Environmental science

This work presents a new online method using gas chromatography coupled to the multicollector-inductively coupled plasma-mass spectrometer for methylmercury (MMHg) isotope ratio measurement. An extraction method using distillation was developed that effectively extracted MMHg from up to 5 grams of sediment, imparting no isotope fractionation on MMHg during extraction. Isotope ratios from transient signals were calculated using three different data treatment approaches, facilitated by a data processing application, IsoCor. Peak Area Integration using 80% of the peak gave the most accurate and precise results. Using the proposed methodology, an external precision (2 SD) of ± 0.59‰ for NIST 3177 was measured. This method can be applied to samples with MMHg concentration as low as 0.1 ng/g and was successfully applied to real sediment samples however, additional research to improve the precision of the method is required for the detection of small differences between samples.

Author Keywords: compound specific isotopic ratios, isotope ratio measurement, MC-ICP-MS, methylmercury

This thesis presents a case of the aquatic plant species Fanwort (Cabomba caroliniana) significantly naturalizing in Kasshabog Lake in bays where it had been invasive. This significant naturalization presents major implications for invasive species management and invasion biology because the naturalization of invasive species is a phenomenon that has been largely omitted from study within ecology. There are several reasons for this: 1) the most used definition of the term naturalization within invasion biology categorically excluded the sense in which naturalization refers to community integration; 2) the most cited frameworks that have been created and used to describe and study biological invasions have no conception of invasive species naturalization; 3) boundary work has been conducted to exclude consideration of the naturalization of invasive species. Incorporation of an understanding of naturalization into science and management of biological invasions will make our understanding of them more complete.

Author Keywords: Ecological Restoration, Invasion Biology, Invasive Species, Naturalization

Naphthenic acids are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters, OSPW. Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation. A deeper evaluation of the effect naphthenic acid structural differences have on uptake affinity is warranted. In this thesis an in-depth exploration of naphthenic acid adsorption onto activated carbon is provided including many more model naphthenic acid species than what have been assessed previously in adsorption studies. Both adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW were evaluated. Given the time sensitive application of most adsorbents towards treating contaminated waters such as OSPW, achieving fast adsorption rates for model naphthenic acids is an important goal worth considering. Textural properties of activated carbon most conducive for fast adsorption kinetics were assessed using several candidate model species. Clear evidence is presented, demonstrating the influence of both the pore size distribution and particle size of porous adsorbents on uptake rates of naphthenic acids, demonstrating that careful optimization of these adsorbent properties can result in adequate uptake rates. Adsorption isotherms were used to assess model naphthenic acid affinity towards activated carbon. Uptake for the model naphthenic acids varied considerably regardless of the activated carbon used, ranging from 350 mg g-1 to near zero highlighting recalcitrant species. The equilibrium data was explored to identify important structural features of these species and key physiochemical properties that influence adsorption. It was demonstrated that certain naphthenic acids are resistant to adsorption when hydrophobic adsorbents are used. Adsorption isotherm modelling helped explore interactions occurring at the interface between naphthenic acids and adsorbent surfaces. Naphthenic acid hydrophobicity was identified as an importance physiochemical property for achieving high adsorption capacities onto activated carbon. Evidence is also presented that indicates favorable hydrogen bonding between naphthenic acids and surface site hydroxyl groups, demonstrating the importance of adsorbent surface functionality for naphthenic acid uptake. The adsorption mechanism was further explored through use of a thermodynamic analysis of the model naphthenic acid system using activated carbon. Standard state enthalpy and isosteric enthalpy of adsorption values were used to further support the proposed mechanisms occurring between model species and activated carbons. This research highlights the challenges associated with removing naphthenic acids from OSPW through adsorption and identifies how adsorbent surface chemistry modification will need to be used to increase the removal efficiency of recalcitrant naphthenic acid species when using activated carbon.

Author Keywords: Activated Carbon, Isotherms, Kinetics, Modelling, Naphthenic Acids, Thermodynamics

The Great Lakes represent nearly a fifth of the global freshwater surface supply, and support culturally, economically, and ecologically important fish species such as Walleye (Sander vitreus). With water temperatures projected to rise by several degrees in the coming century, understanding the energetic impacts on fishes is crucial for effective habitat and fisheries management. I measured the swimming performance, accelerometer-based activity, and metabolism of walleye in relation to body size, sex, and water temperature to assess potential responses to climate variability. Both acceleration and swim speed predicted metabolic rate with reasonable accuracy. Temperature had a positive effect on oxygen consumption whereas body mass had a negative effect. Critical swimming speed increased with temperature, and tailbeat frequency had positive relationships with swim speed and acceleration. My laboratory-based calibrations should enable remote field monitoring of energy use of walleye (via accelerometers) and help conserve an important species through bioenergetic modelling.

