Doctor of Philosophy / Department of Horticulture, Forestry, and Recreation Resources / Dale J. Bremer / Jack Fry / Increasing water scarcity may result in greater irrigation restrictions for turfgrass. Drought tolerance and recovery of Kentucky bluegrasses (Poa. pratensis L.) (KBG) were evaluated during and after 88 and 60 day dry downs in 2010 and 2011, respectively, under a rainout shelter. Changes in green coverage were evaluated with digital images. Green coverage declined slowest during dry downs and increased fastest during recoveries in the cultivar ‘Apollo’, indicating it had superior drought tolerance. Electrolyte leakage, photosynthesis, and leaf water potential were evaluated in 7 KBG cultivars during and after the dry downs. Soil moisture at 5 and 20 cm was measured. There were generally no differences in physiological parameters among cultivars during or after dry down. The highest reduction in soil moisture at 5 and 20 cm was in Apollo, suggesting it had a better developed root system for mining water from the profile during drought. Weed prevention and turfgrass establishment of ‘Legacy’ buffalograss (Buchloe dactyloides [Nutt.] Engelm.) and ‘Chisholm’ zoysiagrass (Zoysia japonica Steud.) grown on turf reinforcement mats (TRM) was evaluated. ‘Chisholm’ zoysiagrass stolons grew under the TRM; as such, use of TRM for this cultivar is not practical. Buffalograss had 90% or greater coverage when established on TRM in 2010 and 65% or greater coverage in 2011; coverage was similar to that in oxadiazon-treated plots at the end of each year. ‘Legacy’ buffalograss plugs were established on TRM over plastic for 3 weeks, stored in TRM under tree shade for 7, 14, or 21 days, and evaluated for establishment after storage. In 2010, plugs on mats stored for 7 days had similar coverage to the control, but in 2011 displayed similar coverage to plugs stored on TRM for 14 or 21 day treatments. Green leaf are index (LAI) is an important indicator of turfgrass performance, but its measurement is time consuming and destructive. Measurements using hyperspectral radiometry were compared with destructive measurements of LAI. Results suggest spectral radiometry has potential to accurately predict LAI. The robustness of prediction models varied over the growing season. Finding one model to predict LAI across and entire growing season still seems unrealistic.

Doctor of Philosophy / Department of Agronomy / Charles W. Rice / Nitrogen is critical for plant growth and is a major cost of inputs in production agriculture. Too much nitrogen (N) is also an environmental concern. Agricultural soils account for 85% of anthropogenic N₂O which is a major greenhouse gas. Management strategies for N fertilization and tillage are necessary for enhancing N use efficiency and reducing negative impacts of N to the environment. The different management practices induce changes in substrate availability for microbial activity that may result in increasing or reducing net N₂O emitted from soils. The objectives of this research were to (1) integrate results from field studies to evaluate the effect of different management strategies on N₂O emissions using a meta-analysis, (2) quantify N₂O-N emissions under no-tillage (NT) and tilled (T) agricultural systems and the effect of different N source and placements, (3) perform sensitivity analysis, calibration and validation of the Denitrification Decomposition (DNDC) model for N₂O emissions, and (4) analyze future scenarios of precipitation and temperature to evaluate the potential effects of climate change on N₂O emissions from agro-ecosystems in Kansas. Based on the meta-analysis there was no significant effect of broadcast and banded N placement. Synthetic N fertilizer usually had higher N₂O emission than organic N fertilizer. Crops with high N inputs as well as clay soils had higher N₂O fluxes. No-till and conventional till did not have significant differences regarding N₂O emissions. In the field study, N₂O-N emissions were not significantly different between tillage systems and N source. The banded N application generally had higher emissions than broadcasted N. Slow release N fertilizer as well as split N applications reduced N₂O flux without affecting yield. Simulations of N₂O emissions were more sensitive to changes in soil parameters such as pH, soil organic carbon (SOC), field capacity (FIELD) and bulk density (BD), with pH and SOC as the most sensitive parameters. The N₂O simulations performed using Denitrification Decomposition model on till (Urea) had higher model efficiency followed by no-till (compost), no-till (urea) and till (compost). At the regional level, changes in climate (precipitation and temperature) increased N₂O emission from agricultural soils in Kansas. The conversion from T to NT reduced N₂O emissions in crops under present conditions as well as under future climatic conditions.

