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To support population growth in Las Vegas, Nevada, large scale increases in groundwater pumping are planned across the state. This pumping could affect riparian areas in Great Basin National Park by lowering groundwater levels, reducing stream flows, and xerifying riparian vegetation. Great Basin National Park (GBNP) is mandated to manage its resources unimpaired for future generations. Loss of biodiversity is unacceptable under this mandate. If groundwater levels are reduced beyond a threshold, aquatic and riparian diversity would be lost, but the effects on small mammal communities are less clear. To provide baseline information and to consider the effects of groundwater withdrawal a priori, we sampled and compared small mammal communities in two watersheds susceptible to groundwater withdrawal and one non-susceptible watershed. We also used to stable isotopes of nitrogen, carbon, deuterium and oxygen to characterize small mammal communities. Evenness was higher in susceptible watersheds, which were distinct in species composition. Riparian and upland habitats in susceptible watersheds supported complementary small mammal communities, while communities in the non-susceptible watershed were more homogenous. Susceptible watersheds are located at the lowest elevations of GBNP where habitat heterogeneity due to the contrast between mesic riparian and xeric upland habitats is important in maintaining small mammal diversity. Partitioning was primarily seen in nitrogen and carbon isotopes which reflect feeding ecology (trophic level and primary production source), but was also seen in oxygen isotopes. Major differences in nitrogen and carbon isotopes were between taxonomic groups, while similarity was highest within these groups. Shrews and ermine were highest in nitrogen reflecting their high trophic positions. Harvest and piñon mice were intermediate in nitrogen suggesting omnivory, while chipmunks, voles, woodrats and pocket mice were apparently herbivorous. Carbon ratios were consistent with C3 based diets but were relatively enriched in Sigmodontinae species. Small mammal deuterium was similar to stream water suggesting that stream water is an important water source of water to small mammals. Oxygen enrichment relative to stream water and precipitation suggested that small mammals are sensitive to body water evaporation. Contrary to a previous study, oxygen isotopes were inversely related to water use efficiency. Increases in the rate of groundwater pumping adjacent to Great Basin National Park could lower water tables, reduce stream flows, and xerify riparian vegetation. We suggest that groundwater levels, streams flow and riparian vegetation, in addition to small mammal species composition will be important response variables in monitoring the effects of groundwater withdrawal. If predictions of groundwater withdrawal are realized, groundwater levels, stream flows, vegetation, microclimate, and invertebrates riparian dependent as well as small mammals will be negatively affected resulting in a decrease in diversity and loss of riparian species from affected areas.

Pinnipeds exhibit a wide range of lactation strategies that vary from just a few days to nearly three years in duration. Phocids have a relatively short, intense nursing period culminating with weaning after just a few days or weeks, while dependent otariids generally take several months of consuming a combined milk and solid food diet before being completely independent. The transition to nutritional independence can be particularly challenging for newly weaned pups, which must adjust to behavioral, physiological and nutritional changes as a milk diet is replaced with solid food. An interruption in energy resources during this formative stage could result in a prioritization away from growth, maintenance, or activity resulting in suboptimal development. Three groups of ex situ California sea lion (Zalophus californianus) pups were examined during the initial period of independence after they were weaned at approximately five, seven, and nine months of age. Absolute growth rates of pups were calculated and changes in body composition were estimated using blubber depth measurements and deuterium oxide dilution to determine if weaning age had an effect on subsequent pup development and growth. Blood urea nitrogen and blood glucose levels were observed for their response to changes in body condition, while thyroid hormone levels in the blood were examined as a possible nutritional stress indicator during the pup's transition to solid food. When compared to in situ pups, the 5 month old pups in the present study had significantly greater body mass (39.6 ± 1.6 kg, p < 0.01), axillary girth (85.3 ± 2.9 cm, p < 0.01), and axillary blubber depth (2.3 ± 0.1 cm, p < 0.01) compared to 5 month old in situ pups (26.6 ± 5.2 kg / 70.6 ± 5.34 cm / 1.5 ± 0.2 cm). Nine month old ex situ pups had significantly greater axillary blubber depth (3.7 ± 0.9 cm, p < 0.01) and total body lipid percentage (24.9 ± 4.7%, p= 0.01) than in situ pups (1.5 ± 0.2 cm / 17.1 ± 4.9%). Although all pups in the present study survived the transition to solid food, there were apparent differences in how the different age groups responded physiologically. The five month old pups began the switch to solid food with the lowest overall blubber depth (2.6 ± 0.9 cm) and experienced the greatest change in body mass (-8.5 ± 1.6 kg) and composition while taking the longest to begin physiological recovery (31.7 ± 1.2 d). In contrast, the 9 month old pups entered the transition with more energy reserves (24.9 ± 4.7% TBL), began consuming solid food sooner (16.3 ± 0.6 d), and were able to utilize reserves more efficiently to minimize loss and promote faster growth.

