This research is about the development of a photocatalytic reactor design, Honeycomb, for in-situ groundwater remediation. Photocatalysis, typically a pseudo first order advanced oxidation process, is initiated via the illumination of UVA light on the catalyst, i.e. titanium dioxide (TiO2). In the presence of oxygen, highly reactive oxidising agents are generated such as superoxide (O2-), hydroxyl (OH.-) radicals, and holes (hvb+) on the catalyst surface which can oxidise a wide range of organic compounds. The target contaminant is methyl tert butyl ether (MTBE), a popular gasoline additive in the past three decades, which gives the water an unpleasant taste and odour at 20 μg L-1, making it undrinkable. This research consists of three major parts, i.e. (i) establishing a suitable catalyst immobilisation procedure, (ii) characterisation and evaluation of reactor models and (iii) scale up studies in a sand tank. TiO2 does not attach well onto many surfaces. Therefore, the first step was to determine a suitable immobilisation procedure by preparing TiO2 films using several potential procedures and testing them under the same conditions, at small scale. The coatings were evaluated in terms of photocatalytic activity and adhesion. The photocatalytic activity of the coatings was tested using methylene blue dye (MB), which is a photocatalytic indicator. A hybrid coating, which comprises a sol gel solution enriched with Aeroxide TiO2 P25 powder, on woven fibreglass exhibited the best adhesion and photocatalytic activity among samples evaluated. Thus, it was used to produce immobilised catalyst for this research. Consequently, the immobilisation procedure was scaled up to synthesize TiO2 coatings for the potential photocatalytic reactor design. The photocatalytic activity of the coatings produced from the scaled up immobilisation procedure were reasonably comparable to that produced at small scale. Due to the UVA irradiation and mass transfer limitations, photocatalytic reactors are typically compact in order to maximise their efficiency to accommodate high flows, particularly in water and wastewater treatment. In the case of groundwater, however, the treatment area can span up to meters in width and depth. Groundwater flow is significantly lower than that of water treatment, as the reactor design does not need to be compact. Considering both factors, a photocatalytic reactor design of hexagonal cross-section (Honeycomb) was proposed, in which the structures can be arranged adjacent to each other forming a honeycomb. A model was constructed and tested in a 4 L column (cylindrical) reactor, using the MB test to characterise the reactor performance and operating conditions. This was followed by a hydraulic performance study, which encompasses single and double pass flow studies. The single pass flow study involves the photocatalytic oxidation (PCO) of MB and MTBE, while the double pass flow study was focused on the PCO of MTBE only. The double pass can simulate two serially connected reactors. Single pass flow studies found that the critical hydraulic residence time (HRT) for the PCO of MB and MTBE is approximately 1 day, achieving up to 84 % MTBE removal. Critical HRT refers to the minimum average duration for a batch of contaminant remaining in the reactor in order to maintain the potential efficiency of the reactor. Double pass studies showed the reactor can achieve up to 95 % MTBE removal in 48 hours, and that reactor performance in the field of serially connected reactors can be estimated by sequential order of single pass removal efficiency. In groundwater, there are likely to be other impurities present and the effects of groundwater constituents on the reactor efficiency were studied. The MTBE PCO rate is affected by the presence of organic compounds and dissolved ions mainly due to the competition for hydroxyl radicals and the deactivation of catalyst surface via adsorption of the more strongly adsorbed organic molecules and ions. Despite the presence of organic compounds and dissolved ions, the reactor achieved about 80 % MTBE removal in 48 hours. A double pass flow study showed that the overall efficiency of the photocatalytic reactor in the field can be estimated via sequential order of its efficiency in a single pass flow study using the actual groundwater sample in the laboratory. A sand tank was designed for the simulation of the clean up of an MTBE plume from a point source leakage using the 200 mm i.d. Honeycomb I prototype. Honeycomb I achieved up to 88.1 % MTBE removal when the contaminated groundwater flowed through (single pass) at 14.6 cm d-1. The critical HRT for Honeycomb I was also approximately 1 day, similar to that in the column reactor. The response of MTBE removal efficiency towards flow obtained in the column reactor and sand tank was generic, indicating that the reactor efficiency can be obtained via testing of the model in the column reactor. The presence of toluene, ethylbenzene and o-xylene (TEo-X) decreased the MTBE removal efficiency in both the sand tank and column reactor. The same set of catalyst and 15 W Philips Cleo UVA fluorescent lamp was operated for a total of about 582 h (24 d) out of the cumulative 1039 h (43 d) sand tank experiments, achieving an overall MTBE removal efficiency of about 76.2 %. The experiments in the column reactor and sand tank exhibited the reliability of the immobilised catalyst produced in this research. This research demonstrates the potential of Honeycomb for in-situ groundwater remediation and also proposes its fabrication and installation options in the field.

