The overall aim of this thesis was to investigate the fate of perfluorinated alkyl compounds (PFCs) in biological systems. During the past several years, it has been shown that wildlife are ubiquitously contaminated with two classes of PFCs, the perfluoroalkyl carboxylates (CxF2x+1C(O)OH, PFCAs) and sulfonates (CxF2x+1SO3H, PFSAs). However, there is still considerable uncertainty regarding how wildlife are accumulating these PFCs, particularly in remote areas such as the Canadian arctic. The potential for fluorotelomer acrylate monomers (CxF2x+1CH2CH2OC(O)CH=CH2, FTAcs) to act as precursors to PFCAs through atmospheric oxidation was investigated using smog chamber experiments. FTAc atmospheric fate is determined by OH radical reaction with a lifetime of approximately 1 day. The sole primary product of this reaction was the 4:2 fluorotelomer glyoxylate which is expected to undergo further atmospheric oxidation or photolysis to ultimately yield PFCAs. Temporal and spatial trends of PFCs in arctic ringed seals and seabirds were investigated to assist in understanding PFC transport mechanisms to remote regions. In ringed seals, perfluorooctane sulfonate (PFOS) levels decreased rapidly, coinciding with the phase out by the major manufacturer. These findings are consistent with volatile precursors as the dominant source of PFCs to arctic wildlife. The bioaccumulation and biotransformation of the 8:2 FTAc was investigated in two complimentary studies with rainbow trout. During the in vivo dietary exposure study, fish rapidly accumulated and biotransformed the 8:2 FTAc, with intermediate metabolites observed within 1 hour of dosing. Perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptanoate (PFHpA) were formed and accumulated in low yields. The carboxylesterase activity in the trout liver and stomach was investigated using in vivo sub-cellular (S9) incubations. Very high esterase activities were shown with approximately equal efficiency in the stomach and liver. The metabolic pathway of the 8:2 fluorotelomer alcohol (8:2 FTOH) was investigated by separately dosing whole rainbow trout with three intermediate metabolites that represented important branching points. The 7:3 fluorotelomer saturated carboxylate (FTCA) did not form PFOA, but formed PFHpA and the 7:3 fluorotelomer unsaturated carboxylate (FTUCA). The 8:2 FTCA and 8:2 FTUCA did form PFOA, confirming a “beta-like-oxidation” mechanism.

The overall aim of this thesis was to investigate the fate of perfluorinated alkyl compounds (PFCs) in biological systems. During the past several years, it has been shown that wildlife are ubiquitously contaminated with two classes of PFCs, the perfluoroalkyl carboxylates (CxF2x+1C(O)OH, PFCAs) and sulfonates (CxF2x+1SO3H, PFSAs). However, there is still considerable uncertainty regarding how wildlife are accumulating these PFCs, particularly in remote areas such as the Canadian arctic. The potential for fluorotelomer acrylate monomers (CxF2x+1CH2CH2OC(O)CH=CH2, FTAcs) to act as precursors to PFCAs through atmospheric oxidation was investigated using smog chamber experiments. FTAc atmospheric fate is determined by OH radical reaction with a lifetime of approximately 1 day. The sole primary product of this reaction was the 4:2 fluorotelomer glyoxylate which is expected to undergo further atmospheric oxidation or photolysis to ultimately yield PFCAs. Temporal and spatial trends of PFCs in arctic ringed seals and seabirds were investigated to assist in understanding PFC transport mechanisms to remote regions. In ringed seals, perfluorooctane sulfonate (PFOS) levels decreased rapidly, coinciding with the phase out by the major manufacturer. These findings are consistent with volatile precursors as the dominant source of PFCs to arctic wildlife. The bioaccumulation and biotransformation of the 8:2 FTAc was investigated in two complimentary studies with rainbow trout. During the in vivo dietary exposure study, fish rapidly accumulated and biotransformed the 8:2 FTAc, with intermediate metabolites observed within 1 hour of dosing. Perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptanoate (PFHpA) were formed and accumulated in low yields. The carboxylesterase activity in the trout liver and stomach was investigated using in vivo sub-cellular (S9) incubations. Very high esterase activities were shown with approximately equal efficiency in the stomach and liver. The metabolic pathway of the 8:2 fluorotelomer alcohol (8:2 FTOH) was investigated by separately dosing whole rainbow trout with three intermediate metabolites that represented important branching points. The 7:3 fluorotelomer saturated carboxylate (FTCA) did not form PFOA, but formed PFHpA and the 7:3 fluorotelomer unsaturated carboxylate (FTUCA). The 8:2 FTCA and 8:2 FTUCA did form PFOA, confirming a “beta-like-oxidation” mechanism.

