Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / For solar environmental remediation, a new generation of nanosized (< 10 nm) titanium dioxide photocatalysts codoped with metals and nonmetals, or metals only were prepared by the xero-gel and aero-gel methods. For silver or cobalt-based xero-gel titanium dioxide photocatalysts, photoactivities tests revealed that codoping of titanium dioxide with a metal (1% Ag or 2% Co) and nonmetals (carbon and sulfur) is necessary to achieve high-activities for acetaldehyde degradation under visible light (wavelength > 420 nm). It was concluded that high visible-light-activities for acetaldehyde degradation over codoped titanium dioxide were attributed to an interplay of anatase crystallinity, high-surface area, reduced band-gap (< 3.0 eV), uniform dispersion of doped metal ions, and suppressed recombination rate of photogenerated electron-hole pairs. Moreover, the nature and amount of codoped metals play a significant role in visible-light-induced photocatalysis. Metals (Al, Ga, and In) doped/codoped titanium dioxide photocatalysts were prepared by the aero-gel method. The photocatalytic studies showed that activities of metal doped/codoped photocatalysts under UV light (wavelength < 400 nm) were found to be dependent on pollutants. Indium demonstrated beneficial effects in both textural and photocatalytic properties. Gallium and indium codoped titanium dioxide photocatalysts displayed even better performance in the CO oxidation reaction under UV light. Notably, titanium dioxide codoped with Ga, In, and Pt, exhibited unique photoactivities for the CO oxidation under both UV and visible light irradiation, indicating that this system could have promise for the water-gas shift reaction for hydrogen production. Silver-based nanostructured titanium dioxide samples were developed for killing human pathogens (Escherichia coli cells and Bacillus subtilis spores). Biocidal tests revealed that silver, carbon, and sulfur codoped titanium dioxide nanoparticles (< 10 nm) possess very strong antimicrobial actions on both E. coli (logarithmic kill > 8) and B. subtilis spores (logarithmic kill > 5) for 30 minute exposures in dark conditions compared with Degussa P25. It was believed that the carbon and sulfur codoped titanium dioxide support and Ag species acted synergistically during deactivation of both E. coli and B. subtilis spores. Thus, titanium dioxide codoped with silver, carbon, sulfur can serve as a multifunctional generic biocide and a visible- light-active photocatalyst.

Master of Science / Department of Agronomy / Jay Ham / The exchange of water, carbon, and energy between grasslands and the atmosphere is an important biogeochemical pathway affecting ecosystem productivity and sustainability. The eddy covariance (EC) technique directly measures this mass and energy exchange. However, questions remain regarding the accuracy of EC-derived H[subscript]2O and CO[subscript]2 fluxes in landscapes with irregular topography and variable vegetation. These concerns stem from the "energy balance (EB) closure problem" (i.e., measured energy in does not equal measured energy out). My main objectives were to examine EB closure at two topographical positions within an annually burned tallgrass prairie watershed and to examine the effect of landscape position and woody encroachment on carbon and water exchanges. In tallgrass prairie, 14 km south of Manhattan, KS, USA, EC towers were deployed at three sites in 2007 and 2008. One upland and lowland tower were within an annually burned watershed dominated by C[subscript]4 grasses. Another lowland tower was deployed in a separate quadrennial-burned watershed where significant woody vegetation occupied the tower's sampling area. All towers measured EB components (net radiation, R[subscript]n; soil heat flux, G; sensible heat flux, H; and latent heat flux, [lambda]E). In the annually burned watershed, landscape position had little effect on G, H, and R[subscript]n with differences [less than] 2% between sites. However lowland [lambda]E was 8% higher, owing to larger plant biomass/leaf area and greater soil moisture. Energy balance closure (i.e., [[lambda]E + H] / [R[subscript]n - G]) was 0.87 and 0.90 at the upland and lowland sites, respectively. A nearby large-aperture scintillometer provided good validation of EC-derived H in 2007. Data suggested that underestimates of [lambda]E may have accounted for the closure problem; sample calculations showed that increasing [lambda]E by 17% would have resulted in near prefect closure. Data from this study suggests that EB closure does not strongly correlate with topographical position; however these data raise questions regarding accuracy of the [lambda]E term. Mass exchange analysis shows that the prairie carbon cycle is highly dependent on burning. The lowland and upland annually burned sites saw carbon gains of 281 to 444 g C m[superscript]-[superscript]2 yr[superscript]-[superscript]1 before burning with the shrub lowland showing the least (e.g. 159 and 172 g C m[superscript]-[superscript]2 yr[superscript]-[superscript]1). After the prescribed burn, the upland and lowland sites remained slight carbon sinks (68 to 191 g C m[superscript]-[superscript]2 yr[superscript]-[superscript]1), whereas the unburned shrub site was a carbon sink in 2007 (159 g C m[superscript]-[superscript]2 yr[superscript]-[superscript]1, because no carbon loss was incurred via burning) and a large carbon source in 2008 when it was burned the following year (336 g C m[superscript]-[superscript]2 yr[superscript]-[superscript]1 loss). Evapotranspiration (ET) was highest at the shrub lowland where greater soil moisture and abundance of deep-rooted C[subscript]3 shrub vegetation allowed greater uptake and loss of water.

