Environmental science

One possible solution to acidification and losses of base cations in central Ontario forest soils may be the application of wood ash. Wood ash is generally high in pH and contains large amounts of calcium (Ca) and other nutrients essential for ecosystem health, however it also contains trace metals. Understanding the chemistry of soils following ash application to forests is crucial for future policy recommendations and remediation efforts. In this study, soil and soil water chemistry was measured at two acidic forest sites in central Ontario. Sugar maple (Acer saccharum, Marsh.) seedling growth and chemistry, as well as understory vegetation composition, were also measured. At site one, plots (2 m x 2 m) were established with sugar maple, white pine (Pinus strobus L.) and yellow birch (Betula alleghaniensis Britt.) residential wood ash treatments and applied at rates of 0 and 6 Mg ha-1. The effects of residential wood ash on soil and understory vegetation were measured three- and 12-months following ash addition. At site two, plots (5 m x 5 m) were established with both fly and bottom industrial grade bark ash treatments of 0, 4 and 8 Mg ha-1 (n=4), and tension lysimeters were positioned in each plot at 30, 50, and 100 cm depths. The effects of industrial grade wood ash on soil, soil water and understory vegetation were measured four years following ash addition. Metal concentrations in the ashes were generally low but were higher in the fly ash and yellow birch ash types. At site one, significant increase in soil pH, and Ca and magnesium (Mg) concentrations were observed after three months, however changes varied by treatment. Some metal concentrations increased in the upper organic horizons, but metals were likely immobilized in the soil due to increases in soil pH, electrical conductivity (EC) and high organic matter content of the soil. After one year, changes to metal concentrations in soils could be seen in mineral horizons, and a few metals (aluminum (Al), zinc (Zn), copper (Cu), chromium (Cr), strontium (Sr)) increased in treatment plots. At site two, the effects of industrial-grade bark ashes on soil pH could still be seen after four years and soil water metal concentrations were not elevated relative to controls. Changes to understory vegetation composition following ash application were observed, but ash addition had no significant effect on sugar maple seedling growth (root:shoot ratio) and did not lead to significant increases in foliar metal concentrations. There were significant differences in root chemistry, suggesting metal translocation and uptake could be restricted. Mass balance estimates indicate that the organic horizon is a sink for all metals and simulated drought in this horizon led to a decrease in soil pH and increase in soil water metal concentration, but this occurred in all treatments including control. These results suggest that application of industrial and residential wood ash in moderate doses with trace metal concentrations below or near regulatory limits will increase soil pH and base cation concentrations, as well as increase seedling tissue nutrient concentrations in northern hardwood forest soils. However, depending on the parent material of the ash, increased metal availability can also occur.

Author Keywords: Acer saccharum, calcium decline, forest soil amendment, Haliburton Forest and Wildlife Reserve, heavy metal, wood ash

Water storage is a fundamental component of drainage basins, controlling the synchronization between precipitation input and streamflow output. The ability of a drainage basin to store water and regulate streamflow may mediate sensitivity to climate and land cover change. There is currently no agreement on the best way to quantify basin storage. This study compares results of a combined hydrometric and isotopic approach for characterizing inter-basin differences in storage across the Oak Ridges Moraine (ORM) in southern Ontario. The ratio of the standard deviation of the stable isotope signature of streamflow relative to that of precipitation has been shown to be inversely proportional to mean water transit times, with smaller ratios indicating longer water transit times and implying greater storage. Stable isotope standard deviation ratios were inversely related to baseflow index values. Basins demonstrating longer transit times were associated with hydrological characteristics that promote infiltration and recharge of storage.

Author Keywords: baseflow, basin storage, climate change, mean transit time, Oak Ridges Moraine, stable isotopes

Recent declines in North American shorebird populations could be linked to habitat loss on the non-breeding grounds. Sea-level rise and increased frequency of coastal storms are causing significant erosion of barrier islands, thereby threatening shorebirds who rely on shoreline habitats for foraging. I conducted shorebird surveys on Bulls Island, South Carolina in the winters of 2018 and 2019 and examined habitat selection and foraging behaviour in Dunlin (Calidris alpina), Sanderling (Calidris alba), Semipalmated Plovers (Charadrius semipalmatus), and Piping Plovers (Charadrius melodus). Area, tidal stage, and invertebrate prey availability were important determinants of shorebird abundance, behaviour, and distribution. My study highlights the importance of Bulls Island's habitat heterogeneity to supporting a diverse community of non-breeding shorebirds. Considering both the high rate of erosion and the increased frequency of disturbance along the shoreline of the island, intertidal habitats should be monitored to predict negative effects of changes in habitat composition and area on non-breeding shorebirds.

