No description available.

In this study, a pilot-scale regenerative thermal oxidizer (RTO) was used to test its performance for volatile organic compound (VOC) destruction and degree of thermal energy recovery. The purposes were to improve its performance and establish its operation conditions. The RTO is electrically heated and contains two 0.5 m ¡Ñ 0.5 m ¡Ñ 2.0 m (L ¡Ñ W ¡Ñ H) beds both packed with gravel particles of around 1.16 cm in average diameter to a height of 1.48 m. The bed has a void fraction of 0.405. Experiments include two phases: (1) tests to find the degree of energy conservation and the pressure drop for the air stream with no VOC in the influent air stream, and (2) tests to find the degree of VOC destruction with influent air streams containing one of the three VOCs: trichloroethylene, dichloromethane, and dibutyl ether. Intermediates in the course of VOC destruction were also detected in the second phase experiment. Phase one experiment was conducted for the following conditions: superficial gas velocity (evaluated at ambient temperatures of 26-29oC) Ug = 10-20 m/min, bed shift time ts = 1.5 min, and maximum gravel temperature Tmax = 474-778oC. Results show that the RTO has a thermal recovery efficiency R of over 85% and Ug is the main affecting factor. R is inversely proportional to Ug. Gas pressure drop over the bed height is proportional to the average temperature of the bed gravels. In the phase two experiments, Ug of 10-20 m/min, ts of 1.5 min, and Tmax of 475-487 and 758-778oC were used. Results show that over 90% of the influent VOCs were destructed when Tmax was set in the higher range. However, in the lower Tmax, over 80% destruction was obtained only for dibutyl ether and the VOC destruction was not closely related to Ug. For Tmax = 475-487oC and Ug = 10-20 m/min, complete oxidation products of trichloroethylene and dichloromethane are HCl, CO2, and H2O, and the main intermediates are CO, COCl2, and C2Cl4 (detected only for trichloroethylene). For dibutyl ether, complete oxidation products are CO2, and H2O, and the main intermediates are CO, alkenes, alcohol, alkenes, and acetic acid. For Tmax = 758-778oC and Ug = 10-14.5 m/min, complete oxidation products of trichloroethylene and dichloromethane are HCl, CO2, and H2O, and the main intermediates are CO and COCl2. No acetic acid was detected for dibutyl ether in the higher temperature range. An operation cost of US$ 3.33/(1,000 m3 waste gas) was estimated with the RTO operated in the higher temperatures and a flowrate of 2.5 m3/min (Ug = 10 m/min).

Immiscible liquids, including chlorinated solvents, have proven to be a lasting source of subsurface contamination at many hazardous waste sites. Continued improvement of site characterization and determination of applicable remediation technologies can be achieved by further understanding of the transport and fate of these contaminants. The transport and fate of trichloroethene (TCE) was investigated through miscible displacement and dissolution experiments. Miscible displacement experiments were conducted using homogeneously packed columns with several porous media encompassing a range of particle size distributions. Immiscible liquid dissolution was investigated using homogeneously packed columns containing a residual saturation of trichloroethene. The same porous media were used for immiscible liquid dissolution experiments. Mathematical modeling of miscible displacement and dissolution experiments was conducted using a one-dimensional single region or multi-region model. Imaging of immiscible liquid dissolution was also conducted, using Synchrotron X-ray Microtomography imaging at Argonne National Laboratory, Argonne, IL. Dissolution experiments exhibited nonideal dissolution behavior that was apparent in observed effluent data and in collected imaging data. Nonideal behavior was manifested as secondary regions of relatively constant aqueous concentrations occurring for a number of pore volumes. This behavior was observed to increase in magnitude as particle size distribution of the porous media increased. During imaging, immiscible liquid blobs were observed to dissolve throughout the column during dissolution. This behavior is also indicative of nonideal dissolution, as it would be expected that dissolution would first occur for the blobs nearest the inlet and then proceed upward through the column as dissolution progressed. In many cases, a multi-region modeling approach was necessary to successfully represent the nonideal behavior observed. Comparisons were made between the natural porous media used for this research and a well-sorted sand. Nonideal dissolution was not observed in the well-sorted sand.

