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Graduate Theses & Dissertations
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- Phosphoric Acid Chemically Activated Waste Wood
- Activated Carbon (AC) is commonly produced by gasification, but there has been increasing interest in chemical activation due to its lower activation temperatures and higher yields. Phosphoric acid, in particular, succeeds in both these areas. Phosphoric acid activated carbon (PAC) can be environmentally sustainable, and economically favourable, when the phosphoric acid used in the activation is recycled. This thesis describes the digestion and activation of waste wood using phosphoric acid, as well as methods used to recover phosphoric acid, functionalize the produced activated carbon with iron salts and then test their efficacy on the adsorption of target analytes, selenite and selenate. In order to achieve an efficient phosphoric acid based chemical activation, further understanding of the activation process is needed. A two-step phosphoric acid activation process with waste wood feed stock was examined. The filtrate washes of the crude product and the surface composition of the produced PAC were characterized using X-ray Photoelectron Spectroscopy (XPS), Fourier Transform-Infrared spectroscopy (FT-IR), Ion Chromatography (IC), and 31P Nuclear Magnetic Resonance (NMR). XPS of the unwashed PAC contained 13.3 atomic percent phosphorous, as phosphoric acid, while the washed sample contained 1.4 atomic percent phosphorous as PO43-, and P2O74-. Using 31P NMR, phosphoric acid was identified as the primary phosphorous species in the acidic 0.1 M HCl washings, with pyrophosphates also appearing in the second 0.1 M NaOH neutralizing wash, and finally a weak signal from phosphates with an alkyl component also appearing in the DI wash. IC showed high concentrations of phosphoric acid in the 0.1 M HCl wash with progressively lower concentrations in both the NaOH and DI washes. Total phosphoric acid recovery was 96.7 % for waste wood activated with 25 % phosphoric acid, which is higher than previous literature findings for phosphoric acid activation. The surface areas of the PAC were in the 1500-1900 m2g-1 range. Both pre and post activation impregnation of iron salts resulted in iron uptake. Pre-activation resulted in only iron(III) speciation while post-activation impregnation of iron(II)chloride did result in iron(II) forming on the PAC surface. The pre-activated impregnated PAC showed little to no adsorption of selenite and selenate. The post-activation impregnated iron(II)chloride removed up to 12.45 ± 0.025 mg selenium per g Iron-PAC. Competitive ions such as sulfate and nitrate had little effect on selenium adsorption. Phosphate concentration did affect the uptake. At 250 ppm approximately 75 % of adsorption capacity of both the selenate and the selenite solutions was lost, although selenium was still preferentially adsorbed. Peak adsorption occurred between a pH of 4 and 11, with a complete loss of adsorption at a pH of 13. Author Keywords: Activated Carbon, doping, Iron, phosphoric acid, selenium
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- Near-road assessment of traffic related air pollutants along a major highway in Southern Ontario
- The spatial and temporal variation in atmospheric nitrogen dioxide (NO2), ammonia (NH3), and 17 elements (V, Cr, Fe, Ni, Cu, Zn, As, Cd, Pb, Mg, Al, Ca, Co, Se, Sb, Mn, and Na) were measured at 40 road side locations along a ~250 km traffic density gradient of 40,000–400,000 vehicles on the King’s Highway 401, in Ontario, Canada. Elemental concentrations were measured over a year, using moss bags as passive samplers, for four quarterly three-month exposure periods (October 2015 – October 2016). Gaseous NO2 and NH3 concentrations were measured using Willem’s badge passive diffusive samplers for twelve one-week exposure periods (one per month: October 2015–October 2016). Dry deposition of nitrogen was estimated using the inferential method. There were significant linear relationships between NO2 and NH3 and average annual daily traffic (AADT) volumes across the study area; higher concentrations corresponded to higher volume traffic sites. Average NO2 concentrations at sites ranged from 23.5 to 73 μg/m3, with an annual average of 43.7 μg/m3. Ammonia ranged from 2.56 to 13.55 μg/m3, with an annual average of 6.44 μg/m3. There were significant quarterly variations in NO2, with concentrations peaking during the winter months. In contrast, NH3 showed no significant quarterly variation, but a slight peak occurred during the summer. Gaseous NO2 and NH3 were highly positively correlated (r = 0.63), suggesting a common emission source from traffic. Concentrations in exposed moss were determined by subtracting the total concentration of each metal in the exposed sample from the background concentration present in the moss. Relative accumulation factors (RAF) and contamination factors were also calculated to determine the anthropogenic influence on tissue concentrations in exposed moss. All metals showed elevated levels versus background concentrations, with all metals except Ni and Co showing considerable enrichment. The highest levels of contamination were from V, Cr, Fe, Zn, Cd, Sb, Pb and Na. Principal component analysis indicated 5 clear clusters of related elements, with PC1 accounting for 36.2% and PC2 accounting for 25.6% of the variance. Average annual daily traffic was significantly related to Cr, Fe, Cu, Sb, Mn, Al, and Na. Road side monitoring shows consistently higher concentrations than active monitoring sites located further from the edge of the road, indicating a need for increased road side monitoring in Ontario, Canada. Author Keywords:
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- Late Epigravettian Resource Exploitation in the Southern Pre-Alpine Region
- This study examines the foraging strategies employed by Late Epigravettian occupants at Riparo Tagliente, Italy. The study sample is composed of highly fragmented macrofaunal remains recovered from a single stratigraphic layer (layer 617) located at the cave border in the southern portion of the site. Models derived from foraging theory, chiefly the Central Place Forager Prey Choice Model, are applied to interpret the pattern of faunal exploitation. Red deer (Cervus elaphus) is the most commonly identified species in the sample, followed by roe deer (Capreolus capreolus) and wild boar (Sus scrofa). The faunal analysis suggests that the site occupants focused their foraging efforts in lower–altitude resource patches at short travel distances. The distribution and composition of the sample indicates that bone may have been used as a fuel source in this area. Author Keywords: Archaeozoology, Foraging Theory, Taphonomy, Upper Paleolithic
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- Factors affecting road mortality of reptiles and amphibians on the Bruce Peninsula
- Road mortality is one of the leading causes of global population declines in reptiles and amphibians. Stemming losses from reptile and amphibian road mortality is a conservation priority and mitigation is a key recovery measure. I developed a model of road mortalities relative to non-‐mortalities, based on predictors varying across space (road surface type, traffic volume, speed limit, distance to wetland) and time (weather conditions, traffic volume). Herpetofauna road mortalities were recorded during daily bicycle and vehicle surveys to investigate the impact of roads on reptiles and amphibians within the Bruce Peninsula, Ontario in 2012 and 2013. A total of 2541 observations of herpetofauna on roads were recorded, 79% of which were dead. The major factor influencing turtle road mortality was proximity to the nearest wetland and dates early in the season (spring). For the Massasauga, high daily temperatures and low daily precipitation were associated with road mortality. The major factors driving colubrid snake mortality were also high daily temperature, low daily precipitation, as well as low speeds and paved roads. Frog and toad mortality was driven by proximity to wetland and late summer dates. These models will increase our understanding of factors affecting road losses of herpetofauna and serve as a basis for planned, experimental mitigation within the Bruce Peninsula. Author Keywords: amphibians, hotspot, mitigation, reptiles, road ecology, road mortality
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- origin and ecological function of an ion inducing anti-predator behaviour in Lithobates tadpoles
- Chemical cues are used commonly by prey to identify predation risk in aquatic environments. Previous work has indicated that negatively-charged ions of m/z 501 are possibly a kairomone that induces anti-predator responses in tadpoles. This thesis found that this ion species: (i) is produced by injured tadpoles; (ii) exhibits increased spectral intensity with higher tadpole biomass; and (iii) is not produced by starved predators. These results refute the hypothesis that the ion is a kairomone, and rather support its role as an alarm cue released from tadpoles. High resolution mass spectrometry (HR-MS) revealed a unique elemental composition for [M-H]-, m/z 501.2886, of C26H45O7S-. Collision induced dissociation (CID) of ion m/z 501 formed product ions of m/z 97 and m/z 80, HSO4- and SO3-, respectively, indicating the presence of sulfate. Green frog (Lithobates clamitans) tadpoles exposed to m/z 501, and an industrial analogue, sodium dodecyl sulphate (NaC12H25O4S), exhibited similar anti-predator responses, thereby suggesting the potential role of organic sulfate as a tadpole behavioural alterant. Author Keywords: Alarm cue, Amphibian, Chemical Ecology, Mass spectrometry, Predator-prey interactions
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- Passive sampling of indoor and outdoor atmospheric nitrogen dioxide in the greater Toronto area
