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The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The …

Analytic calculations of the magnetic fields available to magnetic diagnostics are performed for tokamaks with circular and elliptical cross sections. The explicit dependence of the magnetic fields on the poloidal beta and internal inductances is sought. For tokamaks with circular cross sections, Shafranov`s results are reproduced and extended. To first order in the inverse aspect ratio expansion of the magnetic fields, only a specific combination of beta poloidal and internal inductance is found to be measurable. To second order in the expansion, the measurements of beta poloidal and the internal inductance are demonstrated to be separable but excessively sensitive to experimental error. For tokamaks with elliptical cross sections, magnetic measurements are found to determine beta poloidal and the internal inductance separately. A second harmonic component of the zeroth order field in combination with the dc harmonic of the zeroth order field specifies the internal inductance. The internal inductance in hand, measurement of the first order, first harmonic component of the magnetic field then determined beta poloidal. The degeneracy implicit in Shafranov`s result (i.e. that only a combination of beta poloidal and internal inductance is measurable for a circular plasma cross section) reasserts itself as the elliptic results are collapsed to …

This project will develop an analytical tool to calculate performance of HMX based PBXs in the skid test. The skid-test is used as a means to measure sensitivity for large charges in handling situations. Each series of skid tests requires dozens of drops of large billets. It is proposed that the reaction (or lack of one) of PBXs in the skid test is governed by the mechanical properties of the binder. If true, one might be able to develop an analytical tool to estimate skid test behavior for new PBX formulations. Others over the past 50 years have tried to develop similar models. This project will research and summarize the works of others and couple the work of 3 into an analytical tool that can be run on a PC to calculate drop height of HMX based PBXs. Detonation due to dropping a billet is argued to be a dynamic thermal event. To avoid detonation, the heat created due to friction at impact, must be conducted into the charge or the target faster than the chemical kinetics can create additional energy. The methodology will involve numerically solving the Frank-Kamenetskii equation in one dimension. The analytical problem needs to be bounded …

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The Main Injector Neutrino Oscillation Search (MINOS) is a long baseline neutrino oscillation experiment. The MINOS Far Detector, located in the Soudan Underground Laboratory in Soudan MN, has been collecting data since August 2003. The scope of this dissertation involves identifying the atmospheric neutrino induced muons that are created by the neutrinos interacting with the rock surrounding the detector cavern, performing a neutrino oscillation search by measuring the oscillation parameter values of {Delta}m{sub 23}{sup 2} and sin{sup 2} 2{theta}{sub 23}, and searching for CPT violation by measuring the charge ratio for the atmospheric neutrino induced muons. A series of selection cuts are applied to the data set in order to extract the neutrino induced muons. As a result, a total of 148 candidate events are selected. The oscillation search is performed by measuring the low to high muon momentum ratio in the data sample and comparing it to the same ratio in the Monte Carlo simulation in the absence of neutrino oscillation. The measured double ratios for the ''all events'' (A) and high resolution (HR) samples are R{sub A} = R{sub low/high}{sup data}/R{sub low/high}{sup MC} = 0.60{sub -0.10}{sup +0.11}(stat) {+-} 0.08(syst) and R{sub HR} = R{sub low/high}{sup data}/R{sub low/high}{sup MC} …

This document describes the measurements of the branching fractions and isospin violations of the radiative electroweak penguin decays B {yields} ({rho}/{omega}){gamma} at the asymmetric-energy e{sup +}e{sup -} PEP-II collider with the BABAR detector. Together with the previously measured branching fractions of the decays B {yields} K*{gamma} the ratio of CKM-matrix elements |V{sub td}/V{sub ts}| are extracted and the length of the far side of the unitarity triangle is determined.

Calculations of radiation flux and dose distributions for Boron Neutron Capture Therapy (BNCT) of brain tumors are typically performed using sophisticated three-dimensional analytical models based on either a homogeneous approximation or a simplified few-region approximation to the actual highly-heterogeneous geometry of the irradiation volume. Such models should be validated by comparison with calculations using detailed models in which all significant macroscopic tissue heterogeneities and geometric structures are explicitly represented as faithfully as possible. This work describes a validation exercise for BNCT of canine brain tumors. Geometric measurements of the canine anatomical structures of interest for this work were performed by dissecting and examining two essentially identical Labrador Retriever heads. Chemical analyses of various tissue samples taken during the dissections were conducted to obtain measurements of elemental compositions for tissues of interest. The resulting geometry and tissue composition data were then used to construct a detailed heterogeneous calculational model of the Labrador Retriever head. Calculations of three-dimensional radiation flux distributions pertinent to BNCT were performed for the model using the TORT discrete-ordinates radiation transport code. The calculations were repeated for a corresponding volume-weighted homogeneous tissue model. Comparison of the results showed that the peak neutron and photon flux magnitudes were quite …

