Radon in indoor air may cause the exposure of the public to excessive radioactivity. Radiolysis of water vapor in indoor air due to radon decay could produce ({center_dot}OH and HO{sub 2} {center_dot}) that may convert atmospheric constituents to compounds of lower vapor pressure. These lower vapor pressure compounds might then nucleate to form new particles in the indoor atmosphere. Chemical amplification was used to determine HO{sub x}{center_dot} production rate in indoor air caused by radon decay. Average HO{sub x}{center_dot} production rate was found to be (4.31{plus_minus}0.07) {times} 10{sup 5} HO{sub x}{center_dot} per Rn decay per second (Bq) 3.4 to 55.0% at 22C. This work provided G{sub (HO{sub x}{center_dot})}-value, 7.86{plus_minus}0.13 No./100 eV in air by directly measuring [HO{sub x}{center_dot}] formed from the radiolysis procedure. This G value implies that HO{sub x}{center_dot} produced by radon decay in air might be formed by multiple processes and may be result of positive ion-molecule reactions, primary radiolysis, and radical reactions. There is no obvious relation between HO{sub x}{center_dot} production rate and relative humidity. A laser-induced fluorescence (LIF) system has been used for {center_dot}OH production rate measurement; it consists of an excimer laser, a dye laser, a frequency doubler, a gaseous fluorescence chamber, and other optical …

Analysis of the literature indicated that radon transport models significantly and consistently underpredict the advective entry into houses of soil-gas borne radon. Advective entry is the dominant mechanism resulting in high concentrations of radon indoors. My dissertation research investigated the source of the model-measurement discrepancy via carefully controlled field experiments conducted at an experimental basement located in natural soil in Ben Lomond, California. Early experiments at the structure confirmed the existence and magnitude of the model-measurement discrepancy, ensuring that it was not merely an artifact of inherently complex and poorly understood field sites. The measured soil-gas entry rate during structure depressurization was found to be an order of magnitude larger than predicted by a current three-dimensional numerical model of radon transport. The exact magnitude of the discrepancy depends on whether the arithmetic or geometric mean of the small-scale measurements of permeability is used to estimate the effective permeability of the soil. This factor is a critical empirical input to the model and was determined for the Ben Lomond site in the typical fashion using single-probe static depressorization measurements at multiple locations. The remainder of the dissertation research tests a hypothesis to explain the observed discrepancy: That soil permeability assessed using …

In the past multiple-quantum filtered imaging of biexponential relaxation sodium-23 nuclei in the human brain has been limited by low signal to noise ratios; this thesis demonstrates that such imaging is feasible when using a modified gradient-selected triple-quantum filter at a repetition time which maximizes the signal to noise ratio. Nuclear magnetic resonance imaging of biexponential relaxation sodium-23 ({sup 23}Na) nuclei in the human brain may be useful for detecting ischemia, cancer, and pathophysiology related to manic-depression. Conventional single-quantum NMR imaging of in vivo biexponential relaxation {sup 23}Na signals is complicated by the presence of single-exponential relaxation {sup 23}Na signals. Multiple-quantum filters may be used to selectively image biexponential relaxation {sup 23}Na signals since these filters suppress single-exponential relaxation {sup 23}Na signals. In this thesis, the typical repetition times (200--300 ms) used for in vivo multiple-quantum filtered {sup 23}Na experiments are shown to be approximately 5 times greater than the optimal repetition time which maximizes multiple-quantum filtered SNR. Calculations and experimental verification show that the gradient-selected triple-quantum (GS3Q) filtered SNR for {sup 23}Na in a 4% agarose gel increases by a factor of two as the repetition time decreases from 300 ms to 55 ms. The measured relaxation times of …

The Mirrortron is a concept in which heavy ions are accelerated by a large local transient space potential that is produced in a hot electron plasma. The purpose of this experiment is to begin a proof of principle experiment to investigate the feasibility of producing this space potential and its associated electric field. If a large magnetic field is suddenly generated in a hot electron plasma with a loss-cone distribution, then potentials on the order of the electron temperature are expected. This potential lasts a few tens of nanoseconds. The investigation begins with a theoretical analysis of this phenomenon giving the space potential as a function of the applied magnetic field. The theory is further extended to cases of relativistic electron distributions. This is then followed by design work on a mirror confinement system for hot electrons. In this experiment a 50--100 keV electron temperature plasma is created with electron cyclotron resonance heating using two frequencies of relatively low microwave power. The microwaves are coupled to resonant frequencies of the vacuum chamber. The volume averaged plasma density is measured to be in the 10{sup 9} cm{sup {minus}3} range. A strap coil and a flat Blumlein transmission line pulse generator were …