Current prices and demand for petroleum hydrocabons have generated an increase of oil spills around the country and the world. Health and environmental impacts associated to these organic pollutants represent a huge concern for the general public, leading the public and private sector to develop new technologies and methods to minimize or eliminate those risks. Ex-Situ bioremediation through biopiles, as a main remediation technique to treat a wide range of hydrocarbons, has been a topic of considerable research interest over the last years. It provides an economical and environmental solution to restore the environment to background levels. Nevertheless, successful bioremediation under cold climate conditions is of considerable concern in countries like Canada, as low temperatures can delay the rate of bioremediation of oil hydrocarbons, thus limiting the operation of soil treatment facilities to certain times of the year. Recent research has found out that bioremediation could be conducted even at low or cold temperatures with larger periods of times. And even more, the addition of petroleum degrading microorganisms (bioaugmentation) and nutrients or biosurfactants (biostimulation) could enhance the process in some cases. In the present study, a comprehensive assessment of bioaugmentation and biostimulation strategies for ex-situ bioremediation of petroleum contaminated soil under cold climate conditions is proposed. Field scale biopiles were constructed and subjected to different concentrations of commercial microbial consortia and mature compost, as bioaugmentation and biostimulation strategies, in a soil treatment facility at Moose Creek, Ontario over a period of 94 days (November 2012 to February 2013). Assessment and comparison of the biodegradation rates of total petroleum hydrocarbons (TPH) and their fractions were investigated. Furthermore, a response surface methodology (RSM) based on a factorial design to investigate and optimize the effects of the microbial consortia application rate and amount of compost on the TPH removal was also assessed. Results showed that biopiles inoculated with microbial consortia and amended with 10:1 soil to compost ratio under aerobic conditions performed the best, degrading 82% of total petroleum hydrocarbons (TPHs) with a first-order kinetic degradation rate of 0.016 d_1, under cold temperature conditions. The average removal efficiencies for TPHs after 94 days for control biopiles, with no amendments or with microbial consortia or compost only treatments were 48%, 55%, and 52%, respectively. Statistical analyses indicated a significant difference (p < 0.05) within and between the final measurements for TPHs and a significant difference between the treatment with combined effect, and the control biopiles. On the other hand, the modeling and optimization statistical analysis of the results showed that the microbial consortia application rate, compost amendment and their interactions have a significant effect on TPHs removal with a coefficient of determination (R2) of 0.88, indicating a high correlation between the observed and the predicted values for the model obtained. The optimum concentrations predicted via RSM were 4.1 ml m-3 for microbial consortia application rate, and 7% for compost amendment to obtain a maximum TPH removal of 90.7%. This research contributes to provide valuable knowledge to practitioners about cost-effective and existing strategies for ex-situ bioremediation under cold weather conditions.

This thesis presents a model for developing site-specific contingency plans to be used during spill response, remediation, and post-spill monitoring using the Strategic Petroleum Reserve's Bryan Mound site as a case study. Bird and vegetation observations provide baseline data for biological conditions, and sediment sampling for total petroleum hydrocarbons serves as a chemical component of the model. Results demonstrate previously unknown conditions that would hinder remediation and affect the persistence of petroleum contaminants. Results also established previously unmapped dominant bird and vegetation types likely to be impacted by a spill at the site. This model points to a reconsideration of individual facilities' responsibilities when planning for large-scale disasters and protecting the sensitive ecosystems surrounding their sites.

No Brasil, a contaminação do solo por derramamentos de combustíveis representa um dos mais graves problemas ambientais e o impacto da introdução de novas misturas como diesel/biodiesel na matriz energética requer investigação quanto a tecnologias apropriadas de remediação. O presente estudo teve por objetivo avaliar diferentes estratégias de biorremediação no tratamento de solo contaminado experimentalmente com óleo diesel B5. Foram conduzidos três experimentos. No primeiro, quatro microcosmos em duplicata, contendo 500 g de solo e 5% (p/p) de óleo diesel B5, todos suplementados com oxigênio através de revolvimento manual e com ajuste de umidade, tiveram como tratamentos: bioestímulo com ajuste de pH (BE1); bioestímulo com ajuste de pH e nutrientes (BE2); bioaumento com ajuste de pH, nutrientes e adição de consórcio microbiano comercial KMA (BAM) e; controle abiótico, com ajuste de pH e solo esterilizado em autoclave (PA). Paralelamente, foi conduzido tratamento por bioaumento com ajuste de pH e nutrientes, suplementação de oxigênio e consórcio KMA, em solo contaminado apenas por diesel a 5% (BAD). A população microbiana foi monitorada através da contagem de UFC e os tratamentos, avaliados pela remoção de carbono orgânico e de hidrocarbonetos de petróleo (n-alcanos C10-C36). No segundo experimento, o metabolismo microbiano aeróbio foi avaliado através da produção de CO2 em respirômetros de Bartha (triplicatas), em solo contaminado com 5% (p/p) de óleo diesel B5, ajustado para pH e umidade, nas seguintes condições: solo com adição do consórcio KMA; solo com adição de cultura microbiana obtida a partir de outro solo proveniente de um posto de combustível com histórico de vazamento de tanques (RES) e; solo esterilizado por adição de azida de sódio a 0,3% (p/p). Como controle, solo sem contaminação, com sua população microbiana autóctone. No terceiro experimento, a capacidade da microbiota autóctone (EX), assim como do consórcio KMA e da cultura RES, em biodegradar óleo diesel B5, diesel e biodiesel de soja foi testada através do uso de indicadores de oxirredução DCPIP e TTC. Os experimentos em microcosmos indicam que houve uma complementaridade metabólica entre a população nativa e o consórcio comercial de microorganismos KMA, cuja presença promoveu um decaimento mais rápido de n-alcanos nas primeiras semanas do experimento. No entanto, após 63 dias de experimento, os tratamentos BAM, BAD e BE2 