In this study, two regenerative thermal oxidizers (RTO) were used to test the thermal destruction, thermal recovery efficiency and the gas pressure drop over the beds characteristics when burning, respectively, airborne chlorine- and nitrogen-containing volatile organic compounds (VOCs). First, an electrically-heated RTO containing two 0.5 m ¡Ñ 0.5 m ¡Ñ 2.0 m (L ¡Ñ W ¡Ñ H) beds, both packed with gravel particles with an average diameter of around 0.0116 m and a height of up to 1.48 m with a void fraction of 0.41 in the packed section was used to study the destruction characteristics of chlorine-containing VOCs (trichloroethane, TCE and dichloromethane, DCM). With a valve switch time (ts) of 1.5 min, preset maximum destruction temperatures (TS) of 500-800 oC and superficial gas velocity (Ug) of 0.17-0.33 m/s (evaluated at an influent air temperature of around 27 ¢J), tests on the thermal recovery efficiency (TRE) and the pressure drop for the air stream without VOC in the influent air stream have been performed. With a ts of 1.5 min, Ts of 500-800 oC and Ug of 0.17-0.24 m/s (evaluated at an influent air temperature of around 27 ¢J), tests on the degree thermal destruction of VOCs with influent air streams containing one of the two VOCs: trichloroethylene (TCE) and dichloromethane (DCM) have been done. Second, an electrically-heated RTO containing two 0.152 m ¡Ñ 0.14 m ¡Ñ 1.0 m (L ¡Ñ W ¡Ñ H) beds, both packed with gravel particles with an average diameter of around 0.0111 m and a height of up to 1.0 m with a void fraction of 0.42 in the packed section was used to study the destruction and NOx formation characteristics of DMF (N, N-dimethylformamide). With a ts of 1.5 min, Ts of 750-850 ¢Jand Ug of 0.39-0.78 m/s (evaluated at an influent air temperature of around 30 ¢J), TRE and the pressure drop for the air stream without VOC in the influent air stream have been tested. With a ts of 1.5 min, a Ug of 0.39 m/s (evaluated at an influent air temperature of around 30 ¢J), and Ts of 750-950 ¢J and, thermal destruction efficiencies and nitrogen oxides (NOx) formation characteristics in burning air streams containing either DMF or DMF mixed with methyl ethyl ketone (MEK) were performed. Results demonstrate that: (1) a RTO is suitable for destruction of low concentrations (<1,000 ppm as methane) of airborne highly chlorinated VOCs such as TCE and DCM and the destructed products contain no chlorine and only trace of COCl2 (< 1% of the influent VOC); (2) for TS = 800 oC and Ug = 0.17-0.24 m/s, complete oxidation products of TCE and DCM are HCl, CO2, and H2O, and the main intermediates are CO and COCl2; (3) with ts of 1.5 min, a Ug of 0.39 m/s (evaluated at an influent air temperature of around 30 oC) and TS of 750-950 ¢J, no NOx was present in the effluent gas from the RTO when it was loaded with DMF-free air; (4) when only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/Nm3. The ¡§NOx-N formation/DMF-N destruction¡¨ mass ratios were in the range 0.76-1.05, and decreased as the influent DMF concentration increased within the experimental range; (5) when both DMF and MEK were present in the influent gas, the NOx formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NOx formation ratios were in the range 0.75-0.96; (6) the TRE decreased as Ug increased but was invariant with Ts; and (7) the Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.