The Resource Conservation and Recovery Act (RCRA) of 1976 and its subsequent amendments have had a dramatic impact on hazardous waste management for business and industry. The complexity of this law and the penalties for noncompliance have made it one of the most challenging regulatory programs undertaken by the Environmental Protection Agency (EPA). The fundamentals of RCRA include ``cradle to grave`` management of hazardous waste, covering generators, transporters, and treatment, storage, and disposal facilities. The regulations also address extensive definitions and listing/identification mechanisms for hazardous waste along with a tracking system. Treatment is favored over disposal and emphasis is on ``front-end`` treatment such as waste minimization and pollution prevention. A study of large corporations such as Xerox, 3M, and Dow Chemical, as well as the public sector, has shown that well known and successful hazardous waste management programs emphasize pollution prevention and employment of techniques such as proactive environmental management, environmentally conscious manufacturing, and source reduction. Nearly all successful hazardous waste programs include some aspects of Total Quality Management, which begins with a strong commitment from top management. Hazardous waste management at the Rocky Flats Plant is further complicated by the dominance of ``mixed waste`` at the facility. The mixed …

The EQCM was used to study the deposition and composition of electrodeposited pure PbO{sub 2} and Bi-doped PbO{sub 2} active toward anodic oxygen-transfer reactions. Within the doped films, Bi is incorporated as Bi{sup +5} in the form of BiO{sub 2}A, where A is ClO{sub 4}{sup {minus}} or NO{sub 3}{sup {minus}}. For deposition of these 2 materials, changes in hydration between the Au oxide and the depositing film resulted in higher mass-to-charge ratios. XRD and XPS were used to study the films; the rutile structure of PbO{sub 2} is retained even with the Bi doping. The EQCM was also used to study the formation and dissolution of Au oxide and preoxide structures formed on the Au substrate electrodes in acidic media. The preoxide structures were AuOH and increased the surface mass. For the formation of stable Au films on quartz wafers, Ti interlayers between Au and quartz was found to be very effective.

Near-edge soft x-ray photoionization spectra were measured for CO, SF{sub 6}, H{sub 2}S, and D{sub 2}S in the gas phase, using the Free University of Berlin plane-grating SX-700-II monochromator at the synchrotron radiation source BESSY. Photoionization spectra of carbon monoxide were measured near the carbon and oxygen K edges. Vibrational spacings and bond lengths are derived for several resonances. Results are consistent with equivalent-core model and indicate the different influences of the carbon and oxygen Is core holes. Corresponding spectra of H{sub 2}CO and D{sub 2}CO were also measured. Assignment of complex vibrational structure in valence-shell and Rydberg resonances is facilitated by comparison of spectra for the two isotopic species. Geometric and vibrational parameters are derived for several carbon 1s core-excited states. Isotopic shifts are observed in the energies and linewidths of some core-excited states. Sulfur hexafluoride photoionization spectra, measured near the sulfur L{sub 2,3} edges, show several series of weak, narrow Rydberg resonances. High resolution and good counting statistics allow a complete assignment of these states. Lineshapes of the broad inner-well resonances are analyzed to establish the magnitudes of vibrational and lifetime broadening in these states. Spectra of the H{sub 2}S and D{sub 2}S molecules were also measured near …

Theoretical electronic structure techniques are used to analyze widely different systems from Si clusters to transition metal solids and surfaces. For the Si clusters, first principles density functional methods are used to investigate Si{sub N} for N=2-8. Goal is to understand the different types of bonding that can occur in such small clusters where the atomic coordination differs substantially from tetrahedral bonding; such uncoordinated structures can test approximate models of Si surfaces. For the transition metal systems, non-self-consistent electronic structure methods are used to understand the driving force for surface relaxations. In-depth analysis of results is presented and physical basis of surface relaxation within the theory is discussed. Limitations inherent in calculations of metal surface relaxation are addressed. Finally, in an effort to understand approximate methods, a novel non-self- consistent density functional electronic structure method is developed that is about 1000 times faster than more sophisticated methods; this method is tested for various systems including diatomics, mixed clusters, surfaces, and bulk lattices.

