No description available.

In explosive astrophysical environments such as novae, X-ray bursters and supernovae, conditions of extreme temperature and density are achieved. Under such conditions, both the rate of energy release and path of nucleosynthesis are governed by reactions on unstable nuclei. In this light, direct reaction studies using radioactive ion beams play a vital role in determining nuclear reaction rates. However, in the vast majority of cases, direct measurements are not possible and as such, indirect measurements are equally important for the understanding of the main reaction processes driving astrophysical events. In this thesis work, indirect studies of the astrophysically important 19Ne(p,γ)20Na and 29P(p,γ)30S reactions have been performed. For the first reaction, a β-delayed proton decay study of 20Mg was performed to gain information about the spin-parity assignment of the first key resonance above the proton emission threshold in the compound nucleus 20Na. This resonance is expected to dominate the 19Ne(p,γ)20Na reaction rate in explosive astrophysical environments and its identity has been under discussion for a long time, with J π = 1+ and 3+ assignments suggested. In the present study an upper limit on the β-decay branch to this state of 0.02% with a con dence level of 90% is reported. This is signi cantly more stringent than previous studies and makes a 1+ assignment highly unlikely, favouring instead a 3+ assignment. A 3+ assignment is predicted to have a signi cantly higher resonance strength and produce a proportionately higher 19Ne(p,γ)20Na reaction rate in X-ray burst conditions. The second study performed was a detailed gamma-ray spectroscopy study of the nucleus 30S. Excitation energies have been determined with improved precision over previous studies and the first,firm spin-parity assignments of key 29P + p resonant states, expected to dominate the 29P(p,γ)30S reaction in stellar scenarios, have been made. An evaluation of the 29P(pγ)30S reaction over the temperature range T = 0.06-2.5 GK shows that the 3+ and 2+ resonant states located at Er = 292.0(9) and 413.1(10) keV, respectively, dominate the 29P(p,γ)30S reaction rate in ONe novae, while the 413 keV resonance is expected to govern the rate in X-ray burster environments. These new, precise resonance energy measurements and firm spin-parity assignments have signi cantly reduced uncertainties in the 29P(p,γ)30S reaction in ONe novae and X-ray bursters. In particular, the reaction rate is now speci ed precisely enough for calculations of isotopic abundances in ONe novae ejecta.

Este trabalho apresenta as medidas das taxas de reação nuclear ao longo da direção radial da pastilha combustível por irradiação e posterior espectrometria gama de um fino disco de UO2 com enriquecimento de 4,3% no reator IPEN/MB- 01. A partir de sua irradiação, a taxa de captura radioativa e de fissão foram medidas em função do raio do disco utilizando um detector HPGe. Colimadores de chumbo foram utilizados para esse fim. O disco de UO2 é inserido no interior de uma vareta combustível desmontável e esta é então colocada na posição central do núcleo do reator IPEN/MB-01 e irradiada durante uma hora sob um fluxo de nêutrons de aproximadamente 9 x 108 n/cm2s. Na espectrometria gama, 10 colimadores com diâmetros diferentes foram utilizados, consequentemente, as reações nucleares de captura radioativa que ocorrem nos átomos de 238U e as fissões que ocorrem em ambos 235U e 238U são mensuradas em função de 10 regiões distintas do disco combustível. Correções de eficiência geométrica devido à introdução dos colimadores no sistema de detecção HPGe foram estimados usando o código MCNP-4C. Alguns valores calculados da taxa de reação nuclear de captura radioativa e fissão obtidos pela metodologia de Monte Carlo, utilizando o código MCNP-4C, são apresentados e comparados aos dados experimentais apresentando boa concordância. Além de taxas de reação nuclear, os índices espectrais 28ρ e 25δ foram obtidos para cada raio do disco combustível. / This work presents the measurements of the nuclear reaction rates along the radial direction of the fuel pellet by irradiation and posterior gamma spectrometry of a thin slice of fuel pellet of UO2 with 4,3% enrichment. From its irradiation the rate of radioactive capture and fission have been measured as a function of the radius of the pellet disk using a HPGe detector. Lead collimators has been used for this purpose. Simulating the fuel pellet in the pin fuel of the IPEN/MB-01 reactor, a thin UO2 disk is used. This disk is inserted in the interior of a dismountable fuel rod. This fuel rod is then placed in the central position of the IPEN/MB-01 reactor core and irradiated during 1 hour under a neutron flux of around 9 x 108 n/cm2s. For gamma spectrometry 10 collimators with different diameters have been used, consequently, the nuclear reactions of radioactive capture that occurs in atoms of 238U ans fissions that occur on both 235U and 238U are measured in function of 10 different region (diameter of collimator) of the fuel pellet disk. Corrections in the geometric efficiency due to introduction of collimators on HPGe detection system were estimated using photon transport of MCNP-4C code. Some calculated values of nuclear reaction rate of radioactive capture and fission along of the radial direction of the fuel pellet obtained by Monte Carlo methodology, using the MCNP-4C code, are presented and compared to the experimental data showing very good agreement. Besides nuclear reaction rates, the spectral indices 28ρ and 25δ have been obtained at each different radius of the fuel pellet disk.

