<p dir="ltr">This work studies the kinetics of nitrous oxide decomposition over alumina-based catalysts, specifically at the high temperatures and high nitrous oxide (N2O) concentrations that would be experienced in catalyst beds for monopropellant rocket thruster applications. High- and low- order models are developed to understand the interaction between reaction kinetics and mass transfer in monolith catalyst tubes. However, nitrous oxide decomposition is not observed on monolith catalyst tubes on account of their lower geometric surface area leading to a majority of the gas not coming into contact with the catalyst surface. Pellet-bed catalysts are studied for the remainder of this work, starting from experiments with a constant-volume batch reactor. The batch experiments demonstrate N2O decomposition over catalyst pellets, and a one-dimensional, time-varying model is developed to quantify the reaction rate based on measured temperature and pressure rise from experimental data. The reaction rates predicted by the model are significantly lower than predicted in the literature for the same catalysts. The inaccuracy is attributed to the fact that the model cannot capture N2O decomposition occurring during the first few seconds of filling the batch tube. Additionally, the simplified temperature distribution applied in the model may not be accurate, and obtaining a higher fidelity temperature distribution experimentally would require more advanced diagnostics.</p><p dir="ltr">The final experiment is a conventional flow-through pellet bed reactor which uses infrared spectroscopy to measure the concentration of nitrous oxide in the decomposed gas mixture. The analysis method incorporates uncertainties from infrared measurements and other sources, and initial activity results of a cobalt oxide-on-alumina catalyst are consistent with the literature. Results from additional testing indicate that manganese oxide catalysts are more active than nickel oxide or cobalt oxide catalysts. At weight loadings of ~10%, results indicate that the Arrhenius pre-exponential constant is roughly an order or magnitude greater for manganese oxide catalysts than cobalt or nickel oxide catalysts. The results also indicate hysteresis in catalytic activity of all oxides. Surface area and x-ray diffraction measurements do not reveal any permanent change in the surface area or crystal structure of these catalysts. The findings lead to the conclusion that the temperature and surrounding environment of the catalyst (either nitrous oxide or nitrogen during system purges) cause short-lived changes to the crystal structure of the active phase, leading to the observed hysteresis.</p>

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The global nitrogen cycle has been disrupted by large anthropogenic inputs of reactive nitrogen to the environment. Excess nitrogen underlies environmental problems such as eutrophication, and can negatively affect human health. Managing the natural microbial process of denitrification is advocated as a promising avenue to reduce excess nitrogen, and denitrifying bioreactors (DNBRs) are an emerging technology harnessing this biochemical process. Previous DNBR research has established successful nitrate removal, whereas this study examines the potential to expand DNBR functionality to address excess phosphorus and mitigate the production of nitrous oxide, a potent greenhouse gas. Results from a laboratory experiment supported the hypothesis that the addition of biochar, a charcoal-like soil amendment and novel organic carbon source in DNBR research, would increase nitrate and phosphorus removal as well as decrease the accumulation of nitrous oxide, an intermediate product of microbial denitrification. In order more closely examine the ratio of the products nitrous oxide and inert dinitrogen, development of a novel analytical method to quantify dissolved gases in environmental water samples using gas chromatography mass spectrometry was undertaken. Although static headspace analysis is a common technique for quantifying dissolved volatiles, the variation in sample preparation has recently been revealed to affect the determination of dissolved concentrations of permanent gases and convolute comparison between studies. This work demonstrates the viability of internal calibration with gaseous standard addition to make dissolved gas analysis more robust to variable sample processing and to correct for matrix effects on gas partitioning that may occur in environmental samples. / Master of Science

No / Improving the patient's experience of a bone marrow biopsy ¿ an RCT Aims. To compare nitrous oxide 50%/oxygen 50% (N2O/O2 ¿ entonox) plus local anaesthetic (LA) with placebo (oxygen) plus LA in the management of pain experienced by patients undergoing a bone marrow biopsy. . Bone marrow biopsies are a common procedure for many haematological conditions. Despite the use of a LA, pain during the procedure has frequently been reported by patients. Previous research in pain management of other invasive diagnostic procedures (e.g. sigmoidoscopy) has reported N2O/O2 as an effective alternative to LA. Design. Double-blind randomized controlled trial. Methods. Forty-eight patients requiring a bone marrow biopsy were randomized to receive either N2O/O2 or oxygen in addition to their LA. Participants were asked to complete a pain score and comment on their experience of the procedure. Results. Although the overall pain scores were moderate, there was a wide range of scores. N2O/O2 resulted in significantly less pain for men, but not for women. All patients who had had previous biopsies reported significantly more pain, regardless of the gas used. There were no significant adverse effects in either group. Conclusion. N2O/O2 is a safe, effective, easy-to-use analgesic which merits further investigation in potentially painful diagnostic (and other) interventions.