This dissertation contains results of research conducted in two different areas: (1) organometallic synthesis and reactivity, and (2) organometallic surface chemistry. In the synthesis and reactivity studies, sulfur coordination of thiophene and benzo[b]thiophene to the metal center in organometallic rhenium complexes is examined. In the surface chemistry studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to analyze the adsorption of several isocyanides on the surface of gold powder. Results are compared and contrasted to known organometallic chemistry.

As the field of computational fluid dynamics (CFD) continues to mature, algorithms are required to exploit the most recent advances in approximation theory, numerical mathematics, computing architectures, and hardware. Meeting this requirement is particularly challenging in incompressible fluid mechanics, where primitive-variable CFD formulations that are robust, while also accurate and efficient in three dimensions, remain an elusive goal. This dissertation asserts that one key to accomplishing this goal is recognition of the dual role assumed by the pressure, i.e., a mechanism for instantaneously enforcing conservation of mass and a force in the mechanical balance law for conservation of momentum. Proving this assertion has motivated the development of a new, primitive-variable, incompressible, CFD algorithm called the Continuity Constraint Method (CCM). The theoretical basis for the CCM consists of a finite-element spatial semi-discretization of a Galerkin weak statement, equal-order interpolation for all state-variables, a 0-implicit time-integration scheme, and a quasi-Newton iterative procedure extended by a Taylor Weak Statement (TWS) formulation for dispersion error control. Original contributions to algorithmic theory include: (a) formulation of the unsteady evolution of the divergence error, (b) investigation of the role of non-smoothness in the discretized continuity-constraint function, (c) development of a uniformly H{sup 1} Galerkin weak statement …

Goal was to study effect of power level and distribution on thermocapiilary-induced weld shape and of arc factors on weld shape. Thermocapillarity was apparent in both conduction mode EB welds and GTA welds, particularly in the former. A non-Gaussian arc distribution is suggested for accounting for the differences between the twoss processes. At higher current levels (200--300 A), plasma shear force also contributes to weld shape development. Evidence suggests that thermocapillary flow reversal is not a factor in normal GTA welds; EDB flow reversal occurs only at high power density levels where the keyhole mode is present.

Gamma-ray excited emission spectrum, absolute scintillation yield, rise and decay time constants, and thermoluminescence emissions of CsI(Tl) were measured at {minus}100 to +50 C, for crystals from 4 different vendors. The thermoluminescence glow curves were the only property that varied significantly from crystal to crystal; room temperature operation in current mode could be susceptible to temperature fluctuations. The CsI(Tl) emission spectrum has emission bands peaking around 400 and 560 nm; the former band disappears between {minus}50 and {minus}75 C. The RT absolute scintillation yield was calculated to be 65,500{plus_minus}4,100 photons/MeV. The two primary decay time constants increases about exponentially with inverse temperature. An ultra-fast decay component was confirmed. Applications are discussed.

Replicate column experiments were done to quantify the effects of temperature and bacterial motility on advective transport through repacked, but otherwise unaltered, natural aquifer sediment. The bacteria used in this study, A0500, was a flagellated, spore-forming rod isolated from the deep subsurface at DOE`s Savannah River Laboratory. Motility was controlled by turning on flagellar metabolism at 18{degrees}C but off at 40{degrees}C. Microspheres were used to independently quantify the effects of temperature on the sticking efficiency ({alpha}), estimated using a steady-state filtration model. The observed greater microsphere removal at the higher temperature agreed with the physical-chemical model, but bacteria removal at 18{degrees}C was only half that at 4{degrees}C. The sticking efficiency for non-motile A0500 (4{degrees}C) was over three times that of the motile A0500 (18{degrees}C), 0.073 versus 0.022 respectively. Analysis of complete breakthrough curves using a non-steady, kinetically limited, transport model to estimate the time scales of attachment and detachment suggested that motile A 0500 bacteria traveled twice as far as non-motile A 0500 bacteria before becoming attached. Once attached, non-motile colloids detached on the time scale of 9 to 17 days. The time scale for detachment of motile A0500 bacteria was shorter, 4 to 5 days. Results indicate that bacterial …

This technique worked well for determining the thickness and densities for composite components having the higher linear attenuation coefficient; it accurately determined thickness of epoxy-resin and Al metal, and the denisty of bone, to {le} 4% in the graphite-epoxy, bone-plexiglas, and Al-Al corrosion composites. Accuracy is dictated by the magnitude and uncertainty of the linear attenuation coefficient. Use of Ge detector and multichannel analyzer are limited by inspection time (1 day for point measurement) and access limitation. Immediate development of a rapid in-service inspection tool is limited by the amplifier and MCA systems. The MCA should be replaced with a single-channel analyzer, and an electronic device should be built for monitoring the incoming signal for Pile-Up-Rejection.

