Environmental and Life Sciences

Soils play a crucial role in ecosystem functioning, for example, soil minerals provide important provisioning and regulate ecosystem services. This study used major soil oxides from the North American Soil Geochemical Landscapes Project (n=560) to assess elemental associations and infer soil minerals through exploratory data analysis and to determined quantitative soil mineralogy using a normative method, Analysis to Mineralogy (n=1170). Results showed elemental variability of oxides across the provinces of Canada and strong correlations occurred between elements indicative of soil mineral composition (e.g., Silicon and Aluminium). Principal component analysis inferred soil minerals from soil oxides trends on biplots and classified minerals, generally, as carbonates, silicates, and weathered secondary oxides. Spatial variability in minerals (quartz, plagioclase, potassium feldspar, chlorite, and muscovite) was related to the underlying bedrock geology. The use of Analysis to Mineralogy led to a reliable method of quantifying soil minerals at a large scale.

Author Keywords: Analysis to Mineralogy, Exploratory data analysis, Normative procedures, North American Soil Geochemical Landscapes Project, Soil geochemistry, Soil mineralogy

Upland Sandpipers (Bartramia longicauda), like many grassland birds, are undergoing population decline in parts of their range. Habitat fragmentation and change have been hypothesized as potential causes of decline. I used citizen-science occurrence data from Wildlife Preservation Canada's Adopt-A-Shrike Loggerhead Shrike (Lanius ludovicianus) program in conjunction with validation surveys, using similar point-count methods, to examine detectability and determine if landscape level habitat features could predict occupancy of Upland Sandpipers in Southern Ontario. In a single season detectability study, I used Wildlife Preservation Canada's survey protocol to determine detectability in sites that were known to be occupied. Detectability was low, with six surveys necessary to ensure detection using a duration of at least 18 minutes early in the breeding season. The proportion of open habitat did not affect detection on the landscape. Using a larger spatial and temporal scale, with five years of citizen-science data, I showed that Annual Crop Inventory data could not effectively predict Upland Sandpiper occupancy. Model uncertainty could be attributed to survey protocol and life history traits of the Upland Sandpiper, suggesting that appropriate survey methods be derived a priori for maximizing the potential of citizen-science data for robust analyses.

Author Keywords: Bartramia longicauda, citizen-science, detection, landscape, occupancy, Ontario

The parasitic protist Giardia intestinalis has five heme proteins: a flavohemoglobin and several isotypes of cytochrome b5. While the flavohemoglobin has a role in counteracting nitric oxide, the functions of the cytochromes (gCYTb5s) are unknown. In this study, the protein level and cellular localization of three gCYTB5 isotypes (gCYTb5-I, II and III) and flavohemoglobin were examined in Giardia trophozoites exposed to three nitrosative stressors at two different concentrations: nitrite (20 mM, 0.5 mM); GSNO (2 mM, 0.25 mM) and DETA-NONOate (2 mM, 0.05 mM). An increase in protein levels was observed for gCYTb5-II with all stressors at both concentrations. However, the effects of these nitrosative stressors on gCYTb5-I and III were inconclusive due to the variation among the replicates and the poor detection of gCYTb5- III on western blots. The protein level of the flavohemoglobin also increased in response to the three stressors at the low concentrations of stressors that were tested. Only the cellular localization of gCYTb5-I changed in response to nitrosative stress, where it moved from the nucleolus to the nucleus and cytoplasm. This response was extremely sensitive and occurred at the lower doses of the three stressors, suggesting that gCYTb5-I may be involved in a nucleolar- based stress response.

Environmental DNA (eDNA) is rapidly becoming an established method for the detection of species in aquatic systems and has been suggested as a promising tool to estimate species abundance. However, the strength of the relationship between eDNA concentrations and taxon abundance (density/biomass) can vary widely between species. I investigated the relationship between eDNA concentration and species abundance using two common and closely-related amphibians in eastern North America, the wood frog (Rana sylvatica) and northern leopard frog (Rana pipiens). I manipulated tadpole density in 80 L mesocosms and documented the relationship between tadpole density, biomass, and eDNA concentration. Species were comparable in biomass but differed in the amount of detectible genetic material produced; density and biomass were the superior abundance metric correlated with eDNA concentration for wood frogs and leopard frogs, respectively. However, increases in eDNA concentration reflected increasing tadpole biomass, therefore biomass is likely a better metric of abundance than density. Overall my findings support that eDNA concentration can be used as an index of species abundance, but that species-specific calibration may be needed before eDNA concentration can be effectively translated to an abundance metric. Future research should refine our understanding of how biotic and abiotic factors influence eDNA production, degradation, and recovery across species, before the method can receive widespread use as a monitoring tool in natural settings.