Doctor of Philosophy / Department of Geography / Melinda Daniels / Great Plains rivers are unique systems that vary from large, continental scale, to small intermittent streams with grain sizes that range from bedrock to cobbles to silt. These rivers have been subject to widespread hydrologic alteration both within the channel and the watershed, which has resulted in an alteration in their hydrologic and geomorphic regimes. Although there is an acknowledgement of this alteration, to date there has not been a synthesis of the hydrology of Great Plains rivers or of their longitudinal morphologies. Chapters in this dissertation provide, to my knowledge, the first comprehensive analyses of the hydrology and morphology of Great Plains rivers over a range of spatial and temporal scales. In the first study, I found that there was no uniform pattern of hydrologic alteration throughout the Great Plains, which is likely attributable to variable system-specific reservoir management objectives, land use changes, and climatic regimes over the large area the Great Plains encompass. Results of this study are the first to quantify the widespread hydrologic alteration of Great Plains rivers following impoundment. In the second study, I found an apparent decoupling between local moisture conditions and streamflow in intermittent prairie streams. Results of this study used statistical models to identify relationships between flow intermittence, mean annual flow, and flood flow characteristics with moisture to characterize flow in an intermittent prairie stream. In the final study, I found that the downstream trends in hydraulic geometry and substrate characteristics of the Ninnescah River were consistent with the expected trends proposed by hydraulic geometry and substrate theories. However, there were points that deviated from the expected trends, most notably where a substantially large tributary enters the Ninnescah River and as the Ninnescah River approaches the Arkansas River, and causal explanations for these deviations were explored. Results of this study are, to my knowledge, the first of its kind to assess the longitudinal hydraulic geometry and substrate characteristics of a large sand-bed river over a large spatial scale. To our knowledge, there have been no comparable studies exist that attempted to describe hydrologic and geomorphic characteristics of prairie streams.

The overall aim of this thesis was to investigate the fate of perfluorinated alkyl compounds (PFCs) in biological systems. During the past several years, it has been shown that wildlife are ubiquitously contaminated with two classes of PFCs, the perfluoroalkyl carboxylates (CxF2x+1C(O)OH, PFCAs) and sulfonates (CxF2x+1SO3H, PFSAs). However, there is still considerable uncertainty regarding how wildlife are accumulating these PFCs, particularly in remote areas such as the Canadian arctic. The potential for fluorotelomer acrylate monomers (CxF2x+1CH2CH2OC(O)CH=CH2, FTAcs) to act as precursors to PFCAs through atmospheric oxidation was investigated using smog chamber experiments. FTAc atmospheric fate is determined by OH radical reaction with a lifetime of approximately 1 day. The sole primary product of this reaction was the 4:2 fluorotelomer glyoxylate which is expected to undergo further atmospheric oxidation or photolysis to ultimately yield PFCAs. Temporal and spatial trends of PFCs in arctic ringed seals and seabirds were investigated to assist in understanding PFC transport mechanisms to remote regions. In ringed seals, perfluorooctane sulfonate (PFOS) levels decreased rapidly, coinciding with the phase out by the major manufacturer. These findings are consistent with volatile precursors as the dominant source of PFCs to arctic wildlife. The bioaccumulation and biotransformation of the 8:2 FTAc was investigated in two complimentary studies with rainbow trout. During the in vivo dietary exposure study, fish rapidly accumulated and biotransformed the 8:2 FTAc, with intermediate metabolites observed within 1 hour of dosing. Perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptanoate (PFHpA) were formed and accumulated in low yields. The carboxylesterase activity in the trout liver and stomach was investigated using in vivo sub-cellular (S9) incubations. Very high esterase activities were shown with approximately equal efficiency in the stomach and liver. The metabolic pathway of the 8:2 fluorotelomer alcohol (8:2 FTOH) was investigated by separately dosing whole rainbow trout with three intermediate metabolites that represented important branching points. The 7:3 fluorotelomer saturated carboxylate (FTCA) did not form PFOA, but formed PFHpA and the 7:3 fluorotelomer unsaturated carboxylate (FTUCA). The 8:2 FTCA and 8:2 FTUCA did form PFOA, confirming a “beta-like-oxidation” mechanism.