The melting and solidification was studied using in-situ high temperature XRD from melting point to 900{degree}C in 0.2, 0.1, 0.02 atm O{sub 2} and pure N{sub 2}. The incongruent melting point of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} was lowered by decreasing the partial O{sub 2} pressure from 870C (in .2 atm O{sub 2}) to 830C (in pure N{sub 2} atmosphere). As temperature was increased the incongruent melting of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} followed a phase sequence in which (Ca, Sr)CuO{sub 2} {r_arrow} (Ca, Sr)CuO{sub 2} {r_arrow} (Ca,Sr)O occur in presence of Bi-rich liquid. At 900C, the only crystalline phase present in the melt was (Ca,Sr)O. This phase sequence remained the same for all four different partial O{sub 2} pressures. During the solidification of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, from 10C below the melting point to 760C, the major phases that form depend on the partial O{sub 2} pressure. As partial O{sub 2} pressures was lowered from 0.2 to 0 atm, the major second phase formation out of the melt follows the sequence of (Ca, Sr)CuO{sub 2} {r_arrow} (Ca, Sr)CuO{sub 2} {r_arrow} (Ca,Sr)O respectively. At 0.1 Atm partial O{sub 2} pressure and below, Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} solidified out …

Preparation, characterization, and reactivity of ({eta}{sup 2}- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The {eta}{sup 2}- alkyne complexes are prepared by reaction of (TTP)TiCl{sub 2} with LiAlH{sub 4} in presence of alkyne. Structure of (OEP)Ti({eta}{sup 2}-Ph-C{triple_bond}C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline){sub 2} was also determined by XRD. Reaction of (TTP)Ti{double_bond}O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl{sub 2} is reacted with (OEP)Ti{double_bond}O.

The majority of this research has been in developing a model to describe the magnetostrictive properties of Terfenol-D, Tb{sub 1{minus}x}Dy{sub x}Fe{sub y} (x = 0.7-0.75 and y = 1.8--2.0), a rare earth-iron alloy which displays much promise for use in device applications. In the first chapter an introduction is given to the phenomena of magnetization and magnetostriction. The magnetic processes responsible for the observed magnetic properties of materials are explained. An overview is presented of the magnetic properties of rare earths, and more specifically the magnetic properties of Terfenol-D. In the second chapter, experimental results are presented on three composition of Tb{sub 1{minus}x}Dy{sub x}Fe{sub y} with x = 0.7, y= 1.9, 1.95, and x= 0.73, y= 1.95. The data were taken for various levels of prestress to show the effects of composition and microstructure on the magnetic and magnetostrictive properties of Terfenol-D. In the third chapter, a theoretical model is developed based on the rotation of magnetic domains. The model is used to explain the magnetic and magnetostrictive properties of Terfenol-D, including the observed negative strictions and large change in strain. The fourth chapter goes on to examine the magnetic properties of Terfenol-D along different crystallographic orientations. In the fifth …

A desolvation scheme for introducing aqueous and organic samples into an argon inductively coupled plasma is described; the aerosol generated by nebulizer is heated (+140 C) and cooled ({minus}80 C) repeatedly, and the dried aerosol is then injected into the mass spectrometer. Polyatomic ions are greatly suppressed. This scheme was validated with analysis of seawater and urine reference samples. Finally, the removal of organic solvents by cryogenic desolvation was studied.

Ferrocenocyclobutene is prepared by flash vacuum pyrolysis (FVP) of the N-amino-2-phenylaziridine hydrazone of 2-methylferrocenealdehyde. In the second section of this dissertation, a series of hydrocarbon rearrangements were observed. FVP of o-allyltoluene at 0.1 Torr (700--900 C) gives 2-methylindan and indene, accompanied by o-propenyltoluene. FVP of 2-methyl-2`-vinylbiphenyl gives 9-methyl-9,10-dihydrophenanthrene, which fits the proposed mechanism. However, FVP of 2-(o-methylbenzyl)styrene gives mainly anthracene and 1-methylanthracene. This cyclization reaction was also successful with o-allylphenol and o-(2-methylallyl)phenol.

