Chemistry Commons^™

Aerobic Biodegradation Of Alternative Fuel Oxygenates In Unsaturated Soil Columns, Kevin A. Mares

Theses and Dissertations

Groundwater contamination problems caused by methyl-tertiary butyl ether (MTBE) in subsurface waters have prompted the search for a gasoline oxygenate replacement. In order to avoid the problems encountered with MTBE, it is prudent to evaluate the fate and transport in the subsurface of proposed replacements, such as ethanol. In this study, ethanol transport and degradation in unsaturated soil was investigated using a series of eight soil columns. This preliminary study was to see if the soil column system components functioned properly, how similarly the eight soil columns performed, and if soil oxygen concentration affected degradation of ethanol. Tracer tests, using …

An Evaluation Of Formic Acid As An Electron Donor For Palladium (Pd) Catalyzed Destruction Of Nitroaromatic Compounds, Mark R. Stevens

Theses and Dissertations

The Department of Defense is responsible for over 2,000 hazardous waste sites containing nitroaromatic compounds (NACs) such as 2,4,6-TNT, 2,4- and 2,6-DNT that resulted from the production and use of munitions throughout the nation and world, NACs are typically persistent in natural environments, though they can be oxidized or reduced under engineered conditions, NACs and their reduction products are toxic chemicals and suspected human carcinogens, Both TNT and 2,4-DNT are listed as priority pollutants by the U,S EPA, This study investigates the effectiveness of using a palladium (Pd) catalyst in concert with formic acid as an electron donor to reduce …

Gas Phase Studies Of Molecular Clusters Containing Metal Cations, And The Ion Mobility Of Styrene Oligomers, Edreese Housni Alsharaeh

Theses and Dissertations

This study is divided into three parts. Part I deals with the mechanism of the self-initiated polymerization (or thermal polymerization) of styrene in the gas phase. In this work, we present the first direct evidence for the thermally self-initiated polymerization of styrene in the gas phase. Our approach is based on on-line analysis of the gas phase Oligomers by mass-selected ion mobility. The mobility measurements provide structural information on the ionized oligomers based on their collision cross-sections (Ω) which depend on the geometric shapes of the ions. Theoretical calculations of possible structural candidates of the Oligomers ions are then used …

Experimental Studies On Nucleation, Nanoparticle's Formation And Polymerization From The Vapor Phase, Victor Maher Abdelsayed

Theses and Dissertations

This research is divided into three major parts. In part I, the critical supersaturations required for the homogeneous nucleation of 2,2,2-trifluorothanol (TFE) vapor have been measured over a temperature range (266-296 K) using an upward thermal diffusion cloud chamber (DCC). The measured supersaturations are in agreement with the predictions of both the classical and the scaled theory of nucleation. Moreover, the condensation of supersaturated TFE vapor on laser-vaporized magnesium nanoparticles has been studied under different experimental conditions, such as the supersaturation, the pressure and the electric field. In part II, the laser vaporization controlled condensation (LVCC) technique was used to …

Analysis Of Anion Distributions In The Developing Strata Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Joshua D. Kovacic

Theses and Dissertations

Perchloroethene (PCE), Trichloroethene (TCE) and their degradation products are among the most common organic groundwater contaminants in the United States. Constructed wetlands utilizing upward flow harbor reduction-oxidation conditions that have demonstrated the potential to promote both partial and total mineralization of PCE and TCE through the process of natural attenuation. Organic acid and inorganic anion concentrations are indicative of reduction-oxidation processes that drive chlorinated ethene degradation. These analytes were investigated to assess their development within three vertically stratified regions of a constructed wetland cell at Wright-Patterson Air Force Base fed by groundwater contaminated with PCE and TCE. Data collected during …

Resonance Two Photon Ionization Study Of Binary Clusters Of Styrene With Polar Molecules, Hatem Ahmed Mahmoud

Theses and Dissertations

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the …

Application Of Horizontal Flow Treatment Wells For In Situ Treatment Of Perchlorate Contaminated Groundwater, Jeffrey C. Parr