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Pt-supported catalysts are widely used industrially for hydrogenation reactions. However, the kinetics of hydrogen activation, a critical step for any hydrogenation reaction, is still not well understood on supported Pt surfaces. Recent studies had shown that activity and selectivity vary with Pt nuclearity for the acetylene semihydrogenation reaction, increasing in activity and decreasing in selectivity while increasing the particle size from single atoms (SA) to sub-nanoclusters to nanoparticles (NP), attributing the cause of these differences on activities to the activity of H2 activation in the H/D isotopic exchange reaction. In this work, the kinetics of H2 is studied by performing the H2-D2 isotopic exchange reaction on Pt-supported catalysts with different nuclearity to extract the activation barriers and pre-exponential factors for dissociating adsorption and associative desorption (Eads, Edes, and vads, vdes respectively) from the microkinetic model derived from the Bonhoeffer Farkas mechanism, this to perform a more in-depth analysis regarding the differences in activity when comparing the H2 adsorption energy (Eads+ = Eads-Edes) and frequency factors as a function of nuclearity. Experiments were carried out in a quartz tubular fixed bed reactor coupled with a Mass Spectrometer to analyze the product gas by carrying out both, an integral analysis (from 0 to equilibrium conversion) by performing light-off experiments and differential analysis (low conversions) by performing Arrhenius experiments in the low and high coverage regions. / Master of Science / Hydrogenation is a chemical reaction widely used in the petrochemical industry for the refining process where a substance reacts with molecular hydrogen H2 adding pairs of H atoms to compounds. However, hydrogen is unreactive towards other substances in the absence of metal catalysts such as platinum (Pt), which dramatically accelerates the reaction rates making hydrogenation reaction possible. In industry, metallic catalysts are found as supported catalysts where the precious metal is supported on materials with higher thermal and mechanical stability to endure the operation conditions. Depending on the pretreatment conditions the size of metallic particles on the support can be manipulated, giving place to samples made of the same materials but different particle sizes with different properties. There are two critical steps during hydrogenation reactions the first one is the hydrogen activation which consists of the dissociation and adhesion of the two hydrogen atoms from the molecular hydrogen on the metallic surface and the second one is the reverse process where two hydrogen atoms recombine and are released from the metallic surface. Both steps involve a minimum amount of energy to dissociate and recombine hydrogen atoms which are strongly dependent on the metallic particle sizes. The goal of this thesis is to extract these dissociation and recombination energies of hydrogen on platinum particles of different sizes supported on alumina.

Earth's near-surface environment sustains nearly all terrestrial life, yet this critical zone is threatened by the environmental migration of new and potentially harmful compounds produced to support a growing human population. Traditional transport equations often fail to capture the environmental behavior of these emerging contaminants due to issues such as flow heterogeneity. Thus, there is a need to better evaluate controls on pollutant partitioning in Earth's critical zone. Our first study investigated the transport and distribution of the neonicotinoid insecticide thiamethoxam (TMX) by growing TMX-coated corn seeds in coarse vs fine-textured soil columns maintained with versus without growing corn plants. Fine-textured soil transported TMX at concentrations that were two orders of magnitude higher than coarse-textured soil, due to preferential flow in the fine-textured soil columns and higher evapotranspiration (ET) concentrating more TMX in the coarse-textured soil. Living plants increased the concentration of TMX at depth, indicating that growing plants may drive preferential transport of neonicotinoids. For the second study we planted TMX-coated corn seeds and maintained field plots with and without viable crops (n = 3 plots per treatment), measuring TMX concentrations in three hydrological compartments (surface runoff, shallow lateral flow, and deep drainage) and soil. TMX was transported in the highest concentrations via surface runoff, while also showing continual migration within the subsurface throughout the growing season. Plants facilitated downward migration of TMX in soil yet restricted losses in drainage. For our final study, we used a simple isotope mixing method to evaluate how preferential flow alters the influence of compound chemical properties on solute transport. We applied deuterium-labeled rainfall to plots containing manure spiked with eight veterinary antibiotics with a range of mobility, and quantified transport to suction lysimeters (30 and 90 cm). We showed that low preferential flow (<20%) eliminates the influence of compound chemical properties and, contrary to conventional understanding, more preferential flow (~ >20%) amplifies these chemical controls, with more mobile compounds appearing in significantly higher concentrations than less mobiles ones. Altogether, we provide a refined understanding of solute partitioning in the critical zone necessary to improve process-based transport modeling. / Doctor of Philosophy / Earth’s near-surface environment sustains nearly all terrestrial life, yet this critical zone is threatened by the environmental migration of new and potentially harmful pollutants produced to support a growing human population. Additionally, traditional mathematical methods fail to accurately describe the behavior of these emerging pollutants in soils due to complex flow patterns. Thus, scientists need to better understand how these pollutants contaminate water bodies in the critical zone. We first conducted a greenhouse experiment to understand and measure the amount of the neonicotinoid insecticide thiamethoxam (TMX) that could move from coated corn seeds through the soil environment. Water draining from fine-textured soil had >100 times more TMX than water draining from course-textured soil, due to commonly occurring fractures/cracks in the finer-particle soil and more evaporation from soil and plant leaves sequestering TMX in the sandy soil. Growing plants amplified TMX movement through soil voids to lower depths. We then conducted a field study to determine how much TMX could move to the surrounding environment throughout the corn growing season. We found that plants aided in downward movement of TMX yet restricted total losses from the plot overall by removing soil water. Our third study investigated the degree to which chemical pollutant properties control movement of solutes when water flows preferentially through soil void space. Common dairy manure was spiked with eight pollutants ranging in chemical attraction to soil and was added to an agricultural field. After irrigation, we found that when total drainage water was less than 20% derived from preferential flow, chemical properties had a negligible effect on the amount of pollutant in draining soil water. Contrary to conventional understanding, when draining water contained more than 20% preferential flow, chemical properties had a strong influence on the amount of pollutant detected. Altogether, we provide new understanding of how solutes move though the critical zone. These findings are necessary to create mathematical tools that more accurately depict pollutant behavior below-ground.

State of the art conductivity equipment has been used to measure deuterium isotope effects on the molar conductivity of strong electrolytes in the temperature range of 298 K to 598 K as a means of exploring solvation effects under hydrothermal conditions. Individual ionic contributions were determined by extrapolation of published transference number data to elevated temperature. The temperature dependence of the Walden product ratio indicates that there is little difference in the transport of ions between light and heavy water . Excess conductivity observed in hydrogen and deuterium compounds arising from proton hopping in hydrogen-bonded networks has been determined in the temperature range of 318 K to 598 K for the first time