Doctor of Philosophy / Department of Agronomy / Ganga M. Hettiarachchi / Urban soils may contain harmful levels of potentially toxic contaminants. These contaminants transfer to humans via two exposure pathways: direct transfer (soil-humans by soil ingestion, dermal exposure and inhalation) and food chain transfer (soil-plant-humans). Soil amendments alter the speciation of the contaminants in soils and thereby modify their bioavailability. The objectives of this research were to access the plant availability of lead (Pb), arsenic (As), and polycyclic aromatic hydrocarbons (PAHs); bioaccessibility and speciation of soil Pb, and As; and dermal absorption of soil PAHs in contaminated urban soils; and effectiveness of soil organic amendments on reducing contaminant bioavailability. Two field experiments were conducted in Kansas City, MO and Indianapolis, IN. Both sites had elevated concentrations of Pb in soils (Kansas City site: 30-380 mg kg⁻¹ and Indianapolis site: 200-700 mg kg⁻¹) . Indianapolis site’s soils also had elevated concentrations of As (40-100 mg kg⁻¹) and PAHs (benzo[a]pyrene: 1-10 mg kg⁻¹) . A control treatment (no-compost) and compost-types (leaf compost and/or composted biosolids, non-composted biosolids, mushroom compost) were used as treatments. A leafy vegetable, a fruiting vegetable and a root crop were grown for two growing seasons. The treatments were arranged in split-plot design (main plot factor: compost; sub-plot factor plant-type). An in vitro steady fluid experiment was conducted using human skins to examine the dermal transfer of soil PAHs. The concentrations of Pb, As, and PAHs in the vegetables were low, except Pb in root crops. Compost reduced the bioaccessibility of Pb, but did not change the bioaccessibility of As. Selected soil samples were analyzed for speciation of Pb using extended x-ray absorption fine structure spectroscopy. The predominant Pb species were Pb sorbed to Fe oxy(hydr)oxide and to organic C. Stable Pb phosphates (pyromorphite) was formed during the in vitro extraction. Dermal transfer experiments showed PAHs in the contaminated soils did not transfer through the skin. Stratum conium of the skin acted as a barrier for dermal transfer of soil PAHs. In general, the risk of food chain transfer of soil Pb, As, and PAHs were low in the studied sites and can be further reduced by compost addition. Bioaccessibility of Pb and As in urban soils were low. Dermal absorption of soil PAHs was insignificant.

Master of Science / Department of Chemistry / Kenneth Klabunde / Remediation of the indoor environment led to the development of novel catalysts which can absorb light in the visible range. These catalysts were prepared using the wet chemistry method known as sol-gel chemistry because preparation via sol-gel provides a homogeneous gel formation, which can be treated via supercritical drying to produce an aerogel. These aerogels have been found to have high surface areas when a combination of titania/silica is used. The increase in surface area has been shown to enhance the activity of the catalysts. Mixed metal oxide systems were prepared using titanium isopropoxide and tetraethyl orthosilicate to yield a 1:1 system of titania/silica (TiO2/SiO2). These systems were doped during the initial synthesis with transition metals (Mn or Co) to create mixed metal oxide systems which absorb light in the visible light range. These materials were assessed for potential as heterogeneous catalysts via gas-solid phase reactions with acetaldehyde. Degradation of acetaldehyde as well as the formation of CO2 was monitored via gas chromatography-mass spectrometery. To increase the activity, visible light was introduced to the system. Experiments have shown that a 10 mol % manganese doped titania/silica system, in the presence of light, can degrade acetaldehyde. The cobalt doped counterpart showed dark activity in the presence of acetaldehyde resulting in the formation of CO2 without the addition of visible light. In the hope of increasing surface area a mixed solvent (toluene/methanol) synthesis procedure was applied to the manganese doped catalyst. The resulting materials were of a low surface area but showed a significant increase in degradation of acetaldehyde. Examination of the interactions between mixed metal oxide systems and semivolatile organic compounds (SVOCs) was studied. The pollutant, triphenyl phosphate, was dissolved in n-pentane and exposed to 10 mg of a given catalyst. These reactions were monitored using UVVis. All systems but the manganese doped titania/silica system resulted in the observation of no activity with triphenyl phosphate. The manganese doped catalyst shown a peculiar activity, the increase in absorbance of the triphenyl phosphate peaks as well as the formation of a new peak.

