Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / Solar energy driven catalytic systems have gained popularity in environmental remediation recently. Various photocatalytic systems have been reported in this regard and most of the photocatalysts are based on well-known semiconducting material, Titanium Dioxide, while some are based on other materials such as Silicon Dioxide and various Zeolites. However, in titania based photocatalysts, titania is actively involved in the catalytic mechanism by absorbing light and generating exitons. Because of this vast popularity of titania in the field of photocatalysis it is believed that photocatalysis mainly occurs via non-localized mechanisms and semiconductors are extremely important. Even though it is still rare, photocatalysis could be localized and possible without use of a semiconductor as well. Thus, to support localized photocatalytic systems, and to compare the activity to titania based systems, degradation of organic air pollutants by nanostructured silica, titania and mixed silica titania systems were studied. New materials were prepared using two different approaches, precipitation technique (xerogel) and aerogel preparation technique. The prepared xerogel samples were doped with both metal (silver) and non-metals (carbon and sulfur) and aerogel samples were loaded with Chromium, Cobalt and Vanadium separately, in order to achieve visible light photocatalytic activity. Characterization studies of the materials were carried out using Nova BET analysis, DR UV-vis spectrometry, powder X-ray diffraction, X-ray photoelectron Spectroscopy, FT-IR spectroscopy, Transmission Electron Microscopy, etc. Kinetics of the catalytic activities was studied using a Shimadzu GCMS-QP 5000 instrument using a closed glass reactor. All the experiments were carried out in gaseous phase using acetaldehyde as the model pollutant. Kinetic results suggest that chromium doped silica systems are good UV and visible light active photocatalysts. This is a good example for a localized photocatalytic activity. In contrast, our xerogel system shows comparatively high visible light photocatalytic activity for the titania based system, showing the importance of non-localized nature of photocatalysis. The Cobalt doped silica system shows interesting dark catalytic activity towards acetaldehyde and several other pollutants. Thus, in summary, based on the different activities we observed during our studies these materials could be successfully used to improve the quality of both indoor and outdoor air.

Doctor of Philosophy / Department of Biochemistry and Molecular Biophysics / Lawrence C. Davis / Synthetic dyes are capable of producing the whole color spectrum on account of their structural diversity but this diversity poses challenges in the degradation of dyeing wastes. Laccases and peroxidases from bacterial or fungal sources and parts of plants in the presence of hydrogen peroxide (H₂O₂) plus a mediator have been exploited in the bioremediation of synthetic dyes. However, intact plants have not found much favor despite their phytoremediation potential. The goal of this research was to further clarify ways by which whole plants bring about decolorization of different types of synthetic dyes. Hydroponically cultivated plants from two dicot families namely Arabidopsis thaliana and sunflowers (Helianthus annuus) were exposed to representative dyes from several classes: monoazo (Methyl Red and Methyl Orange), disazo (Trypan Blue, Evans Blue and Chicago Blue 6B), and arylmethane (Brilliant Blue G, Bromocresol Green, Malachite Green and Phenol Red). Tests were done in presence or absence of externally added H₂O₂, with or without a free radical mediator, 1-hydroxybenzotriazole, using UV-Visible spectrophotometry. The initial rate of decolorization and the overall percentage decolorization was calculated for each dye in the different treatments. Decolorization of the dyes from different classes varied between plant species and depending on the treatment. Except for Methyl Red, all dyes required added H₂O₂ as well as mediator to achieve rapid decolorization. Added H₂O₂ was found to be the limiting factor since it was degraded by plants within a few hours. Both species were able to slowly decolorize dyes upon daily addition of fresh dye even in the absence of added H₂O₂ and mediator, provided that nutrients were supplied to the plants with the dye. A. thaliana was found to be more effective in dye decolorization per gram tissue than sunflower when treated under similar conditions. Analysis of the residual dye solution by ESI/MS did not reveal any potential by-products following the decolorization treatment with plants, suggesting that the plant roots might be trapping the by-products of dye decolorization and preventing their release into the solution. All these findings support the potential application of whole plants for larger scale remediation.