"A one dimensional, multiple reaction pathway model of the dechlorination reactions of trichloroethylene (TCE) and tetrachloroethylene (PCE) as these species pass through a zero valent iron permeable reactive barrier (PRB) was produced. Three different types of rate equations were tested; first order, surface controlled with interspecies competition, and surface controlled with inter and intra species competition. The first order rate equations predicted the most accurate results when compared to actual data from permeable reactive barriers. Sensitivity analysis shows that the most important variable in determining TCE concentration in the barrier is the first order rate constant for the degradation of TCE. The velocity of the water through the barrier is the second most important variable determining TCE concentration. For PCE the concentration in the barrier is most sensitive to the velocity of the water and to the first order degradation rate constant for the PCE to dichloroacetylene reaction. Overall, zero valent iron barriers are more effective for the treatment of TCE than PCE. "

Trichloroethene (TCE) and tetrachloroethene (PCE) are among the most commonly detected groundwater contaminants, and are often difficult to remediate due to their presence as dense non-aqueous phase liquids (DNAPLs) in the subsurface. The objective of this study was to assess the potential of using a passive in situ carbon/hydrogen releasing barrier system to bioremediate TCE-contaminated groundwater. The slow carbon/hydrogen releasing material would cause the aerobic cometabolism and reductive dechlorination of TCE in aquifer. The carbon/hydrogen releasing materials would release carbon when contacts with groundwater and release hydrogen after the anaerobic biodegradation of released carbon, thus cause the reductive dechlorination of TCE. Results from the microcosm study indicate that the addition of emulsified substrate, cane molasses, Simple GreenTM (a biodegradable surfactant), or lecithin would enhance the biodegradation rate of TCE under anaerobic conditions. However, addition of multivitamin would increase the bacterial population in the media but would not be able to enhance the TCE degradation rate. Results show that a significant pH drop was observed due to the production of organic acids after the aerobic biodegradation process of cane molasses and lecithin. This also caused the inhibition of microbial growth in microcosms. Results reveal that higher TCE removal efficiency was observed in microcosms with Simple GreenTM addition followed by the addition of cane molasses, lecithin, multivitamin, emulsified substrate, groundwater (without substrate addition). Results from the microcosm study indicate that the addition of emulsified substrate would enhance the biodegradation rate of TCE under anaerobic conditions. However, appearance of high nitrate concentration would inhibit the TCE degradation process due to the occurrence of denitrification. Compared with nitrate, high sulfate concentration would not have significant impact on the reductive dechlorination of TCE. Results reveal that higher TCE removal efficiency was observed in microcosms with emulsified substrate addition followed by the addition of high sulfate concentration, high nitriate concentration, groundwater (without substrate addition). Results from the gene analysis show that phenol monooxygenase, toluene monooxygenase, and toluene dioxygenase were observed in the microcosms with lecithin, cane molasses, Simple GreenTM, and emulsified substrate. This indicates that the addition of substrates would induce the potential of TCE-degrading enzyme. Addition of emulsified substrate and emulsified substrate in nitrate or sulfate-rich media would stimulate Dehalococcoides sp. to induce tceA, bvcA, and vcrA, enzymes for TCE reductive dechlorination.

Chlorinated solvents are among the most prevalent contaminants at Superfund sites. Perchloroethylene (PCE) and its degradative byproducts pose a particular problem because of their persistence in the subsurface and their threat to ecological health. In this study, microcosms were used to test the viability of bioaugmentation as a possible remediation strategy at a PCE contaminated site at the Naval Amphibious Base at Little Creek located in Virginia Beach, Virginia. All microcosms were created in duplicate using spatially diverse soils and the bioaugmented series innoculated with a mixed microbial culture provided by the Dr. Frank Loffler. This culture has been found to be capable of completely degrading PCE to ethene. The aqueous ethene concentration was monitored over time. It is clear from the results that bioaugmentation successfully increased the degree of reductive dechlorination over their static counterpart. Without innoculation, shallow static microcosms showed an accumulation of cis-DCE, while deep soils never showed conversion beyond TCE. Shallow bioaugmented microcosms showed the production and loss of vinyl chloride indicated probable complete conversion of PCE to ethene while deep soils showed the production of cis-DCE. These differences in dechlorination between shallow and deep soils indicate a possible disparity in reduction capacity. At day 78, microcosms were spiked with higher concentrations of PCE resulting in a reduction in dechlorination activity. Static microcosms exhibited similar degradative trends but bioaugmented batches experienced dramatic reductions in dechlorination activity indicating possible inhibition effects of native organisms due to concentration or potential toxic shock. It appears that bioaugmentation is a remediation alternative worthy of further study including possible delivery methods, toxicity or inhibition effects of concentration, and fate/transport studies. / Master of Science

Numerical models (GMS MODFLOW, SEAM3D, and SEAM3D Interface) were applied to simulate groundwater flow, petroleum hydrocarbon compound (PHC) transport and biodegradation, and the transport and biotransformation of chlorinated ethenes at Site FT-002 Plattsburgh Air Force Base (PAFB), NY. Site FT-002 was contaminated with waste jet fuel and chlorinated ethenes used as a fire source during fire fighting training. The results of groundwater analysis indicated that the aquifer exhibited aerobic, nitrate reducing, ferrogenic, sulfate reducing and methanogenic conditions due to the biodegradation of the PHCs. Additional groundwater analysis showed the biotransformation of TCE to DCE, VC, and ethene. A numerical model was developed to simulate and assess the extent to which reductive dechlorination and direct anaerobic oxidation were responsible for the biotransformation of the chlorinated ethenes. Reductive dechlorination accounted for the 100%, 98.3%, and 97.5% of the biotransformation of TCE, DCE, and VC respectively. Direct anaerobic oxidation accounted for 1.7% and 2.5% of the biotransformation of DCE and VC respectively. Though direct anaerobic oxidation only accounted for a small percentage of total biotransformation it was necessary to fully develop the biotransformation of the DCE and VC in the ferrogenic zone. This study focused on the mechanisms responsible for the biotransformation of chlorinated ethenes, specifically reductive dechlorination and direct anaerobic oxidation. By further defining the NAPL source and initial conditions it could be used as a tool to accurately predict the monitored natural attenuation (MNA) of the FT-002 contaminant plume. / Master of Science

Remediation of chlorinated ethene contaminated sites presents a problem for the environmental industry. Many innovative technologies exist to remove these chemicals from the subsurface; however, most of these technologies require extensive time and incur significant cost. A technology called bioremediation utilizes microorganisms to break down contaminants such as perchloroethene (PCE), trichloroethene (TCE), dichloroethene (DCE), and vinyl chloride (VC) to non-toxic compounds in a process called reductive dechlorination. Microorganisms that are capable of dechlorination usually require reducing conditions as well as bioavailable hydrogen and carbon sources. Emulsified vegetable oil has emerged as a cost-effective source of degradable organic matter to facilitate reductive dechlorination in the subsurface. Through Æ Ã -oxidation, microorganisms can break down the long chain fatty acids in vegetable oil into smaller fatty acids such as acetate, propionate, and butyrate. The fermentation of the oil provides reduced conditions as well as a slow release of hydrogen and carbon into the subsurface. This study consisted of an evaluation the effectiveness of emulsified vegetable oil in stimulating reductive dechlorination using sixteen laboratory microcosms constructed from soil and groundwater from an aquifer contaminated with TCE located at the Naval Weapons Station in Charleston, South Carolina. Each microcosm was monitored for chloroethenes, volatile fatty acids, long chain fatty acids, and total carbon on a weekly basis. Results show successful fermentation of fatty acids and reduced conditions favorable for dechlorination. / Master of Science

No description available.