Over the past couple of decades, the Standard Model of high energy particle physics has clearly established itself as an invaluable tool in the analysis of high energy particle phenomenon. However, from a field theorists point of view, there are many dissatisfying aspects to the model. One of these, is the large number of free parameters in the theory arising from the Yukawa couplings of the Higgs doublet. In this thesis, we examine various issues relating to the Yukawa coupeng structure of high energy particle field theories. We begin by examining extensions to the Standard Model of particle physics which contain additional scalar fields. By appealing to the flavor structure observed in the fermion mass and Kobayashi-Maskawa matrices, we propose a reasonable phenomenological parameterization of the new Yukawa couplings based on the concept of approximate flavor symmetries. It is shown that such a parameterization eliminates the need for discrete symmetries which limit the allowed couplings of the new scalars. New scalar particles which can mediate exotic flavor changing reactions can have masses as low as the weak scale. Next, we turn to the issue of neutrino mass matrices, where we examine a particular texture which leads to matter independent neutrino …

Inductively coupled plasma mass spectrometry (ICP-MS) has become the method of choice for elemental and isotopic analysis. Several factors contribute to its success. Modern instruments are capable of routine analysis at part per trillion levels with relative detection limits in part per quadrillion levels. Sensitivities in these instruments can be as high as 200 million counts per second per part per million with linear dynamic ranges up to eight orders of magnitude. With standards for only a few elements, rapid semiquantitative analysis of over 70 elements in an individual sample can be performed. Less than 20 years after its inception ICP-MS has shown to be applicable to several areas of science. These include geochemistry, the nuclear industry, environmental chemistry, clinical chemistry, the semiconductor industry, and forensic chemistry. In this introduction, the general attributes of ICP-MS will be discussed in terms of instrumentation and sample introduction. The advantages and disadvantages of current systems are presented. A detailed description of one method of sample introduction, laser ablation, is given. The paper also gives conclusions and suggestions for future work. Chapter 2, Quantitative analysis of solids by laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for calibration, has been removed …

Addition of a novel anionic surfactant, namely lauryl polyoxyethylene sulfate, to an aqueous-acetonitrile electrolyte makes it possible to separate nonionic organic compounds by capillary electrophoresis. Separation is based on differences in the association between analytes and the surfactant. Highly hydrophobic compounds such as polyaromatic hydrocarbons are well separated by this new surfactant. Migration times of analytes can be readily changed over an unusually large range by varying the additive concentration and the proportion of acetonitrile in the electrolyte. Several examples are given, including the separation of four methylbenz[a]anthracene isomers and the separation of normal and deuterated acetophenone. The effect of adding this new surfactant to the acidic electrolyte was also investigated. Incorporation of cetyltrimethylammonium bromide in the electrolyte is shown to dynamically coat the capillary and reverse electroosmotic flow. Chiral recognition mechanism is studied using novel synthetic surfactants as chiral selectors, which are made from amino acids reacting with alkyl chloroformates. A satisfactory separation of both inorganic and organic anions is obtained using electrolyte solutions as high as 5 M sodium chloride using direct photometric detection. The effect of various salts on electrophoretic and electroosmotic mobility is further discussed. Several examples are given under high-salt conditions.

The peak profile of individual degranulation events from the on-column release of serotonin from single rat peritoneal mast cells (RPMCs) was monitored using capillary electrophoresis with laser-induced native fluorescence detection (CE-LINF). Serotonin, an important biogenic amine, is contained in granules (0.25 fL) within RPMCs and is extruded by a process termed exocytosis. The secretagogue, Polymyxin B sulfate, was used as the CE running buffer after injection of a single RPMC into the separation capillary to stimulate the release of the granules. Because the release process occurs on a ms time scale, monitoring individual exocytotic events is possible with the coupling of high-speed CE and LINF detection.

Catalytic reactions of solvent refined coal (SRC) were studied using mixed metal oxide and low melting Lewis acid catalysts in extracting solvent media. From characterization of the benzene- and cyclohexane-soluble products, ZnCl/sub 2/ and SnCl/sub 2/ were determined to be the most effective at hydrogenating and solubilizing SRC while assisting in heteroatom removal. ZnCl/sub 2/ and SnCl/sub 2/ were also found to be more effective at producing oil-like products rather than alphaltene-like products. Further enhancement of the solubilization of SRC could be achieved by the addition of isopropanol to the Lewis acid-substrate-solvent reaction mixture. Dry HCl was also investigated for its effect on the solubilization of SRC. Characterization of the solubilized products and residues was performed by elemental analysis, /sup 1/H-NMR, and gel permeation chromatography. Investigations were performed to determine what effect reaction temperature, hydrogen pressure, and catalyst loading had on the yield of soluble products as well as the chemical analyses of the products. The results showed that the conversion of SRC to soluble products increases monotonically with hydrogen pressure and catalyst loading. The effect of temperature is not as straightforward.