Biological nutrient removal is used as an indicator of SBR performance at nine different SBRplants operated for a long period at low water temperatures (5 – 10oC). Typically needed aeratedSRT (Solids Residence Time) for complete nitrification is found to be in the range of 6 – 10 days.Biological phosphorus removal has been found to take place at 5oC. The specific nitrification and denitrification rates (g N/kg VSS/h) have been found to besubstantially higher than those found in design recommendations. At temperatures < 10 oC thenitrification rates have been found up to 4 g Nox/kg VSS/h. It has also been possible to establish a relation between the COD/N ratio and the nitrificationrate, showing that the rate increases to high rates when the ratio decreases. Enhanced biological phosphorus removal has been demonstrated at two different plants even atlow water temperatures 5 – 7 oC. Efficient biological nitrogen removal and phosphorus removal has been demonstrated at bothlow water temperatures and in presence of very high Chromium concentrations in inlet water, upto 20 mg Cr/l. The plants operated with a short fill time in comparison with the total cycle time for the SBRprocess have all demonstrated good sludge settling properties, suggesting that the SBR processmay incorporate a good sludge selection performance. Once a flexible operation strategy has been installed (in most cases through PLC systems) it hasbeen possible to meet load variations to maintain good treatment results. This has been found tobe true for most of the plants included in the thesis. Finally, a modified way to assess the energy efficiency for the system is analysed and suggested.Instead of using the traditional ratio kWh/kg BODremoved the use of kWh/kg OCPremoved as a basisfor energy efficiency is used as a far more relevant efficiency measurement. / QC 20100803

Este trabalho apresenta as medidas das taxas de reação nuclear ao longo da direção radial da pastilha combustível por irradiação e posterior espectrometria gama de um fino disco de UO2 com enriquecimento de 4,3% no reator IPEN/MB- 01. A partir de sua irradiação, a taxa de captura radioativa e de fissão foram medidas em função do raio do disco utilizando um detector HPGe. Colimadores de chumbo foram utilizados para esse fim. O disco de UO2 é inserido no interior de uma vareta combustível desmontável e esta é então colocada na posição central do núcleo do reator IPEN/MB-01 e irradiada durante uma hora sob um fluxo de nêutrons de aproximadamente 9 x 108 n/cm2s. Na espectrometria gama, 10 colimadores com diâmetros diferentes foram utilizados, consequentemente, as reações nucleares de captura radioativa que ocorrem nos átomos de 238U e as fissões que ocorrem em ambos 235U e 238U são mensuradas em função de 10 regiões distintas do disco combustível. Correções de eficiência geométrica devido à introdução dos colimadores no sistema de detecção HPGe foram estimados usando o código MCNP-4C. Alguns valores calculados da taxa de reação nuclear de captura radioativa e fissão obtidos pela metodologia de Monte Carlo, utilizando o código MCNP-4C, são apresentados e comparados aos dados experimentais apresentando boa concordância. Além de taxas de reação nuclear, os índices espectrais 28ρ e 25δ foram obtidos para cada raio do disco combustível. / This work presents the measurements of the nuclear reaction rates along the radial direction of the fuel pellet by irradiation and posterior gamma spectrometry of a thin slice of fuel pellet of UO2 with 4,3% enrichment. From its irradiation the rate of radioactive capture and fission have been measured as a function of the radius of the pellet disk using a HPGe detector. Lead collimators has been used for this purpose. Simulating the fuel pellet in the pin fuel of the IPEN/MB-01 reactor, a thin UO2 disk is used. This disk is inserted in the interior of a dismountable fuel rod. This fuel rod is then placed in the central position of the IPEN/MB-01 reactor core and irradiated during 1 hour under a neutron flux of around 9 x 108 n/cm2s. For gamma spectrometry 10 collimators with different diameters have been used, consequently, the nuclear reactions of radioactive capture that occurs in atoms of 238U ans fissions that occur on both 235U and 238U are measured in function of 10 different region (diameter of collimator) of the fuel pellet disk. Corrections in the geometric efficiency due to introduction of collimators on HPGe detection system were estimated using photon transport of MCNP-4C code. Some calculated values of nuclear reaction rate of radioactive capture and fission along of the radial direction of the fuel pellet obtained by Monte Carlo methodology, using the MCNP-4C code, are presented and compared to the experimental data showing very good agreement. Besides nuclear reaction rates, the spectral indices 28ρ and 25δ have been obtained at each different radius of the fuel pellet disk.