apresentaram, respectivamente, em média, 92,7%, 89,4% e 81,7% de remoção dos hidrocarbonetos n-alcanos C10-C36, sendo tais diferenças, sem significância estatística. Nos respirômetros, o bioaumento com cultura microbiana RES apresentou a maior produção de CO2 e a maior remoção de hidrocarbonetos (46,2%) após 29 dias. Tanto nos ensaios em microcosmos quanto nos respirométricos, não foi possível estimar a contribuição dos processos abióticos, tendo em vista evidências da existência de atividade microbiana no solo esterilizado térmica ou quimicamente. Os ensaios com os dois indicadores redox mostraram que apenas a microbiota nativa do solo em estudo e a cultura microbiana RES apresentaram potencial para degradar óleo diesel B5, biodiesel de soja ou diesel, quando colocadas em meio mineral contendo tais combustíveis como única fonte de carbono. / In Brazil, the contamination of soils due to spill of fuels is one of the most serious environmental problems. The impact of introducing new fuel mixtures in the energy matrix, such as diesel/biodiesel requires investigation regarding appropriate remediation technologies. The objective of this study was to assess different bioremediation strategies for treatment of soil spiked with diesel B5 (diesel plus 5% of biodiesel w/w). Three experiments were carried out. In the first, four microcosms (in duplicate), with 500g of soil and 5% (w/w) of diesel B5 each, being all of them supplied with oxygen by manual stirring and with moisture, performed the following treatments: bio-stimulation with pH adjustment (BE1); bio-stimulation with pH and nutrients (N, P) adjustment (BE2); bio-augmentation with pH and nutrients adjustment and addition of a commercial consortium of microorganisms KMA (BAM); abiotic processes control with pH adjustment and soil that underwent thermal sterilization (PA). As a control of the effect of biodiesel, a bio-augmentation treatment was carried out with pH and nutrients adjustment, oxygen supply and addition of KMA consortium, in soil contaminated only with diesel at 5% (w/w) (BAD). The microorganisms populations were monitored through colony-forming units CFU, and the treatment efficiency was estimated based on removal of total organic carbon (TOC) and petroleum hydrocarbon (n-alkanes C10-C36). In the second experiment, the microorganisms aerobic metabolism was assessed through measurement of the CO2 production in Barthas respirometers in triplicates, pH and moisture adjustment, under the following conditions: Contaminated soil inoculated with KMA consortium; contaminated soil inoculated with a microorganisms culture obtained from another soil excavated from a gas station with leaking from the tanks (RES); contaminated soil sterilized with sodium azide 0.3% (w/w) (PA). As a control, soil with no contamination and its indigenous microbiota was monitored. In the third experiment, the capacity of the indigenous microbiota (EX), as well as the consortia KMA and RES in biodegrading diesel B5 and pure biodiesel from soil-beans were assessed by using the oxi-reduction indicators DCPIP and TTC. The experiments in microcosms showed a higher percentage of decay in n-alkanes C10-C36 during the first weeks, in those microcosms where commercial consortium KMA was added, suggesting metabolic complementation between the indigenous and the KMA microbiota. However, after 63 days, the treatments BAM, BAD and BE2 showed respectively the average removal of 92.7%, 89.4% and 81.7% of n-alkanes C10-C36, been the differences statistically not significant. In both experiments (microcosms and Bartha respirometers) it was not possible to estimate the contribution of the abiotic processes alone, due to clear indication of microbiological activity in the soils that underwent thermal or chemical sterilization. In the Bartha respirometers, bio-augmentation with the RES culture presented higher CO2 production and the highest hydrocarbons removal (46.2%) after 29 days. The assays with the redox indicators showed that both the native microbiota of the soil and the RES microbial culture presented potential to degrade diesel B5, biodiesel and diesel, when placed in mineral media with these fuels as the only carbon source.

[pt] O presente trabalho avaliou a eficácia da dessorção térmica in situ em remediar materiais contaminados por hidrocarbonetos de petróleo em refinarias. Paralelamente, foi projetado e construído um novo sistema modular para ser empregado sob dutovias para remediação de britas contaminadas. Os resultados do programa experimental revelaram ser possível a remediação de pavimentos de concreto contaminados por óleo combustível. A aplicação de calor na superfície do pavimento reduziu em até 65 por cento a sua resistência, porém propiciou a restauração de sua cor original. Verificou-se que os resíduos do processo, após análises mineralógicas por difração de raios X e químicas por espectroscopia de fluorescência, apresentavam uma composição muito semelhante ao solo empregado como material de construção dos aterros da refinaria, sugerindo que o resíduo possa ser advindo de transporte eólico. O sistema desenvolvido no presente trabalho apresentou um desempenho satisfatório. Verificou-se a necessidade de aeração do material remediado para eliminar a produção de coque. Adicionalmente, observou-se a importância de um bom isolamento térmico para minimizar o consumo energético e impedir a propagação de calor e das emissões para a atmosfera. As emissões geradas pelo aquecimento consistiam de olefinas e parafinas que podem ser devidamente tratadas pelo oxidador térmico. / [en] This dissertation assessed the adequacy of in situ thermal desorption (istd) in cleaning oil contaminated debris from Refineries. A new modulated istd system was designed and built in order to remediate oiled cobbles under pipeways. The experimental results revealed the possibility of cleaning concrete pavements contaminated by heavy oil. The thermal desorption process restored their original color but reduced their resistance up to 65 percent. It was observed that the resulting debris, after mineralogical analyses by X-ray diffraction and chemical analysis by X-Ray fluorescence, have a similar composition to the soil employed in the fills throughout the Refinery, indicating that the debris could well have been transported by the wind. The system devised here had a satisfactory performance. It was observed the necessity of aeration during the treatment in order to avoid the production of coke. Additionally, it was also observed the importance of a good thermal insulation in order to minimize power consumption and the propagation of heat and gas emissions to the atmosphere. The gases emissions consisted mainly of olefins and paraffins that had been reasonably been treated by the thermal oxidizer devised herein.