Master of Science / Apparel, Textiles, and Interior Design / Sherry J. Haar / This study compared the colorfastness of potassium aluminum sulfate (PAS) mordanted and nonmordanted 30/2 wool yarn, dyed with black walnut (Juglans Nigra), Osage orange (Maclura pomifera), and eastern redcedar (Juniperus virginiana) sawdust. Information from this study is intended to inform natural dye artisans and to increase the profitability of sawdust for farmers, ranchers, and mill owners who would otherwise find little use for this byproduct of timber manufacturing. Pre-testing ensured dyeings of visually comparable color depth and dye concentrations were pre-tested to find a standard depth of shade between the same dye on PAS mordanted and nonmordanted wool yarns. Tests for colorfastness to light, laundering and staining were performed in accordance to AATCC test methods. Resulting colors for exposed and unexposed specimens were rated using CIE L* a* b* values and AATCC gray scale for color change. GLM Anovas and two-sample t-tests were used to statistically analyze CIE L* a* b* values. As expected, findings indicated that dye absorption was improved with the use of a PAS mordant, especially for black walnut and eastern redcedar. For yarns premordanted with PAS the dyewoods became yellower. A PAS mordant slightly improved colorfastness to light for black walnut and eastern redcedar, but did not influence Osage orange which had an unexpected color change from bright yellow to warm brown after exposure to light. Colorfastness to laundering was slightly improved with PAS for Osage orange, while black walnut and eastern red cedar had slightly less color change without the mordant. This research was supported by the Agricultural Research Experiment Station and Kansas State University.

Master of Science / Department of Journalism and Mass Communications / Joye C. Gordon / Global warming and its implications have astounding consequences for the global community. Although some research has been done on the trends within environmental reporting, few studies have looked at the issue of global warming in particular. Global warming is a troublesome issue for reporters for a number of reasons, and hence, it is important that we delve into how newspapers cover the topic. Latin America, especially the Caribbean region, is expected to suffer extreme consequences due to global warming, yet no studies regarding global warming coverage have been done in these regions. The first purpose of this study was to discover how a Mexico newspaper frames the issue of global warming. Next, this study sought to expand the current knowledge of global warming coverage by the media. Lastly, this study sought to expand on existing literature to discover how journalists outside of the United States communicate, to the public, the issue of global warming. Based on previous studies on global warming a frame analysis was conducted to explore how the Mexico City-based newspaper Reforma covers the issue of global warming. This study identified that ecology/science and consequences are the most frequently occurring themes of coverage, while scientific conflict and North/South conflict are present, but in low frequencies and near the end of stories. This study also identified international relations as the most frequent solution to global warming, while global warming story frequencies peaked during international conferences. These results confirm previous research, which has found that news media outside of the United States tend to emphasize international relations and de-emphasize conflicts and controversies.

Doctor of Philosophy / Department of Sociology, Anthropology, and Social Work / Gerad D. Middendorf / In the almost 40 years since the passage of the Clean Water Act and 25 years of regulating nonpoint source pollution, and despite countless state and local community projects focused on water quality issues, clean water goals have not been met. To comprehend this failure and understand how water resources are governed and how water quality goals are pursued, I explore how watershed-level governance structures emerged and function in their specific local environment, within the state hierarchy of water governance, and as implementation of state and national policy. To this end, the structure, process, and outcomes of two newly organized and local watershed-level governance structures in Kansas were examined. An actor-oriented political ecology approach informed by environmental governance and watershed management literature was used to guide the study. Attaining water quality goals necessitates recognizing the connections between the political economy of agriculture, the cultural factors acting upon agricultural producers, and the natural, biophysical environment. Thusly, a comparative case study strategy was employed for the overall research design. Documents and interview transcripts were analyzed employing a grounded theory approach for differences and similarities; they were also sorted into topical categories and coded for common themes. The research questions focused on the agency and capacity of local watershed structures to determine the relations regarding water resource use in their watershed. Central questions addressed structure responsiveness to local versus state or national concerns; the underlying interests reflected by community member participation; and the effectiveness of local water-governance in protecting water resources. Governance models that began with holistic, alternative, participatory strategies are evolving into targeted, problem-solution strategies, and what began as watershed management is becoming problem shed management.

Master of Science / Department of Architectural Engineering and Construction Science / Fred L. Hasler / This paper discusses photopic and scotopic vision of the human eye and the implications that could result in the design process of the lighting industry. The incorporation of scotopic vision in lighting effects the perceived illumination in all settings; but these affects and benefits are seen more prevalently at night, as this is when scotopic vision is utilized by the eye the most. The paper will begin with an overview of the eye including discussions of exactly what photopic and scotopic vision are, as well as how the eye works. This will lay a foundation for the paper to help the reader better comprehend and understand the remainder of the content. After the groundwork has been laid, the factors that affect how the eye perceives light will be discussed. These factors include pupil size and color of the light. A discussion of the basis for current lighting industry design and how light levels are measured will follow. Once these topics have been fully explored, there will be a discussion of the changes that could occur in the lighting industry if scotopic vision is taken into account. Increased energy efficiency would result if the scotopic vision is incorporated, resulting from the decrease in needed total lumen output. There have been a few applications that have utilized the effects of the scotopic vision in their design, these cases will be presented. Following the case study discussions, will be a discussion of a survey conducted by myself on the change-out of high pressure sodium (HPS) fixtures to LED fixtures in the downtown Poyntz Avenue area of Manhattan, KS. After all studies have been reviewed, conclusions and correlations among them will be explored. Following this analysis, suggestions will be given to improve the way lighting is designed in the industry.