Water and other volatiles (e.g. CO2, H2, CH4, etc.) are crucial components on Earth that ensure the habitability of the planet and play an important role in many geological processes. Small aliquots of these fluids can be preserved in the geological record as fluid inclusions and can provide valuable information about the physical and chemical environment in which they formed. The ocean is the largest water reservoir on the Earth's surface, and seawater participates in important water-rock reactions such as hydrothermal alteration of the ocean floor, a process that is currently in the spotlight for hypotheses on the origin of life, as it is an environment where generation of abiotic carbohydrates occur. The ocean chemistry varied in the geologic past to reflect major changes in the intensity of weathering, rates of midocean ridge hydrothermal discharge, changes in the climate and atmospheric CO2 concentration, and also played an important part in mass extinction events. Understanding the history of Earth's ancient oceans may hold the key to answer some of the important questions about the future of the Earth. Today, oceans hold valuable resources, such as offshore basalt formations which have been considered for submarine CO2 sequestration to mitigate greenhouse gas emissions associated with global warming. In the chapters of this dissertation, the reader will be presented with studies using fluid inclusions to advance our knowledge about the chemical evolution of seawater and reaction kinetics involving CO2, seawater and olivine – an abundant mineral in the oceanic lithosphere. Chapter I "Redox conditions in Late Permian seawater based on trace element ratios in fluid inclusions in halite from the Polish Zechstein Basin" describes application of a new redox proxy for paleo-seawater that involves analysis of redox-sensitive trace elements (e.g., Fe, Mn, U, V, Mo) in ancient seawater trapped as fluid inclusions in halite. Chapter II "Partitioning behavior of trace elements during evaporation of seawater" investigates the behavior of trace elements during the evaporation of seawater. This information is required to interpret trace element data from fluid inclusions in halite. In Chapter III "In situ monitoring of the carbonation of olivine under conditions relevant to carbon capture and storage using synthetic fluid inclusion micro-reactors: Determination of reaction rates", fluid inclusions are used as micro-reactors to monitor the reaction progress of olivine carbonation in situ and in real time at elevated temperatures (50-200 °C) and pressures using non-destructive analytical techniques such as Raman spectroscopy. / Doctor of Philosophy / Many geological processes on Earth involve water and other volatiles (e.g. CO2, H2, CH4, etc.) which are crucial components that ensure the habitability of the planet. These fluids can be preserved in the geological record in the form of fluid inclusions which are small aliquots of fluids trapped in minerals that provide information about the physical and chemical environment in which they formed. The majority of water on the Earth's surface is stored in the oceans. Seawater participates in important water-rock reactions, one of which is the hydrothermal alteration of the ocean floor. This reaction is in the spotlight currently because it represents an environment where generation of abiotic carbohydrates occur, giving rise for hypotheses about the origin of life on Earth. The chemical composition of seawater varied in the geologic past reflecting major changes in the intensity of weathering, discharge rate of midocean ridge hydrothermal systems, climate, and atmospheric CO2 concentration, and affected the survival of various marine species throughout Earth's history. For example, periodic extensions of oxygen minimum zones in the oceans played an important part in mass extinction events in the last 488 million years. Understanding the history of Earth's ancient oceans may hold the key to answer some of the important questions about the future of the Earth. Today, oceans hold valuable resources, such as offshore basalt formations which have been considered for submarine CO2 sequestration to mitigate greenhouse gas emissions associated with global warming. This dissertation explores ways to use fluid inclusions to advance our knowledge about the chemical evolution of seawater in the past and present, and the reaction of seawater with CO2 and olivine – an abundant mineral in the oceanic lithosphere – to facilitate long-term storage of CO2 in minerals to decrease the rate of global warming. Chapter I describes the application of a new redox proxy for paleo-seawater that involves analysis of redox-sensitive trace elements (elements whose solubility changes significantly as the oxidation state changes, such as Fe, Mn, U, V, Mo) in ancient seawater trapped as fluid inclusions in halite. The results suggest that trace element abundances in fluid inclusions in halite vary in response to redox changes in seawater and provide a potential redox proxy. Chapter II investigates the behavior of trace elements during the evaporation of seawater. This information is required to interpret trace element data from fluid inclusions in halite. The results of this study indicate that some elements remain in the water during evaporation of seawater (e.g. Li, B, Mo, U), while others are partially removed by precipitation of various mineral phases (e.g. Ba, Sr, Cs, Rb, Mn, V) as seawater evaporates. In Chapter III, fluid inclusions are used as micro-reactors to monitor the reaction progress of olivine carbonation in situ and in real time at elevated temperatures (50-200 °C) and pressures using non-destructive analytical techniques such as Raman spectroscopy. The results highlight that this reaction occurs rapidly, which makes it an ideal candidate for safe storage of CO2 by commercial CO2 injection projects in mafic and ultramafic rocks.

