In order to preserve groundwater resources from contamination by volatile organic compounds and to clean up sites contaminated with the compounds, we should understand fate and transport of contaminants in the subsurface systems and physicochemical processes involving remediation technologies. To enhance our understanding, numerical studies were performed on the following topics: (i) multiphase flow and contaminant transport in subsurface environments; (ii) biological transformations of contaminants; (iii) in-situ air sparging (IAS); and, thermal-enhanced venting (TEV). Among VOCs, trichloroethylene (TCE) is one of the most-frequently-detected chemicals in the contaminated groundwater. TCE and its daughter products (cis-1,2-dichloroethylene (cDCE) and vinyl chloride (VC)) are chosen as target contaminants. Density-driven advection of gas phase is generated by the increase in gas density due to vaporization of high-molecular weight contaminants such as TCE in the unsaturated zone. The effect of the density-driven advection on fate and transport of TCE was investigated under several environmental conditions involving infiltration and permeability. Biological transformations of contaminants can generate byproducts, which may become new toxic contaminants in subsurface systems. Sequential biotransformations of TCE, cDCE, and VC are considered herein. Under different reaction rates for two bioreaction kinetics, temporal and spatial concentration profiles of the contaminants were examined to evaluate the effect of biotransformations on multispecies transport. IAS injects clean air into the subsurface below the groundwater table to remediate contaminated groundwater. The movement of gas and the groundwater as a multiphase flow in the saturated zone and the removal of TCE by IAS application were analyzed. Each fluid flow under IAS was examined in terms of saturation levels and fluid velocity profiles in a three-dimensional domain. Several scenarios for IAS systems were simulated to evaluate remedial performance of the systems. TEV was simulated to investigate its efficiency on the removal of a nonaqueous phase liquid in the unsaturated zone under different operational conditions. For numerical studies herein, the governing equations for multiphase flow, multispecies transport, and heat energy in porous media were developed and solved using Galerkin finite element method. A three-dimensional numerical model, called TechFlowMP model, has been developed.

De nos jours, la préservation de l’environnement est un enjeu majeur. Avant cette prise de conscience, de nombreux polluants ont été rejetés dans la nature. Parmi eux, les hydrocarbures sont très souvent rencontrés. Or, ils sont reconnus pour leur toxicité et leur persistance accrue. La mise en place de méthodes efficaces de dépollution est donc primordiale. Les méthodes classiques nécessitent l’excavation ou le pompage des zones contaminées, imposant un coût de dépollution élevé. C’est pourquoi des techniques de dépollution in-situ ont été développées afin de réduire ces coûts, tout en garantissant des rendements de dépollution efficaces. Les travaux menés durant cette Thèse ont permis de déterminer, pour plusieurs techniques de traitement, les facteurs limitants inhérents à la technique, mais aussi de quantifier le rôle du contact entre agents de traitement et zone polluée ou des effets densitaires. Les techniques in-situ utilisées sont : l’oxydation chimique in situ, le lavage par tensio-actifs, l’injection d’air (sparging) et le traitement thermique. Trois niveaux d’expérience ont été étudiés : le batch, la colonne et le pilote 3D. Les réacteurs fermés, ont permis la comparaison des oxydants en statiques face à une matrice plus ou moins riche en matières organiques. Les colonnes ont mis en avant l’influence du mode d'injection appliqué vis-à-vis des propriétés physico-chimiques des polluants (cinétique réactionnelle, pression de vapeur, température d’ébullition, etc.). Les pilotes 3D, d’un volume d’un 1 m3, ont permis de comparer les différentes techniques sur un milieu hétérogène présentant des zones peu perméables, difficiles à traiter. A partir des résultats acquis et de modélisation numérique des expériences, il est dorénavant possible de mieux ajuster la méthode de traitement et surtout de comparer différentes méthodes pour un contexte hydrogéologique donné. / Pollution of soils and aquifers by Diesel fuel compounds is a widespread remediation issue. Problems due to soil remediation are more and more difficult to treat. Hydrocarbons are often encountered. But they are known for their toxicity and increased persistence. The establishment of effective remediation methods is paramount. Conventional methods require excavation or pumping contaminated areas requiring a high abatement costs. That is why, in-situ remediation techniques have been developed to reduce these costs while ensuring efficient pollution control returns. The work done during this thesis has determined for several treatments, the limiting factors inherent the treatment, but also quantifies the role of contact between agents and pollutants or density effects. In-situ treatments are: in situ chemical oxidation, surfactants flushing, air sparging and thermic treatment. Three levels of experience were investigated: batch, column and 3D Pilot. Batchs, enabled the comparison of oxidants in sand and natural soil. The columns have highlighted the influence of the injection method applied occurs toward the physical and chemical properties of contaminants (reaction kinetics, vapor pressure, boiling temperature, etc.). 3D Pilot, have a volume of 1m3. They were used to compare the different treatments on a heterogeneous medium having low permeability zones, difficult to treat. From the results of numerical modeling and experiences, it is possible to adjust the treatment method and especially to compare different methods for a given hydrogeological context.