Master of Arts / Department of Geography / Melinda Daniels / Large woody debris, (LWD), defined as pieces measuring ≥ 1 meter in length and ≥ 10 centimeters in diameter (Swanson and Lienkaemper, 1978; Marston, 1982) is an influential stream component. Once stable LWD obstructs streamflow and regulates key processes, causing increases in storage capacity, scouring, and variations to the bed, the extent contingent upon LWD’s average length of residence time within a system. Several North American studies have acknowledged the effects of interactions between wood, sediment, and flow regimes (Bilby, 1981; Keller, E.A., and Swanson, F.J., 1979; Montgomery et al., 1995; Wohl, E., 2008), linking the triad to geomorphic changes, the redistribution of bed materials, and ecological benefits. A consensual baseline reference for LWD’s function over time does not exist however, partly due to previous research being primarily conducted in the Northeast and Pacific Northwest regions where historic actions of humans, particularly riparian logging and stream clearing, have greatly impacted the condition of the watersheds. Researchers having long-overlooked the Great Plains and other regions not commonly associated with woody vegetation has increased the ambiguity regarding the transferability of LWD findings between regions. By shifting the focus to a non-forested region, the goal of this thesis is to measure the dynamics and influence of a prairie stream’s wood load on sediment storage and bed morphology. The Kings Creek network study area is located on the Konza Prairie Biological Station in northeastern Kansas, and drains one of few remaining unaltered North American watersheds. Results document the ongoing forest expansion into the surrounding pristine grassland, and provide a temporal context of the regions changing climate representative of atypical stream conditions caused by drought. In total, 406 individual pieces of wood were measured. The wood load was lower than most forest streams referenced (13.05 m[superscript]³/100 m), though higher than expected resulting from the absence of streamflow. LWD stored 108 m[superscript]³ of sediment within the channel, and the cumulative volume of LWD-formed pools was 169 m[superscript]³. Additionally, statistical analysis showed longitudinal bed variations to be strongly associated to LWD abundance, further indicating that LWD influences prairie stream processes similarly to those in a forest stream.

Doctor of Philosophy / Department of Agronomy / Ganga M. Hettiarachchi / The milling and mining operations of metal ores are one of the major sources of heavy metal contamination at earth’s surface. Due to historic mining activities conducted in the Tri-State mining district, large area of land covered with mine waste, and soils enriched with lead (Pb), zinc (Zn) and cadmium (Cd) remain void of vegetation influencing ecosystem and human health. It has been hypothesized that if these minewaste materials are disposed of in the flooded subsidence pits; metals can be transformed into their sulfide forms under reduced conditions limiting their mobility, and toxicity. These mine waste materials are high in pH, low in organic carbon (OC) and sulfur (S). The objective of this study was to examine the effect of OC and S addition on the biogeochemical transformations of Pb, Zn and Cd in submerged mine waste containing microcosms. Advanced molecular spectroscopic and microbiological techniques were used to obtain a detail, mechanistic, and molecular scale understanding of the effect of natural and stimulated redox conditions on biogeochemical transformation and dynamics of Pb, Zn and Cd essential for designing effective remediation and mitigation strategies. The results obtained from these column studies indicated that Pb, Zn and Cd were effectively immobilized upon medium (119-day) and long-term (252-day) submergence regardless of treatment. The OC plus S treatment enhanced sulfide formation as supported by scanning electron microscopy- energy dispersive X-ray technique, and synchrotron based bulk-, and micro-X-ray fluorescence and absorption spectroscopy analyses. Microbial community structure changed with OC and S addition with the enhancement sulfur reducing bacteria genes (dsrA/B), and decreased metal resistance genes over time. The long-term submergence of existing mine tailings with OC plus S addition reduced trace metals mobility most likely through dissimilatory sulfate reduction under stimulated reduced conditions. Colloidal assisted metal transportation (<1% of both Pb and Cd) occurred during initial submergence. Retention filters are suggested to avoid colloidal metal transport in order to meet the maximum concentration limit for Pb and Cd in surface and groundwater. This research enhances our understanding of the redox processes associated with the sequestration of non-redox sensitive metals through dissimilatory reduction of sulfates in mine waste materials and/or waste water and provides regulators with useful scientific evidence for optimizing remediation goals.