A better way to improve understanding and quantification of nitrous oxide (N₂O) emitted from intensive maize cropping systems is to develop an advanced emissions measurement method This study developed an open path (OP) method to measure N₂O emissions from four adjacent maize plots managed by tillage practices of no-till (NT) and chisel plow (ChP), and different nitrogen (N) treatments from 2014 to 2016. Anhydrous ammonia (220 kg NH₃-N ha^-1) was applied in once or equally split (full vs. split rate) and applied in different timing (Fall vs. Spring). The spring N application occurred either before planting (pre-plant) or in season (side-dress). Emissions measurements were conducted by using the OP method (the scanning OP Fourier transform infrared spectrometry (OP-FTIR) + the gas point-sampling system + a backward Lagrangian stochastic (bLS) dispersion model) and static closed chamber methods. The performance and feasibility of the OP measurements were assessed by a sensitivity analysis, starting with errors associated with the OP-FTIR for calculating N₂O concentrations, and then errors associated with the bLS model for estimating N₂O emissions. The quantification of N₂O concentrations using the OP-FTIR spectrum was influenced by ambient humidity, temperature, and the path length between a spectrometer and a retro-reflector. The optimal quantitative method mitigated these ambient interference effects on N₂O quantification. The averaged bias of the calculated N₂O concentrations from the spectra acquired from wide ranges of humidity (0.5 – 2.0 % water vapor content), temperature (10 – 35 °C), and path length (100 – 135 meters) was 1.4 %. The precision of the OP-FTIR N₂O concentrations was 5.4 part per billion(3σ) in a stationary flow condition for a 30-minute averaging period. The emissions measurement from multiple sources showed that the field of interest was likely interfered by adjacent fields. Fields with low emission rates were more sensitive to the adjacent fields with high emissions, resulting in substantial biases and uncertainties. The minimum detection limit of the N₂O emission rates was 1.2 µg m^-2 s^-1 (MDL; 3σ). The OP measurements showed that the NT practice potentially reduced N₂O emission compared with ChP. Under the long-term NT treatments, the split-N rate application (110 kg NH₃-N ha^-1 in the fall and spring) resulted in lower N₂O emissions than the full application (220 kg NH₃-N ha^-1 in the fall). The management of NT coupled with split-N rate application minimized N₂O emissions among treatments in this study, resulting in N₂O-N losses of 3.8, 13.2, and 6.6 N kg ha^-1 over 9-, 35-, and 20-days after the spring NH₃ application in 2014, 2015, and 2016, respectively. The spring pre-plant N application in 2015 also resulted in higher N₂O emissions than the spring side-dress application in 2016, and the increased N₂O-N loss was corresponding to lower N recovery efficiency in 2015 measurements. A comparison of chamber and OP measurements showed that soil N₂O emissions were likely underestimated by 10x without considering the wind-induced effect on gas transport at the ground-atmospheric interface. This study showed that the OP method provides a great opportunity to study agricultural N₂O emissions as well as management optimization for the sustainability of the agroecosystems.

Doctor of Philosophy / Department of Horticulture, Forestry, and Recreation Resources / Dale J. Bremer / Turfgrass covers 1.9% of the nation’s surface area and is the largest irrigated crop in the USA. Developed urbanized land is projected to double by 2025, which will increase turf’s environmental impact. Studies were conducted to evaluate environmental impacts by characterizing nitrogen, carbon, and water fluxes in turfgrass ecosystems. Emissions of nitrous oxide (N[subscript]2O), a major greenhouse gas and ozone depleter were measured from bermudagrass (Cynodon dactylon L. Pers. x C. transvaalensis Burtt-Davy) (bermuda), perennial ryegrass, (Lolium perenne L.) (rye), and zoysiagrass, (Zoysia japonica Steud.) (zoysia) under regional N management. In a separate study, N2O fluxes were measured from bermuda fertilized with controlled-release N fertilizers including polymer-coated and organic-N, and quick release urea. Emissions of N2O were measured using static surface chambers and gas chromatography. Zoysia, with less N requirements, had lower emissions than bermuda. Cumulative N[subscript]2O emissions were similar among N types. To measure water and carbon fluxes, a portable non-steady state chamber was designed and tested. The chamber had minimal affects to the canopy during field measurements: leak values averaged <1.5 micromol CO[subscript]2 m[superscript]-2 s[superscript]-1; average chamber pressure was 0.09 Pa ±0.01 Pa; temperature rise inside the chamber averaged 0.74C; and the chamber had 90% photosynthetically active radiation transmittance. Using the chamber, differences were detected in net photosynthesis (Pnet), gross photosynthesis (Pg), evapotranspiration (ET), canopy stomatal conductance (gc), and water use efficiency (WUE) in well-watered tall fescue (Festuca arundinacea Schreb.), Kentucky bluegrass (Poa pratensis L.) (KBG), zoysia, and bermuda. Irrigation requirements, visual quality ratings, and genetic rooting potential of 28 KBG cultivars and 2 Texas bluegrass hybrids (P. pratensis x P. arachnifera Torr.) were quantified in greenhouse and rainout facility studies. Average water applied ranged from 23.4 to 40.0 cm among cultivars. Bedazzled, Preakness, and Bartitia required less water and had higher average quality than other cultivars. Compact America and Mid-Atlantic phenotypes exhibited greatest potential for success in integrating reduced water inputs with maintenance of acceptable visual quality. Results indicated that turfgrass management could mitigate N[subscript]2O emissions and conserve water while maintaining healthy turfgrass, and the new chamber will enhance turfgrass studies by providing rapid measurements of photosynthesis.