Author Keywords: abundance estimates, environmental DNA, mesocosm, Rana pipiens, Rana sylvatica

Recent developments at an aluminum (Al) smelter in Kitimat, BC resulted in a permitted increase of 27 to 42 tonnes of sulphur dioxide (SO2) emissions per day. Gaseous SO2 is a pollutant known to contribute to acidic deposition through processes of wet and dry deposition and can additionally react in-atmosphere to form particulate sulphate (pSO42-). Between June 2017 to October 2018, an extensive network consisting of ion exchange resin (IER) column, passive-diffusive, and active filter-pack samplers was established to provide an estimate of total annual S deposition and pSO42- variation throughout the Kitimat Valley. Filter-pack sampling determined the relative concentration of pSO42- increased downwind of the smelter. Comparison of observation-based and modelled total annual deposition suggested CALPUFF was accurate in representing the spatial viability of S deposition (R2 = > 0.85). However, the model appeared to overpredict near-field deposition suggesting the potential of underestimation further downwind of the smelter.

Author Keywords: aluminum smelter, atmospheric deposition, filter-pack sampler, ion-exchange column sampler, pSO42-, SO2

Populations have long been delineated by physical barriers that appear to limit reproduction, yet increasingly genetic analysis reveal these delineations to be inaccurate. The eastern and mid-continent populations of sandhill cranes are expanding ranges which is leading to convergence and warrants investigation of the genetic structure between the two populations. Obtaining blood or tissue samples for population genetics analysis can be costly, logistically challenging, and may require permits as well as potential risk to the study species. Non-invasively collected genetic samples overcome these challenges, but present challenges in terms of obtaining high quality DNA for analysis. Therefore, methods that optimize the quality of non-invasive samples are necessary. In the following thesis, I examined factors affecting DNA quality and quantity obtained from shed feathers and examined population differentiation between eastern and mid-continent sandhill cranes. I found shed feathers are robust to environmental factors, but feather size should be prioritized to increase DNA quantity and quality. Further, I found little differentiation between eastern and mid-continent populations with evidence of high migration and isolation-by-distance. Thus, the two populations are not genetically discrete. I recommend future population models incorporate migration between populations to enhance our ability to successfully manage and reach conservation objectives.

Author Keywords: feathers, genetic differentiation, non-invasive DNA, population genetics, population management, sandhill crane (Antigone canadensis)

Elemental selenium has been extensively quantitatively measured in sediments; however, its physical composition is largely unknown, despite it being the dominant selenium species in some reducing environments. Here, for the first time, it is shown that small, cyclic selenium compounds can account for a quantitatively-relevant fraction of the total elemental selenium present.

A new method was developed to analyze for cyclooctaselenium (Se8) in both synthetic samples and selenium-impacted sediments. Despite some analytical limitations, this gas chromatography-mass spectrometry (GC-MS) method is the first GC-MS method developed to identify and quantify Se8 in sediments. Once this method was established, it was then applied to more complex systems: first, the identification of compounds in mixed selenium-sulfur melt solutions, and then the determination of SenSm in selenium-impacted sediments. Despite complications arising from pronounced fragmentation in the ion source, assignment of definitive molecular formulae to chromatographically-resolved peaks was possible for five compounds.

Developing a fully quantitative method to obtain elemental ratio information can aid in the assignment of molecular formulae to chromatographically-resolved SeS-containing chromatographic peaks. Coupling the existing gas chromatography method to an inductively coupled plasma-mass spectrometer (ICP-MS) system should accomplish this. However, due to a number of complications, this was not completed successfully during the duration of this thesis project. High detection limits for sulfur, retention time discrepancies, and inconsistent injection results between the GC-MS and GC-ICP-MS system led to difficulties in comparing results between both analytical methods. Despite these limitations, GC-ICP-MS remains the most promising method for the identification and quantification of SenSm compounds in synthetic melt mixtures and selenium impacted sediments.