Master of Science / Department of Chemical Engineering / Larry E. Erickson / Photocatalytic oxidation (PCO) is a promising and emerging technique in controlling indoor air contaminants, including volatile organic compounds (VOCs). It has broad air cleaning and deodorization applications in indoor environments ranging from residential and office buildings to healthcare and nursing facilities as well as spacecrafts, aircraft cabins and clean rooms in the agricultural and food industry. Numerous studies have been conducted to improve the effectiveness and performance of this technology. These include development of new configurations, energy-efficient catalysts and other parameters to control the process. However, only limited research has been conducted under realistic indoor environmental conditions. One of the most recent developments in photocatalysis is the synthesis of 2% C- and V-doped TiO[subscript]2, which is active under both dark and visible light conditions. However, like most research conducted in photocatalysis, the study on the reactivity of this catalyst has been performed only under laboratory conditions. This study investigated the possible application of the novel C and V co-doped TiO[subscript]2 in cleaning indoor air. Mathematical modeling and simulation techniques were employed to assess the potential use of some of the promising systems that utilize the catalyst (i.e., packed bed and thin films) as well as the effect of mass transfer limitations in the degradation of acetaldehyde, one of the VOCs that can be found in offices, residential buildings and other facilities.

Doctor of Philosophy / Department of Biological and Agricultural Engineering / Ronaldo Maghirang / Emission of greenhouse gases (GHGs), including nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2), from open beef cattle feedlots is becoming an environmental concern; however, scientific information on emissions and abatement measures for feedlots is limited. This research was conducted to quantify GHG emissions from feedlots and evaluate abatement measures for mitigating emissions. Specific objectives were to: (1) measure N2O emissions from the pens in a commercial cattle feedlot; (2) evaluate the effectiveness of surface amendments in mitigating GHG emissions from feedlot manure; (3) evaluate the effects of water application on GHG emissions from feedlot manure; and (4) compare the photo-acoustic infrared multi-gas analyzer (PIMA) and gas chromatograph (GC) in measuring concentrations of N2O and CO2 emitted from feedlot manure. Field measurements on a commercial beef cattle feedlot using static flux chambers combined with GC indicated that N2O emission fluxes varied significantly with pen surface condition. The moist/muddy surface had the largest median emission flux; the dry and compacted, dry and loose, and flooded surfaces had significantly lower median emission fluxes. Pen surface amendments (i.e., organic residues, biochar, and activated carbon) were applied on feedlot manure samples in glass containers and evaluated for their effectiveness in mitigating GHG emissions. Emission fluxes were measured with the PIMA. For dry manure, all amendments showed significant reduction in N2O and CO2 emission fluxes compared with the control (i.e., no amendment). For moist manure, biochar significantly reduced GHG emissions at days 10 and 15 after application; the other amendments had limited effects on GHG emissions. The effect of water application on GHG emissions from feedlot manure was evaluated. Manure samples (with and without water application) were placed in glass containers and analyzed for GHG emission using a PIMA. For the dry manure, GHG emissions were negligible. Application of water on the manure samples resulted in short-term peaks of GHG emissions a few minutes after water application. Comparison of the GC and PIMA showed that they were significantly correlated but differed in measured concentrations of N2O and CO2. The PIMA showed generally lower N2O concentrations and higher CO2 concentrations than the GC.