Solos de ecossistemas tropicais são considerados maiores emissores naturais de óxido nitroso (N2O) para a atmosfera. Grande parte do N2O produzido a partir destes solos é originada por dois processos microbiológicos, desnitrificação e nitrificação. A dinâmica de produção e decomposição de raízes e de serapilheira também contribuem para os estoques de carbono e nitrogênio no solo e para a produção de N2O e outros gases de efeito estufa. Diante do exposto e da grande importância, produtividade e extensão da Mata Atlântica, o presente estudo apresenta como objetivo principal investigar se as perdas de nitrogênio (N) pela emissão de N2O é um componente importante no ciclo do N na Mata Atlântica e se há uma variação nesses fluxos em relação às diferentes altitudes (100, 400 e 1000 m) e em relação a outros parâmetros (sazonalidade, temperatura, umidade do solo, dinâmica de produção e decomposição de serapilheira e raízes, e razão C:N da serapilheira). Não houve diferença na quantidade de chuva entre as áreas estudadas. A temperatura diminuiu com a altitude e foi significativamente mais baixa na altitude 1000 m. A umidade do solo determinada através dos espaços porosos do solo preenchidos por água diminuiu com a altitude. As áreas localizadas a 100 m apresentaram maior produção de serapilheira e entre as demais altitudes não houve diferença significativa na produção. Ao contrário da produção, o estoque de serapilheira e o tempo para decomposição também aumentou com as altitudes. O solo das parcelas localizados a 1000 m apresentaram biomassa de raízes vivas e mortas significativamente maior (P<0,05) e a razão C:N das raízes foi similar para todas as áreas. Os fluxos médios anuais encontrados para cada altitude durante o ano desta pesquisa foram: 3,2 kg-N ha-1 ano-1, 1,3 kg-N ha-1 ano-1 e 0,6 kg-N ha-1 ano-1 para as altitudes 100, 400 e 1000m, respectivamente. As emissões de N2O foram fortemente influenciadas pela umidade do solo e pela temperatura e diminuíram significativamente com a altitude. Os baixos fluxos de N2O a 1000 m são decorrentes da baixa disponibilidade de NO3- que viabiliza os processo de geração de N2O, que é produzido por desnitrificação.Com base nestes resultados, a Floresta de Mata Atlântica apresenta um ciclo de N mais conservador em relação às florestas da região Amazônica tanto pelas diferenças físico-químicas do solo como temperatura e regimes pluviométricos / Soils of tropical ecosystems are considered one of the major natural sources of nitrous oxide (N2O) to the atmosphere. Most of the N2O in soils is produced by two microbial processes, denitrification and nitrification. Litterfall and fine root dynamics are believed to contribute to the labile carbon (C) and nitrogen (N) and also contribute to the production greenhouse gases. According to these assumptions and regarding to the magnitude of the Brazilian Atlantic Forest this study aimed to investigate the losses of N by the emission of N2O along an altitudinal gradient and the relation between these fluxes and other climatic and edaphic parameters (precipitation, temperature, soil moisture, litterfall and fine roots dynamics). There was no difference in precipitation among the studied areas. Temperature and soil moisture decreased with altitude. Lower altitudes showed high litter production and low stock of soil litter. Root mass was significantly higher at altitude 1000m but root C:N ratio showed no difference among the altitudes. N2O annual soil fluxes were 3,2 kg-N ha-1yr-1, 1,3 kg-N ha-1yr-1, and 0,6 kg-N ha-1yr-1 at 100, 400 and 1000m, respectively. N2O fluxes were significantly influenced by soil moisture and temperature and decreased with altitude. Lower fluxes at 1000m are due to low NO3- availability and thus low N2O production. According to these results, The Atlantic Forest is considered to have a more conservative N cycle related to the Amazon forests due to the differences of soil chemical and physical properties and pluviometric conditions