The overall aim of this thesis was to investigate the fate of perfluorinated alkyl compounds (PFCs) in biological systems. During the past several years, it has been shown that wildlife are ubiquitously contaminated with two classes of PFCs, the perfluoroalkyl carboxylates (CxF2x+1C(O)OH, PFCAs) and sulfonates (CxF2x+1SO3H, PFSAs). However, there is still considerable uncertainty regarding how wildlife are accumulating these PFCs, particularly in remote areas such as the Canadian arctic. The potential for fluorotelomer acrylate monomers (CxF2x+1CH2CH2OC(O)CH=CH2, FTAcs) to act as precursors to PFCAs through atmospheric oxidation was investigated using smog chamber experiments. FTAc atmospheric fate is determined by OH radical reaction with a lifetime of approximately 1 day. The sole primary product of this reaction was the 4:2 fluorotelomer glyoxylate which is expected to undergo further atmospheric oxidation or photolysis to ultimately yield PFCAs. Temporal and spatial trends of PFCs in arctic ringed seals and seabirds were investigated to assist in understanding PFC transport mechanisms to remote regions. In ringed seals, perfluorooctane sulfonate (PFOS) levels decreased rapidly, coinciding with the phase out by the major manufacturer. These findings are consistent with volatile precursors as the dominant source of PFCs to arctic wildlife. The bioaccumulation and biotransformation of the 8:2 FTAc was investigated in two complimentary studies with rainbow trout. During the in vivo dietary exposure study, fish rapidly accumulated and biotransformed the 8:2 FTAc, with intermediate metabolites observed within 1 hour of dosing. Perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptanoate (PFHpA) were formed and accumulated in low yields. The carboxylesterase activity in the trout liver and stomach was investigated using in vivo sub-cellular (S9) incubations. Very high esterase activities were shown with approximately equal efficiency in the stomach and liver. The metabolic pathway of the 8:2 fluorotelomer alcohol (8:2 FTOH) was investigated by separately dosing whole rainbow trout with three intermediate metabolites that represented important branching points. The 7:3 fluorotelomer saturated carboxylate (FTCA) did not form PFOA, but formed PFHpA and the 7:3 fluorotelomer unsaturated carboxylate (FTUCA). The 8:2 FTCA and 8:2 FTUCA did form PFOA, confirming a “beta-like-oxidation” mechanism.

Doctor of Philosophy / Environmental Design and Planning Program / Timothy D. Keane / The original purpose of this investigation was to develop streambank erosion prediction curves for Northeast Kansas streams. Rosgen's (2001, 2006) methods were employed and eighteen study banks were measured and monitored over a four-year period, summer 2007 through summer 2010. At each study bank, a toe pin and two to three bank pins were set at a recorded longitudinal profile station of the stream. Vertical and horizontal measures from the toe pin to the bank face were taken each summer, 2007 as the baseline measure and 2008 - 2010 as bank change years. Bank profiles were overlaid to gain insight into bank area lost or gained due to erosional or depositional processes. A Bank Erosion Hazard Index (BEHI) and Near Bank Stress (NBS) combination rating was assessed and calculated for each study bank during the initial survey of 2007. The streambanks experienced varied erosion rates for similar BEHI/NBS combinations producing R2 values from 0.43 as the High/Very High BEHI rating and 0.80 as the Moderate BEHI rating. In addition, Moderate BEHI ratings provided higher erosion rates than the High/Very High BEHI rating and curves intersected at lower NBS ratings, suggesting a discrepancy in the fit of the model used in the Northeast Kansas region and conditions. In this light, modification of the BEHI model was evaluated and variables were assessed in the model for additional influence exerted in the Northeast Kansas region. Vegetation seemed to provide the most influence to bank resistance and was more closely evaluated. Banks with and without woody riparian vegetation were then plotted against BEHI and NBS values, as banks lacking woody vegetation eroded at higher rates. This study's findings can allow us to calibrate the BEHI model according to woody vegetation occurrence levels along streambanks in the Black Vermillion watershed. Modifications regarding vegetation occurrence of the BEHI model was completed and the results of these modifications generated R2 values of 0.78 for High/Very High BEHI and 0.82 for Moderate BEHI ratings. High/Very High ratings provided higher predicted erosion rates than Moderate ratings, while the curve slopes did not intersect at lower NBS ratings.