The main objective of this study was to evaluate the feasibility of using nanoscale zero-valent iron (nZVI) as the source of hydrogen to enhance in situ anaerobic biodegradation of trichloroethylene (TCE). In the first part of this study, microcosms were constructed to evaluate the effects of different controlling factors [e.g., different redox conditions (aerobic and anaerobic conditions), different microorganisms (in situ microorganisms, activated sludge, and anaerobic sludge), and different sources of substrates and electron donors (phenol, cane molasses, hydrogen, and nZVI)] on TCE biodegradation. In the second part of this study, batch experiments were conducted to evaluate the feasibility of hydrogen production by nZVI and bimetallic particles. Results from the microcosm study indicate that in-situ microorganisms were capable of degrading TCE under aerobic and anaerobic conditions. Results also show that TCE removal was more effective by activated sludge and anaerobic sludge. Aerobic biodegradation of TCE was enhanced by the addition of phenol and cane molasses. Under anaerobic conditions, TCE removal could be improved when cane molasses and hydrogen were supplied. In addition, anaerobic TCE degradation was more effective with the presence of hydrogen. Results of microcosms conducted with the addition of nZVI reveal that TCE was degraded completely in both live and autoclaved microcosms. This indicates that chemical reductive dechlorination seemed to dominate the removal of TCE in microcosms. Therefore, further studies with higher TCE concentrations or lower nZVI doses need to be conducted to determine the effects of the produced hydrogen on TCE biodegradation. Results from the hydrogen production experiments indicate that efficiency of hydrogen production by nZVI ranged from 30% to 76%. Higher dose of nZVI addition resulted in higher amount of hydrogen production. The total amounts of hydrogen production were correlated with the doses of nZVI. In addition, rates and efficiency of hydrogen production by bimetallic particles were better than those of nZVI. Results of the batch experiments reveal that nZVI and bimetallic particles had good efficiency on hydrogen production. This indicates that nZVI and bimetallic particles have high potential to be used as hydrogen producers. In this study, a simple system consisted of only water and nZVI or bimetallic particles was applied to produce hydrogen. Although TCE in microcosms with nZVI addition was totally consumed by nZVI, results of microcosms with hydrogen addition demonstrated that hydrogen was able to improve the efficiency of anaerobic TCE biodegradation. Thus, it may be feasible to use nZVI as the source of hydrogen to enhance in situ anaerobic biodegradation of TCE. The advantages of using nZVI as the source of hydrogen include: (1) rapid removal of significant contaminant concentrations in the early stage of nZVI injection; (2) creation of a more reducing environment; (3) safer than liquid hydrogen, which is stored in steel containers; and (4) direct hydrogen supply without transfer of biological mechanisms compared to commercial hydrogen release compounds and other organic substrates. Results of this study suggest that biological reductive dechlorination of TCE can be enhanced if proper doses of nZVI are supplied in situ. Knowledge and comprehension obtained in this study will be helpful in designing an enhanced in situ anaerobic bioremediation system for a TCE-contaminated site.

The industrial solvent trichloroethylene (TCE) and petroleum hydrocarbons (e.g., fuel oil) are among the most ubiquitous organic compounds found in subsurface contaminated environment. The developed treatment train system included the first stage of groundwater and surfactant flushing followed by the second stage of chemical oxidation such as potassium permanganate (KMnO4) and Fenton-like treatment. The third stage was the application of enhanced bioremediation for the further removal of residual contaminants after the first two treatment processes. The objectives of this study were to (1) assess the applicability of treatment train system for the remediation of organic compounds contaminated subsurface environment, (2) determine the optimal operational conditions of the three-stage treatment system, and (3) evaluate the effects of residual surfactant Simple GreenTM (SG) and hydrogen peroxide (H2O2) after chemical oxidation stage on the efficiency of bioremediation process. In this study, three different surfactants [SG, Triton X-100, and Tween 80] were evaluated in batch experiments for their feasibility on contaminants removal. Results from the surfactant biodegradation and microbial enumeration study indicate that SG was more biodegradable and was able to enhance the microbial activity of the intrinsic microorganisms. Thus, SG was applied in the following batch or column experiments of the treatment train system. Results from this study indicate that approximately 87.6% of TCE in the system (with initial concentration of 40 mg L-1) could be removed from the simulated dense non-aqueous-phase liquids (DNAPLs) system after groundwater flushing followed by biodegradable surfactant (1 g L-1 of SG) flushing, while the TCE concentrations dropped from 40 to 4.96 mg L-1 at the end of the flushing experiment. Moreover, approximately 10.7% of the remaining TCE could be removed from the system after the oxidation process using KMnO4 as the oxidant. Results from the oxidation process show that TCE was reduced from 4.96 to 0.69 mg L-1, and chloride concentation was increased from ND to 0.88 mg L-1 with the presence of 1 g L-1 of SG. The residual 1.7% of the TCE could be further remediated via the enhanced bioremediation stage, and the TCE concentrations dropped from 0.69 mg L-1 to below detection limit at the end of the bioremediation experiment. Results also indicate that the remaining KMnO4 had no significant inhibition on bacterial growth and TCE biodegradation. Thus, SG flushing and KMnO4 oxidation would not cause adverse effect on subsequent bioremediation process using intrinsic bacteria. Thus, complete TCE remediation was observed in this study using the three-stage treatment scheme. Results from the column experiment reveal that a complete TPH removal could be obtained after the application of three consecutive treatment processes. Results show that TPH concentration could be reduced from 50,000 mg kg-1 to below detection limit. This indicates that the treatment train system is a promising technology to remediate fuel-oil contaminated soils. Results from the column study indicate that approximate 80.3% of initial TPH in the soil could be removed after the SG [50 pore volumes (PVs)] followed by groundwater (30 PVs) flushing. The Fenton-like oxidation (with 6% of H2O2 addition) was able to remove another 15.0% of TPH. The observed first-order reaction rate constant of TPH oxidation was 2.74¡Ñ10-2 min-1, and the half-life was 25.3 min during the first 40 min of reaction. The residual 4.7% of the TPH could be further remediated via the aerobic bioremediation process. Thus, complete TPH removal was obtained in this study using the three-stage treatment scheme. The proposed treatment train system would be expected to provide a more efficient and cost-effective alternative to remediate chlorinated solvent and petroleum hydrocarbons contaminated sites.