No Brasil, a contaminação do solo por derramamentos de combustíveis representa um dos mais graves problemas ambientais e o impacto da introdução de novas misturas como diesel/biodiesel na matriz energética requer investigação quanto a tecnologias apropriadas de remediação. O presente estudo teve por objetivo avaliar diferentes estratégias de biorremediação no tratamento de solo contaminado experimentalmente com óleo diesel B5. Foram conduzidos três experimentos. No primeiro, quatro microcosmos em duplicata, contendo 500 g de solo e 5% (p/p) de óleo diesel B5, todos suplementados com oxigênio através de revolvimento manual e com ajuste de umidade, tiveram como tratamentos: bioestímulo com ajuste de pH (BE1); bioestímulo com ajuste de pH e nutrientes (BE2); bioaumento com ajuste de pH, nutrientes e adição de consórcio microbiano comercial KMA (BAM) e; controle abiótico, com ajuste de pH e solo esterilizado em autoclave (PA). Paralelamente, foi conduzido tratamento por bioaumento com ajuste de pH e nutrientes, suplementação de oxigênio e consórcio KMA, em solo contaminado apenas por diesel a 5% (BAD). A população microbiana foi monitorada através da contagem de UFC e os tratamentos, avaliados pela remoção de carbono orgânico e de hidrocarbonetos de petróleo (n-alcanos C10-C36). No segundo experimento, o metabolismo microbiano aeróbio foi avaliado através da produção de CO2 em respirômetros de Bartha (triplicatas), em solo contaminado com 5% (p/p) de óleo diesel B5, ajustado para pH e umidade, nas seguintes condições: solo com adição do consórcio KMA; solo com adição de cultura microbiana obtida a partir de outro solo proveniente de um posto de combustível com histórico de vazamento de tanques (RES) e; solo esterilizado por adição de azida de sódio a 0,3% (p/p). Como controle, solo sem contaminação, com sua população microbiana autóctone. No terceiro experimento, a capacidade da microbiota autóctone (EX), assim como do consórcio KMA e da cultura RES, em biodegradar óleo diesel B5, diesel e biodiesel de soja foi testada através do uso de indicadores de oxirredução DCPIP e TTC. Os experimentos em microcosmos indicam que houve uma complementaridade metabólica entre a população nativa e o consórcio comercial de microorganismos KMA, cuja presença promoveu um decaimento mais rápido de n-alcanos nas primeiras semanas do experimento. No entanto, após 63 dias de experimento, os tratamentos BAM, BAD e BE2 apresentaram, respectivamente, em média, 92,7%, 89,4% e 81,7% de remoção dos hidrocarbonetos n-alcanos C10-C36, sendo tais diferenças, sem significância estatística. Nos respirômetros, o bioaumento com cultura microbiana RES apresentou a maior produção de CO2 e a maior remoção de hidrocarbonetos (46,2%) após 29 dias. Tanto nos ensaios em microcosmos quanto nos respirométricos, não foi possível estimar a contribuição dos processos abióticos, tendo em vista evidências da existência de atividade microbiana no solo esterilizado térmica ou quimicamente. Os ensaios com os dois indicadores redox mostraram que apenas a microbiota nativa do solo em estudo e a cultura microbiana RES apresentaram potencial para degradar óleo diesel B5, biodiesel de soja ou diesel, quando colocadas em meio mineral contendo tais combustíveis como única fonte de carbono. / In Brazil, the contamination of soils due to spill of fuels is one of the most serious environmental problems. The impact of introducing new fuel mixtures in the energy matrix, such as diesel/biodiesel requires investigation regarding appropriate remediation technologies. The objective of this study was to assess different bioremediation strategies for treatment of soil spiked with diesel B5 (diesel plus 5% of biodiesel w/w). Three experiments were carried out. In the first, four microcosms (in duplicate), with 500g of soil and 5% (w/w) of diesel B5 each, being all of them supplied with oxygen by manual stirring and with moisture, performed the following treatments: bio-stimulation with pH adjustment (BE1); bio-stimulation with pH and nutrients (N, P) adjustment (BE2); bio-augmentation with pH and nutrients adjustment and addition of a commercial consortium of microorganisms KMA (BAM); abiotic processes control with pH adjustment and soil that underwent thermal sterilization (PA). As a control of the effect of biodiesel, a bio-augmentation treatment was carried out with pH and nutrients adjustment, oxygen supply and addition of KMA consortium, in soil contaminated only with diesel at 5% (w/w) (BAD). The microorganisms populations were monitored through colony-forming units CFU, and the treatment efficiency was estimated based on removal of total organic carbon (TOC) and petroleum hydrocarbon (n-alkanes C10-C36). In the second experiment, the microorganisms aerobic metabolism was assessed through measurement of the CO2 production in Barthas respirometers in triplicates, pH and moisture adjustment, under the following conditions: Contaminated soil inoculated with KMA consortium; contaminated soil inoculated with a microorganisms culture obtained from another soil excavated from a gas station with leaking from the tanks (RES); contaminated soil sterilized with sodium azide 0.3% (w/w) (PA). As a control, soil with no contamination and its indigenous microbiota was monitored. In the third experiment, the capacity of the indigenous microbiota (EX), as well as the consortia KMA and RES in biodegrading diesel B5 and pure biodiesel from soil-beans were assessed by using the oxi-reduction indicators DCPIP and TTC. The experiments in microcosms showed a higher percentage of decay in n-alkanes C10-C36 during the first weeks, in those microcosms where commercial consortium KMA was added, suggesting metabolic complementation between the indigenous and the KMA microbiota. However, after 63 days, the treatments BAM, BAD and BE2 showed respectively the average removal of 92.7%, 89.4% and 81.7% of n-alkanes C10-C36, been the differences statistically not significant. In both experiments (microcosms and Bartha respirometers) it was not possible to estimate the contribution of the abiotic processes alone, due to clear indication of microbiological activity in the soils that underwent thermal or chemical sterilization. In the Bartha respirometers, bio-augmentation with the RES culture presented higher CO2 production and the highest hydrocarbons removal (46.2%) after 29 days. The assays with the redox indicators showed that both the native microbiota of the soil and the RES microbial culture presented potential to degrade diesel B5, biodiesel and diesel, when placed in mineral media with these fuels as the only carbon source.

La bio-remédiation in situ est une technique de réhabilitation couramment utilisée pour le traitement des sols et des nappes contaminés, notamment par les hydrocarbures pétroliers. Si démontrer la pertinence de ce type de traitement constitue un préalable incontournable pour chacun des sites où il est mis en œuvre, l’efficacité du traitement dépend de ses conditions de mise en œuvre dans le contexte spécifique d’un site. Le suivi et le contrôle des différents processus qui gouvernent les phénomènes de biodégradation est complexe, et leur optimisation constitue un élément clé de la réussite du traitement tant au plan technique qu’économique. La démarche générale du travail de thèse porte sur le développement d’une méthodologie permettant d’employer la modélisation dans une démarche de gestion (au sens des textes de 2007) d’un site contaminé par des hydrocarbures pétroliers traité par biodégradation in situ. L’originalité du travail de thèse porte sur l’utilisation de la modélisation comme outil de compréhension des mécanismes et d’aide à la décision à chaque étape du traitement : (i) Dimensionnement de l’installation : définir la meilleure option envisageable, (ii) suivi de l’efficacité du traitement : optimiser le procédé et (iii) prédiction et justification de l’arrêt du traitement : sécuriser en termes de garantie de résultat. Les données d’un site d’étude servent de support dans la définition de l’approche méthodologique de modélisation. A chaque étape d’un projet de bio-remédiation in situ peut être associée une étape de modélisation qui fera appel à des moyens plus ou moins sophistiqués avec des exigences de précision variables. Le premier outil développé concerne l’estimation des incertitudes prédictives dans les modèles mis en œuvre. Cet aspect est fondamental, dès lors que l’on souhaite utiliser la modélisation dans un processus d’aide à la décision. Les processus de bio-remédiation in situ impliquent des relations complexes et incertaines entre la biomasse, les contaminants et les mesures de contrôle appropriées. Prévoir la performance du traitement (en termes de réduction du flux et/ou de la masse) constitue un défi en raison des incertitudes liées aux propriétés du milieu, de la source et aux incertitudes liées aux mécanismes de bio-remédiation. L’étude de la contribution des incertitudes paramétriques dans la prédiction de la performance du traitement est réalisée avec la méthode du « Null Space Monte Carlo » (NSMC) implémentée dans l’outil PEST. Le second outil utilisé concerne l’optimisation du design et/ou du monitoring d’un procédé de bio-traitement in situ. Dans ce contexte, deux objectifs peuvent être envisagés à savoir la réduction du flux de contaminants d’une part, et l’élimination de la masse à la zone source d’autre part. L’outil utilisé est un algorithme d’optimisation mathématique dénommé “Particle Swarm Optimisation” (PSO). Le choix de la fonction objectif à optimiser est particulièrement important et s’avère lié au comportement spécifique hydrogéochimique du site considéré. Cette étude montre que les outils NSMC et PSO s’avèrent appropriés dans l'utilisation de modèles de transport réactif dans la gestion environnementale. Les temps de calcul de ces modèles hautement paramétrés et non linéaires limitent encore l'utilisation de la modélisation comme outil d’aide à la décision. Malgré ces limites, l’approche proposée pour gérer la bio-remédiation in situ des eaux souterraines sur site réel peut être efficace pour fournir un soutien dans la gestion du traitement d’une pollution, étendant ainsi le domaine d’application de la modélisation numérique. Cette approche permet aussi de mettre en évidence des difficultés dues aux spécificités du site ou à la technique même de traitement choisie, permettant d’alerter à temps les gestionnaires. / In-situ bioremediation is a commonly used remediation technology to clean up the subsurface of petroleum-contaminated sites. Although demonstrating the relevance of this type of treatment is an essential prerequisite for each site where it is implemented, the effectiveness of the treatment depends on its implementation conditions in the site-specific context. The monitoring and control of different processes that govern biodegradation phenomena is complex, and optimization is a key element of successful treatment both technically and economically. The general approach of the thesis is the development of a methodology for using modelling in a management approach (as defined in the French regulatory text) of petroleum-contaminated site treated by in situ biodegradation. The work focuses on the use of modelling as a tool for understanding mechanisms and for decision support at every stage of treatment: • System design: defining the best possible option.• Monitoring the effectiveness of treatment: process optimization.• Prediction and justification of stopping treatment: analysis of the uncertainty on the treatment result. Data from two study sites are used to define the modelling methodology. At each stage of the bio-remediation project (design, conception, monitoring and optimization) may be associated a modelling stage that will be more or less sophisticated depending on accuracy requirements. The first tool developed involved predictive uncertainty analysis, which is crucial when modelling is used as a decision support tool, and can be used at the design process step or for predicting the effectiveness of treatment. The process of in-situ bioremediation involves complex and uncertain relationships among biomass, contaminants and appropriate control actions. Forecasting remedial performance (in terms of flux and mass reduction) is a challenge due to uncertainties associated with (i) the medium and source properties and (ii) the efficiency of concentration reducing mechanisms. Parametric uncertainty contributions involved in forecasting treatment performance is carried out with the “Null-Space Monte Carlo” (NSMC) method implemented in the PEST tool. The second tool relates design and / or monitoring optimization of the bio-treatment method. In this context, two purposes can be considered: the reduction of contaminants flux or mass in the source zone. The tool used is a mathematical optimization algorithm called "Particle Swarm Optimization" (PSO). The choice of the objective function to be optimized is particularly important and appears to be related to hydrogeochemical site-specific behavior. This study showed that the NSMC and PSO methods are suitable tools for an efficient use reactive transport models in environmental management. The computation time of these highly parameterized and nonlinear models still limit the use of modelling as a decision support tool. Despite these limitations, the proposed approach for managing the bioremediation in-situ groundwater on actual site can be effective to provide support in managing the treatment of pollution, extending the field of application of numerical modelling. This approach also allows to highlight difficulties due to site-specific behavior or to the treatment technique applied, and to inform decision support managers in consequence.

Native and naturalized California plant species were screened for their phytoremediation potential for the cleanup of soil contaminated with petroleum hydrocarbons (PHCs), poly-aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated dioxins/furans, and heavy metals. This screening was followed by controlled greenhouse experiments to further evaluate the phytoremediation potential of the best candidates. Field specimens and soils used for this study were collected from the former Energy Technology Engineering Center (ETEC) at the Santa Susana Field Laboratory in Southern California that was operated by the Department of Energy (DOE). Soils at this site contain all of the contaminants of interest (COIs). Nine plant species were screened in the field: Purple Needlegrass (Nassella pulchra), Blue Elderberry (Sambucus nigra), Laurel Sumac (Malosma laurina), Mule Fat (Baccharis salicifolia), Palmer’s Goldenbush (Ericameria palmeri), Summer Mustard (Hirschfeldia incana), Narrowleaf Milkweed (Asclepias fascicularis), Coyote Brush (Baccharis pilularis), and Thickleaf Yerba Santa (Eriodictyon crassifolium). In the field three samples of each species growing in contaminated soil and one of each species growing in uncontaminated soil were selected for harvesting and analysis. The roots, above ground plant tissue, and soil around the roots were sampled separately and analyzed for the COIs: PHCs, PAHs, PCBs, chlorinated dioxins/furans, and metals (which include mercury, silver, cadmium, and lead). All of the plants in the field appeared to generate compounds which result in higher measured PHC concentrations than those measured in the associated soil. The highest concentrations of PAHs in the roots were observed for Blue Elderberry (1740 ug/kg), Purple Needlegrass (703 ug/kg), and Yerba Santa (200 ug/kg). No uptake of PCBs was observed in the roots or foliage of any species. The highest concentrations of total chlorinated dioxins/furans in the roots were observed for Purple Needlegrass (2237 ng/kg), Blue Elderberry (1026 ng/kg), Palmer’s Goldenbush (432 ng/kg), and Yerba Santa (421 ng/kg). The highest concentrations of total chlorinated dioxins/furans in the foliage were observed for Yerba Santa (901 ng/kg), Palmer’s Goldenbush (757 ng/kg), and Purple Needlegrass (694 ng/kg). No uptake of mercury was observed in the roots or foliage of any species. The highest concentration of silver in the roots was observed for Laurel Sumac (7.34 mg/kg). Summer Mustard (SM) was the only species that showed uptake of silver into the foliage (0.405 mg/kg). The highest concentrations of cadmium in the roots and foliage were observed for Mule Fat (1.84 mg/kg and 3.64 mg/kg) and Coyote Brush (1.52 mg/kg and 2.12 mg/kg) and the greatest concentration of lead in the roots and foliage was observed for Purple Needlegrass (8.92 mg/kg and 1.17 mg/kg). Plants with a wide variety of observed contaminant uptake in the field were selected for a second phase of research in which three of the most promising species were grown in greenhouse microcosms to quantify the removal of contaminants from the soil. The three species selected based on preliminary results from the field study were Coyote Brush, Mule Fat, and Purple Needlegrass. Microcosms consisted of 2.17 kg of soil in 4-L glass jars with glass marbles for an underdrain. Plants were watered with deionized water and no leachate was collected. Five replicates of each microcosm type were created and incubated for 211 days with soil sampling at 85 and 211 days. Soil, plant roots/above ground tissue, and volatilization from the plants were analyzed for COIs to determine the mechanisms of phytoremediation. One set of microcosms was used to test the effect of addition of achelating agent (ethylenediaminetetraacetic acid) and another set was used to test the effect of fertilizer addition on phytoremediation potential. Three control treatments were tested: sterilized (gamma irradiation) soil planted with Purple Needlegrass, unplanted soil, and sterilized unplanted soil. None of the plant species demonstrated volatilization of COIs under these conditions. Volatilization of mercury was not tested for. The average PCB concentration (measured as Aroclor 1260) reductions in soils with Purple Needlegrass and chelated Coyote Brush were 49.4% and 51.4% respectively (p < 0.05). However, the sterilized unplanted control also had a decrease of Aroclor 1260 concentrations in the soil of 36.6% (p < 0.05). None of the species phytoextracted PCBs, so the mechanism of PCB remediation appears to be phytostimulation of the rhizosphere. Purple Needlegrass showed the greatest uptake of dioxins/furans into the foliage but did not appear to reduce the dioxin/furan concentrations in the soil. Coyote Brush, fertilized Coyote Brush, and Mule Fat also showed uptake of dioxins/furans into the roots and foliage. Only the Coyote Brush and fertilized Coyote Brush significantly (p = 0.036, p = 0.022) reduced the total dioxin/furan concentration in the soil (17.8% and 19.8% respectively). Coyote Brush may have stimulated microbes in the rhizosphere to better degrade the dioxins/furans. None of the plants were identified as hyper-accumulators of metals, and none of the soil metal concentrations significantly decreased in any of the microcosms. All of the metals (except mercury) were taken into the roots of plants to some degree, with Purple Needlegrass showing the most promise for metal extraction as it showed some of the highest concentrations of metals in roots and was the only species that contained mercury and silver in the foliage. This study suggests that there is some potential for phytoremediation of PCBs and chlorinated dioxins/furans. The results for petroleum hydrocarbons were inconclusive. Metal uptake was not substantial enough to lower metal concentrations in the soils. Thus phytoremediation of COIs at the site is limited and more aggressive forms of remediation may be required to reduce the concentrations of COIs quickly.

Submitted by Maicon Juliano Schmidt (maicons) on 2015-07-06T13:37:21Z No. of bitstreams: 1 Joice Brochier Schneider.pdf: 4213539 bytes, checksum: 49fa8f402cb598050e77b581c7d7d449 (MD5) / Made available in DSpace on 2015-07-06T13:37:21Z (GMT). No. of bitstreams: 1 Joice Brochier Schneider.pdf: 4213539 bytes, checksum: 49fa8f402cb598050e77b581c7d7d449 (MD5) Previous issue date: 2012-08-21 / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / Projeconsult Engenharia Ltda. / A ideia de se transformar resíduos em matéria prima tem produzido esforços no sentido de estudá-los e qualificá-los, já que o aproveitamento integral de resíduos é uma necessidade cada vez maior na indústria moderna, principalmente pela crescente escassez de recursos naturais não renováveis e a necessidade de preservação e recuperação do meio ambiente. O resíduo cinza de casca de arroz (CCA), resultante da queima da casca de arroz para geração de energia, vem sendo utilizado em diversos ramos industriais. Destaca-se sua aplicação na construção civil e também como material adsorvente. A CCA utilizada neste trabalho está misturada com carvão ativado (CA). Esta mistura é proveniente de filtros de adsorção de sistemas de remediação de áreas degradadas com hidrocarbonetos de petróleo. Com isto, o objetivo deste trabalho foi avaliar a solidificação/estabilização de hidrocarbonetos de petróleo, em especial, benzeno, tolueno, etilbenzeno e xileno (BTEX), contidos no adsorvente composto por CCA e CA, em matriz de cimento Portland. Para tal, foram confeccionadas argamassas com substituição do agregado natural, em volume, pelos seguintes materiais: resíduo, nos teores de 10% e 30%, adsorvente CCA/CA in natura no teor de 30% e adsorvente CA in natura, também no teor de 30%. Essas argamassas foram caracterizadas ambientalmente, através dos ensaios descritos nas Normas Brasileiras. Analisou-se também a influência dessa substituição, através da determinação de propriedades no estado fresco (evolução da temperatura semi-adiabática de hidratação, penetração de cone e tempo de pega), de propriedades mecânicas (resistência à tração na flexão e à compressão) e caracterização dos produtos de hidratação através das técnicas de difração de Raio-X e espectroscopia de infravermelho. A argamassa RESÍDUO 10% atingiu a maior temperatura e menor tempo entre o início e fim da evolução da temperatura devido à hidratação. Já a argamassa RESÍDUO 30%, ao contrário, apresentou o maior tempo, fato justificado pela ação do óleo, presente no resíduo incorporado, que impediu, em parte, a passagem da água, retardando o processo de hidratação. Todas as argamassas, em relação a REFERÊNCIA, apresentaram menor consistência, na penetração de cone, e menor tempo de início e fim de pega. Resultados estes que corroboram, para as argamassas RESÍDUO 10%, CCA/CA 30% e CA 30% com a evolução da temperatura semi-adiabática da temperatura. A incorporação do resíduo não interferiu na formação dos compostos de hidratação do cimento, porém, a hidratação, conforme os resultados obtidos na evolução da temperatura semi-adiabática, ocorreu mais lentamente com a substituição de 30% da areia natural pelo resíduo. Os resultados da espectroscopia de infravermelho sugerem a presença BTEX nas argamassas RESÍDUO 30% e RESÍDUO 10%. Carbonatos e silicatos também foram identificados em todas as argamassas. Quanto aos resultados de resistência mecânica, observou-se, na resistência à tração na flexão, que a diferença entre o maior e menor desempenho, entre as argamassas REFERÊNCIA, RESÍDUO 10% e RESÍDUO 30%, foi de 8,9% e 5,6% para 7 e 21 dias, respectivamente. Já na resistência à compressão, aos 7 dias, os resultados obtidos das argamassas RESÍDUO 10% e RESÍDUO 30% foram superiores ao de REFERÊNCIA. Aos 21 dias, a REFERÊNCIA apresentou o melhor desempenho, 31,7% e 52,5% superior à argamassa RESÍDUO 30% e RESÍDUO 10%, respectivamente. Com os resultados de resistência mecânica obtidos, não foi possível avaliar a melhoria de desempenho com relação à idade. Porém, observou-se que a contaminação presente contribuiu para a resistência das argamassas, quando comparadas a CCA/CA 30%. Logo, sugere-se que a presença do contaminante possivelmente contribuiu quanto à aderência entre as partículas da mistura. Na caracterização ambiental, as argamassas confeccionadas foram classificadas como Classe II A, resíduo não perigoso, não inerte. A análise do extrato lixiviado e solubilizado das argamassas RESÍDUO 30% e RESÍDUO 10% não identificou a presença de hidrocarbonetos de petróleo. Estes resultados, associados à espectroscopia de infravermelho, às propriedades mecânicas bem como ao odor característico dos corpos de prova, confirmam a s/s do contaminante na matriz de cimento Portland. Este resultado positivo representa um avanço na busca da viabilidade de se empregar o resíduo CCA/CA contaminado com hidrocarbonetos de petróleo, direta ou indiretamente, para algum fim comercial. / The idea of turning waste into raw material has made efforts to study them and qualify them as the full utilization of waste is an increasing need in modern industry, mainly by increasing scarcity of non-renewable natural resources and need for preservation and restoration of the environment. The residue of rice husk ash (RHA), resulting from the burning of rice husk for power generation, has been used in various industries. We highlight its application in construction and as adsorbent material. The CCA used in this work is mixed with activated carbon (AC). This mixture is from adsorption filter remediation systems of degraded with petroleum hydrocarbons. With this, the objective of this study was to evaluate the solidification / stabilization of petroleum hydrocarbons, in particular benzene, toluene, ethylbenzene and xylene (BTEX), composed of adsorbent contained in CCA and CA, in Portland