- The reliability and performance of four passive sampler membrane coatings specific to nitrogen dioxide (NO2) were evaluated through co-exposure at multiple Ontario Ministry of Environment and Climate Change (OMOECC) active monitoring stations. All four coatings performed relatively similar under a wide range of meteorological conditions, notably showing exposure-specific atmospheric uptake rates. Further, indoor and outdoor atmospheric concentrations of NO2 (a marker of traffic-related air pollution) were evaluated at multiple elementary schools in a high-density traffic region of Toronto, Ontario, using a Triethanolamine based passive sampler membrane coating. Samplers were also co-exposed at OMOECC active monitoring stations to facilitate calibration of exposure-specific atmospheric uptake rates. Indoor NO2 atmospheric concentrations were 40 to 50% lower than outdoor concentrations during the spring−summer and autumn−winter periods, respectively. In large cities such as Toronto (Population 2,700,000), the influence of a single major road on outdoor and indoor NO2 concentrations is predominantly masked by spatially-extensive high-density traffic. Author Keywords: active sampler, membrane coating type, nitrogen dioxide, passive sampler, Toronto, traffic density
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- 'Land Displacement and Coping Strategies'
- This thesis explores the social history of the Marange people of eastern Zimbabwe from the 1960s to 2015. It uses historical episodes like the recurring droughts, the 1970s war of independence, the ‘crisis in Zimbabwe,’ that has been traced from the late - 1990s, and the diamond mining story to demonstrate how the inhabitants interacted with their environment. It argues that the relocation project that began in 2010 had a severely disruptive impact on the families relocated to the relocation area - ARDA Transau - making the case that the Marange relocation project was a ‘development disaster.’ While the provision of accommodation had a notable positive impact on the majority of the displaced households, family needs were not always met. For instance, large families such as those of the dominant polygamous followers of the African Apostolic Church of Johanne Marange were not provided with adequate housing. Also, the livelihoods of the displaced households were shattered by the relocation exercise. In their efforts to creatively adapt to these new constraints, the displacees had diverse coping strategies like selling firewood, illegally extending space for crop cultivation, artisanal mining, vending and begging for food to eke out a living. Author Keywords: Coping Strategies, Crisis in Zimbabwe, Development, Displacement, Land, Livelihoods
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- Altered Hippocampal Regulation of Immediate Early Genes after Pentylenetetrazol-Induced Seizures
- Seizures induce long-term changes in gene expression in the hippocampus. Experimental evidence has demonstrated a significant effect of epileptic activity on the activity of neurons that participate in complex cognitive and behavioural processes. The present series of experiments involving kindling with subconvulsive doses of PTZ demonstrates a link between seizures and altered immediate early gene expression within the hippocampus and dentate gyrus. In addition, newborn hippocampal neurons were shown to have decreased induction of plasticity-related genes, suggesting deficits in activity-dependent recruitment. These findings may shed light on the mechanisms underlying epileptogenesis and epilepsy-related hippocampal dysfunction in human patients. Author Keywords: hippocampus, IEGs, kindling, neurogenesis, seizures
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- An Investigation of Rare Earth Element Patterns and an Application of Using Zn and Cd Isotope Ratios in Oysters to Identify Contamination Sources in an Estuary in Southern China
- Environmental monitoring and investigation of metal biogeochemical cycling has been carried out in the Pearl River Estuary (PRE), an important and complex system in Southern China. In this study, rare earth element (REE) patterns as well as isotope ratios (i.e., Zn and Cd) were evaluated as tools to identify contamination sources in environmental compartments (i.e., water and suspended particles (SP)) as well as in oysters collected from estuarine sites. Results show elevated concentrations (also called anomalies) of Pr, Nd, Dy and Ho, relative to other REE elements, in water samples, potentially from REE recycling and other industrialized activities in this area. Unlike water samples, no REE anomalies were found in SP or oysters, suggesting that the dominate REE uptake pathway in oysters is from particles. Secondly, site to site variations in Zn isotope ratios were found in water and SP, showing the complexity of the source inputs in this area. Also, in estuarine locations, larger spatially differences in Zn isotope ratios were found in water collected in wet season than those in dry season, which may due to mixing of different source inputs under the water circulations in different seasons. A series of laboratory experiments were conducted during which changes in Zn isotope ratios were measured during uptake under varying salinity and Zn concentrations and during depuration. Neither in vivo Zn transportation among the various tissues within the oysters nor water exposure conditions (i.e., different salinities or Zn concentrations) caused Zn isotopic fractionation in the oysters. Cd and Zn isotope ratios were also determined in oysters obtained from the PRE. Large variations in Cd and Zn isotope ratios suggest that oysters were receiving contaminants from different input sources within the PRE. A consistent difference (approximately 0.67‰) was observed for Zn isotope ratios in oysters collected from the east side of the PRE compared to those from sampling locations on the western side of the PRE, suggesting different Zn sources in these two areas. Ultimately, by combining biogeochemistry with physiology, this study represents a first attempt to assess pollution status, monitor contaminants using oysters and model/identify contamination sources using both REEs and metal isotope ratios. Author Keywords:
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- How Abiotic and Biotic Factors Can Alter the Competitive Landscape in an Aggressive Species Complex (Genus
- Competition is known to impact population dynamics through both indirect and direct interactions, and direct interactions can often lead to injury in one or both parties. As such, response to injury through tissue regeneration can be important for surviving post-competitive interaction. However, the impacts of outside factors like temperature and genome size (e.g. polyploidy) are not well studied, especially in syntopic systems. We addressed this knowledge gap by comparing regeneration rates of diploid Ambystoma laterale and triploid unisexual Ambystoma at two ecologically-relevant temperatures. Environmental factors appeared to have stronger effects on regeneration than ploidy level, but overall mass was impacted more strongly by ploidy level. Interestingly, there was an interaction between temperature and time within unisexuals that was absent when comparing different ploidy levels, implying temperature has a more complex effect on polyploids. This study supports the hypothesis that polyploid organisms are better equipped to respond to shifts in their environments, which can give them a competitive advantage at the northern range limit of this species complex. Author Keywords: Ambystoma, Genome dosage, Hybrid vigor, Polyploidy, Thermal optimum, Tissue regeneration
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- Temporo-spatial patterns of occupation and density by an invasive fish in streams
- Since its introduction to North America in the 1990s, the Round Goby has spread throughout the Great Lakes, inland through rivers and is now moving into small tributary streams, a new environment for this species in both its native and invaded ranges. I explored density and temporal occupation of Round Gobies in four small streams in two systems in south-central Ontario, Canada in order to determine what habitat variables are the best predictors of goby density. Two streams are tributaries of Lake Ontario and two are tributaries of the Otonabee River, and all of these streams have barriers preventing upstream migration. I found that occupation and density differed between the systems. In the Otonabee River system, Round Gobies occupy the streams year round and the most important factor determining adult density is distance from a barrier to upstream movement, with the entire stream occupied but density highest next to the barriers. In the Lake Ontario system, density is highest at mid-stream and Round Gobies appear to occupy these streams mainly from spring to fall. Adult density in Lake Ontario tributaries is highest in sites with a high percentage of cobble/boulder and low percentage of gravel substrate, while substrate is less important in Otonabee River tributaries. Occupation and density patterns may differ due to contrasting environmental conditions in the source environments and distance to the first barrier preventing upstream movement. This study shows diversity in invasion strategies, and provides insight into the occurrence and movement patterns of this species in small, tributary streams. Author Keywords: biological invasion, Generalised Additive Mixed Model, habitat, Neogobius melanostomus, Round Goby, stream
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- Influence of Canopy Water Partitioning on the Isotopic Signature of Plant Water in a Mixed Northern Forest
- This study seeks to clarify the way in which the differing canopy characteristics among tree species influence the partitioning of precipitation, and therefore the source of water available for plant water uptake, in the Plastic Lake catchment near Dorset, ON. Three dominant tree species were compared: red oak (Quercus rubra), eastern white pine (Pinus strobus), and eastern hemlock (Tsuga canadensis). Above-canopy precipitation, throughfall, stemflow, and soil water content were monitored weekly from June 2016 until October 2016 and the 18O and 2H isotopic signatures of each were analyzed. Plant water and bulk soil water samples were also collected from five trees of each species at five stages of the growing season to compare the isotopic signature of xylem water to that of their surrounding soils. Both plant water and bulk soil water displayed evidence of isotopic fractionation; however, plant water was more depleted in δ2H and δ18O than bulk soil water. Water interacting with the tree canopies as throughfall and stemflow did not display significant evidence of isotopic fractionation. This suggests that the vegetation could have accessed an isotopically distinct source of water stored within the soil or that an unknown isotopic fractionation process occurred throughout this study. Author Keywords: