Ce manuscrit s'intéresse au devenir de contaminants organiques dans le sol, et plus précisément celui des composés organo-halogénés volatils (COHV).Il propose des outils d'aide à la décision en utilisant la modélisation numérique appliquée à des problématiques environnementales portant sur le traitement de sites et sols pollués par des COHV. Il présente, à ma connaissance, la première modélisation numérique en 3D, grâce au simulateur TMVOC, d'une technique de dépollution physique, à savoir le pompage réussi au sein d'un aquifère d'un liquide en phase non-aqueuse plus dense que l'eau ou Dense Non-Aqueous Phase Liquid (DNAPL). Les très bons résultats de cette simulation permettent d’envisager l’optimisation d’un système de pompage asservi pour dépolluer un site contaminé aux COHV. Cette thèse s'intéresse aussi à une méthode de d'évaluation, à la fois qualitative et quantitative, de l'efficacité du pompage : un test de traçage utilisant des traceurs bisolubles à coefficients de partage variables (partitioning interwell tracer test – PITT). Ce PITT permet de connaître à la fois la répartition spatiale, au sein d’un aquifère, d’une bulle de DNAPL et aussi d’en évaluer sa saturation et donc son volume. Ce manuscrit met à disposition des outils élaborés et adaptés au traitement d'un DNAPL dans un aquifère. La combinaison des deux techniques présentées, à savoir la modélisation d'un pompage de DNAPL et un PITT, sont parfaitement reproductibles dans des environnements similaires et à l'échelle industrielle. Enfin, ces méthodes permettent de réduire considérablement les coûts de caractérisation (PITT) et d'exploitation par l'optimisation de systèmes de pompage / This manuscript deals with the fate of organic contaminants in soil, more precisely of volatile organo-chlorinated compounds (VOHC) and offers some decision making techniques and tools using numerical modelling applied to environmental issues about the treatment of soils contaminated by VOHC. It presents, to the best knowledge of the auhor, the first 3D numerical modelling, with the simulator TMVOC, of a physical treatment technique, namely the successful pumping within an aquifer, of a Dense Non-Aqueous Phase Liquid (DNAPL). The very good results of this simulation give the opportunity to design a controlled and automated pumping system to remediate a polluted site. This thesis also deols with a tracer test assessment method, both qualitative and quantitative, for the efficiency of this pumping : a partitioning interwell tracer test (PITT). The PITT allows us to determine the spatial repartion of the DNAPL and also to assess its saturation, hence its volume. This manuscript offers elaborated tools adapted to the remediation of a DNAPL in an aquifer. The combination of these two techniques, namely the DNAPL pumping and the PITT, are perfectly reproducible in similar environments up to an industrial scale. Finally, exploitation and characterisation costs for DNAPL remediation can be extremely reduced by numerical modelling and optimisation

Les zones sources formées par les organochlorés dans les sols (DNAPL) peuvent contaminer les aquifères pour plusieurs siècles en alimentant un panache de composés dissous. Pour épuiser ces zones sources, pomper le DNAPL est la solution la plus simple, mais l’efficacité est limitée par le cheminement préférentiel de l'eau dans le sol et les forces capillaires qui piègent le DNAPL. Les stratégies plus agressives (dissolution, traitement thermique, dégradation chimique…) sont aussi plus coûteuses. Dans cette thèse, deux stratégies de traitement à base de mousse de surfactant ont été développées et évaluées au laboratoire en préparation d’un essai terrain. La première stratégie utilise l’injection de mousse en zone source pour mobiliser de façon contrôlée le DNAPL et le diriger vers des puits de pompage. Dans les meilleures conditions, la saturation en DNAPL après traitement a pu être abaissé en dessous de 1 % avec une consommation de surfactant inférieure à 10 g kg-1 de DNAPL éliminé. La seconde stratégie utilise la mousse comme vecteur de réactif (hydrogène) pour accélérer la biodégradation des composés dissous dans le panache. Sous forme de mousse, l’hydrogène a été délivré de façon ciblée et plus rémanente dans l’horizon à traiter. Les technologies développées se sont montrées très prometteuses à l’échelle du terrain et lors de l’évaluation technico-économique. De la recherche reste nécessaire pour rendre ces procédés plus prédictibles lors de leur mise en œuvre. / Source zones formed by chlorinated organic compounds in soils (DNAPL) can contaminate aquifers for several centuries by feeding a plume of dissolved compounds. To deplete those source zones, DNAPL pumping is the simplest option, but the efficacy is limited by preferential water flow in the soil and capillary forces that are trapping the DNAPL. More aggressive strategies (dissolution, thermal treatment, chemical degradation...) are also costlier. Within this thesis work, two treatment strategies using surfactant foam were developed and assessed at lab-scale to prepare field assessment. The first strategy relies on foam injection in the source zone to mobilize the DNAPL in a controlled fashion to drive it ahead to pumping wells. In the best conditions, DNAPL saturation was lowered below 1% after treatment with a surfactant consumption below 10 g kg-1 of DNAPL removed. The second strategy uses foam as a reagent (hydrogen) carrier to accelerate the biodegradation of dissolved compounds in the plume. When injected as a foam, hydrogen was delivered in a targeted and more persistent manner in the strata to be treated. Developed technologies showed to be promising at field-scale and when the technico-economic assessment was conducted. Research still remains to be done to make those techniques more predictable during their implementation.

A study was carried out in a sedimentary fractured rock site located in south central Wisconsin, US, which was impacted by DNAPL releases estimated to occur in the 1950’s and 1960’s. The majority of the DNAPL has accumulated in the upper portion of the Lone Rock Formation at a depth between 140 and 180 ft bgs referred as Layer 5 in this study. A groundwater VOC plume of more than 3km long has formed in this Layer. The DNAPL is mainly composed of 1,1,1-TCA, PCE, TCE and BTEX, while large amounts of biodegradation products such as cis-DCE and 1,1-DCA are present in the plume. Long term VOC data have been collected at the site and diverse geological and hydrogeological techniques have been applied to have a better understanding of the DNAPL history and behavior of the VOC plume. Evidence of biodegradation was also documented near the DNAPL source in these studies. The thesis objectives of the present study aimed first to have a better understanding of the long term contaminant distribution and degradation history at the site. This objective was accomplished reviewing the VOC historical concentration data collected from 1992 to 2006 in the wells tapping the most contaminated. hydrogeological unit in the bedrock (Layer 5) and in the overburden aquifer (referred as Layer 2). The second objective aimed to evaluate the current degree or extent of biodegradation of chlorinated compounds, which was accomplished evaluating the current groundwater redox conditions and using a combined analysis of VOC concentration and carbon isotope data collected in groundwater in September 2007. The historical data collected between1992 to 2006 showed the degradation of the VOC plume in Layer 5 was controlled by the availability of electron acceptors and redox conditions in the fracture bedrock aquifer. This pattern and the extension of the VOC plume were linked to different DNALP pumping events in the source zone and the operation of a Hydraulic Barrier System. The current geochemical and isotope study showed a different pattern of biodegradation of chlorinated compounds in different parts of the plume. The cis-DCE tend to accumulate in the area from the source to the middle of the plume and around 80 % of biodegradation of 1,1,1-TCA to 1,1-DCA was observed in this area. The fringes of the plume were characterized by a dominant presence of TCE and 1,1,1 TCA. These patterns were linked to different redox conditions and amount of electron acceptors. The cis-DCE dominated area is characterized by anaerobic conditions and the presence of relative high amount of BTEX. The TCE-dominated area is under aerobic condition and no BTEX was found in this area. The operation of the Hydraulic Barrier System seems to have change redox condition which influenced the extent of degradation in the plume, especially in the area between the extraction wells. The formation of large amounts of VC in Layer 2 and the more reducing (at least sulfate reducing and maybe methanogenic conditions) of the groundwater in this Layer compared to Layer 5 confirmed the extent of VOC biodegradation is linked to the availability of electron donors. This study provides information about the current degree of the biodegradation of chlorinated compounds at a fracture rock site. This information is very valuable for the evaluation of natural attenuation as strategy for long term plume management or for future remediation strategies such as biostimulation or bioaugmentation at the site. This study also shows the present and long term behavior of the chlorinated compounds (degradation history) in the most contaminated hydrogeologic unit (Layer 5), has mainly been controlled by plume management strategies including DNAPL pumping in the source and the creation of a Hydraulic Barrier System. The ketones and BTEX, that acted as electron donors and carbon substrate for the microbial community responsible for the dechlorination of chlorinated compounds were shown to have controlled the past and current redox conditions and thus the degree and potential of biodegradation of chlorinated ethenes and chlorinated ethanes at the study site.