cement matrix. To this end, mortars were prepared with substitution of natural aggregate, by volume, of the following materials: residue, content of 10% and 30%, adsorbent CCA / CA in natura content of 30% and CA adsorbent in nature, also the content 30%. These environmentally mortars were characterized by the tests described in the Brazilian Standards. It was also analyzed the influence of substitution by determining the properties in the fresh state (temperature evolution semi-adiabatic hydration, penetration cone and setting time), mechanical properties (tensile strength in bending and compression), and characterization of the hydration products through the techniques of X-ray diffraction and infrared spectroscopy. The mortar RESIDUE 10% reached the highest temperature and shortest time between the beginning and end of the temperature due to hydration. Already 30% RESIDUE mortar, instead, showed the greatest time, which may be explained by the action of the oil present in the residue incorporated, which prevented partly the passage of water, slowing the hydration process. All mortars, for the reference, showed less consistency, cone penetration, and shorter start and end of the handle. These results corroborate that, for mortars RESIDUE 10% CCA/CA 30% CA and 30% with the temperature evolution of the semi-adiabatic temperature. The incorporation of the residue did not affect the formation of the compounds of the cement hydration, however, hydration, as the results in the evolution of semi-adiabatic temperature, was slower by replacing 30% of the natural sand residue. The results of infrared spectroscopy suggests the presence BTEX in mortars RESIDUE RESIDUE 30% and 10%. Silicates and carbonates have also been identified in all mortars. Regarding the results of mechanical strength was observed in tensile strength in bending, the difference between the highest and lowest performance among REFERENCE mortars, 10% Residue and Residue 30%, was 8.9% and 5 6% for 7 and 21 days, respectively. In the compressive strength after 7 days, the results of mortar RESIDUE RESIDUE 10% and 30% were higher than the reference. At 21 days, the REFERENCE showed the best performance, 31.7% and 52.5% higher than the mortar WASTE WASTE 30% and 10%, respectively. With the results obtained from mechanical strength, it was not possible to evaluate the performance improvement with respect to age. However, it was observed that this contributed to the contamination resistance of mortars, compared to CCA / CA 30%. Therefore, it is suggested that the presence of the contaminant as possibly contributing to adhesion between the particles of the mixture. In characterizing environmental mortars made were classified as Class II, non-hazardous waste, not inert. The analysis of the extract solubilized and leached mortar WASTE WASTE 30% and 10% failed 17 to identify the presence of petroleum hydrocarbons. These results, combined with the infrared spectroscopy, the mechanical properties and the odor of the specimens, confirm / s of the contaminant in the matrix of Portland cement. This result represents a breakthrough in the search for feasibility of employing the waste CCA/CA contaminated with petroleum hydrocarbons, directly or indirectly, for any commercial purpose.

Sulfate- and Fe(III)-reducing, and methanogenic prokaryotes (SRP, FRP, MGP) are key players in metabolic pathways involved in anaerobic biodegradation processes. Understanding the metabolic activity of these microbes in environments can enhance microbe-mediated processes such as oil spill bioremediation and methane biogas production. In this study, anaerobic microbial activities in Deepwater Horizon oil spill-impacted salt marsh sediments, and in methanogenic coal bed production water enrichment cultures amended with trace elements (TE), were elucidated by employing an approach combining methods in molecular biology and geochemistry. In situ metabolic activity of SRP, FRP and MGP were monitored seasonally and metabolically-active communities were identified in oil-impacted sediments using quantitative real time Reverse Transcription -PCR and clone library analysis of key functional genes: Dissimilatory (bi)sulfite reductase (dsrAB), Geobactereceae-specific citrate synthase (gltA), methyl coenzyme M reductase (mcrA), and benzyl succinate synthase (bssA). In situ application of montmorillonite clay was assessed for its potential at accelerating PHC degradation by stimulating microbial activities. Levels of dsrA, gltA and bssA transcripts suggested that PHC-oxidizing SRP are more active in summer while FRP are more active in winter, indicating their activities linked to the seasonal changes of redox potential and vegetation. BssA gene expression peaked in winter, and was highest at more highly oil-impacted sites. Expression of all genes was higher in clay-amended sites. bssA transcript level and Fe(II) production were highest in clay-amended microcosm. Total petroleum hydrocarbon (TPH) levels were lower in oil and clay-amended microcosm incubation than one with oil only amendment, suggesting enhanced TPH degradation by clay amendment. Pyrosequencing analysis 16S rRNA gene in clay-amended microcosms demonstrated the highest percentage abundance of groups closely related to known anaerobic aromatic degraders. Levels of mcrA transcripts correlated with methane production rates in TE-amended coal bed production water enrichments. The findings of the present study clearly support the advantage of gene expression analyses for estimating microbial activity. To the best of our knowledge, this is the first in situ study which employs key functional gene markers as molecular proxies for metabolic activity and diversity assessments in anaerobic oil-contaminated salt marsh sediment and also elucidates clay-enhanced in situ TPH degradation.