Call number: LD2668 .T4 1986 H47 / Master of Science / Mechanical and Nuclear Engineering

Utilization of toluene by Pseudomonas putida as its sole carbon and energy source affects morphology, outer membrane protein composition, and glycolipid production. Two strains of P. putida were found to utilize toluene and to coexist in continuous and batch culture. The two strains were designated translucent and opaque, based upon their readily identifiable coloration when grown on Luria agar. The translucent strain was the dominant strain in continuous culture conditions. The outer membrane proteins of P. putida were separated by sodium dodecyl sulphate polyacrylamide gel electrophoresis. When toluene is the carbon and energy source, the trend in protein composition was towards a general increase in concentration of lower molecular weight proteins (wt). A similar decrease occurred in the concentration of higher molecular weight proteins in the range of 70X104-9X104 mol wt. P. putida produces glycolipids when grown on toluene as a sole carbon and energy source. Three glycolipids have been isolated from chemostat and batch culture spent media, using thin layer chromatography on silica gel GF254· The glycolipids are believed to be previously reported mono- and di-rhamnolipids that function as biosurfactants. The release of glycolipid into the media is believed to function to emulsify toluene, aiding in toluene uptake.

Benzene and toluene are known groundwater contaminants . Male CD-I mice were continuously exposed to 0, 31, 166, and 790 mg/ L benzene and 0, 17, 80, and 405 mg/L toluene, respectively, in drinking water for four weeks. Benzene caused a reduction of leukocytes, lymphocytes and erythrocytes, and resulted in a macrocytic anemia. Lymphocyte response to both B- and T-cell mitogens, mixed lymphocyte response to alloantigens, and the ability of cytotoxic lymphocytes to lyse tumor cells were enhanced at the lowest dose of benzene and depressed in the higher dosage animals. Benzene at doses of 166 and 790 mg/L decreased the number of sheep red blood cell (SRBC) -specific plaque-forming cells, the level of serum anti-SRBC antibody, and the activity of interleukin-2 (IL -2). Benzene treatment increased endogenous concentrations of the brain biogenic amines norepinephrine (NE), dopamine (DA) and serotonin (5-HT), and concomitantly, elevated the levels of their respective major metabolites vanillymandelic acid (VMA), 3,4-dihydroxyphenyl acetic acid (DOPAC) and homovanillic acid (HVA), and 5-hydroxyindoleacetic acid (5-HIAA), in several brain regions . In most cases, the changes were dose related; in several instances, maximum effects occurred at the 166 mg/L benzene dose. Toluene did not adversely affect the hematological parameters. Depression of immune function was evident at the highest dose (405 mg/L), except for mitogeneses. Increased neurochemical concentrations caused by toluene displayed a dose-dependent biphasic manner which began at a dose of 17 mg/L, peaked at 80 mg/L, and decreased at 405 mg/L. Toluene treatment had more selective effects on NE, 5-HT ,VMA and 5-HIAA, than DA, DOPAC and HVA. Both compounds, by increasing concentrations of the hypothalamic NE and its major metabolite VMA, stimulated the hypothalamic-pituitary-adrenocortical axis activity, resulting in an elevated plasma adrenocorticotropic hormone and serum corticosterone which had an additive adverse effect on IL-2 synthesis. Toluene, 325 mg/ L, completely inhibited benzene-induced cytopenia and immunosuppression when it was coadministered with benzene (166 mg/L). The low dose of toluene (80 mg/L ) did not antagonize benzene immunotoxicity. Mice given the combined exposures exhibited raised levels of regional neurochemicals when compared to the untreated controls. Increased levels of monoamine metabolites in several brain regions were greater in the combined treatments of benzene and toluene than when either chemical was used alone. The results of the interaction studies support the known metabolic interaction mechanisms of benzene and toluene.