Biodiesel use and production has significantly increased in the United States and in other parts of the world in the past decade. This change is driven by energy security and global climate legislation mandating reductions in the use of petroleum-based diesel. Recent air quality research has shown that emission of some pollutants such as CO, particulate matter (PM), SO2, hydrocarbons, and carcinogenic polycyclic aromatic hydrocarbons (PAHs) is greatly reduced with biodiesel. However, studies have also shown that some unregulated emissions, such as gas-phase carbonyls, are increased with biodiesel combustion. Very limited research has been done to investigate the particle-phase carbonyl and quinone emissions from biodiesel combustion. Also, very limited studies have investigated the ozone oxidation of biodiesel exhaust PM. Fatty acid methyl esters (FAMEs) are found in high abundance in biodiesel exhaust PM. The presence of these FAMEs in biodiesel exhaust PM can potentially alter the kinetics of the reactions between ozone and particle-phase PAHs. In this study, an Armfield CM-12 automotive light-duty diesel engine operated on a transient drive cycle was used to generate PM from various waste vegetable oil (WVO) and soybean biodiesel blends (containing 0%, (B00), 10% (B10), 20% (B20), 50% (B50), and 100% (B100) biodiesel by volume). The primary PM emissions were sampled using Teflon-coated fiberfilm filters. Laboratory PAHs, FAMEs, and B20 exhaust PM were exposed to ~0.4 ppm ozone for time periods ranging from 0-24 hours in order to study the effect of FAMEs and biodiesel exhaust PM on the ozonolysis of PAHs. Organic chemical analysis of samples was performed using gas chromatography/mass spectrometry (GC/MS). PAHs, carbonyls, FAMEs, and n-alkanes were quantified in the exhaust PM of petrodiesel, WVO and soybean fuel blends. The emission rates of the total PAHs in B10, B20, B50, and B100 exhaust PM decreased by 0.006-0.071 ng/µg (5-51%) compared to B00, while the emission rates for the FAMEs increased with increasing biodiesel content in the fuel. The emission rates of the total n-alkanes in B10, B20, B50, and B100 exhaust PM decreased by 0.5-21.3 ng/µg (4-86%) compared to B00 exhaust PM. The total emission rates of the aliphatic aldehydes in biodiesel exhaust PM (B10, B20, B50, and B100) increased by 0.019-2.485 ng/µg (36-4800%) compared to petrodiesel. The emission rates of the total aromatic aldehydes, total aromatic ketones, and total quinones all generally decreased with increasing biodiesel content in the fuel. With the exception of benzo[a]pyrene, the pseudo-first order ozone reaction rate constants of all the PAHs decreased by 1.2-8 times in the presence of the FAMEs. Phenanthrene, fluoranthene, and pyrene were the only PAHs detected in the B20 exhaust PM, and their ozone reaction rate constants were about 4 times lower than those obtained when the PAHs alone were exposed to ozone. The findings of this study indicate that there are both positive and negative effects to emissions associated with biodiesel use in light-duty diesel engines operating on transient drive cycle.