A study was carried out in a sedimentary fractured rock site located in south central Wisconsin, US, which was impacted by DNAPL releases estimated to occur in the 1950’s and 1960’s. The majority of the DNAPL has accumulated in the upper portion of the Lone Rock Formation at a depth between 140 and 180 ft bgs referred as Layer 5 in this study. A groundwater VOC plume of more than 3km long has formed in this Layer. The DNAPL is mainly composed of 1,1,1-TCA, PCE, TCE and BTEX, while large amounts of biodegradation products such as cis-DCE and 1,1-DCA are present in the plume. Long term VOC data have been collected at the site and diverse geological and hydrogeological techniques have been applied to have a better understanding of the DNAPL history and behavior of the VOC plume. Evidence of biodegradation was also documented near the DNAPL source in these studies. The thesis objectives of the present study aimed first to have a better understanding of the long term contaminant distribution and degradation history at the site. This objective was accomplished reviewing the VOC historical concentration data collected from 1992 to 2006 in the wells tapping the most contaminated. hydrogeological unit in the bedrock (Layer 5) and in the overburden aquifer (referred as Layer 2). The second objective aimed to evaluate the current degree or extent of biodegradation of chlorinated compounds, which was accomplished evaluating the current groundwater redox conditions and using a combined analysis of VOC concentration and carbon isotope data collected in groundwater in September 2007. The historical data collected between1992 to 2006 showed the degradation of the VOC plume in Layer 5 was controlled by the availability of electron acceptors and redox conditions in the fracture bedrock aquifer. This pattern and the extension of the VOC plume were linked to different DNALP pumping events in the source zone and the operation of a Hydraulic Barrier System. The current geochemical and isotope study showed a different pattern of biodegradation of chlorinated compounds in different parts of the plume. The cis-DCE tend to accumulate in the area from the source to the middle of the plume and around 80 % of biodegradation of 1,1,1-TCA to 1,1-DCA was observed in this area. The fringes of the plume were characterized by a dominant presence of TCE and 1,1,1 TCA. These patterns were linked to different redox conditions and amount of electron acceptors. The cis-DCE dominated area is characterized by anaerobic conditions and the presence of relative high amount of BTEX. The TCE-dominated area is under aerobic condition and no BTEX was found in this area. The operation of the Hydraulic Barrier System seems to have change redox condition which influenced the extent of degradation in the plume, especially in the area between the extraction wells. The formation of large amounts of VC in Layer 2 and the more reducing (at least sulfate reducing and maybe methanogenic conditions) of the groundwater in this Layer compared to Layer 5 confirmed the extent of VOC biodegradation is linked to the availability of electron donors. This study provides information about the current degree of the biodegradation of chlorinated compounds at a fracture rock site. This information is very valuable for the evaluation of natural attenuation as strategy for long term plume management or for future remediation strategies such as biostimulation or bioaugmentation at the site. This study also shows the present and long term behavior of the chlorinated compounds (degradation history) in the most contaminated hydrogeologic unit (Layer 5), has mainly been controlled by plume management strategies including DNAPL pumping in the source and the creation of a Hydraulic Barrier System. The ketones and BTEX, that acted as electron donors and carbon substrate for the microbial community responsible for the dechlorination of chlorinated compounds were shown to have controlled the past and current redox conditions and thus the degree and potential of biodegradation of chlorinated ethenes and chlorinated ethanes at the study site.