Theses and Dissertations

Groundwater contamination by perchlorate has recently been recognized as a significant environmental problem across the United States, and especially at Department of Defense facilities. In this study, a model is used to evaluate the potential of a innovative in situ bioremediation technology using Horizontal Flow Treatment Wells (HFTWs) to manage perchlorate-contaminated groundwater. The technology uses HFTWs to mix an electron donor into perchlorate-contaminated groundwater in order to promote reduction of the perchlorate by indigenous microorganisms in bioactive zones within the aquifer, as well as recirculate the contaminated water between treatment well pairs to achieve multiple passes of contaminated water through …

An Anion Characterization Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Bradley M. Bugg

Theses and Dissertations

Chlorinated ethenes physical properties as well as its ubiquitous state at DOD installations makes it a priority for innovative remediation efforts. Current techniques are expensive and time consuming to maintain. Constructed wetlands suggest an inexpensive and operational alternative to conventional technologies. Sub-surface flow wetlands provide the anaerobic zones necessary to reduce the recalcitrant chlorinated solvents prior to anaerobic or aerobic mineralization of its daughter products. A vertical flow cell to include sequential sedimentary layers of two hydric soil lifts and a mix of hydric soil and woody compost was the subject of this investigation. This study focused on the statistical …

Optimization Of Palladium-Catalyzed In Situ Destruction Of Trichloroethylene-Contaminated Groundwater Using A Genetic Algorithm, Manuel Fernandez

Theses and Dissertations

Conventional technologies for the treatment of groundwater contaminated with chlorinated solvents have limitations that have motivated development of innovative technologies. One such technology currently under development involves using palladium-on-alumina (Pd/Al) as a catalyst to promote dechlorination. Pd/Al catalyst may be used in-well as part of a re-circulating horizontal flow treatment well (HFTW) system. An HFTW system involves two or more dual-screened wells, with in-well reactors, to capture and treat contaminated groundwater without the need to pump the water to the surface. In this study, objective and fitness functions, based on system costs and TCE concentration requirements, were developed to optimize …

Use Of Quantum Mechanical Calculations To Investigate Small Silicon Carbide Clusters, Jean W. Henry

Theses and Dissertations

Density Functional Theory (DFT) method was employed to model silicon carbide small clusters. Comparing the DFT calculation results with experimental results that observed by using photoelectron spectroscopy (PES), DFT predicts the same structures that experiment observed. For electron affinity, DFT results are in good agreement with experimental results, the root mean square negative offset 0.1 eV found using medium size of basis set (cc-pVDZ+) calculation. DFT results for vibrational frequencies are in good agreement with experiment results; the root mean square error is 72.5 cm^-1 wave number. 16 ground state structures of Si_mC_n (m ≤ 4, …

Dissolution Of Chromium From Inhalable Primer Paint Particles Into A Simulated Lung Fluid, David A. Kauth

Theses and Dissertations

The use of chromate as a corrosion inhibitor in primer paint is an essential component for the protection of aluminum-skinned aircraft and the primary source of hexavalent chromium (Cr (VI)) exposure to USAF aircraft painters. The objective of this research was to quantify the dissolution of chromate from freshly sprayed paint particles into a simulated lung fluid (SLF). Two primer paints were sprayed with a paint spray gun to generate overspray particles for collection into impingers filled with SLF. Particles were allowed to soak in SLF for 24 and 48 hours and then the particles were removed by centrifugation. The …

In Situ Treatment Of Chlorinated Ethene-Contaminated Groundwater Using Horizontal Flow Treatment Wells, Derek R. Ferland

Theses and Dissertations

The limitations of conventional containment technologies for groundwater contaminated with chlorinated solvents have motivated development of innovative technologies to achieve national groundwater remediation objectives. One inn9vative technology that is currently under development involves metal reductants or catalysts to chemically destroy the dissolved chlorinated solvent. Models are important tools that can be used to help transition this technology to the field. Model studies can be used to gain understanding about the technology, help determine when the prospective technology might work for a given site, and design full-scale field applications.