Master of Science / Department of Biology / Craig Paukert / We investigated spatial variation in fish assemblage and food web structure in the Kansas River, USA in relation to habitat changes. Fishes were collected at ten sites throughout the Kansas River for assessing assemblage structure in summer 2007 using fish community metrics and at 3 sites in 2006 for food web structure using stable isotope analysis. Satellite imagery indicated riparian habitat on the Kansas River was dominated by agriculture in the upper reaches (>35%) and tended to increase in urban land use in the lower reaches (>58%). Instream habitat complexity also decreased with increased urban area (<25%) becoming more channelized. Jaccard's similarity and percent similarity indices suggested that large-bodied fishes show changes in species presence and composition longitudinally within the river. Also, reaches directly above Bowersock Dam in Lawrence, Kansas and below the Johnson County Weir, near Kansas City, Kansas had low percent similarity compared to other reaches, suggesting the dam and the weir affect community composition. Canonical correspondence analysis indicated that species that prefer high velocity flows and sandy substrate (blue sucker and shovelnose sturgeon) are associated with the upper river reaches. Also, there was a higher abundance of omnivorous and planktivorous fish species in the lower more channelized river. The lower reaches contain more tolerant, macrohabitat generalist species and the upper river contained more intolerant, fluvial specialist species. Fish, macroinvertebrates, and detritus were collected at three river reaches classified as the heterogeneous instream habitat (>40% grass islands and sand bars) intermediate (22% grass islands and sand bars), and homogeneous (6% grass islands and sand bars) instream habitat reaches in June 2006. Riparian land use (proportion as agricultural and urban) was related to instream habitat with homogeneous areas having more urban riparian area compared to the heterogeneous and intermediate reaches. The heterogeneous habitat reach had higher variability in [Delta][superscript]13C for fish classified as piscivores/invertivores (P=0.029) and macroinvertebrates (P=0.004) suggesting the complex habitat in the heterogeneous habitat reach provided more variable food sources. The [Delta}15N values also indicated that ten of the twelve fish species tended to consume prey at higher trophic levels in the heterogeneous habitat reach suggesting a more complex food web. Land use practices are leading to homogenization of instream habitat and this homogenization of habitats may be related to food web diversity and trophic position of fishes. Conserving intolerant, native species in the Kansas River may require maintaining suitable habitat for these species and restoration of impacted areas of the river.

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Ronaldo G. Maghirang / Nanostructured particles possess unique chemical and physical properties, making them excellent candidates for air purification, smoke clearing, and obscuration. This research was conducted to investigate the aerodynamic, charging, and infrared (IR) extinction properties of nanostructured particles. Specific objectives were to: (1) measure the size distribution and concentration of aerosolized nanostructured particles; (2) evaluate their IR extinction properties; (3) determine their relative chargeability; and (4) numerically model their transport in enclosed rooms. The size distribution and concentration of two nanostructured particles (NanoActive® MgO and MgO plus) were measured in an enclosed room. The particles differed in size distribution and concentration; for example, the geometric mean diameters of NanoActive® MgO and MgO plus were 3.12 and 11.1 [Mu]m, respectively. The potential of nanostructured particles as IR obscurants was determined and compared with other particles. Four groups of particles were considered: nanostructured particles (NanoActive® MgO plus, MgO, TiO[subscript2]); nanorods (MgO, TiO[subscript2]); conventional particles (NaHCO[subscript3] and ISO fine test dust); and common obscurants (brass, graphite, carbon black). The extinction coefficients of the nanostructured particles were generally significantly smaller than those of the other particles. Graphite flakes had the greatest mass extinction coefficient (3.22 m[superscript2]/g), followed by carbon black (1.72 m[superscript2]/g), and brass flakes (1.57 m[superscript2]/g). Brass flakes had the greatest volume extinction coefficient (1.64 m[superscript2]/cc), followed by NaHCO[subscript3] (0.93 m[superscript2]/cc), and ISO fine test dust (0.91 m[superscript2]/cc). The relative chargeability of nanostructured particles was also investigated. Selected particles were passed through a Teflon tribocharger and their net charge-to-mass ratios were measured. Tribocharging was able to charge the particles; however, the resulting charge was generally small. NanoActive® TiO[subscript2] gained the highest net charge-to-mass ratio (1.21 mC/kg) followed by NanoActive® MgO (0.81 mC/kg) and ISO fine test dust (0.66 mC/kg). The transport of NanoActive® MgO plus and hollow glass spheres in an enclosed room was simulated by implementing the discrete phase model of FLUENT. In terms of mass concentrations, there was reasonable agreement between predicted and measured values for hollow glass spheres but not for NanoActive® MgO plus. In terms of number concentration, there was large discrepancy between predicted and measured values for both particles.

