation with the Kačák extinction event and the two pulses associated with the Frasnian-Famennian (F/F) mass extinction. The episodic expansion of terrestrial plants appears to be tied to variations in regional and global climate, and in the case of the F/F extinction, also to atmospheric changes associated with large scale volcanism. Using P data presented here as an input into an Earth system model of the coupled C-N-P-O2-S biogeochemical cycles shows that globally scaled riverine phosphorus export during the Frasnian-Famennian mass extinction generates widespread marine anoxia consistent with the geologic record. While timing precludes land plants as an initiating mechanism in the F/F extinction, these results suggest they are implicated in every marine extinction event in the Mid to Late Devonian.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

The marine shallow-water hydrothermal vent system of Tutum Bay, Ambitle Island, PNG discharges hot, acidic, arsenic-rich, chemically reduced fluid into cool, alkaline, oxygenated seawater. Gradients in temperature, pH, total arsenic (TAs) and arsenic species, among others, are established as the two aqueous phases mix. Hydrous ferric oxides (HFO) are precipitated around focused venting, and coat the surrounding sediments visibly to 150 m away. HFO coatings, mechanical transport and weathering of volcanoclastic sediments, as well as dissolution of carbonate sediments nearer to venting, combine to alter sediment chemistry substantially. Tutum Bay surface sediments have a mean As concentration of 527 mg/kg. Arsenic at concentrations up to 50 mg/kg (mean = 19.7 mg/kg) was extracted from the easily extractable fraction of surface sediments. Arsenic is elevated in surface seawaters (8 µg/L) directly over hydrothermal vents, and As(III) is substantially enriched in both surface and bottom seawater throughout Tutum Bay. Surprisingly, aqueous As(V) far exceeded aqueous As(III) at almost all distances and depths investigated for Tutum Bay pore waters. These data indicate that throughout Tutum Bay, chemical disequilibria among As species provides potential metabolic energy for arsenite oxidizing and arsenate reducing microorganisms, and that As is bioavailable from two major environments: 1) easily-exchangeable As from surface sediments, and 2) in surface seawaters, which may allow for biological uptake and trophic transfer through plankton. The soft coral Clavularia sp., the calcareous algae Halimeda sp., and the tunicate Polycarpa sp. were collected and analyzed to assess bioaccumulation and biotransformation patterns. All organisms collected from the hydrothermal area displayed higher (2 to 20 times) TAs. Concentrations of arsenic species in their tissues were also elevated compared to the control site. Increased concentrations were observed near focused venting. Distinct arsenic speciation patterns in Clavularia and Polycarpa collected from near hydrothermal venting suggest rapid methylation/detoxification of arsenic, with enhanced bioaccumulation of dimethylarsenate and arsenobetaine as products of the organisms metabolic pathways. Elevated concentrations of As(III) in Halimeda suggest that this organism is not as efficient at methylating inorganic arsenic. The presence of arsenobetaine in Halimeda suggests the biomethylation pathway for calcareous algae is different from commonly studied seaweeds.

Mercury (Hg) is a potent neurotoxin, has both natural and anthropogenic sources to the environment, and is globally dispersed. Humans have been using Hg since antiquity and continue its use in large quantities, mobilizing Hg from stable long-lived geologic reservoirs to actively cycling surface terrestrial and aquatic ecosystems. Human activities, such as mining and coal combustion, have perturbed the natural biogeochemical cycle of Hg. However, the distribution of natural versus anthropogenic Hg in the environment today and the extent of anthropogenic perturbation (i.e., enrichment) are uncertain. Previous model estimates of anthropogenic enrichment have been limited by a lack of information about historical emissions, examined only near-term effects, or have not accounted for the full coupling between biogeochemical reservoirs. Presented here is a framework that integrates recently available historical emission inventories and overcomes these barriers, providing an improved quantitative understanding of global Hg cycling. / Earth and Planetary Sciences

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

This Master’s degree study examined concentration and isotopic trends of dissolved methane, isotopic trends of phospholipid fatty acids (PLFA), and generated 1st order flux calculations to identify and assess biogeochemical cycling of dissolved methane in the first full-scale demonstration of EPL technology in the Alberta Oil Sands Region (AOSR). Base Mine Lake (BML) was commissioned by Syncrude Canada Ltd. in 2012 to facilitate the long-term storage and remediation of Fluid Fine Tailings (FFT) that are generated as a result of bitumen extraction via the Clark Hot Water Extraction (CHWE) processes. The results of this project provide evidence of methane oxidation by type I methanotrophs in BML, reducing dissolved oxygen concentrations in the hypolimnion layer. The FFT layer is identified as a source zone of fermentative methanogenesis, creating saturated conditions of dissolved gases. Dissolved methane is transferred to the water column primarily by advective processes related to FFT consolidation, while diffusion is a significant secondary transfer mechanism. Dissolved methane concentrations decrease significantly across the FFT-water interface where diffusive flux rates decrease by several orders of magnitude. Concentrations decreased linearly through the hypolimnion to trace concentrations by the metalimnion, resulting in a minor enrichment of δ13C of the residual dissolved methane pool. A minor enrichment of δ13C in C14:0, C16:0, and C16:1 PLFA coincided across the same interval, indicating utilization of a less depleted carbon source further away from the FFT-water interface where dissolved methane concentrations were lower. PLFA δ13C signatures were depleted relative to expected values of typical DOC substrates, further supporting the incorporation of a depleted signature by transfer of depleted carbon from dissolved methane. / Thesis / Master of Science (MSc)