Plant-derived protein such as pea protein is a promising replacement for animal protein and is becoming popular in recent years because of its high nutritional value and potential reduction of environmental footprint. However, the increasing demand for plant-derived proteins is accompanied by the increase of wastes during protein processing such as wastewater containing dilute protein content, which may raise the cost for the downstream processing. Therefore, there is an emerging need to develop novel processing strategies to reduce waste while valorizing useful ingredients. Several researchers suggest that foam fractionation technology can be a viable approach to extract and concentrate protein from dilute wastewater effluent. This technology has already been applied to the chemical and food industry for the extraction of surfactant and animal proteins from wastewater. To design and apply foam fractionation to the plant-derived protein industry, fundamental knowledge on foaming properties of dilute plant-derived protein solution is needed and is currently lacking. Therefore, the objective of this thesis is to advance a fundamental understanding of the foaming properties of dilute pea protein solutions (protein concentration ≤ 1wt%). To achieve the objective, a multiscale approach is used, which is comprised of a detailed investigation of both bulk and interfacial properties of pea protein solutions and foaming properties such as foaming capacity and stability with the help of bubble structure and foam volume kinetics. The focus of this thesis is on the effect of protein concentration. Results demonstrate that protein adsorption kinetics can be characterized by four distinctive regimes: lag phase, diffusion-limited regime, transitional regime, and conformation change regime, which are highly dependent on the protein concentration. However, apparent viscosity is less affected by the protein concentration. Results also show that depending on the protein concentration, two regimes can be distinguished for foam capacity and foam stability. For the first time, these regimes can be rationalized by contrasting characteristics times of protein adsorption kinetics and processing time scale – residence time of bubbles during the foam formation. New findings from this fundamental research will shed light on the control and optimization of foaming properties of plant-derived protein solutions for applications ranging from food processing design to food product development.

published_or_final_version / Earth Sciences / Doctoral / Doctor of Philosophy

To meet the growing energy world demands, and in conjunction, lower CO2 production levels, near zero emission energy sources must be pushed to the forefront as alternatives to fossil fuels. Photoelectrochemical (PEC) cells are a potential alternative to fossil fuels and have recently generated much interest because of their potential to electrolyze water into hydrogen fuel from sunlight. But in order to be competitive with fossil fuels, understanding the mass-transfer limitations in PEC systems is critical. This work focuses on the addressing the mass-transfer limitations in a conceptually novel PEC cell reactor, the Dual Bed Colloidal Suspension Reactor (DBCSR). Mass-transfer correlations for the DBCSR are presented. The correlations are based on experimental data obtained using two fabricated diffusion cells. The working correlation representative of both cells is given. An analysis of the orientation of the gas sparger suggests that the transport phenomena in both cells is not the same, and therefore using two correlations to represent similar systems is justified. An energy analysis is presented that shows that gas sparging is a low energy consumption option to mitigate mass-transfer limitations. Future work is suggested for better understanding the mass-transfer behavior in the DBCSR.