Participatory action research (PAR) oriented by an eco-system health framework is one approach to involving marginalised peoples in their own problem solving. A PAR project during 2005-06 that engaged peri-urban farmers in Senegal using popular education documented change on environment and health perceptions and behaviour. Health as a theme took on greater importance, as farmers related good health to their ability to work and their overall productivity. Farmers came to better recognize the symptoms of pesticide poisoning and to establish more clearly the link between pesticide-related work practices and health effects. Less clear remained their recognition of symptoms and links with wastewater use practices, though malaria and parasitic infection were linked to urban agriculture. African worldviews, including notions of locus of power, were important determinants of perceived vulnerability to risks. Farmers cited fatigue as an important clue to the work-health interface and indicator of overall wellbeing. Farmers’ understanding evolved to become more dynamic, describing the complex web of environmentally-related health risk. By 2006, farmers experimented more with less toxic pest control methods, adjusted their clothing to protect their skin and mouth, and reduced some exposure pathways through improved hygiene behaviour. However, toxic pesticides continued to be used and exposure to wastewater with limited protection remained widespread. Change was dependent upon: the researcher’s deep understanding of how farmers learned; farmers’ trust in the purveyors of new information; and the clarity, consistency and relevance of messages devised. Change varied with farmers’ literacy; the language used; and the way in which tools and media were interpreted culturally and technically. The health belief model provided a partial explanation for changes in perceptions and behaviour. Social, political and economic barriers preventing change included: leaving the onus for change on farmers, diminishing the responsibility of pesticide manufacturers and governments; land tenure arrangements which reduced investment in health and environment protection; urban poverty and illiteracy; and eco-system constraints. Examination of the PAR process, its leadership, owners, tools and ideas developed, and knowledge created provided useful insight into issues of power and control.

Forestry activities play a crucial role in climate change mitigation. To make carbon credits generated from such activities a tradable commodity, it is important to analyze the price dynamics of carbon markets. This dissertation contains three essays that examine various issues confronting world’s carbon markets. The first essay investigates cointegration of carbon markets using Johansen maximum likelihood procedure. All carbon markets of the world are not integrated. North American carbon markets show integration and so do the CDM markets. For future, the possibilities of arbitrage across world’s markets are expected to be limited, and carbon trading in these markets will be globally inefficient. There is a strong need of a global agreement that allows carbon trade to prevent climate change at the least cost options. The second essay evaluates various econometric models for predicting price volatility in the carbon markets. Voluntary carbon market of Chicago is relatively more volatile; and like other financial markets, its volatility is forecasted best by a complex non-linear GARCH model. The compliance market of Europe, on the other hand, is less volatile and its volatility is forecasted best by simple econometric models like Historical Averages and GARCH and hence is different from other markets. Findings could be useful for investment decision making, and for making choice between various policy instruments. The last essay focuses on agent based models that incorporate interactions of heterogeneous entities. Artificial carbon markets obtained from such models have statistical properties - lack of autocorrelations, volatility clustering, heavy tails, conditional heavy tails, and non-Gaussianity; which are similar to the actual carbon markets. These models possess considerably higher forecasting capabilities than the traditional econometric models. Forecast accuracy is further improved considerably through experimentation, when agent characteristics like wealth distribution, proportion of allowances and number of agents are set close to the real market situations.