Iron-based degradative solidification/stabilization (Fe(II)-DS/S) is a treatment method that could be economically applied to smaller DNAPL-contaminated sites and to those sites with impermeable soils. Reductive dechlorination is achieved by compounds that are formed by reaction of ferrous iron with components of Portland cement or with defined chemicals (FeCl3 + Ca(OH)2). These dechlorinating agents can effectively degrade chlorinated hydrocarbons (PCE, TCE, and 1,1,1-TCA) that are dissolved in aqueous solution. This research investigated the application of Fe(II)-DS/S to remove chlorinated hydrocarbons that are present as DNAPLs in source zones and to compared the reactivity of ferrous iron in different mixtures, including the conventional mixture with cement (Fe(II)+C) and an iron-solid mixture (ISM) that was synthesized without the addition of cement. The modified first-order model, which the rate was proportional to the concentration of target in the aqueous phase and it was also nearly constant when DNAPL was present, was developed to describe dechlorination kinetics. The modified second-order model assumed that the rate was proportional to the product of the concentration of target in the aqueous phase and the concentration of reductive capacity of the solid reductant. The modified first-order model was used to describe degradation of target compounds with ISM, and the modified second-order model was used to describe removals for TCE and 1,1,1-TCA with Fe(II)+C. Results of experiments on PCE dechlorination with ISM indicated that the increase of Fe(II) in ISM increased rate constants and decreased the solubility of targets. The half-life was increased with increasing total PCE concentration. The product analysis implied that degradation of PCE with ISM was via a combination of the hydrogenolysis and β-elimination pathways. A comparison of the types of targets and reductants indicated that Fe(II)+C had better reactivity for chlorinated ethenes (PCE and TCE) than ISM. However, ISM could dechlorinate a chlorinated ethane (1,1,1-TCA) as rapidly as Fe(II)+10%C. The ratio of [RC]o/[Fe(II)]o implied that Fe(II) in Fe(II)+C was more involved in reducing chlorinated ethenes than was Fe(II) in ISM. Dechlorination of a DNAPL mixture followed the same order of reactivity as with individual DNAPLs with both reductants.

La pollution des sols par les solvants chlorés constitue un problème environnemental majeur avec des conséquences importantes sur la pollution des eaux, et donc, sur l'utilisation de cette ressource essentielle. Parmi les procédés de traitement, l'oxydation in situ apparaît comme une alternative viable, de grand intérêt, en ce qui concerne le traitement des polluants en phase organique (DNAPL). L'objectif principal de ce travail a été d'analyser les limitations cinétiques contrôlant l'oxydation du percloroethylène (PCE) en phase DNAPL avec des solutions de KMnO4, et cela dans des conditions diverses d'opération : concentration d'oxydant, aire interfaciale, mode de contact et phases en contact, principalement. Au préalable à cette étude, des méthodes analytiques ont été développées, notamment pour l'analyse du PCE en phase aqueuse. Dans un système homogène à température constante et en phase aqueuse la vitesse de la réaction a été mesurée et une loi cinétique a été proposée, valable dans une gamme étendue des compositions. Puis la réaction a été étudiée en système polyphasique, L/L (réacteur agité) et S/L/L (milieu poreux). La démarche consistait à déterminer dans des expériences sans oxydant (dites de dissolution) le coefficient de transfert de matière caractéristique du système, puis de l'appliquer au calcul du nombre de Hatta. Ce critère adimensionnel apporte des informations sur la localisation de la réaction, et donc sur la vitesse relative des phénomènes de transfert et réaction en série. Dans les conditions expérimentales étudiées plusieurs régimes de fonctionnement, caractérisés par des valeurs du critère de Hatta allant de 0,03 à 3,6 ont été observés. Par conséquent, le processus d'oxydation peut être contrôlé soit par le transfert soit par la réaction, et cela que l'on soit en réacteur agité qu'en milieu poreux. / The pollution of soils with chlorinated solvents is a major environmental problem with important consequences for the water contamination, hence for the utilisation of this essential resource. Among the treatment processes, in situ chemical oxidation appears as a viable alternative, of great interest for the treatment of dense non aqueous phase liquids (DNAPL). The aim of this work was to analyse the kinetic limitations controlling perchloroethylene (PCE) oxidation in dense non aqueous phase liquid with permanganate (KMnO4) solutions and that in diverse operational conditions: oxidant concentration, interfacial area, contact mode and contact phases, mainly. First, analytical methods were developed, especially for PCE analyse in aqueous phase. In a homogeneous system, at constant temperature and in aqueous phase, the real reaction rate was measured and a kinetic low was proposed, applicable to a large range of compositions. Then, the reaction was studied in a multiphase system, L/L (batch reactor) and S/L/L (porous media). The procedure consisted in establishing the mass transfer coefficient of the system in experiments without oxidant (so-called of dissolution), then applying it to the identification of Hatta number. This dimensionless criterion brings us information about the reaction location and consequently, about the relative rate of the global process. In the studied experimental conditions, several operational regimes, characterised by Hatta values in a range from 0.03 to 3.6, were observed. Therefore, the oxidation process can be controlled either by transfer or by reaction and that even in batch reactor and in porous media

No description available.