This research explores the application of a new technique, termed electrochemically modulated liquid chromatography (EMLC), to the chiral separations of pharmaceutical compounds. The introduction section provides a literature review of the technique and its applications, as well as brief overview of the research described in each of the next two chapters. Chapter 2 investigates the EMLC-based enantiomeric separation of a group of chiral benzodiazepines with {beta}-cyclodextrin as a chiral mobile phase additive. Chapter 3 demonstrates the effects of several experimental parameters on the separation efficiency of drug enantiomers. The author concludes with a general summary and possible directions for future studies. Chapters 2 and 3 are processed separately.

This report summarized the four parts of the research study and describes the general conclusions. Individual chapters have been removed for separate processing. The chapter titles are: A study of the dissociation of CH{sub 3}SH{sup +} by collisional activation: Observation of non-statistical behavior; High resolution vacuum ultraviolet pulsed field ionization photoelectron band for OCS{sup +}(X{sup 2}{Pi}): An experimental and theoretical study; Rotationally resolved pulsed field ionization photoelectron bands of H{sub 2}{sup +} ({Chi}{sup 2}{Sigma}{sup +}{sub g}, v{sup +} = 0--18); and Rotationally resolved pulsed field ionization photoelectron bands of HD{sup +} ({Chi}{sup 2}{Sigma}{sup +}, v{sup +} = 0--21).

Numerical studies of the linear and nonlinear evolution of magnetic tearing type modes in three-dimensional toroidal geometry are presented. In addition to traditional resistive MHD effects, where the parameter {Delta}{prime} determines the stability properties, neoclassical effects have been included for the first time in such models. The inclusion of neoclassical physics introduces and additional free-energy source for the nonlinear formation of magnetic islands through the effects of a bootstrap current in Ohm`s law. The neoclassical tearing mode is demonstrated to be destabilized in plasmas which are otherwise {Delta}{prime} stable, albeit once an island width threshold is exceeded. The simulations are based on a set of neoclassical reduced magnetohydrodynamic (MHD) equations in three-dimensional toroidal geometry derived from the two-fluid equations in the limit of small inverse aspect ratio {epsilon} and low plasma pressure {beta} with neoclassical closures for the viscous force {del} {center_dot} {leftrightarrow}{pi}. The poloidal magnetic flux {psi}, the toroidal vorticity {omega}{sup {zeta}}, and the plasma pressure p are time advanced using the parallel projection of Ohm`s law, the toroidal projection of the curl of the momentum equation, and a pressure evolution equation with anisotropic pressure transport parallel to and across magnetic field lines. The equations are implemented in an …

The MINOS Far Detector is a 5400 ton iron calorimeter located at the Soudan state park in Soudan Minnesota. The MINOS far detector can observe atmospheric neutrinos and separate charge current {nu}{sub {mu}} and {bar {nu}}{sub {mu}} interactions by using a 1.4 T magnetic field to identify the charge of the produced muon. The CPT theorem requires that neutrinos and anti-neutrinos oscillate in the same way. In a fiducial exposure of 5.0 kilo-ton years a total of 41 candidate neutrino events are observed with an expectation of 53.1 {+-} 7.6(system.) {+-} 7.2(stat.) unoscillated events or 31.6 {+-} 4.7(system.) {+-} 5.6(stat.) events with {Delta}m{sup 2} = 2.4 x 10{sup -3} eV{sup 2}, sin{sup 2}(2{theta}) = 1.0 as oscillation parameters. These include 28 events which can have there charge identified with high confidence. These 28 events consist of 18 events consistent with being produced by {nu}{sub {mu}} and 10 events being consistent with being produced by {bar {nu}}{sub {mu}}. No evidence of CPT violation is observed.

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An electron beam generated plasma reactor (EBGPR) is used to determine the plasma chemistry kinetics, energetics and decomposition pathways of six chlorinated ethylenes and ethanes: 1,1,1-trichloroethane, 1,1-dichloroethane, ethyl chloride, trichloroethylene, 1,1-dichloroethylene, and vinyl chloride. A traditional chemical kinetic and chemical engineering analysis of the data from the EBGPR is performed, and the following hypothesis was verified: The specific energy required for chlorinated VOC decomposition in the electron beam generated plasma reactor is determined by the electron attachment coefficient of the VOC and the susceptibility of the molecule to radical attack. The technology was demonstrated at the Hanford Reservation to remove VOCs from soils.