Cette thèse fait partie du projet FLUXOBAT (ANR-PRECODD 2008), qui a pour objectif global de développer une méthodologie robuste et fiable d4estimation des transferts de Composés Organiques Volatils (COV) du milieu souterrain vers l4air intérieur et extérieur. Ce travail concerne l4étude à l4échelle du laboratoire des transferts d4un COV type, le trichloréthylène (TCE), au travers d4un sol modèle (sable) et surtout du béton, en conditions isothermes et pour des milieux secs. Les moyens utilisés sont la modélisation numérique et une série d4expériences en laboratoire. Une étude préliminaire reproduisant des expériences existant dans la littérature dans le sable uniquement, a tout d4abord permis de mettre en place les outils expérimentaux et numériques nécessaires à la modélisation du problème, avant la réalisation de l4étude sur le matériau béton, bien plus complexe. L4étude des transferts dans le béton a été divisée en plusieurs étapes. Dans un premier temps, les transferts dans la pâte de ciment, plus homogène, ont été caractérisés. En particulier, la valeur du coefficient de sorption du TCE dans ce matériau a été obtenue à l4aide du suivi expérimental de la réponse à un « pulse » de polluant. Puis, les paramètres caractéristiques (porosité, perméabilité, ouverture des fissures, coefficient de diffusion effectif) des échantillons tests de « béton complet » ont été mesurés. Un protocole de caractérisation complète des galettes de béton a été mis au point, associé à la création d4un dispositif permettant la mise en place d4expériences de transferts du TCE (composé dont l4étude est complexifiée par son caractère particulièrement agressif) et applicables à tout milieu poreux consolidé. La problématique de l4hétérogénéité du béton, due à la présence de granulats et de fissures, a été traitée afin de proposer des équations de transfert moyennées donnant une meilleure description des transferts. Les conditions d4un cas de pollution « réel » ont été reproduites à l4échelle du laboratoire, sur un modèle réduit, dans une colonne de sable surmontée d4une galette de béton et d4une cavité en dépression représentant un bâtiment, pour étudier les transferts de TCE et valider la caractérisation développée dans l4étude. Les expériences de transferts réalisées sont reproductibles, ont été interprétées numériquement (sous Comsol multiphysics®), et ont permis de confirmer la pertinence de la simulation des transferts à l4aide de la caractérisation développée dans cette étude. Ce travail a permis de mettre, en particulier, en évidence l4importance de la caractérisation fine du béton, dont les propriétés et l4hétérogénéité sont des facteurs très influents sur les transferts, qui ne peuvent pas être décrits correctement avec des modèles analytiques simplifiés. Les résultats comportent l4estimation des paramètres caractérisant les transferts de COV dans le béton, et une compréhension fine des transferts du TCE dans ce matériau. / This thesis is part of the project FLUXOBAT (ANR-PRECODD 2008), which has the overall objective to develop, a robust and reliable methodology for estimating the transfer of Volatile Organic Compounds (VOC) from the soil to the indoor and outdoor air. This work concerns the study, at laboratory scale, of a typical VOC, the Trichlorethylene (TCE), transfer through a model soil (sand) and through the concrete material, under isothermal and dry conditions. Methods used include numerical modeling and a series of laboratory experiments. A preliminary study replicating experiences existing in the literature, with sand only, was first implemented to develop the tools necessary for experimental and numerical modeling of the problem, before the completion of the study with the concrete material, although more complex. The study of transfers in concrete has been divided into several stages. Initially, the transfers in the cement paste, more homogeneous, have been characterized. In particular, the value of the sorption coefficient of TCE in this material was obtained using the experimental response to a "pulse" of pollutant. Then the characteristic parameters (porosity, permeability, crack opening, effective diffusion coefficient) of "complete concrete" test samples were measured. A protocol for complete characterization of concrete slabs has been developed, associated with the creation of a device for the implementation of TCE transfer experiences (compound whose study is complicated by its very aggressive character) and applicable to any consolidated porous medium. The problem of heterogeneity of concrete, due to the presence of aggregates and cracks, has been treated to propose averaged transfer equations, giving a better description of the transfers. The conditions of a "real" pollution incident were reproduced in laboratory, modeled by a sand column topped by a concrete slab and a vacuum cavity representative of a building, in order to study the transfer of TCE and validate the characterization developed in the study. The transfer experiments are reproducible, were numerically interpreted (with COMSOL Multiphysics®), and have confirmed the relevance of the transfer simulation using the characterization developed in this study. This work has enabled, in particular, to highlight the importance of detailed characterization of the concrete, which properties and heterogeneity are exceedingly influential on transfers, and which cannot be described correctly with simplified analytical models. The results include the estimation of parameters characterizing the transfer of VOCs into the concrete, and a keen understanding of transfer of TCE in this material.