The rate of removal of benzene, toluene, ethylbenzene and the xylene isomers (BTEX) from contaminated groundwater is needed to design remediation processes. Benzylsuccinic acid (BSA) and methyl-benzylsuccinic acid (methyl BSA) are unambiguous metabolites of anaerobic BTEX biodegradation. An analytical method for quantitative determination of BSA in groundwater samples was developed. Samples containing BSA and methyl BSA were extracted onto 0.5 g of styrene-divinylbenzene, eluted with ethyl acetate, and methylated with diazomethane. Gas chromatography coupled to mass spectrometry with electron impact ionization was used for separation and detection. The recovery from spiked 1 L groundwater samples was 88 to 100 %. The precision of the method, indicated by the relative standard error was ± 4% with a method detection limit of 0.2 μg/L. The method was then used to analyze samples from single-well push-pull tests conducted by injecting deuterated toluene and xylene into BTEX-contaminated wells in order to demonstrate in-situ biodegradation. Unambiguous evidence for deuterated toluene and xylene biodegradation was obtained with the observation of deuterated BSA and methyl BSA coupled with the utilization of nitrate presumably due to denitrification as terminal-electron-accepting process. Minimum first-order degradation rates for deuterated toluene estimated from formation of BSA were 0.0004 to 0.001 day⁻¹. Rates of methyl BSA formation were not calculated because methyl BSA, although detected, was not above the quantitation limit. Removal rates of deuterated toluene and o-xylene were not directly measurable because the rates were too low to measure significant changes in parent compound concentrations. Wells for which the formation of deuterated BSA and methyl BSA were observed had lower relative concentrations of toluene and xylenes relative to total BTEX than wells for which no deuterated BSA and methyl BSA were observed. Retardation factors for injected deuterated toluene and background toluene of 2 and 14, respectively, were obtained from push-pull tests conducted to determine toluene transport properties. Differences in retardation factors for injected and background toluene indicate differences between injected and background solute transport and is a topic that requires further study. / Graduation date: 2002

Toluene is one of the most prevalent aromatic volatile organic compounds (VOCs) in the atmosphere and has large secondary organic aerosol (SOA) yields compared to many other aromatic VOCs. Recent photo-oxidation studies highlight that toluene oxidation produces more SOA than observed previously, particularly at low levels of nitrogen oxides (NOx). This study focuses on: 1.) the development of a gas-phase chemical mechanism describing toluene oxidation by hydroxyl radicals (OH); 2.) the prediction of SOA formation from toluene oxidation products; and 3.) the impact of NOx level on SOA formation. The oxidation mechanism, which includes multiple pathways after the initial OH attack, has been incorporated into the Caltech Atmospheric Chemistry Mechanism (CACM). Toluene concentrations simulated in chamber experiments by the updated CACM as a function of time are typically within 5% of observed values for most experiments. Predicted ozone and NO2 concentrations are typically within 15% of the experimental values. The gas-phase mechanism indicates the importance of bicyclic peroxy radical reactions in determining the product distribution and thus the likelihood of SOA formation. A gas-aerosol partitioning model is used in conjunction with the gas-phase mechanism to simulate SOA formation. Predicted SOA concentrations are typically within 15% of the experimental values. Under low NOx conditions, simulation shows that more than 98% of SOA mass is contributed by bicyclic products from reactions between bicyclic peroxy radicals and other peroxy radicals. Increasing NOx levels cause bicyclic peroxy radicals to react with NO or nitrate radical, leading to fragmentation products that are less likely to form SOA. SOA yield dropped from 19.26% with zero initial NOx to 13.27% with 100 ppb initial NO because of the change in the amount of toluene consumed. Composition of NOx also has an impact on SOA yield and formation, showing that NO has a greater impact on SOA yield and formation than NO2.

Abstract Aluminum oxide was utilized as a carrier of active metals copper and manganese. Catalysts with various metal ratios and weight loadings were produced by incipient impregnation to treattoluene. From the 24 catalysts we prepared, this investigation selected the most effective catalyst, based on the conversion rate of toluene and CO2 yield. The influence of operating parameters of toluene oxidization on the conversion rate and long-term variations in catalytic activity were investigated, and the physical properties of catalysts were determined by SEM and XRD. The conversion rate for toluene and CO2 yield reached 95% when the Cu/Mn catalyst was used with a metal ratio of 1:1 and 20% loading at 350¢XC, an influent toluene concentration of 1000ppm, oxygen concentration of 21%, a space velocity of 12000 hr-1, and relative humidity of 26%. The toluene conversion rate increased as reaction temperature and influent concentration of oxygen increased, but decreased as the initial toluene concentration and space velocity increased. The long-term test proceeded for seven days at a constant influent toluene concentration of 1000ppm, constant oxygen concentration of 21%, constant space velocity of 12000hr-1 and constant relative humidity of 26%. The stability of the Cu/Mn catalyst structure was assessed. Differences between fresh and aged catalysts were analyzed using analytical instruments such as SEM, and XRD. No obvious deactivation of the catalytic surface was detected. Keywords aluminum oxide, Cu/Mn catalyst, toluene, and operational parameters

Thesis (M.S.)--Ohio University, November, 2009. / Release of full electronic text on OhioLINK has been delayed until December 1, 2010. Title from PDF t.p. Includes bibliographical references.

