Hydrogeologists collect data through studies that originate from a diverse and growing set of instruments that measure, for example, geochemical constituents of surface and groundwater. Databases store and publish the collected data on the Web, and the volume of data is quickly increasing, which makes accessing data problematic and time consuming for individuals. One way to overcome this problem is to develop ontology to formally and explicitly represent the domain (e.g., contaminant hydrogeology) knowledge. Using OWL and RDF, contaminant hydrogeology ontology (CHO) is developed to manage hydrological spatial data for Georgia, USA. CHO is a conceptual computer model for the contaminant hydrogeology domain in which concepts (e.g. contaminant, aquifer) and their relationships (e.g. pollutes) are formerly and explicitly defined. Cyberinfrastructure for exposing CHO and datasets (i.e., CHKb) as Linked Data on the Web is developed. Cyberinfrastructure consists of storing, managing, querying, and visualizing CHKb that can be accessed from URL: cho.gsu.edu.

This research ranked the adsorbability of 115 emerging contaminants by granular activated carbon (GAC) from drinking water, mainly the organic chemicals identified on the Contaminant Candidate List 3 (CCL3), using classical and quantum quantitative structure activity relationships (QSAR). 80% of the investigated contaminants were classified as cost effectively treatable by GAC based on the models. A rapid small-scale column test (RSSCT) conducted with Lake Ontario water spiked with 8 selected emerging contaminants showed the modeling results were accurate. This research also tested the hypothesis that GAC exhaustion for geosmin and 2-methylisoborneol would be due entirely to natural organic matter, and would occur independently of the presence of these two compounds. RSSCT results confirmed this hypothesis. Mathematical modeling supported this observation by demonstrating that the ratio of the effluent concentration to the influent concentration of a trace organic contaminant is only dependent on the NOM loading state at any bed depth.

Bioremediation of chlorinated contaminants in groundwater can be achieved by reductive dechlorination by anaerobic dechlorinating cultures. However, at sites impacted with multiple different chlorinated contaminants, reductive dechlorination is often inhibited by co-contaminants. The inhibitory effects of trichloroethene, cis-dichloroethene and vinyl chloride on chloroform dechlorination were studied using a Dehalobacter-containing chloroform dechlorinating mixed culture (ACT-3). The inhibitory effect of chloroform on chlorinated ethene dechlorination was studied in a Dehalococcoides-containing trichloroethene dechlorinating mixed culture (KB-1). Vinyl chloride was found to be the strongest inhibitor of chloroform in ACT-3. Chloroform exerted a complex and strong inhibitory effect on chlorinated ethene dechlorination in KB-1. The potential for microbial reductive defluorination was also examined in the enrichment cultures. Quantifying the substrates and substrate interactions in dechlorinating cultures is necessary to most efficiently use these cultures to remediate contaminated sites.

This research ranked the adsorbability of 115 emerging contaminants by granular activated carbon (GAC) from drinking water, mainly the organic chemicals identified on the Contaminant Candidate List 3 (CCL3), using classical and quantum quantitative structure activity relationships (QSAR). 80% of the investigated contaminants were classified as cost effectively treatable by GAC based on the models. A rapid small-scale column test (RSSCT) conducted with Lake Ontario water spiked with 8 selected emerging contaminants showed the modeling results were accurate. This research also tested the hypothesis that GAC exhaustion for geosmin and 2-methylisoborneol would be due entirely to natural organic matter, and would occur independently of the presence of these two compounds. RSSCT results confirmed this hypothesis. Mathematical modeling supported this observation by demonstrating that the ratio of the effluent concentration to the influent concentration of a trace organic contaminant is only dependent on the NOM loading state at any bed depth.