Phytoremediation is an attractive remediation technology due to its relative low cost and maintenance requirement. Acceptance of phytoremediation requires that the contaminant removal mechanisms are characterized and demonstrated in the field. Quantification of contributions from each mechanism to the overall remediation rate is crucial for optimization of phytoremediation systems, risk management and prediction of the total remediation time. The objective of this research was to characterize and quantify removal mechanisms for naphthalene at a creosote-contaminated site with poplar trees in Oneida, Tennessee. Groundwater monitoring for seven years in the surficial aquifer at this site demonstrated a reduction in polycyclic aromatic hydrocarbons (PAHs) with selective removal of naphthalene and three-ring compounds. Naphthalene mass loss mechanisms investigated at this site are biodegradation in the saturated zone, volatilization and biodegradation in the vadose zone and phytovolatilization. This is probably the most comprehensive field study of PAH phytoremediation mechanisms conducted to date. The significance of this research is to contribute to predictions of remediation time and end result for phytoremediation of PAHs. The understanding of in situ factors controlling each mechanism can facilitate future optimization of phytoremediation systems as well as improve risk assessment and monitoring strategies. Biodegradation rates were determined for different conditions at this site with in situ respiration tests, laboratory soil microcosms and laboratory soil columns. The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated in the field and in laboratory columns. Field measurements show that lower groundwater elevations in the summer and early fall lead to elevated groundwater concentrations of naphthalene and increased volatilization. The increase in the fraction of the porespace occupied by gas (gas saturation) in the unsaturated zone during the summer and fall further enhances the volatilization by increasing effective diffusion rates. Water consumption and interception by the phytoremediation system are believed to enhance mass transfer to the vadose zone. Column experiments and field measurements show that more than 90% of the naphthalene vapors are biodegraded within 5-10 cm above the groundwater table. The data indicate that biodegradation increases the overall volatilization flux out of the source by 10-300 times, when the source is exposed directly to the gas phase. In situ the naphthalene is generally dissolved from the source into the groundwater and then volatilezed from the groundwater to the gas phase. Under these conditions biodegradation in the vadose zone will still indirectly have an enhancing effect on the flux out of the source. This is the result of removal naphthalene from the soil gas by biodegrdation driving removal from the groundwater by volatilization, which in turn drives dissolution form the source into the groundwater. Phytovolatilization was quantified in flux chambers mounted on trees and calculated from transpiration rates. A laboratory uptake study and analysis of tree cores from the site provided supplementary evidence for naphthalene uptake by poplar trees. Phytovolatilization was detected throughout the year and was highest in the summer and fall when the groundwater concentrations were highest and transpiration was active. The role of biodegradation relative to physical removal mechanisms was compared for a year, for winter and summer conditions and with and without the impact of phytoremediation. Biodegradation of naphthalene in the saturated zone dominates by orders of magnitude over the removal by volatilization and phytovolatilization of naphthalene at this site. The removal of the total residual naphthalene mass was estimated to require up to 100 years with phytoremediation, but more than twice as long without phytoremediation. The estimated removal of naphthalene was three times larger in the summer than in the winter due to slower biodegradation in the saturated zone and smaller rates of volatilization to the vadose zone in the winter. The research shows that phytoremediation enhances the overall naphthalene removal, mainly by stimulating faster biodegradation in the rhizosphere and promoting mass transfer of naphthalene to the vadose zone followed by rapid vadose zone biodegradation. In the future, phytoremediation research focusing on the capillary zone is desirable. / Ph. D.

Volatile organic compound (VOC) contamination of low permeability geologic deposits due to Dense Non-Aqueous Phase Liquid (DNAPL) penetration through fractures is exceptionally difficult to remediate using in-situ methods as the low permeability of the sediments limits the delivery of reagents proximal to contaminant mass. This thesis examines in detail the extent of organic contaminant treatment away from hydraulically-induced fractures injected with particulate Zero Valent Iron as (1) ZVI and glycol (G-ZVI) and (2) an emulsified ZVI (EZVI) mixture within a contaminated glaciolacustrine clayey deposit. Continuous vertical cores were collected through the treatment zone at 2 and 2.5 years after substrate injections and soil sub-sample spacing was scaled to show the extent of the treatment zone adjacent to the ZVI in the fractures, expecting the treatment would be controlled by diffusion limited transport to the reaction zone. Analytical results show evidence of treatment in both the EZVI and the G-ZVI containing fractures with the presence of degradation by-products and reduced VOC concentrations in the fracture and surrounding clay matrix. / Natural Sciences and Engineering Research Council of Canada, University Consortium for Field-Focused Groundwater Contamination Research

No description available.