Master of Science / Department of Geography / Melinda Daniels / The Lesser Prairie-Chicken (Tympanuchus pallidicinctus) is a prairie grouse of conservation concern in the Southern Great Plains. In response to declining population numbers and ongoing threats to its habitat, the Lesser Prairie-Chicken was listed as threatened under the Endangered Species Act in May 2014. In western Kansas, the Lesser Prairie-Chicken occupies the Sand Sagebrush Prairie, Mixed-grass Prairie, and Short-grass/CRP Mosaic Ecoregions. Since the beginning of the 20th century, the overall range and population has declined by 92% and 97% respectively. Much of this decline is attributed to the loss and fragmentation of native grasslands throughout the Lesser Prairie-Chicken range. Whereas much of the loss and degradation of native grassland have been attributed to anthropogenic activities such as conversion of grassland to cropland and energy exploration, federal legislation since the 1980s to convert cropland on highly erodible soils to perennial grasses through the U.S. Department of Agriculture (USDA) Conservation Reserve Program (CRP) may curtail or reverse these trends. My objective was to document changes in the areal extent and connectivity of grasslands in the identified Lesser Prairie-Chicken range in Kansas from the 1950s to 2013 using remotely sensed data. I hypothesized that the total amount of grassland decreased between the 1950’s and 2013 because of an increase in agricultural practices, but predicted an increase of grassland between 1985 and 2013 in response to the CRP. To document changes in grassland, land cover maps were generated through spectral classification of LANDSAT images and visual analysis of aerial photographs from the Army Map Service and USDA Farm Service Agency. Landscape composition and configuration were assessed using FRAGSTATS to compute a variety of landscape metrics measuring changes in the amount of grassland present as well as changes in the size and configuration of grassland patches. Since 1985, the amount of grassland in the Lesser Prairie-Chicken range in Kansas has increased by 210,9963.3 ha, a rise of 11.9%, while the mean patch size and area-weighted mean patch size of grassland increased 18.2% and 23.0% respectively, indicating grassland has become more connected during this time in response to the CRP. Prior to the implementation of CRP, the amount of grassland had been decreasing since 1950, as 66,722.0 ha of grassland was converted to croplands. The loss of grassland had a considerable effect on the patch size of grasslands, as mean patch size and area-weighted mean patch size decreased by 8.8% and 11.1% respectively. The primary driver of grassland loss between 1950 and 1985 was the emergence of center pivot irrigation, which had its greatest impact in western and southwestern parts of the range in Kansas. In particular, while the amount of grassland in Range 5, a region of the Lesser Prairie-Chicken range found in southwest Kansas, has increased overall since the 1950s by 4.7%, the area-weighted mean patch size has decreased by 53.0% in response to center pivot irrigation fragmenting the landscape. While the CRP has been successful in increasing and connecting grassland throughout the Lesser Prairie-Chicken range to offset the loss of grassland since the 1950s, continuation of the CRP faces an uncertain future in the face of rising commodity prices, energy development, and reduction in program scope leaving open the possibility that these areas that have created habitat for Lesser Prairie-Chickens could be lost. As time progresses, a reduction in the scope of the CRP would reduce the amount of habitat available to Lesser Prairie-Chickens, threatening the persistence of their population.

Master of Science / Department of Biology / Craig Paukert / Improperly designed stream crossings may prohibit movement of stream fishes by creating physical or behavioral barriers and may alter the form and function of stream ecosystems. A mark-recapture and geomorphological study was conducted to evaluate fish passage and stream morphology at three types of vehicle crossings (compared to control sites) located on streams in the Flint Hills of Northeast Kansas. We investigated five concrete box culverts, five low-water crossings (concrete slabs vented by one or multiple culverts), and two single corrugated culverts. A total of 6,433 fish were marked April to May 2007 and 709 were recaptured June to August 2007. Fish passage occurred at all crossing types, but upstream movement of recaptured fish was higher at controls (41.1%) than at crossing reaches (19.1%) for low-water crossings. Control sites had more species in common upstream and downstream than did crossings. There was reduced overall abundance of fish upstream at low-water crossings, commonly percids and centrarchids. A comparison of channel and road crossing dimensions showed that box culverts and corrugated culverts would be more effective than low-water crossings at transporting water, sediments, and debris during bankfull flows, and fish passage at base flows. Upstream passage of Topeka shiner (Notropis topeka), green sunfish (Lepomis cyanellus), red shiner (Cyprinella lutrensis), and Southern redbelly dace (Phoxinus erythrogaster) was tested through three simulated crossing designs (box culverts, round corrugated culverts, and natural rock) across 11 different water velocities (0.1 m/s to 1.1 m/s) in an experimental stream. Upstream movement did not differ among designs, except natural rock crossings had lower movement than box or corrugated culverts for red shiners. A greater proportion of Topeka shiners moved upstream at higher velocities. These results suggest that crossing type affects fish passage and the morphology of the stream, although water velocity in different crossing designs alone may not be a determining factor in fish passage. Low-water crossings had the greatest impact on fish community and movement, but barriers to fish movement are likely caused by other variables (e.g. perching). Use of properly designed crossing structures has great promise in conserving critical stream habitat and preserving native fish communities.