The overall objective of this research is to identify and optimize enzymatic applications that have the potential to degrade middle lamella lignin, so as to decrease economic and environmental costs associated with the production of mechanical pulp. Non-productive binding of enzyme to lignin in lignocellulosic biomass reduces enzyme availability and efficiency. The elucidation of non-productive binding behavior between hydrolytic enzymes and lignocellulosic substrates could significantly improve the efficiency of corresponding industrial bioprocesses. The first part of this report presents a study that characterizes non-catalytic interactions between enzymes and fibre. The second part of this report presents the biochemical and mutational studies of a novel, small laccase SCO6712 from Streptomyces coelicolor. The findings from this research support the design, control, and optimization of enzymatic treatments of lignocellulosic fibres in the pulp and biofuel industries.

Little is known about the enzyme-substrate interactions occurring during the dechlorination of chloroform (CF) and 1,1,1-trichloroethane (1,1,1-TCA) by the enrichment culture containing Dehalobacters, hereafter called DHB-CF/MEL. Compound specific isotope analysis (CSIA) is used to investigate the factors which may affect the isotope fractionation observed for CF and 1,1,1-TCA dechlorination. This thesis reports the first isotope enrichment factors observed for CF biodegradation at -27.5‰ ± 0.9‰, thus providing fundamental information for comparing isotope enrichment factors observed during trichlorinated alkane degradation by DHB-CF/MEL. The thesis also reports how the presence of CF and 1,1,1-TCA influences isotope fractionation and explores the possible influence of substrate inhibition on isotope fractionation during 1,1,1-TCA dechlorination. The data suggests that substrate inhibition during 1,1,1-TCA dechlorination by DHB-CF/MEL may not affect carbon isotope fractionation. The results suggest that CSIA is a promising monitoring tool even for the simultaneous biodegradation of CF and 1,1,1-TCA at different 1,1,1-TCA starting concentration.

There have been no landscape-scale studies on earthworm populations in Canada comparing vegetation types; previous studies on edge habitats have been conducted in agricultural systems. I examined the spatial variations of earthworm populations by measuring abundance based on regional municipality, vegetation type, and edge habitat. Earthworms were sampled throughout the season across a gradient of vegetation types including meadow, forest edge, and interior at a local-scale; and at the landscape level with vegetation types including meadow, deciduous forest, pine plantation and mixed forest. Regional effects were more significant than vegetation type likely due to a gradient of soil characteristics in southern Ontario; edges had intermediate earthworm abundance and a higher proportion of epigeic species. My research provides insight into the patterns of earthworm populations in southern Ontario and the possible effects of edge creation through landscape fragmentation. Field sampling of earthworm parasitoid cluster-flies (Calliphoridae: Pollenia) using synomones was also discussed.

Private Environmental Preference (PEP), measured by the willingness to spend on pollution reduction and its casual factors. A PEP model is constructed for Canada, China, India, and USA using data from the World Value Survey and Structural Equation Models. The results revealed that the most important factors are: environmental organization membership, acknowledgement of global environmental problems, Machiavellian attitudes towards money, and confidence in governing bodies. Other significant factors include: the acknowledgement of local environmental problems, income level, occupational characteristics, and work ethic. The acknowledgement of global problems and confidence in governing bodies increase PEP, while Machiavellian attitudes towards money reduce PEP across all four countries. Environmental organizational membership on PEP increase PEP in Canada and USA, but decrease PEP in India. White-collar occupational characteristics have a positive effect on PEP in Canada, but negative in China and India. Policy recommendations are provided given these observations.