O método de injeção de ar é utilizado para a descontaminação de solos e lençóis freáticos contaminados com Compostos Orgânicos Voláteis (VOCs). O ar injetado no solo na zona saturada, ao subir para a zona não saturada, volatiliza os contaminantes. A eficiência da remediação por esse método está diretamente ligada à região de solo em que ocorre o fluxo de ar. Essa região é denominada de zona de influência e é afetada por vários fatores tais como: tipo e estrutura do solo, permeabilidade e pressão de injeção. No presente trabalho foram realizados estudos de fluxo de ar em solos saturados em um modelo físico bidimensional com o objetivo de avaliar a zona de influência formada. Os ensaios bidimensionais têm por finalidade a visualização dessa zona de influência; para isso foi utilizado um tanque transparente feito de placas de acrílico. Para a realização dos ensaios foram utilizados três tipos distintos de solo, uma areia natural denominada de Areia Osasco, uma areia comercial e uniforme (Areia do IPT) e um solo residual utilizado para criar as lentes de baixa permeabilidade. Também foram realizados ensaios de laboratório para a caracterização dos solos em estudo, tais como: curva de retenção, índice de vazios máximo e mínimo, granulometria, permeabilidade a água e ao ar. Os ensaios realizados no modelo (tanque) mostraram, como visto na literatura, que a granulometria e a estrutura do solo são as principais responsáveis pela formação de caminhos preferenciais de ar no solo. A zona de influência formada durante a injeção de ar nos ensaios com a Areia Osasco não foi simétrica devido à heterogeneidade do solo, já a formada nos ensaios com a Areia do IPT foi simétrica por causa da uniformidade do solo. A Areia do IPT apresentou uma zona de influência mais estreita do que a da Areia Osasco, isso ocorreu em função da menor porosidade da Areia Osasco, pois quanto menor a porosidade maior a tortuosidade e maior a expansão lateral. Os ensaios com as lentes de baixa permeabilidade mostraram que pequenas variações na configuração do solo podem influenciar a eficiência do método já que a região logo acima das lentes não foi atingida pelo ar. O aumento da pressão de injeção durante os ensaios fez com que mais canais de ar fossem formados causando um aumento do tamanho da zona de influência. / The method of air sparging is used for remediation of soil and groundwater contaminated with Volatile Organic Compounds (VOCs). In this process the air is injected into the soil in the saturated zone to ascend to the vadose zone and volatilizes the contaminants. The efficiency of air flow remediation is directly linked with the region of soil in which the flow occurs. This region is called as zone of influence and is affected by several factors such as: type and structure of the soil, permeability and pressure of injection. In the present work the air flow in saturated soils was investigated using a bidimensional physical model to evaluate the zone of influence formed. The objective of the tests was to obtain informations about zone of influence. A transparent tank made by acrylic plates was used. For these tests it was used three different types of soil: natural sand, called Osasco sand, a commercial and uniform sand called IPT sand and a residual soil used to create the lenses with low permeability. Laboratory tests such as water retention, minimum and maximum voids ratio, water and air permeability were performed to characterize the soils used in this study. Tests performed in the model (tank) showed, like those in the literature, that the particle size and soil structure are mainly responsible to create the preferential paths of air in soil. The zone of influence formed during the injection of air in the tests with Osasco sand was not symmetrical due to the heterogeneity of the soil; on the other hand the test performed with IPT sand was symmetrical due to its uniformity. The IPT sand showed a narrower zone of influence than Osasco sand, this was due to the lower porosity of the Osasco sand. Lower porosity imply in higher tortuosity and greater lateral expansion. Testes performed with low permeability lenses within the sand showed that small variations in the structure of the soil can affect the efficiency of the method because the region immediately above the lens is not reached by the air. The increase in the pressure of injection during the experiments induced the formation of more air channels causing an increase in the size of the zone of influence.