Doctor of Philosophy / Department of Chemical Engineering / Larry E. Erickson / Over the past decade, nanomaterials have been the subject of enormous interest. Their defining characteristic is a very small size in the range of 1-100 nm. Due to their nanometer size, nanomaterials are known to have unique mechanical, thermal, biological, optical and chemical properties, together with the potential for wide-ranging industrial applications. Here, we synthesized nanocrystalline metal oxides through the sol-gel process and used these materials as desulfurization adsorbents and photocatalysts. Deep desulfurization of fuels has received more and more attention worldwide, not only because of health and environmental consideration but also due to the need for producing ultra-low-sulfur fuels, which can only be achieved under severe operating conditions at high cost using hydrodesulfurization (HDS). Consequently, development of new and affordable deep desulfurization processes to satisfy the decreasing limit of sulfur content in fuels is a big challenge. Sol-gel derived Cu/Al[subscript]2O[subscript]3 and Zn/Al[subscript]2O[subscript]3 adsorbents have been demonstrated to be effective in the removal of thiophene from a model solution. Results showed that Cu[superscript]+ was the active site and thermal treatment under vacuum was critical for Zn/Al[subscript]2O[subscript]3 since a defective, less crystalline spinel led to stronger interaction between zinc ions and thiophene molecules in the adsorption process. The kinetic study suggested that most of the adsorption occurred in the first 30 min, and adsorption equilibrium was attained after 1.5 h. Both adsorbents showed good regenerative property. TiO2 is considered the most promising photocatalyst due to its high efficiency, chemical stability, non-toxicity, and low cost for degradation and complete mineralization of organic pollutants. However, the use of TiO[subscript]2 is impaired because it requires ultraviolet (UV) activation ([Lambda]<387 nm). The shift of optical response of TiO[subscript]2 from the UV to the visible light region would have a profound positive effect on the efficient use of solar energy in photocatalytic reactions. We shifted the optical response of TiO[subscript]2 and improved the photocatalytic efficiency through size modification and transition metal ion and nonmetal atom doping. Experimental results showed that C and V co-doped TiO[subscript]2 catalysts had much higher activity than commercial P25 TiO[subscript]2 towards the degradation of acetaldehyde under visible light irradiation. For the first time, we reported that activities were comparable in the dark and under visible light irradiation for co-doped TiO[subscript]2 with 2.0 wt% V. C and N co-doped TiO[subscript]2 exhibited higher activity for the degradation of methylene blue than pure TiO[subscript]2 under visible light and UV irradiation. Possible mechanisms were discussed based on the experimental results.

Master of Science / Department of Agronomy / Ganga M. Hettiarachchi / Phosphorus (P) management in reduced tillage systems has been a great concern for farmers. Conclusive results for benefits of deep banding of P fertilizers for plant yield in reduced tillage system are still lacking. Knowledge of the dominant solid P species present in soil following application of P fertilizers and linking that to potential P availability would help us to design better P management practices. The objectives of this research were to understand the influence of placement (broadcast- vs. deep band-P or deep placed-P), fertilizer source (granular- versus liquid-P), and time on reaction products of P. Greenhouse and field based experiments were conducted to study P behavior in soils. Soil pH, resin extractable P, total P, and speciation of P were determined at different distances from the point of fertilizer application at 5 weeks (greenhouse and field) and 6 months (field) after P application (at rate 75 kg/ha) to a soil system that was under long-term reduced tillage. X-ray absorption near edge structure spectroscopy technique was used to speciate reaction products of fertilizer P in the soil. The reaction products of P formed upon addition of P fertilizers to soils were found to be influenced by soil pH, P placement methods, and P sources. Acidic pH (below~5.8) tended to favor formation of Fe-P and Al-P like forms whereas slightly acidic near neutral pH soils favored formation of Ca-P like forms. Scanning electron microscope with energy dispersive X-ray analysis of applied fertilizer granules at 5-wk showed enrichment of Al, Fe and Ca in granule- indicating these elements begin to react with applied P even before granules dissolve completely. The availability of an applied P fertilizer was found to be enhanced as a result of the deep banding as compared to the surface broadcasting or deep placed methods. Deep banded liquid MAP was found to be in more adsorbed P like forms and resulted greater resin extractable P both at 5 wk and 6 month after application. Deep banding of liquid MAP would most likely result both agronomically and environmentally efficient solution for no-till farmers.