Dissociation of trichloroethylene (TCE) molecules on the Si(111)-7x7 and the Si(100)-2x1 surfaces was studied using STM. Though molecular adsorption may also be observed on the Si(111)-7x7 surface, dissociation is the dominant process. From the STM images acquired, products of dissociation were identified, namely chlorine atoms and dichlorovinyl groups. Dissociation of chlorine from the TCE molecule was confirmed by studying not just appearance in STM images but also from studies of tip-induced diffusion. Different binding configurations were proposed for the vinyl group on the Si (111)-7x7 and the Si(100)-2x1 surfaces. Site preference for each product of dissociation is reported on the Si(111)-7x7 surface. Dissociation of molecules such as ammonia, dimethylamine and methyl chloride on the Si(111)-7x7 and Si(100)-2x1 surfaces is reviewed. The field emission process is explained in detail. The usefulness of making field emission measurements is in evaluating the sharpness of STM tips. / xviii, 175 leaves : ill. (some col.) ; 29 cm

The development of Parkinson's disease (PD) in humans has been linked to genetic and environmental factors for many years. However, finding common single insults which can produce pathology in humans has proved difficult. Exposure to trichloroethylene (TCE) or traumatic brain injury (TBI) has been shown to be linked to PD and it has also been proposed that multiple insults may be needed for disease development. The present studies show that exposure to TCE prior to a TBI can result in pathology similar to early PD and that the interaction of both insults is required for impairment in behavioral function, and cell loss. Following exposure to TCE for 2 weeks there is a 75% impairment in mitochondrial function but it has yet to be shown if the addition of a TBI can make this worse. If the exposure to TCE is reduced to 1 week and combined with TBI a 50% reduction in mitochondrial function is observed following the dual injury which requires both insults. These studies provide further support for the hypothesis that PD may result from a multifactorial mechanism. It had been established that regional differences exist in mitochondrial function across brain regions. The present studies indicate that previous findings are not likely to be the result of differences in individual mitochondria isolated from the cortex, striatum, and hippocampus. Further analysis of the effect of mitochondrial inhibitors on enzyme activity and oxygen consumption reveal that the different regions of the brain are similarly affected by the inhibitors. These results suggest that findings from previous studies indicating regionally specific deficits following systemic toxin exposure, such as with TCE, are not the result of regional differences in the individual mitochondria. Given that TBI results in significant dysfunction, finding effective therapeutics for TBI will provide substantial benefits to individuals suffering an insult. Treatment with Pioglitazone following TBI reduced mitochondrial dysfunction, cognitive impairment, cortical tissue loss, and inflammation. These findings provide initial evidence that treatment with Pioglitazone may be an effective intervention for TBI.