BaF{sub 2} has the advantage over other scintillators, when comparing radiation hardness, scintillation decay time, and fast scintillation yield. Since the fast BaF{sub 2} emissions have peak wavelengths of 220, 195, and 170 nm, a wavelength shifter (WLS) is needed. Organic fluors were evaluated as WLS components. Results indicate that spectral separation using WLS is possible, but not to the extent desired; other techniques must be used also. Alternative scintillators, such as CeF{sub 3}, should be investigated.

Hale and Cohen (1991) developed software to generate two-dimensional computer models of complex geology. Their method uses a triangulation technique designed to support efficient and accurate computation of seismic wavefields for models of the earth`s interior. Subsequently, Hale (1991) used this triangulation approach to perform dynamic ray tracing and create synthetic seismograms based on the method of Gaussian beams. Here, I extend this methodology to allow an increased variety of ray-theoretical experiments. Specifically, the developed program GBmod (Gaussian Beam MODeling) can produce arbitrary multiple sequences and incorporate attenuation and density variations. In addition, I have added an option to perform Fresnel-volume ray tracing (Cerveny and Soares, 1992). Corrections for reflection and transmission losses at interfaces, and for two-and-one-half-dimensional (2.5-D) spreading are included. However, despite these enhancements, difficulties remain in attempts to compute accurate synthetic seismograms if strong lateral velocity inhomogeneities are present. Here, these problems are discussed and, to a certain extent, reduced. I provide example computations of high-frequency seismograms based on the method of Gaussian beams to exhibit the advantages and disadvantages of the proposed modeling method and illustrate new features for both surface and vertical seismic profiling (VSP) acquisition geometries.

In this dissertation the possibility that chaos and simple determinism are governing the dynamics of reversed field pinch (RFP) plasmas is investigated. To properly assess this possibility, data from both numerical simulations and experiment are analyzed. A large repertoire of nonlinear analysis techniques is used to identify low dimensional chaos in the data. These tools include phase portraits and Poincare sections, correlation dimension, the spectrum of Lyapunov exponents and short term predictability. In addition, nonlinear noise reduction techniques are applied to the experimental data in an attempt to extract any underlying deterministic dynamics. Two model systems are used to simulate the plasma dynamics. These are the DEBS code, which models global RFP dynamics, and the dissipative trapped electron mode (DTEM) model, which models drift wave turbulence. Data from both simulations show strong indications of low dimensional chaos and simple determinism. Experimental date were obtained from the Madison Symmetric Torus RFP and consist of a wide array of both global and local diagnostic signals. None of the signals shows any indication of low dimensional chaos or low simple determinism. Moreover, most of the analysis tools indicate the experimental system is very high dimensional with properties similar to noise. Nonlinear noise reduction …

It is shown with resistivity and near-IR absorption measurements that NiI{sub 2}, CoI{sub 2}, and FeI{sub 2} metallize under pressure by closure of the charge-transfer energy gap at pressures of 17, 10, and 23 GPa, respectively, which is close to the antiferromagnetic-diamagnetic transition in NiI{sub 2} and CoI{sub 2}. Thus, the magnetic transitions probably are caused by the metallization; in NiI{sub 2} and CoI{sub 2}, the insulator-metal transitions are first order. Moessbauer and XRD data were also collected. Figs, 46 refs.

The continuous recrystallization (CRX) appears to be fundamental in Al-Sc because it occurs irrespective of solute composition. It appears to be due to a combination of subgrain coalescence at low strains and incorporation of additional dislocations generated during grain boundary sliding at higher strains when the misorientation has increased sufficiently. Alloying additives such as Mg, Li are more important with respect to deformation after CRX is completed. Mg, and to a lesser extent Li, affect the max m-values (strain-rate sensitivities) in Al-Sc by changing the melting points (mp). Max m- values correlate inversely with mp so that the alloy with the greatest Mg had the highest m-values and lowest mp; the stress is raised at which power-law creep and breakdown occurs. The power-law breakdonw at much lower stresses in Al-0.5Sc and Al-1.2Li-0.5Sc causes the m-value to decrease more rapidly with strain rate. Al alloys for commercial superplastic applications should contain elements that raise the power-law strength so that the m-values are maximized while preserving the post-formed mechanical properties. Refs, figs, tabs.