In recent years the nutrient levels of the Upper Floridan aquifer have been increasing (USGS, 2008). An example of this is found in Ocala, Florida where Silver Springs nitrate concentrations have risen from 0.5 mg/L in the 1960 s to approximately 1.0 mg/L in 2003 (Phelps, 2004). Because stormwater is a contributor to surficial and groundwater aquifer recharge, there is an increasing need for methods that decrease nitrogen and phosphorus levels. A laboratory column study was conducted to simulate a retention pond with saturated soil conditions. The objectives of the column studies reported in this thesis were to investigate the capabilities of a natural soil and soil augmentations to remove nitrogen and phosphorus for a range of concentrations at three different temperatures. An analytical attempt to model the columns through low order reaction kinetics and derive the corresponding temperature conversion constant to relate the rate constants is also presented. The Media Mixes were selected through a process of research, preliminary batch testing and then implemented in column studies. Three columns measuring three feet in length and 6 inches outer diameter were packed with a control and two media mixes. Media Mix 1 consisted of 50% fine sand, 30% tire crumb, 20% sawdust by weight and Media Mix 2 consisted of 50% fine sand, 25% sawdust, 15% tire crumb, 10% limestone by weight. The control column was packed with natural soil from Hunter s Trace retention pond located in Ocala, Florida. The reaction rates for nitrate are best modeled as first order for Media Mix 1, and zero order for the Control and Media Mix 2. The reaction rates for orthophosphate are best modeled as zero order, second order and first order for the Control, Media Mix 1, and Media Mix 2 respectively. The best overall media for both nitrate and orthophosphate removal from this study would be Media Mix 1. Media Mix 2 does have the highest average orthophosphate removal of all the mixes for all of the temperatures; however Media Mix 1 outperforms Mix 2 for the other two temperatures. The best column for Nitrate removal is the Media Mix 1 column. The temperature conversion factors for nitrate were found to be 1.11, 1.1, and 1.01 for Media Mix 1, the Control and Media Mix 2 respectively. The temperature conversion factors for orthophosphate were found to be 1.02, 0.99, and 0.95. As well as temperature conversion factors, the activation energies and frequency factors for the Arrhenius Equation were investigated. Average values corresponding to each column, species, and temperature would be inaccurate due to the large variation in calculated values.

The following dissertation is divided into two parts. Part I deals with the modeling of helium trapping at oxide-iron interfaces in nanostructured ferritic alloys (NFAs) using density functional theory (DFT). The modelling that has been performed serves to increase the knowledge and understanding of the theory underlying the prevention of helium embrittlement in materials. Although the focus is for nuclear reactor materials, the theory can be applied to any material that may be in an environment where helium embrittlement is of concern. In addition to an improved theoretical understanding of helium embrittlement, the following DFT models will provide valuable thermodynamic and kinetic information. This information can be utilized in the development of large-scale models (such as kinetic Monte Carlo simulations) of the microstructural evolution of reactor components. Accurate modelling is an essential tool for the development of new reactor materials, as experiments for components can span decades for the lifetime of the reactor. Part II of this dissertation deals with the development, and use of, kinetic Monte Carlo (KMC) simulations for improved efficiency in investigating catalytic chemical reactions on surfaces. An essential technique for the predictive development and discovery of catalysts relies on modelling of large-scale chemical reactions. This requires multi-scale modelling where a common sequence of techniques would require parameterization obtained from DFT, simulation of the chemical reactions for millions of conditions using KMC (requiring millions of separate simulations), and finally simulation of the large scale reactor environment using computational fluid dynamics. The tools that have been developed will aid in the predictive discovery, development and modelling of catalysts through the use of KMC simulations. The algorithms that have been developed are versatile and thus, they can be applied to nearly any KMC simulation that would seek to overcome similar challenges as those posed by investigating catalysis (such as the need for millions of simulations, long simulation time and large discrepancies in transition probabilities). / Ph. D.

A normative experimental study was undertaken to establish whether engaging in positive, negative, and neutral mental imagery affected the reaction rate of participants to positive, negative, and neutral word stimuli. The sample consisted of computer literate, English speaking participants with no history of clinical disorders. A total of 80 participants took part in the study, with 40 participants from either gender. The results of a factorial ANOVA indicated that the type of mental imagery engaged in had a significant effect on the rate at which participants responded to stimuli (p=.00023, F=8.4057), whilst the emotional valence of the stimuli did not have a significant effect (p=.30503, F=1.1877). However, the interaction between the type of mental imagery and the emotional valence of the stimuli was highly significant (p=.00794, F=3.4576), thereby indicating that engaging in positive or negative mental imagery did bias participants towards a faster reaction rate to positive or negative stimuli respectively. / M.A. (Psychology) / Psychology