Isotopic methods have been developed over the last 10 years as a method for determining chemical interactions of chlorinated solvents. These methods are especially promising for. This study attempts to employ and develop compound specific isotopic analyses of TCE and cDCE, along with chemical data, to characterize the degradation of TCE in a fractured bedrock aquifers. The Smithville site is a contaminated field site with extremely high levels of TCE contamination that is currently undergoing monitored remediation. From December 2008 until April 2010 extended samples were collected from the site to provide additional data analyses including isotopic data. The redox conditions at the site are anoxic to reducing, with sulfate reduction and methanogenesis as dominant terminal electron accepting processes. Redox data indicates that well electrochemical conditions are highly variable within the site, including areas near the source zone that not very reducing. Documented changes in groundwater conditions to much more reducing environments indicate that oxidation of organic matter is occurring at the Smithville site in select wells. Chemical analyses of TCE, DCE, VC, ethene and ethane are employed determine whether reductive dechlorination was occurring at the site. Results of field testing indicate that many wells on site, especially in the proximity of the source zone, dechlorination products were found. The isotopic data had a high range in both carbon and chlorine isotopes. Chlorine isotopic data ranges from a δ37Cl(TCE) of 1.39 to 4.69, a δ37Cl(cDCE) of 3.57 to 13.86, a δ13C(TCE) of -28.9 to -20.7, and a δ13C(cDCE) of -26.5 to -11.82. The range in values indicate varying degrees of degradation throughout the site, with the same wells grouping together. Combined chemical, redox and isotopic data shows that degradation seems to be a removal process for TCE at the Smithville site. Concentrations of chemicals created as a result of TCE degradation verify degradation, especially in wells 15S9, R7 and 17S9. Historically production of DCE in significant amounts, above 1.0 ppb, was observed to only occur after 2003. In addition to this, DCE data shows that the percentage of DCE made up of cDCE is above 96%. This indicates that microbes most likely mediate the processes that formed DCE from TCE. The linear regression of the delta-delta plot for isotopic TCE data shows line that is likely a direct function of the carbon and chlorine isotopic fractionation imparted upon the original TCE released. The slope found is consistent with data collected from other studies though cannot be applied to determining the process directly given the range of variability in isotopic field data.

abstract: This study investigates the effect of the virgin granular activated carbon (GAC) on the properties of synthesized iron (hydr)oxide nanoparticles impregnated GAC (Fe-GAC) media and its ability to remove arsenate and organic trichloroethylene (TCE) from water. Fe-GAC media were synthesized from bituminous and lignite-based virgin GAC via three variations of a permanganate/Fe(II) synthesis method. Data obtained from an array of characterization techniques indicated that differences in pore size distribution and surface chemistry of the virgin GAC favor different reaction paths for the iron (hydr)oxide nanoparticles formation. Batch equilibrium isotherm testing (120 µg-As/L; 6 mg-TCE/L, 10 mM NaHCO3 at pH = 7.2 ± 0.1 and pH = 8.2 ± 0.1) showed arsenic removal capability was increased as a result of iron (nanoparticles) impregnation, while TCE removal properties were decreased in Fe-GAC media. This tradeoff was displayed by both lignite and bituminous Fe-GAC but was most pronounced in lignite-based Fe-GAC having the highest Fe content (13.4% Fe) which showed the most favorable Freundlich adsorption and intensity parameters for arsenic of Ka = 72.6 (µg-As/g-FeGAC)(L/µg-As)1/n, 1/n = 0.6; and least favorable adsorption for TCE of Ka = 0.8 (mg-TCE/g-FeGAC)(L/mg-TCE)1/n, 1/n = 4.47. It was concluded that iron content was the main factor contributing to enhanced arsenic removal and that this was affected by base GAC properties such as pore size distribution and surface functional groups. However high Fe content can result in pore blockage; reduction in available adsorption sites for organic co-contaminants; and have a significant effect on the Fe-GACs overall adsorption capacity. / Dissertation/Thesis / M.S. Technology 2010

abstract: The advantages and challenges of combining zero-valent iron (ZVI) and microbial reduction of trichloroethene (TCE) and perchlorate (ClO4-) in contaminated soil and groundwater are not well understood. The objective of this work was to identify the benefits and limitations of simultaneous application of ZVI and bioaugmentation for detoxification of TCE and ClO4- using conditions relevant to a specific contaminated site. We studied conditions representing a ZVI-injection zone and a downstream zone influenced Fe (II) produced, for simultaneous ZVI and microbial reductive dechlorination applications using bench scale semi-batch microcosm experiments. 16.5 g L-1 ZVI effectively reduced TCE to ethene and ethane but ClO4- was barely reduced. Microbial reductive dechlorination was limited by both ZVI as well as Fe (II) derived from oxidation of ZVI. In the case of TCE, rapid abiotic TCE reduction made the TCE unavailable for the dechlorinating bacteria. In the case of perchlorate, ZVI inhibited the indigenous perchlorate-reducing bacteria present in the soil and groundwater. Further, H2 generated by ZVI reactions stimulated competing microbial processes like sulfate reduction and methanogenesis. In the microcosms representing the ZVI downstream zone (Fe (II) only), we detected accumulation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) after 56 days. Some ethene also formed under these conditions. In the absence of ZVI or Fe (II), we detected complete TCE dechlorination to ethene and faster rates of ClO4- reduction. The results illustrate potential limitations of combining ZVI with microbial reduction of chlorinated compounds and show the potential that each technology has when applied separately. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2017