Author Keywords: gas chromatography-mass spectrometry, sediments, selenium

Due to their effective antibacterial and antifungal properties, silver nanoparticles (AgNPs) have quickly become the most commonly used nanomaterial, with applications in industry, medicine and consumer products. This increased use of AgNPs over the past decade will inevitably result in an elevated release of nanoparticles into the environment, highlighting the importance of assessing the environmental impacts of these nanomaterials on aquatic ecosystems. Although numerous laboratory studies have already reported on the negative effects of AgNPs to freshwater organisms, only a handful of studies have investigated the impacts of environmentally relevant levels of AgNPs on whole communities under natural conditions. This thesis examines the effects of chronic AgNP exposure on natural freshwater littoral microcrustacean, benthic macroinvertebrate and pelagic zooplankton communities. To assess the responses of these communities to AgNPs, I focused on a solely field-based approach, combining a six-week mesocosm study with a three-year whole lake experiment at the IISD – Experimental Lakes Area (Ontario, Canada). Our mesocosm study tested the effects of AgNP concentration (low, medium and high dose), surface coating (citrate- and polyvinylpyrrolidone [PVP]-coated AgNPs), and type of exposure (chronic and pulsed addition) on benthic macroinvertebrates in fine and stony sediments. Relative abundances of metal-tolerant Chironomidae in fine sediments were highest in high dose PVP-AgNP treatments; however, no negative effects of AgNP exposure were seen on biodiversity metrics or overall community structure throughout the study. I observed similar results within the whole lake study that incorporated a long-term addition of low levels of AgNPs to an experimental lake. Mixed-effects models and multivariate methods revealed a decline in all species of the littoral microcrustacean family Chydoridae in the final year of the study within our experimental lake, suggesting that this taxon may be sensitive to AgNP exposure; however, these effects were fairly subtle and were not reflected in the overall composition of littoral communities. No other negative effects of AgNPs were observed on the pelagic zooplankton or benthic macroinvertebrate communities. My results demonstrate that environmentally relevant levels of AgNPs have little impact on natural freshwater microcrustacean and benthic macroinvertebrate communities. Instead, biodiversity metrics and community structure are primarily influenced by seasonal dynamics and nutrient concentrations across both lakes. This thesis highlights the importance of incorporating environmental conditions and the natural variability of communities when examining the potential risks posed by the release of AgNPs into the environment, as simplistic laboratory bioassays may not provide an adequate assessment of the long-term impacts of AgNPs on freshwater systems.

Author Keywords: Benthic macroinvertebrates, IISD - Experimental Lakes Area, Littoral microcrustaceans, Silver nanoparticles, Whole lake experiment, Zooplankton

Species ranges are changing and the rate at which the climate is warming is faster than anything previously seen in the past, consequently species will need to adapt quickly, track the climate or perish. Cold adapted terrestrial species are the most vulnerable, because they are limited by the availability of land at the cold edge of their range. This means that many alpine, boreal and polar species essentially have nowhere to go as the climate warms. Habitat generalists are widely distributed across the globe and are highly adaptable to anthropogenic change. Our future biodiversity may only consist of several habitat generalists. The Canada lynx (Lynx canadensis) is a boreal species that has limited range expansion potential at the cold end of its range and its range has already contracted by 40%. The lynx has nowhere to go as climate warming progresses in this current century. Therefore, understanding the causes of its range contraction could enlighten us on conservation and management strategies that we might undertake as climate warms. My analyses indicated that the Canada lynx seems to have tracked the habitat that it is adapted to in more northern homogenous boreal forests and the bobcat (Lynx rufus), a habitat generalist, has simply replaced it in the south.

Author Keywords: Anthropogenic Change, Competition, Connectivity, Lynx canadensis, Lynx rufus, Range change

Thawing permafrost due to increasingly warm temperatures in northern subarctic regions is releasing mercury. The consequent formation of thaw ponds in the peatland palsa valley of the Sasapimakwananisikw (SAS) river in Whapmagoostui-Kuujjuarapik, Québec may provide a pool for MMHg formation and a potential risk to aquatic and human life, if these ponds facilitate MMHg export through hydrological connections to nearby waterways. Hg methylation and MMHg demethylation activities were examined in thaw pond sediments using a Hg tracer isotope incubation experiment. Analysis by coupling gas chromatography cold-vapor atomic fluorescence spectrophotometry (GC-CVAFS) with inductively coupled mass spectrometry (ICP-MS) techniques showed that MMHg was produced at a higher rate and within the first 2 h of incubation for both summer and winter seasons. For thaw ponds SAS1A, SAS1B and SAS2A, MMHg was formed at 0.0048 % h-1, 0.0012 % h-1, and 0.0008 % h-1, respectively during winter and at 0.0001 % h-1, 0.0016 % h-1, and 0.0010 % h-1, respectively during summer. Detection of MMHg losses were not as expected likely due to limitations of the combined tracer spike and overestimation of the in situ ambient mercury levels. Physical and chemical properties vary within ponds, among ponds and between winter and summer. SAS1B's location nearby an organic carbon rich palsa may be ideal to study DOC – Hg interactions. Variability in pond characteristics including depth, surface area, age, pH, temperature, colour, oxygen concentration, total dissolved and suspended solids, conductivity, carbon, mercury, ammonium, calcium, magnesium, sulfate, total phosphorous, potassium, and sodium between seasons indicate the challenge of predicting future environmental impacts of climate change related thaw pond creation in the north.

Author Keywords: demethylation, mercury, methylation, methylmercury, SAS, thaw ponds