Author Keywords: accelerometry, bioenergetics, climate change, metabolism, respirometry, walleye

In Ontario, farmers commonly use a MZ (Maize (Zea mays L.))-SB (Soybean (Glycine max))/WW (Winter wheat (Triticum aestivum)) – CC (mixed cover crop) rotation to maximize economic benefits. This study aimed to investigate the short-term impacts of the crop rotation phases and their associated management practices in this diversified cash crop rotation on soil health and the abundance of nitrogen (N)-cycling soil microbial communities (SMCs). Additionally, the abundance of N-cycling SMCs and plant-available N in both surface (0-5 cm) and rooting zone (5-15 cm) depths were characterized in tile-drained (TD) and non-TD fields. In the present study, soils collected under the CC phase had the highest labile carbon levels (10-17% higher) and water-stable aggregates (35-50% higher) compared to the other two crop phases. Lower nitrifying (amoA) gene abundances and soil NO3--N levels were observed in the CC phase compared to the MZ and SB-WW phases, suggesting a potential for decreased nitrification in the CC phase. The presence of SB potentially influenced the soil N concentration in the subsequent WW phase likely due to the release of symbiotically fixed N in the SB-WW phase. Further, higher amoA abundances and NO3--N in the SB-WW phase imply a potential for increased nitrification in the SB-WW phase. Additionally, higher amoA/nosZI and nirS+nirK/nosZI ratios were observed in the MZ phase than in SB-WW and CC phases, suggesting a potential capacity for increased N2O emissions from the reactions mediated by N-cycling SMCs in soils planted to MZ during fall sampling days. In the TD and NTD field study, higher NO3--N levels were observed in TD-SB-WW fields at 5-15 cm vs. 0-5 cm depths, which was possibly facilitated by tile drainage. The TD-CC fields displayed higher nosZI gene abundances and lower nirS+nirK/nosZI abundance ratios, suggesting a greater potential capacity for decreased N2O emissions in soils planted to CCs during the spring sampling days. When examining changes in plant available N by soil depth, reduced downward movement of NO3- through shallow soil depths (0-15 cm depth) was observed in the CC phase compared to cash crops. This short-term study highlights the potential contribution of the CC phase, particularly within TD agricultural fields, for improving soil health and reducing potential N2O emissions. Together, these results suggest that management-associated differences in crop rotation phases have temporary effects on soil health and the abundance of SMCs. Future studies linking N-cycling SMC's potential activity and field-scale N2O fluxes will provide a better insight into the longer-term sustainability of Ontario's cash crop management systems.

Author Keywords: denitrification, maize-soybean-winter wheat- cover crop rotation, nitrification, soil depth, Sustainable agriculture, tile-drainage

In an effort to improve upon existing analytical methods, electrochemical sensors offer portable, cost-effective alternatives to traditional lab-based techniques. Recent advances in supramolecular chemistry offer a unique alternative to achieve high selectivity while also benefitting from facile scaling for mass production. Thus, by incorporating host-guest chemistry with electrochemical sensors, the development of simple and selective sensors is possible. To that extent, novel hosts and electroactive ion pairs were investigated for their ability to transduce an electrochemical signal representative of host-guest complexation. Results demonstrated that the upper rim modifications of resorcinarene hosts attenuated their affinity for electroactive probes whilst maintaining structural integrity upon extended cycling. Further work revealed that guests may be directly quantified via their complexation with electroactive hosts. The sensing method was further validated by quantification of surfactant pollutants in the Otonabee River. Through a fundamental understanding of the electrochemical behaviour of host-guest systems a general sensing platform can be developed, where hosts are interchangeable for specificity towards any desired analyte. Therefore, moving away from expensive lab-based methods and significantly reducing the barriers for biological or environmental monitoring.

Author Keywords: Electrochemistry, Ferrocene, Host-Guest, Resorcinarenes, Supramolecular Chemistry, Surfactants

The detection of ciguatoxins (CTXs) in biological samples is challenging due to their low concentrations, the presence of various congeners, and the absence of standardized methods. This study uses high resolution mass spectrometry (HRMS) with P-CTX-3B as a reference standard. The protonated molecules ([M+H]+) were most prevalent, especially when acetonitrile/water was utilized, providing enhanced sensitivity. Optimized collision energies of 15 eV for protonated molecules and flow rates of 10 µl/min enhance sensitivity and peak intensities, respectively. Acetonitrile/water (ACN/H2O) is recommended as the primary solvent for HRMS method, an aspect underexplored in existing literature. The detection of CTX-3B in fish tissue samples proved to be challenging, caused by variations in ion peak intensities and matrix effects, requiring a deeper exploration of the impact of complex matrices on CTX detection. The study emphasizes the need for a reliable internal standard to mitigate these effects and highlights the ongoing challenge of developing a rapid, simple, and sensitive detection method. The study's specific focus on the P-CTX-3B analogue significantly contributes to methodology development for this congener, serving as a foundational step in understanding and detecting CTX. Despite notable progress, the study acknowledges the absence of an ideal assay, outlining key challenges for future research on ciguatera analysis. It underscores the continuous necessity for method reevaluation, testing, and the broader goal of establishing a more clarified and rugged method for the identification of CTX in fish.

Author Keywords: Analytical Chemistry, Ciguatera Fish Poisoning, Ciguatoxin, High-Resolution Mass Spectrometry, Optimization, P-CTX-3B

Northern flying squirrels (NFS) are mycophagous specialists (fungi-dominated diet) thatmay be displaced with southern flying squirrel (SFS) range expansion, thereby limiting fungal dispersal in forest communities. To understand the implications of squirrel species turnover on mycophagy, we investigated the home ranges of both flying squirrel species who are living in stable sympatry. We found no significant difference in home range sizes and identified spatial overlap between the two species. Through habitat selection ratios we found SFS were strongly selecting for deciduous-dominated habitats more than NFS. Lastly, we conducted microscopy on flying squirrel scat and found NFS were eating more fungi than SFS. We conclude that the squirrels are sharing the same habitat landscape but are finding ways to partition the habitat accordingly to allow for sympatry. SFS may contribute to the spore-dispersal cycle similarly to their northern counterpart through moderate fungus consumption and large home range sizes.

Author Keywords: diet, flying squirrels, Glaucomys, home range, mycophagy, sympatry