Trichloroethylene (TCE) is a toxic pollutant that has become a widespread problem by seeping into groundwater across the developed world. Clean-up of sites contaminated with TCE is extremely difficult due to the absence of an efficient and cost-effective method for clean-up. Bioremediation efforts include a variety of potential microbial candidates with various metabolic capabilities as clean up options of contaminated sites. Cupriavidus necator, a soil bacterium was found to possess the ability to degrade TCE via a phenol-dependent pathway. Previous research by Ayoubi and Harker (1998) created a strain (MM02) capable of constitutive TCE degradation but the underlying genetic alteration causing constitutive production of the phenol hydroxylase pathway (PHL) and TCE breakdown was poorly characterized. We attempted to gain further understanding of the alterations that occurred in the PHL pathway to cause TCE to break down and replicate constitutive TCE degradation in a new strain with reduced foreign elements that may be introduced into the environment. Strain MM02 possessing this constitutive degradation activity and strain MM01were sequenced and compared to discover the source of this variation. A 210 base-pair deletion in the beginning of the PHL operon was identified and is likely the cause of this altered activity. The new strain of C. necator (MM14) was created using traditional bacterial mating methods and included a cleanly introduced kanamycin resistance gene and its associated promoter which could drive constitutive expression of the PHL pathway. The TCE degradation abilities of strains MM01, MM02, and MM14 were evaluated through the TCE degradation assay and gas chromatography. We had difficulty accurately measuring the concentration of TCE due to its volatile nature and dramatically altered the method ultimately reducing variation and capturing TCE concentrations in assays. When accurate readings were obtained, none of the strains measured exhibited quantifiable TCE degradation activity when compared to controls. Our results showed .08% of the degradation by strain MM02 measured previously (P. J. Ayoubi, 1997). Based on our findings, we were unable to replicate the TCE degradation caused my MM02 and our genetically modified strain also failed to breakdown TCE.

Past use of trichloroethylene (TCE) as a degreasing solvent for aircraft maintenance has resulted in widespread groundwater contamination at Air Force Bases around the world. Travis AFB in California and Fairchild AFB in Washington are evaluating phytoremediation as a treatment option, since trees have been reported to take up dissolved TCE from shallow groundwater and volatilize it to the atmosphere while enhancing the volatilization of TCE from surrounding soil. Previous studies generally focused on the identification of removal mechanisms. The emphasis of this research was to quantify total TCE removal from phytoremediation demonstration plots at Travis and Fairchild AFBs. Tree cores, collected using an increment borer and analyzed using headspace GC/MS, were used to determine the relative TCE concentrations within the plume beneath the trees and to estimate the mass of TCE in each tree. To estimate the volatilization of TCE from leaves, a small section of tree branch was placed inside a flow-through glass chamber. Continuous air flow through the chamber maintained normal transpiration and temperature. Air exiting the chamber was sampled for TCE using Tenax® tubes. Humidity probes placed at the chamber entry and exit were used to estimate transpiration. Volatilization of TCE from tree trunk and soil surfaces was measured by enclosing a section of trunk or ground surface within a small stainless steel chamber. Fans in the chamber mixed the air that was recirculated through Tenax® tubes to continuously remove TCE. After a measured time interval, the Tenax® tubes were analyzed for TCE by thermal desorption GC/MS. By using a Thiessen polygon method, the removal of TCE was estimated to be 839 g/yr at Travis and 18 g/yr at Fairchild with the majority from leaf and soil volatilization. Soil surface volatilization of TCE was greater inside the planted areas than outside the planted areas, indicating that the trees enhance this removal by this mechanism. Based on these estimates phytoremediation removed 5 and 50% of the mass of TCE in the groundwater at Fairchild and Travis Air Force sites, respectively.