Thesis. Delayed neutron characteristics of six fission product nuclides were determined using a mass separator operated on-line with a nuclear reactor. Beta-decay half-lives were- measured using neutron multiscaling techniques for the precursors /sup 88/Br, /sup 89/Br, /sup 98/Kr, /sup 93/Kr, /sup 137/I, and / sup 138/I. The observed half-lives were 16.52 plus or minus .17 seconds, respectively.. Energy spectra were measured for delayed neutrons emitted in the beta-decays of /sup 17/N, /sup 137/I, /sup 93/Kr , and /sup 93/Rb. The spectra of neutron emissions in the mass 93 parentdaughter decay chain were observed using a moving tape collector to effect isobaric separation. Two different types of /sup 3/He- filled neutron spectrometer were used to determine the spectra; a proportional counter with risetime discrimination electronics, and a high resolution ionization chamber. The measured delayed, neutron spectra using both detector types are presented, and the results compared, where possible, with other reported measurements. (auth)

ALS Bending magnet beamline 9.3.2 is for high resolution spectroscopy, with circularly polarized light. Fixed included-angle SGM uses three gratings for 30--1500 eV photons; circular polarization is produced by an aperture for selecting the beam above or below the horizontal plane. Photocurrent from upper and lower jaws of entrance slit sets a piezoelectric drive feedback loop on the vertically deflecting mirror for stable beam. End station has a movable platform. With photomeission data from Stanford, structure of c(2{times}2)P/Fe(100) was determined using angle-resolved photoemission extended fine structure (ARPEFS). Multiple-scattering spherical-wave (MSSW) calculations indicate that P atoms adsorb in fourfold hollow sites 1.02A above the first Fe layer. Self-consistent-field X{alpha} scattered wave calculation confirm that the Fe{sub 1}-Fe{sub 2} space is contracted for S/Fe but not for P/Fe; comparison is made to atomic N and O on Fe(100). Final-state effects on ARPEFS curves used literature data from the S 1s and 2p core levels of c(2{times}2)S/Ni(001); a generalized Ramsauer-Townsend splitting is present in the 1s but not 2p data. An approximate method for analyzing ARPEFS data from a non-s initial state using only the higher-{ell} partial wave was tested successfully. ARPEFS data from clean surfaces were collected normal to Ni(111) (3p core …

With the ever increasing awareness of the toxicity of Pb, significant pressure has been put on the electronics industry to get the Pb out of solder. This work pertains to the development and characterization of an alloy which is Pb-free, yet retains the proven positive qualities of current Sn-Pb solders while enhancing the shortcomings of Sn-Pb solder. The solder studied is the Sn-4.7Ag-1.7Cu wt% alloy. By utilizing a variety of experimental techniques the alloy was characterized. The alloy has a melting temperature of 217{degrees}C and exhibits eutectic melting behavior. The solder was examined by subjecting to different annealing schedules and examining the microstructural stability. The effect of cooling rate on the microstructure of the solder was also examined. Overall, this solder alloy shows great promise as a viable alternative to Pb-bearing solders and, as such, an application for a patent has been filed.

Thesis. The development of a directional high energy (20 to 160 MeV) neutron detector which was flown to satellite altitudes (500 km; circular equatorial orbit) in the NASA Orbiting Solar Observatory (OSO-6) in August 1969 is described. Both the angle of incidence and the energy of the neutron are determined by a proton-recoil telescope (Pilot B scintillation plastic) which provides the source for proton-recoils and defines the dE/dX versus E method for particle identification and energy determination. The telescope is embedded in a scintillation plastic guard counter envelope which eliminates the unwanted charged particle background as well as recoil protons (electrons) whose energies and direction do not satisfy neutron (gamma-ray) detection requirements, respectively. Results from a Monte Carlo calculation indicate that the overall average efficiency within an average angular acceptance of about 29 deg (FWHM) is approximately (2.25 plus or minus 0.113) x 10/sup -4/. The inflight calibration procedure, the main frame data bit error analysis, and the method for determining the orientation of the detector axis in the spacecraft spin plane are described. Results indicate a discrepancy in the measured (0.461 x 10/sup -2/ plus or minus 0.254 x 10/sup -2/ n/cm/sup 2/sec) and theoretical (2 to 70 n/cm/ …

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