Author Keywords: foraging behaviour, habitat loss, habitat selection, invertebrate prey, non-breeding, shorebirds

Invasive species that alter habitats can have significant impacts on wildlife. The invasive graminoids Phragmites australis (Cav.) Trin. ex Steud, hereafter Phragmites, and Typha × glauca Godr. are rapidly spreading into North American wetlands, replacing native vegetation. Invasive Phragmites is considered a potential threat to several species-at-risk (SAR), including some turtle species. My study wetland contained large stands of Phragmites, as well as Typha spp. (including invasive T. × glauca) that have similar structural traits to Phragmites. To explore the hypothesis that Phragmites and Typha spp. do not provide suitable habitat for turtles, I tested the prediction that turtles avoid Phragmites- and Typha-dominated habitats. I used VHF-GPS transmitters to follow Blanding's turtles (Emydoidea blandingii, n = 14) and spotted turtles (Clemmys guttata, n = 12). I found that both turtle species did not avoid Phragmites- or Typha-dominated habitats when choosing a home range, or while moving within their home range. I also tested whether the microhabitat selection of Blanding's turtles and spotted turtles is affected by shoot density of Phragmites, Typha spp., or both. I compared shoot densities of Phragmites and Typha spp. in 4 m2 plots, from locations used by tracked turtles with paired, random locations in these turtles' home ranges. For both turtle species, the densities of Phragmites and Typha shoots were comparable between used and random locations within the home ranges (generalized linear mixed model; p > 0.05). The use of Phragmites- and Typha-dominated habitats by Blanding's turtles and spotted turtles suggests that these habitats do not automatically constitute "unsuitable habitats" for turtles. Phragmites and Typha spp. (especially T. × glauca) can replace preferred habitats of some turtle species, and the control of these invasive macrophytes can help to preserve habitat heterogeneity. However, the presence of SAR turtles in Phragmites and Typha spp. stands should inform risk-assessments for invasive plant species control methods that include mechanical rolling of stands, where heavy machinery might encounter turtles.

Author Keywords: Blanding's turtles, compositional analysis, habitat selection, Phragmites australis, spotted turtles, Typha x glauca

Populations of grassland birds, including the Bobolink (Dolichonyx oryzivorus), are experiencing steep declines due to losses of breeding habitat, land use changes, and agricultural practices. Understanding the variables affecting reproductive success can aid conservation of grassland species. I investigated 1) whether artificial nest experiments accurately estimate the impacts of cattle on the daily survival rate of Bobolink nests and 2) which local, landscape, and temporal variables affect daily survival rate of Bobolink nests in Southern Ontario. I replicated an artificial nest experiment performed in 2012 and 2015 to compare the daily survival rate of artificial and natural nests at multiple stocking rates (number of cattle × days × ha-1). I also monitored Bobolink nests and modeled daily survival rate using local variables (e.g., stocking rate, field use, patch area), landscape variables (e.g., percent forest within 2, 5, and 10 km), and temporal variables (e.g., year, date of season). Results indicate that artificial nest experiments using clay shooting targets overestimated the impacts of stocking rate on the daily survival rate of Bobolink nests. With natural nests, region (confounded by year and field use), stocking rate, and date of season were the strongest predictors of daily survival rate; with stocking rate and date of season both having a negative effect. Management should focus on conserving pastures with low stocking rates (< 40 cattle × days × ha-1), late-cut hayfields, fallow fields, and other grasslands to protect breeding grounds for the Bobolink and other declining grassland bird species.

Author Keywords: Bobolink, Daily survival rate, landscape variables, local variables, Nest survival, temporal variables

Dissolved organic matter (DOM) in oceans provides nutrients and ultraviolet radiation protection to microbes. Some DOM compounds can chelate with metals, including copper, controlling their transport and bioavailability in marine systems. As copper functions as both a nutrient and toxicant, studies into the chemical structures of Cu-ligands is important, however currently limited. In this thesis, the chemical composition of total and Cu-binding DOM is investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in the Canadian Arctic and North Pacific. Chapter 2 reveals chemical differences in DOM composition between the southern and northern Canada Basin, revealing the influence of terrestrial and biological sources. Chapter 3 shows the uniqueness of Cu-binding ligands found in the Canadian Arctic and North Pacific Ocean. Studying the composition of DOM gives insight into the chemical diversity of marine DOM, helping to predict the effects of a changing climate on marine ecosystems.

Author Keywords: biological, dissolved organic matter, fluorescence, immobilized metal-ion affinity chromatography, mass spectrometry, terrestrial

Environmental and seasonal processes are important watershed drivers controlling the amount, composition, and fate of dissolved organic matter (DOM) in aquatic ecosystems. We used ten months of water samples and eight months of bioassay incubations from two

contrasting catchments (agriculture and natural, forested) to assess the effects of seasonal variability on the composition, export, and biodegradability of DOM. As expected, the DOM composition and exports were more allochthonous-like and autochthonous-like in

the forest and agriculture streams, respectively. However, we found no relationship between DOM composition and biodegradability in our study, suggesting that broad environmental factors play a large part in determining bioavailability of DOM. We found that both differences between the catchments and seasonal variability in hydrology and water temperature cause shifts in DOM composition that can affect exports and potentially affect its susceptibility to microbial activity. More research is needed to fully understand the impact of land use and temporal variability on bioavailability and delivery to downstream ecosystems.