O método de injeção de ar é utilizado para a descontaminação de solos e lençóis freáticos contaminados com Compostos Orgânicos Voláteis (VOCs). O ar injetado no solo na zona saturada, ao subir para a zona não saturada, volatiliza os contaminantes. A eficiência da remediação por esse método está diretamente ligada à região de solo em que ocorre o fluxo de ar. Essa região é denominada de zona de influência e é afetada por vários fatores tais como: tipo e estrutura do solo, permeabilidade e pressão de injeção. No presente trabalho foram realizados estudos de fluxo de ar em solos saturados em um modelo físico bidimensional com o objetivo de avaliar a zona de influência formada. Os ensaios bidimensionais têm por finalidade a visualização dessa zona de influência; para isso foi utilizado um tanque transparente feito de placas de acrílico. Para a realização dos ensaios foram utilizados três tipos distintos de solo, uma areia natural denominada de Areia Osasco, uma areia comercial e uniforme (Areia do IPT) e um solo residual utilizado para criar as lentes de baixa permeabilidade. Também foram realizados ensaios de laboratório para a caracterização dos solos em estudo, tais como: curva de retenção, índice de vazios máximo e mínimo, granulometria, permeabilidade a água e ao ar. Os ensaios realizados no modelo (tanque) mostraram, como visto na literatura, que a granulometria e a estrutura do solo são as principais responsáveis pela formação de caminhos preferenciais de ar no solo. A zona de influência formada durante a injeção de ar nos ensaios com a Areia Osasco não foi simétrica devido à heterogeneidade do solo, já a formada nos ensaios com a Areia do IPT foi simétrica por causa da uniformidade do solo. A Areia do IPT apresentou uma zona de influência mais estreita do que a da Areia Osasco, isso ocorreu em função da menor porosidade da Areia Osasco, pois quanto menor a porosidade maior a tortuosidade e maior a expansão lateral. Os ensaios com as lentes de baixa permeabilidade mostraram que pequenas variações na configuração do solo podem influenciar a eficiência do método já que a região logo acima das lentes não foi atingida pelo ar. O aumento da pressão de injeção durante os ensaios fez com que mais canais de ar fossem formados causando um aumento do tamanho da zona de influência. / The method of air sparging is used for remediation of soil and groundwater contaminated with Volatile Organic Compounds (VOCs). In this process the air is injected into the soil in the saturated zone to ascend to the vadose zone and volatilizes the contaminants. The efficiency of air flow remediation is directly linked with the region of soil in which the flow occurs. This region is called as zone of influence and is affected by several factors such as: type and structure of the soil, permeability and pressure of injection. In the present work the air flow in saturated soils was investigated using a bidimensional physical model to evaluate the zone of influence formed. The objective of the tests was to obtain informations about zone of influence. A transparent tank made by acrylic plates was used. For these tests it was used three different types of soil: natural sand, called Osasco sand, a commercial and uniform sand called IPT sand and a residual soil used to create the lenses with low permeability. Laboratory tests such as water retention, minimum and maximum voids ratio, water and air permeability were performed to characterize the soils used in this study. Tests performed in the model (tank) showed, like those in the literature, that the particle size and soil structure are mainly responsible to create the preferential paths of air in soil. The zone of influence formed during the injection of air in the tests with Osasco sand was not symmetrical due to the heterogeneity of the soil; on the other hand the test performed with IPT sand was symmetrical due to its uniformity. The IPT sand showed a narrower zone of influence than Osasco sand, this was due to the lower porosity of the Osasco sand. Lower porosity imply in higher tortuosity and greater lateral expansion. Testes performed with low permeability lenses within the sand showed that small variations in the structure of the soil can affect the efficiency of the method because the region immediately above the lens is not reached by the air. The increase in the pressure of injection during the experiments induced the formation of more air channels causing an increase in the size of the zone of influence.

Prior to the passage of the 1976 Resource Conservation and Recovery Act (RCRA) 1.6 million bare steel Underground Storage Tanks (UST) were in use in the United States. Many of them were leaking. In Indiana approximately 13,000 UST remain but have been upgraded to meet current industry and regulatory standards. Cleaning up the petroleum releases from leaking UST has continued since it became evident that bare steel underground tanks leaked. In Northwest Indiana glacial moraine and outwash deposits from the Wisconsin Ice Age that retreated 10,000 years ago left 200 feet of glacial till above the underlying bedrock. Soil Vapor Extraction (SVE) and Air Sparging (AS) have proven to be effective and provide significant cost savings for remediation in the glacial deposits in Northwest Indiana. Indiana also has the Excess Liability Trust Fund (ELTF) to help pay for and to expedite clean-up of releases from registered UST. Cleaning up petroleum releases requires the appropriate technology for the localized geology, adequate funding, and appropriate guidance from state and federal regulations. This study discusses these issues at three sites in Northwest Indiana to demonstrate how technology, funding, and regulatory compliance must collaborate to work in the field.