Master of Arts / Department of Geography / Richard Marston / Slope failures play a significant role as a mass movement hazard in the deglaciated mountain canyons in Grand Teton National Park. The park’s geologic and glacial histories are unique in comparison to other areas in the Rocky Mountain range. However, few detailed maps and statistical analyses of slope failures as hazards exist for park officials and visitors. The purpose of this study is to produce a comprehensive map of slope failures in five of the most accessible and commonly used canyons of the park: Cascade, Death, Garnet, Granite, and Paintbrush. This project combined fieldwork, LiDAR imagery, and GIS mapping to document five main categories of slope failures—rock slides, rock/debris flows, rock falls, and snow avalanches, as well as complex slope failures involving a combination of these categories. Summary statistics, maps, and histograms of average slope gradient, aspect, and curvature conditions as well as precipitation conditions at the “source” area of slope failures were generated for individual canyons as well as the entire study area. Snow avalanche source areas where debris flows were not readily present occurred most commonly on north and northeast facing slopes, slopes averaging a 40% gradient, and slightly convex slopes. Debris flow source areas occurred most commonly on south and southeast facing slopes, slopes with an average 42% gradient, and on slightly convex slopes. Rock fall source areas were most common on north facing slopes, slopes of an average 55% gradient, and a mostly flat curvature. Rock slide source points were most common on north facing slopes, slopes of an average 54% gradient, and flat to slightly concave slopes. Rock Mass Strength (RMS) values were sampled at a rate of every 0.5 kilometers on the hiking trail of each canyon to provide an introductory insight into rock stability conditions in each canyon. Slope failures not only impact the physical landscape of canyons in Grand Teton National Park but can affect human structures as well. Physical attributes and locations of slope failures were compared to locations of camping zones and hiking trails in the Park to determine areas of common human usage that were most susceptible to past movement events.

Master of Science / Geology / Matthew E. Brueseke / Previous K-Ar dating and petrography (Obradovich, 1978) have identified Pilot Knob as an ~3.4 (±0.06) Ma alkaline intrusive body. Bulk rock geochemistry obtained via XRF from four samples of Pilot Knob verifies the transitionally alkaline composition of the body, and new REE data also show enriched La, Ce, and Nd concentrations, consistent with rare earth element (REE) enrichment. Given the increased demand for REEs over the past ~30 years and China accounting for > 90% of global REE production (Kynicky, et al. 2012), it is important to evaluate new domestic REE sources. This includes those associated with alkaline intrusive complexes, because they are demonstrated to host high REE concentrations (Verplanck and Van Gosen, 2011). Such alkaline igneous occurrences show complex mineralization and consist of many minerals containing substitutional REEs (Mariano and Mariano, 2012). This study evaluates the petrogenesis and mineralogy of Pilot Knob (and a secondary field site, Wildcat Hill) and determines whether the intrusive body is consistent with an economically viable REE deposit. Additionally, given its geographic location and Pliocene faulting and magmatism (e.g., predating the earliest volcanism at Yellowstone), Pilot Knob may represent one of the earliest structural manifestations of the “arrival” of the Yellowstone hotspot at its current location under the North American lithosphere or magmatism associated with lithospheric extension to the south at the Leucite Hills, WY. Inspection of satellite imagery, which has been verified with field data, shows that other intrusive igneous bodies (e.g. - Wildcat Hill) exist, along an apparent normal fault zone along strike with a major extensionally related fault zone documented ~10 km northwest of Pilot Knob. Clinopyroxene geobarometry, coupled with Nd isotope data (εNd[subscript 3.5Ma] = -21.9), indicates that Pilot Knob formed via a multi-stage development history that initiated with melting of ancient lithospheric mantle, where crystallization occurred at a variety of depths. As an alkaline intrusive complex, Pilot Knob has been identified, based on mineral and chemical compositions, as a kersantite, and has been found to contain approximately 600 ppm total light-rare earth element ore lode with ~150 ppm Nd, ~175 ppm La, and ~338 ppm Ce enrichment. Apatite was found to be the primary REE-bearing mineral via petrography and electron microprobe analyses. Based on current technology and processing methods, REE concentrations were not found to be significant enough to denote an economically viable REE ore deposit at Pilot Knob.