Author Keywords: Bioavailable dissolved organic carbon, Biodegradability, Dissolved organic matter, Export, Seasonality, Streams

This thesis uses three approaches to assess the potential of permaculture in Central Ontario. This was done using a vegetable field trial and modelling programs to determine the effectiveness of permaculture to decrease negative impacts of climate change based on projected climate values derived from regional circulation models. The first approach showed no statistical difference (P<0.05) of applying varied volumes and combinations of organic amendments on crop yields. The second approach indicated permaculture may be a sustainable production system with respect to soil erosion when compared to traditional agricultural practices. The third approach was inconclusive due to the lack of quantitative literature on permaculture management impacts on biomass yields, soil carbon or nutrient retention, which were missing from basic and scientific literature searches. The models used within this thesis include USLE, RUSLE2, AgriSuite, RothC and Holos.

Author Keywords: Agriculture, Climate Change, Computer Modelling, Permaculture, Soil Erosion and Assessment

Opioid drugs are among the microcontaminants that are discharged with domestic wastewater into the aquatic environment with the potential to affect the development and reproductive capacity of aquatic organisms. To study the effects of exposure of fish to opioid drugs, Japanese medaka (Oryzias latipes) were exposed over a full life cycle to environmentally relevant (i.e. ng/L) concentrations of two opioids, codeine and fentanyl. Acute exposure of early life stage (ELS) of medaka to codeine resulted in slightly extended times to hatch, but no increase in embryo mortalities or reduced hatching success. Chronic exposure to codeine at a nominal concentration of 25,000 ng/L over a full life cycle interfered with growth, reducing the weight of the fish at maturity. Life cycle treatments with codeine at all test concentrations resulted in a significant reduction in the number of eggs produced in reproductive trials, as well as a reduction in the numbers of mature oocytes in adult females. High treatments with codeine also increased the percentage of immature sperm cells in adult males. Life cycle exposures to codeine also resulted in reduced whole-body concentrations of several hypothalamic-pituitary-gonadal (HPG) axis hormones, including reduced levels of luteinizing hormone in male and female fish and a reduction in 11-ketotestosterone in males and 17β-estradiol in females. Fentanyl did not affect reproduction or HPG hormones at the exposure concentrations tested, but high fentanyl exposures increased the mortality rate among ELS's of the F1 generation offspring from life cycle exposed adults. The results of this thesis contribute to the literature on the environmental impacts of microcontaminants of wastewater origin and, the potential for effects in fish exposed to opioids.Keywords: Opioids, microcontaminants, fentanyl, codeine, sexual development, reproduction.

Author Keywords: codeine, fentanyl, microcontaminants, opioids, reproduction, sexual development

Road runoff is a vector for the transport of potentially toxic chemicals into receiving waters. In this study, selected tire-derived chemicals were monitored in surface waters of rivers adjacent to two high traffic highways in the Greater Toronto Area in Ontario, Canada. Composite samples were collected from the Don River and Highland Creek in the GTA during 5 hydrological events that occurred in the period between early October 2019 and late March 2020, as well as an event in August 2020. Grab samples were collected from these rivers during a period of low flow in August 2020, as well as during a storm event in July of 2020. Analysis was performed using ultra-high pressure liquid chromatography with high resolution mass spectrometric detection (UHPLC-HRMS). Hexamethoxymethylmelamine (HMMM), a cross-linker of tire material, was detected at elevated concentrations (> 1 µg/L) during rain events in the fall and winter of 2019-20 and during a period of rapid snow melt in early March of 2020. These samples were also analyzed for the tire additive, 6PPD, and its oxidation by-product, 6PPD-quinone, as well as 1,3-diphenylguanidine (DPG). In many samples collected from the Don River and Highland Creek during storm events, the estimated concentrations of 6PPD-quinone exceeded the reported LC50 of 0.8 µg/L for Coho salmon exposed to this compound. Temporal samples collected at 3-hour intervals throughout rain event the October 2020 showed that there was a delay of several hours after the start of the event before these compounds reached their peak concentrations. In addition, 26 candidate transformation products and precursor compounds of HMMM were monitored; 15 of these compounds were detected in surface waters in the GTA. The maximum total concentration of this class of methoxymethylmelamine compounds in surface water samples was estimated to be 18 µg/L. There is limited knowledge about the properties of HMMM, its precursor contaminants, and its transformation compounds, as well as their fate in the environment. COSMO-RS solvation theory was used to estimate the physico-chemical properties of HMMM and its derivatives. Using the estimated values for these properties (e.g., solubility, vapour pressure, log Kow) as inputs to the Equilibrium Criterion (EQC) fugacity-based multimedia model, the compounds were predicted to readily partition into aqueous media, with mobility in water increasing with the extent of loss of methoxymethyl groups from HMMM. Overall, this study contributes to the growing literature indicating that potentially toxic tire-wear compounds are transported via road runoff into urban surface waters. In addition, this study provides insight into the environmental behaviour of HMMM and its transformation products.

Author Keywords: 6PPD-quinone, COSMOtherm, Fugacity, Hexamethoxymethylmelamine, Road runoff, Tire wear