Chromate Dissociation From Primer Paint In Simulated Lung Fluid, Tiffany J. R. Morgan

Theses and Dissertations

OSHA has proposed a new strontium chromate exposure standard that would potentially cause Air Force paint facilities to be in violation of the proposed standard if adopted. This proposed reduction make the continued use of chromate containing primer paints very difficult. There is currently no acceptable replacements for chromate containing primer paints on AF aircraft. This study suggests that paint particles with chromate bound in primer paint may be unavailable for bodily absorption if inhaled and a reduced standard for painting applications may be unnecessary. Primer paint overspray was collected into simulated lung fluid (SLF) and allowed 6 hr, 24 …

Modeling Chlorinated Ethene Removal In Constructed Wetlands: A System Dynamics Approach, Colby D. Hoefar

Theses and Dissertations

The purpose of this study is to gain understanding of the dynamics of the processes that degrade Perchloroethene (PCE) to ethylene, or carbon dioxide (CO₂), within the confines of a constructed wetland. A system dynamics approach will be used. This model is focused on identifying and optimizing the naturally occurring processes in stratified wetland sediment that reduce mass, toxicity, mobility, volume or concentration of contaminants in groundwater. Contaminant fate and transport within a wetland system is extremely complex and the mechanisms that drive wetland behavior are dynamic. Confidence in the model was built through verification and testing. Reasonable …

Neural Networks In The Analysis Of Water-Soluble Sulfonylurea Herbicides Using An Lc/Ms, Joseph Michael Pompano

Theses and Dissertations

In this research, a hidden node pruning algorithm was developed for an artificial neural network (ANN) that automatically determined a more efficient size of the hidden layer, caused the ANN to resize itself, and then continued to train using a standard back-propagation algorithm. The hidden-node pruning algorithm was based on determining the number of significant eigenvalues present in the matrix of values produced by the hidden layer, starting with an excessive number of hidden nodes.

Eight sulfonylurea herbicides were used as the target analytes in this study. The ability of an ANN to simplify the sample preparation needed for analysis …

A Modeling Study For The Implementation Of In Situ Cometabolic Bioremediation Of Trichloroethylene-Contaminated Groundwater, John A. Christ

Theses and Dissertations

The limitations of conventional groundwater remediation technologies have led to the development of innovative technologies which may achieve national hazardous waste site remediation goals. Before an innovative technology can be implemented in the field, remedial project managers, regulators and other stakeholders require adequate modeling tools to help assess the applicability of the technology at a particular site. This modeling study investigates how an innovative technology, in situ cometabolic bioremediation, might be implemented to remediate a TCE-contaminated site, under different site conditions. A steady-state model is developed which couples an analytical expression to simulate the effect of flow between multiple pumping …

Evaluation Of The Natural Biodegradation Of Aircraft Deicing Fluid Components In Soils, Laura M. Johnson

Theses and Dissertations

This research effort was conducted to analyze the biodegradation of propylene glycol (PG) and tolyltriazole in two different soil types; a sandy soil and a high clay soil. Both an automated respirometer and a high performance liquid chromatograph (H PLO) were used in the analysis. Two separate experiments were conducted. In the first experiment, one level of tolyltriazole was added to the soils to determine whether or not there was a difference in the biodegradation rates of tolyltriazole in the two soils. The respirometer results indicated that there was a significant difference between the respiration rates of the microorganisms in …

Modeling The Uptake And Transpiration Of Tce Using Phreatophytic Trees, Douglas P. Wise

Theses and Dissertations

Phytoremediation is a recent addition to the numerous methods used today to remediate ground water contaminants. It is proving more effective and efficient compared to existing remediation techniques. The use of phreatophytes, or water seeking trees, has great potential for phytoremediation. These trees are fast growing, long lived, grow their roots down to the ground water table, transpire large amounts of water, and are proven to actively remove contaminants from the soil horizon. The purpose of this research is to develop quantitative concepts for understanding the dynamics of TCE uptake and transpiration by phreatophytic trees over a short rotation woody …

Hybrid Quantum And Molecular Mechanics Embedded Cluster Models For Chemistry On Silicon And Silicon Carbide Surfaces, James R. Shoemaker