El reactor anaerobio de membranas sumergidas (SAnMBR) está considerado como tecnología candidata para mejorar la sostenibilidad en el sector de la depuración de aguas residuales, ampliando la aplicabilidad de la biotecnología anaerobia al tratamiento de aguas residuales de baja carga (v.g. agua residual urbana) o a condiciones medioambientales extremas (v.g. bajas temperaturas de operación). Esta tecnología alternativa de tratamiento de aguas residuales es más sostenible que las tecnologías aerobias actuales ya que el agua residual se transforma en una fuente renovable de energía y nutrientes, proporcionando además un recurso de agua reutilizable. SAnMBR no sólo presenta las principales ventajas de los reactores de membranas (i.e. efluente de alta calidad, y pocas necesidades de espacio), sino que también presenta las principales ventajas de los procesos anaerobios. En este sentido, la tecnología SAnMBR presenta una baja producción de fangos debido a la baja tasa de crecimiento de los microorganismos implicados en la degradación de la materia orgánica, presenta una baja demanda energética debido a la ausencia de aireación, y permite la generación de metano, el cual representa una fuente de energía renovable que mejora el balance energético neto del sistema. Cabe destacar el potencial de recuperación de nutrientes del agua residual bien cuando el efluente es destinado a irrigación directamente, o bien cuando debe ser tratado previamente mediante tecnologías de recuperación de nutrientes. El objetivo principal de esta tesis doctoral es evaluar la viabilidad de la tecnología SAnMBR como núcleo en el tratamiento de aguas residuales urbanas a temperatura ambiente. Por lo tanto, esta tesis se centra en las siguientes tareas: (1) implementación, calibración y puesta en marcha del sistema de instrumentación, control y automatización requerido; (2) identificación de los parámetros de operación clave que afectan al proceso de filtración; (3) modelación y simulación del proceso de filtración; y (4) desarrollo de estrategias de control para la optimización del proceso de filtración minimizando los costes de operación. En este trabajo de investigación se propone un sistema de instrumentación, control y automatización para SAnMBR, el cual fue esencial para alcanzar un comportamiento adecuado y estable del sistema frente a posibles perturbaciones. El comportamiento de las membranas fue comparable a sistemas MBR aerobios a escala industrial. Tras más de dos años de operación ininterrumpida, no se detectaron problemas significativos asociados al ensuciamiento irreversible de las membranas, incluso operando a elevadas concentraciones de sólidos en el licor mezcla (valores de hasta 25 g·L-1 ). En este trabajo se presenta un modelo de filtración (basado en el modelo de resistencias en serie) que permitió simular de forma adecuada el proceso de filtración. Por otra parte, se propone un control supervisor basado en un sistema experto que consiguió reducir el consumo energético asociado a la limpieza física de las membranas, un bajo porcentaje de tiempo destinado a la limpieza física respecto al total de operación, y, en general, un menor coste operacional del proceso de filtración. Esta tesis doctoral está integrada en un proyecto nacional de investigación, subvencionado por el Ministerio de Ciencia e Innovación (MICINN), con título ¿Modelación de la aplicación de la tecnología de membranas para la valorización energética de la materia orgánica del agua residual y la minimización de los fangos producidos¿ (MICINN, proyecto CTM2008-06809- C02-01/02). Para obtener resultados representativos que puedan ser extrapolados a plantas reales, esta tesis doctoral se ha llevado a cabo utilizando un sistema SAnMBR que incorpora módulos comerciales de membrana de fibra hueca. Además, esta planta es alimentada con el efluente del pre-tratamiento de la EDAR del Barranco del Carraixet (Valencia, España). / Robles Martínez, Á. (2013). Modelling, simulation and control of the filtration process in a submerged anaerobic membrane bioreactor treating urban wastewater [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/34102 / TESIS / Premios Extraordinarios de tesis doctorales