The aim of this study was to determine in an empirical manner whether the phenomenon of hearing loss due to the exposure to volatile organic solvents was present in the gasification plants of a petrochemical factory. The experimental groups included unexposed (N=20) workers, workers (N=20) exposed to noise and workers (N=19) exposed to noise and volatile organic solvents. The following assessments were made: diagnostic audiometry for the assessment of hearing thresholds; biological monitoring of ortho-cresol and hippuric acid for the biological markers of toluene; passive air sampling and noise measurements. Questionnaires were completed by the three groups to collect information about age, ethnicity, smoking habits, alcohol consumption and work history regarding the exposure to ototoxic substances as well as the period of employment. There were no statistically significant differences between the average ages of the three groups, but more of the workers in the noise group were from a higher age group. This age composition and the work history of the noise group were considered as possible influences on the results of this hearing study. The results of the passive air sampling show that the levels of volatile organic solvents were lower than the occupational exposure limits on the day of sampling. The biological monitoring shows that the markers, namely hippuric acid and o-cresol, were lower than the biological exposure indices. The noise group was exposed to sound pressure levels of 79-90 dB(A) and the noise + hydrocarbon group to levels of 85-88 dB(A). The average hearing thresholds of the noise group were at most of the frequencies (0.5-8 kHz) significantly higher (p≤0,05) than that of the noise + hydrocarbon group. The average hearing thresholds of the control group were overall lower than the noise group's hearing thresholds, but on average a little higher than the noise + hydrocarbon group's hearing thresholds. No relationship was found in this study between the exposure to volatile organic solvents (for example toluene that was used as marker in this study) and the elevation of hearing thresholds of workers at the gasification plants of the petrochemical factory. / Thesis (M.Sc.)--North-West University, Potchefstroom Campus, 2004.

Reflection-absorption infrared spectroscopy (RAIRS) has been used to probe the interaction of cyclohexane, partially deuterated cyclohexane C₆HD₁₁, toluene and ethylene with the Ni{111} surface. The coadsorption of cyclohexane and oxygen on the Ni{111} surface has also been studied in some detail; the effects of differing coverages of both pre- and post- dosed oxygen on cyclohexane adsorption has been investigated. As these experiments were the first to be completed using a new UHV system, an important element of this PhD project involved commissioning the UHV system, including the LEED and Auger apparatus, and setting up the RAIRS optical system. On the clean Ni{111} surface at 110 K adsorbed cyclohexane exhibits a site symmetry of C_3v which persists through to the multilayer regime. Adsorbed molecules in the first layer exhibit a broadened and downshifted vCh stretching vibrational band, thought to arise from CH...M interactions and observed on many metal single crystal surfaces. The effect of coadsorbed oxygen on cyclohexane adsorption is strongly coverage dependent. At lower oxygen coverages, θ_O ≤ 0.25, a further downshifting of the softened vCH stretching vibration is observed, indicating the importance of charge transfer from the filled CHσ orbital to the metal in weakening the C-H bond. Adsorption of cyclohexane on the Ni{111}-(√3x√3)R30°-O surface, θ_O = 0.33, leads to total suppression of any C-H...M interaction, attributed to blocking of the bare metal sites by the adsorbed atoms. Post-dosing of oxygen on the cyclohexane adlayer leads to compression of existing islands of cyclohexane, involving molecular transfer from the first layer to the second. This is attributed to the difference in heats of adsorption of the two adsorbates.

The aim of this study was to determine in an empirical manner whether the phenomenon of hearing loss due to the exposure to volatile organic solvents was present in the gasification plants of a petrochemical factory. The experimental groups included unexposed (N=20) workers, workers (N=20) exposed to noise and workers (N=19) exposed to noise and volatile organic solvents. The following assessments were made: diagnostic audiometry for the assessment of hearing thresholds; biological monitoring of ortho-cresol and hippuric acid for the biological markers of toluene; passive air sampling and noise measurements. Questionnaires were completed by the three groups to collect information about age, ethnicity, smoking habits, alcohol consumption and work history regarding the exposure to ototoxic substances as well as the period of employment. There were no statistically significant differences between the average ages of the three groups, but more of the workers in the noise group were from a higher age group. This age composition and the work history of the noise group were considered as possible influences on the results of this hearing study. The results of the passive air sampling show that the levels of volatile organic solvents were lower than the occupational exposure limits on the day of sampling. The biological monitoring shows that the markers, namely hippuric acid and o-cresol, were lower than the biological exposure indices. The noise group was exposed to sound pressure levels of 79-90 dB(A) and the noise + hydrocarbon group to levels of 85-88 dB(A). The average hearing thresholds of the noise group were at most of the frequencies (0.5-8 kHz) significantly higher (p≤0,05) than that of the noise + hydrocarbon group. The average hearing thresholds of the control group were overall lower than the noise group's hearing thresholds, but on average a little higher than the noise + hydrocarbon group's hearing thresholds. No relationship was found in this study between the exposure to volatile organic solvents (for example toluene that was used as marker in this study) and the elevation of hearing thresholds of workers at the gasification plants of the petrochemical factory. / Thesis (M.Sc.)--North-West University, Potchefstroom Campus, 2004.