Theses and Dissertations

Fabrication of silicon carbide SiC semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO₂ layer on SiC is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics QM, do not exist because of the huge computational cost of solving Schroedingers equation for a molecular cluster large enough to represent a surface. Molecular mechanics MM, which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, …

The Biodegradation Characteristics Of Proposed Fuel Systems Icing Inhibitors (Fsii), Charles E. Meshako

Theses and Dissertations

The biodegradation characteristics of three fuel system icing ihhibitors (FSII) were evaluated. FSII are jet fuel additives that partition into water readily and are present in the water drained from storage tank bottoms in concentrations approaching 40%. These concentrations raise concerns as to the disposal and handling of these wastes. The current FSII, DiEGME was evaluated along with two new candidates, dipropylene glycol and glycerol formal. DiEGME appeared to be moderately but not completely biodegradable. It is likely that much of it would be removed in a wastewater treatment plant. Dipropylene glycol only showed signs of degradation after more than …

Mass Transport Of Volatile Organic Compounds Between The Saturated And Vadose Zones, Monte S. Harner

Theses and Dissertations

Volatile organic compounds (VOCs) dissolved in the saturated zone are transported into the vadose zone primarily by gaseous phase diffusion. If the saturated zone is remediated, VOCs present in the vadose zone may become a secondary source of contamination for the groundwater. The amount of VOCs that remain in the vadose zone is dependent on site hydrology, soil properties, and the chemical properties of the contaminants. The purpose of this study was to determine what conditions caused VOC concentrations in the vadose zone to significantly recontaminate the saturated zone. A one-dimensional numerical model was developed to investigate the transport of …

Modeling Marine Exposure To Polychlorinated Biphenyls From Sunken Ships, Charles N. Wendt

Theses and Dissertations

In the past, the U.S. Navy has routinely conducted SINKing EXercises (SINKEX) for training, weapon effectiveness tests, and economic disposal of aging assets. Recent concern over polychlorinated biphenyl (PCB) chemicals aboard such target vessels has resulted in a suspension of SINKEX. The U.S. Navy has approximately 200 vessels currently requiring such disposal. Environmental legislation and health concerns preclude selling such vessels to foreign governments or scrapping. This work attempted to model the fate and transport of these PCBs by examining their transport to coastal water and their accumulation in the marine food chain. The model includes biodegradation, upwelling, partitioning of …

Interactions Among The Stationary Phase, The Mobile Phase, And The Solute In Liquid Chromatographic Systems, Zengbiao Li

Theses and Dissertations

Interactions among the stationary phase, the mobile phase, and the solute in liquid chromatography' have been studied. A strong dependence of the stationary phase properties on the mobile phase composition may arise from their interactions.

The solvatochromic comparison method, which can give estimates for the dipolarity-polarizability, the hydrogen-bonding acidity, and the hydrogen-bonding basicity of a solvent, represented by the solvatochromic parameters π⁺, α and β, respectively, was used to study the surface properties of silica in the presence of n-hexane-chloroform or n-hexane-ethyl ether mixtures. A high dipolarity- polarizability, a high hydrogen-bonding acidity, and a low hydrogen-bonding basicity …

Effects Of Ammonium Perchlorate On The Thyroid Hormone Levels Of The Sprague-Dawley Rat, James H. King Jr.

Theses and Dissertations

The purpose of this research was to determine the threshold dose for ammonium perchlorate (AP) in the Sprague-Dawley rat. No dose response data exist for AP and the EPA has studied literature on the subject of perchlorates to determine a provisional reference dose. The Perchiorate Group, a consortium of DoD and industry representatives, believes this provisional reference dose is too conservative. This experiment was executed to provide dose response data on which to base a more accurate reference dose. The study consisted of eight groups of 12 Sprague-Dawley rats, six male and six female, which were exposed to incremental doses …

Study Of The Long-Term Desorption Of Trichloroethylene From Clay Soils Using Infrared Spectroscopy, Mary P. Stager