Master of Science / Department of Biological and Agricultural Engineering / Aleksey Sheshukov / The global requirements for food and agricultural products have increased enormously in recent years mainly due to increase in global population. More land is brought under human development and cultivation including marginal lands that are susceptible to degradation processes of erosion, waterlogging, and depletion of organic matter. The resulting effects include; deprivation of the roles performed by the environment, high costs of water treatment, and sedimentation of water reservoirs. This study aims at assessment of ephemeral gully (EG) erosion using topographic and hydrologically based models in two paired watersheds in Central Kansas. The effects of best management practices (BMPs) implementation on EG formation, and erosion rates within the watershed are discussed. The topographic index (TI) models used include: slope area model (SA), compound topographic index model (CTI), wetness topographic index model (WTI), slope area power (SA2), kinematic wave model (nLS), and modified kinematic wave model (nLSCSS). EGs predicted by each model threshold were compared with observed EGs obtained through digitization and field reconnaissance. The agreement of thresholds obtained from location and length approaches were compared by means of drainage density concept. Statistical analysis was performed by error matrix for EG location analysis, and root mean square error (RMSE) and Nash–Sutcliffe efficiency (NSE) for EG length analysis. A TIN-based real-time integrated basin simulator (tRIBS) model, a physically-based, distributed hydrological model was coupled with an EG erosion component (Foster and Lane model) to estimate the erosion rates, and effect of installation of BMPs on reduction of EG erosion rates from agricultural fields. The results indicated that TI models could predict EG location with a maximum total accuracy of 70%. The effectiveness of TI models at prediction of EGs is affected by watershed features such as installed structural best management practices, roads, and culverts. The CTI model outperformed all the TI models at prediction of EGs with maximum Kappa and NSE values of 0.32 and 0.55 respectively, and a minimum RMSE value of 0.087 m. Structural BMPs are effective at controlling erosion from croplands, however, the effectiveness of structural BMPs at reduction of sediment loadings from EGs vary depending on surface cover, and BMP geometry.

La vallée A’ą̈y Chù est située au Sud-Ouest du Yukon dans le Parc National Kluane. Le pergélisol y est isolé et présent sous forme de lithalses, retrouvées dans les milieux humides. La présente étude s’intéresse à ces formes périglaciaires afin de comprendre les conditions et processus de formation et conservation des lithalses. Nous avons effectué huit forages sur deux sites, à l’est et à l’ouest de la vallée. Notre étude cryostratigraphique des lithalses incorpore des analyses sédimentaires, de cryostructure, de contenu en glace, d’ions majeurs et d’isotopes d’eau. Les lithalses se sont développées sous le climat froid du Petit Âge Glaciaire, avec des conditions écosystémiques tel qu’un substrat gélif (silt, sable fin) couplé d’une forte disponibilité en eau. La végétation était composée de mousses, d’herbacées (Carex spp.) et de buissons (Salix spp.), formant un couvert organique poreux et isolant. Le pergélisol était d’une faible épaisseur jusqu’à 2,2 m de profondeur. Sept forages comportaient un talik de 21 à 48 cm d’épaisseur, et débutant dans le premier mètre de sol. Les cryostructures principales étaient lenticulaire et microlenticulaire. Aux sites 1 et 2, le contenu volumétrique en glace moyen était 66,7 % ±9,1 et 63,9 % ±13,7, la glace en excès était responsable jusqu’à 61,3 % et 45,6 % de la hauteur des lithalses. Plusieurs signes de dégradation (talik, ravinement, mares de thermokarst, remparts) indiquent un état mécanique et thermique instable. Une succession d’étés et d’hivers chauds pourraient d’abord faire balancer les lithalses vers un état relique, puis vers un dégel final. / The A’ą̈y Chù valley in southwestern Yukon, Kluane National Park features isolated permafrost occurring in lithalsas formed in wetlands. We investigate these persistent permafrost features to understand the specific conditions and processes that allowed their formation and conservation. We drilled and sampled eight boreholes at two different sites, on the east and west sides of the valley. The lithalsas were studied with a cryostratigraphic approach, with analyses of cryostructure, ice content, sediment characteristics, major ions, and water isotopes. Lithalsas developed during the colder climate of Little Ice Age due to ecosystem conditions that include a frost susceptible substrate composed of silt and fine sand coupled with high water availability. The vegetation cover was mainly moss, herbs (Carex spp.) and shrubs (Salix spp.) which formed a porous insulating cover. The permafrost body was thin with a maximum depth of 2,2 m. Seven boreholes had a talik 21 to 48 cm thick, starting within the first meter of soil. The cryostructures were mainly lenticular and microlenticular. The average volumetric ice content was 66,7 % ±9,1 at Site 1 and 63,9 % ±13,7 at Site 2. The average excess ice content accounts for up to 61,3% and 45,6% of the height of lithalsas, at Site 1 and 2. Many signs of permafrost degradation (talik, gullies, thermokarst ponds, ramparts) indicate an unstable thermal and mechanical state. A succession of warm summers and winters could make the lithalsas balance towards a relic state first then to final thaw.