Environmental science

Mining and smelting degraded landscapes are characterised by heavily eroded soils that are acidic, contaminated with toxic metals, and depleted of essential nutrients. Regreening degraded landscapes has been proposed to support global carbon (C) mitigation measures and protect biodiversity. One of the world's largest regreening programs in the City of Greater Sudbury, Canada has been ongoing since 1978 and involves liming and fertilizing selected areas followed by planting primarily jack pine (Pinus banksiana Lamb.) and red pine (Pinus resinosa Ait.) trees. The main objective of this thesis was to improve our understanding of biogeochemistry in the City of Greater Sudbury regreened forests, and to determine how nutrient pools and cycling change as stands age. I established a chronosequence of forested sites between 15–40 years-old and to account for the effects of erosion, each site was categorized as "stable" (<10% bedrock cover) or "eroded" (>30% bedrock cover). Individual tree growth and nutrient accumulation in aboveground biomass (AGB) did not differ between stable and eroded sites and were comparable to rates reported from pine plantations in similar ecozones. Aboveground nitrogen (N) pools were six times larger than N applied in fertilizer, suggesting N limitation is most likely not a concern. Rates of C cycling were generally similar to those measured at unimpacted jack and red pine plantations. The exception being a decrease in mineral soil and aggregate C concentrations. However, at the ecosystem-scale the loss of soil C is trivial in comparison to increases in AGB C pools, leading to an overall increase in total ecosystem C following regreening (550,547 Mg in aboveground C across the 19,649 ha regreening landscape). Litter decomposition rates were higher at the regreening sites using a site-specific litter compared to a general common litter, indicating a home-field advantage for local decomposers. Soil temperature varied at the regreening sites and higher soil temperatures were related to higher rates of soil respiration. The regreening sites are rich in calcium (Ca) and magnesium (Mg); and while soils were generally poor in phosphorous (P) and potassium (K), foliar concentrations of P and K were comparable to those of "healthy" red pines. Overall, the regreening program appears to have increased tree growth and produced jack and red pine plantations that are biogeochemically similar to conifer plantations unimpacted by over a century of mining and smelting impacts.

Author Keywords: biogeochemistry, degraded landscape, forests, nutrient cycling, regreening, soil carbon

A significant portion (15-20%) of mercury (Hg) in the Arctic Ocean is believed to originate from Arctic rivers, such as the Mackenzie River watershed in the NWT. Recent (2005- 2020) Hg monitoring data of freshwater and fish tissue and environmental model outputs were compiled and used to develop a Bayesian Network Relative Risk model (BN-RRM), a probabilistic model capable of analyzing causal relationships. The objectives of the model were to estimate the risk posed to fish health and the subsequent dietary Hg-exposure to humans; to compare the relative risks between regions of the watershed; and to identify the influential Hg sources. The output of the BN-RRMs differed significantly throughout the watershed, with atmospheric Hg deposition and soil erosion Hg release consistently flagged as important explanatory variables. Analysis of the endpoint uncertainties revealed gaps in knowledge and in Hg datasets, which should be the focus of study for future monitoring programs.

Author Keywords: Aquatic Ecosystems, Arctic, Bayesian Network, Mercury, Risk Assessment, Toxicology

Understanding snowpack variability is important as it plays an imperative role in environmental, hydrologic, and atmospheric systems. Research questions related to three linked areas were investigated in this thesis: 1) scaling issues in snow hydrology, 2) forest-snowpack relationships, and 3) methods of integrating snow water equivalent (SWE) into a hydrologic model for a large, forested drainage basin in central Ontario. The first study evaluated differences in SWE across process, measurement, and model scales. Point scale snowpack measurements could be bias corrected using scaling factors derived from a limited number of transect measurements and appropriately stratified point scale measurements may be suitable for replacing transect scale mean SWE when transect data are not possible to collect. Comparison of modelled products to measurements highlighted the importance of understanding the spatial representativeness of in-situ measurements and the processes those measurements represent when validating snow products or assimilating data into models.The second study investigated the efficacy of field-based, and remotely sensed datasets to describe forest structure and resolve forest-snowpack relationships. Canopy cover was highly correlated with melt rate and timing at the site scale however, significant correlations were present in 2016 but not 2017, which was attributed to interannual differences in climate. Peak SWE metrics did not correlate well with forest metrics. This was likely due to mid-winter melt events throughout both study years, where a mix of accumulation and melt processes confounded forest-snowpack relationships. The third study evaluated the accuracy of the Copernicus SWE product and assessed the impact of calibrating and assimilating SWE data on model performance. The bias corrected Copernicus product agreed with measured data and provided a good estimate of mean basin SWE. Calibration of a hydrologic model to subbasin SWE substantially improved modelled SWE performance. Modelled SWE skill was not improved by assimilating SWE into the calibrated model. All models evaluated had similar streamflow performance, indicating streamflow in the study basin can be accurately estimated using a model with a poor representation of SWE. The findings from this work improved knowledge and understanding of snow processes in the hydrologically significant Great Lakes-St Lawrence Forest region of central Ontario.

Author Keywords: data assimilation, hydrologic model, multi-objective calibration, remote sensing, scale, snow

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