Theses and Dissertations

Slow desorption of contaminants from soil presents one of the greatest challenges to modeling contaminant fate and transport and implementing effective remediation technologies. The kinetics of long-term desorption of trichloroethylene (TCE) from powdered clay soils were studied to determine the desorption rates and mechanism. Infrared absorption spectroscopy was used to monitor the concentration of TCE desorbed from contaminated flint clay for 71 hours. Observed gas phase TCE concentrations as a function of time were compared to that predicted by a one-site Langmuir desorption mechanism. The Langmuir model, with a single type of bonding site, did not account for the release …

Model Of Chlorocarbon (Cfc-12) Chemisorption On Solid Rocket Motor Alumina Exhaust Particles, Gary E. Lund

Theses and Dissertations

Solid Rocket (SRMs) that power Titan IV rockets and Space Shuttles, exhaust large quantities of potentially ozone damaging pollutants directly into the stratosphere, while in powered flight. In the past, studies on potential stratospheric impact of the exhaust products from aluminum/ammonium perchlorate based SRMs have focused on the effect of gaseous HCl from SRMs on the stratosphere. Until recently, the impact of heterogeneous chemistry on stratospheric ozone was believed to be relatively insignificant. This research investigates the potential heterogeneous process of CFC-12 dissociative chemisorption on alumina surfaces and the release of reactive halogen species known to destroy ozone. Through a …

Atmospheric Transport And Diffusion Modeling Of Rocket Exhaust, Chad A. Burel

Theses and Dissertations

Space launches at Vandenberg Air Force Base (VAFB) and the Cape Canaveral Air Station (CCAS) produce exhaust from the solid rocket boosters and liquid hypergolic fuels containing several toxic substances including hydrogen chloride and hydrazine. In order to estimate the health risk that would be imposed upon the public by proposed launches, range safety officials rely on the Rocket Exhaust Effluent Diffusion Model to predict where the exhaust chemicals will go after the launch and how strong the concentrations will be. The original REEDM program averaged the meteorological parameters (wind speed, wind direction, shear, etc.) across the entire mixing level …

Phosphorus Bearing Substrates In Ring Expansion Reactions, Bradley K. Norwood

Theses and Dissertations

A variety of substituted phosphonium salts, phosphorus ylides and phosphonates were studied to assess their utility in ring expansion reactions. The strategy involved formation of fused ring systems whose ring strain could be exploited to accomplish ring expansion to medium sized rings. β-Alkoxy vinylphosphonium salts were found to be unreactive with species such as the dimethylsulfoxonium methylide anion, Simmons-Smith type reagents. and carbenes in attempts to produce cyclopropyl phosphonium salts.

C-Alkylation of β-keto phosphorus ylides using haloalkanes bearing terminal groups that could be converted and reacted with the B-carbonyl, was also examined as a method for accessing strained rings bearing …

Exposure Of A Food Crop To Trichloroethylene From A Contaminated Aquifer, Richard G. Baringer

Theses and Dissertations

This research developed a methodology for assessment of the exposure of a mature corn crop to trichloroethylene from a contaminated aquifer. The methodology was then applied to the case of Hill AFB to determine the ability of the methodology to provide information about a specific exposure. Current procedures sample for food contamination but do not attempt to predict exposure problems. A review of the potential exposure pathways from the aquifer to the crop was conducted. Based on this review, the exposures due to soil gas and irrigation were modeled. Empirical estimated were used to approximate the expected flux of soil …

Modeling Trihalomethane Formation Potential From Wastewater Chlorination, Carol A. Mccormick

Theses and Dissertations

The deletion of federally mandated fecal coliform limits has led many states to review and modify their wastewater disinfection requirements. One issue in analyzing wastewater disinfection is the discharge of potentially carcinogenic halogenated organics formed during the chlorination process. This research investigates the formation of one class of the halogenated organics, the trihalomethanes. The applicability of using drinking water trihalomethane formation models for use with wastewater effluent is examined. Three models are compared for predictive capability by using measured trihalomethane values from previous research data. The results show that a previously developed model is applicable for use based on assumptions …