Doctor of Philosophy / Department of Environmental Design & Planning Program / Lee R. Skabelund / The Restorative Urban Design (RUD) calls for a new urban design and planning approach targeting environmentally responsible re/development of urbanized areas through ecologically responsive impact mitigations. If implemented in a systematic manner, such re/developments can help move urban areas toward the successful restoration of the natural environment of which they are an inseparable part. The RUD model advocates more rigorous assessment and mitigation of urban impacts by carefully evaluating the environmental performance of urban re/developments within five primary dimensions: Atmosphere (emissions, pollutants, ozone depletion); Hydrosphere (stormwater, domestic water, wastewater); Lithosphere (land use, land cover, food and wastes); Ecology (habitat resilience, biodiversity, population and resources); and Energy (renewability, reduction and efficiency, transportation). The model relies on a scenario-comparison process in order to evaluate and optimize the performance of urban re/development projections through four critical scenarios, which are respectively: 1) Natural Baseline (NBASE); 2) Historic Progression (HPROG); 3) Trajectory Forecast (TFORE); and 4) Restorative Projection (RPROJ). The RUD Case Study illustrates how the principles and strategies of Restorative Urban Design can be applied specifically to a typical (densely developed) urban area, namely River North District in Chicago Metropolitan Area. The case study focuses exclusively on mitigation of a single critical human impact on the natural environment: Anthropogenic CO₂ Emissions. The case study focuses on the design assumptions by which the restorative urban re/development scenarios might exceed beyond the full mitigation of emissions into the global remediation by 2040. The restorative projections illustrate that only a certain portion of emissions can be effectively mitigated onsite (5 to 55%), and that the remainder of projected emissions (45 to 95%) need to be mitigated offsite in order to achieve the necessary sequestration and storage. The restorative research suggests that the mitigation of major human impacts on the natural environment – not only CO₂ emissions but also other major impacts – are likely to require significant urban transformations. Moving beyond the strategies of preservation and/or conservation, the restorative approach asserts that comprehensive environmental restoration is achievable if urban impacts are adequately estimated and then entirely mitigated onsite as well as offsite through a systematic process of urban re/development.

Recent literature has recommended that life cycle assessments (LCA) of forest bioenergy supply chains consider the impact of biomass harvest on ecosystem carbon stocks as well as the net emissions arising from combustion of various forms of biofuels compared with reference fossil fuel systems. The present study evaluated the magnitude and temporal variation of ecosystem C stock changes resulting from harvest of roadside residues and unutilized whole trees for bioenergy. The Carbon Budget Model (CBM-CFS3) was applied to the Gordon Cosens Forest, in northeastern Ontario, along with the Biomass Opportunity Supply Model (BiOS-Map), for cost analysis of different types of biomass comminution. Natural gas (NG) steam and electricity, grid electricity, and coal electricity reference systems were analyzed for a pulp and paper mill. The findings showed that the forested landscape becomes a net sink for carbon following the 20th year of roadside residue harvest, compared to whole-tree harvest, where the forested landscape remained a net source of carbon over the entire 100 year rotation. The cumulative ecosystem carbon loss from whole-tree harvest was 11 times greater compared to roadside residue harvest. BiOS-Map analysis suggested that due to technical and operational limits, between 55%-59% and 16%-24% of aboveground biomass was not recovered under roadside residue and whole-tree harvest respectively. The cost of delivering roadside residues was estimated at $52.32/odt–$57.45/odt, and for whole trees $92.63/odt–$97.44/odt. The Life Cycle Assessment (LCA) analysis showed break-even points of 25, 33 and 6 years for roadside residues displacing NG steam, NG electricity, and coal, respectively. No GHG reduction was achieved when forest biomass was used to displace grid electricity that is generated in Ontario. Whole-tree bioenergy resulted in no GHG reduction for NG displacement, and a break-even point of 70-86 years for coal. A net GHG reduction of 67% and 16% was realized when roadside residues and whole trees were used to displace coal, compared to 45% and 38% when roadside residues were used to displace NG steam and NG electricity, respectively. Therefore, it is recommended that bioenergy deployment strategies focus on the utilization of roadside residues, if the main goal is GHG mitigation.