Bioremediation of chlorinated contaminants in groundwater can be achieved by reductive dechlorination by anaerobic dechlorinating cultures. However, at sites impacted with multiple different chlorinated contaminants, reductive dechlorination is often inhibited by co-contaminants. The inhibitory effects of trichloroethene, cis-dichloroethene and vinyl chloride on chloroform dechlorination were studied using a Dehalobacter-containing chloroform dechlorinating mixed culture (ACT-3). The inhibitory effect of chloroform on chlorinated ethene dechlorination was studied in a Dehalococcoides-containing trichloroethene dechlorinating mixed culture (KB-1). Vinyl chloride was found to be the strongest inhibitor of chloroform in ACT-3. Chloroform exerted a complex and strong inhibitory effect on chlorinated ethene dechlorination in KB-1. The potential for microbial reductive defluorination was also examined in the enrichment cultures. Quantifying the substrates and substrate interactions in dechlorinating cultures is necessary to most efficiently use these cultures to remediate contaminated sites.

Alternative strategies involving in situ remediation technologies have been developed to assist with property clean up, however, cost-effectiveness and discrepancies in success rates and timeliness continue. The objective of my research was to critically demonstrate the application and usefulness of an in situ remediation technology at a petroleum hydrocarbon impacted site. This project was proposed as part of the research programs: Groundwater Plume Formation and Remediation of Modern Gasoline Fuels in the Subsurface and Enhancing In Situ Bioremediation at Brownfield Sites funded by the Ontario Centres of Excellence for Earth and Environmental Technologies as part of the multiphase project entitled “Enhancing in situ Bioremediation at Brownfield Sites”. This research focused on the demonstration of nitrate-enhanced in situ bioremediation at a decommissioned service station. Petroleum hydrocarbon impacted soil and groundwater is a common occurrence at gasoline distribution facilities, where toxicological effects are known for gasoline constituents of interest such as benzene, toluene, ethylbenzene and total xylenes (BTEX). These chemicals are volatile, readily soluble, and persistent in groundwater. In particular, residual contaminants present in the saturated zone were targeted for remediation as they serve as a long term source of contamination and contribute to mobile vapour phase and dissolved phase plumes. Site investigations characterized the complex hydrogeological conditions and contaminant distribution present in order to effectively design an in situ bioremediation treatment system. The addition of nitrate as a terminal electron acceptor (TEA) to an aquifer enhances in situ biodegradation of petroleum hydrocarbons, by providing the microbes with a sustainable energy source to promote cell maintenance and growth of the microbial population. The remediation strategy involved pulsed injections of remedial solution amended with a conservative bromide (200 mg/L Br-) and reactive nitrate (90 to 265 mg/L NO3-) tracers with the purpose of providing a continuous supply of TEA available to the indigenous microbial populations. Nitrate was selected as an alternative electron acceptor over the thermodynamically favoured O2 because of typical challenges encountered using O2 in bioremediation applications in addition to the existing anaerobic environment. In situ anaerobic degradation of BTEX compound using TEA amendments has been well documented; however benzene is often recalcitrant under denitrification conditions. The results of the Br- tracer breakthrough curves indicate that different preferential flow pathways were established under the transient saturated conditions present at the Site, although the behaviour of the injected remedial slug was generally consistent between the different units and the test solution was ultimately delivered to the target zone. The delivery of the remedial test solution was greatly influenced by the hydrogeological conditions present at the time of injection. The injectate was preferentially transported in the high permeability zone of sandy gravel aquifer Unit 3 under high saturated condition and background hydraulic gradients. However the seasonal decline in groundwater levels and hydraulic gradients resulted in the lower portion of Unit 4 comprised of higher permeable materials being able to transmit the test solution more effectively. Given the variable hydrogeological conditions present at the Site influenced by seasonal effects, the delivery of the remedial solution to target zones containing petroleum hydrocarbons at residual saturation is more effective under reduced saturated conditions. The delivery of TEA amended water to enhance the in situ biodegradation of petroleum contaminants is more effective when the treatment water has an increased residence time in the target remedial zone, attributed to low gradients and groundwater transport velocities at the Site. Longer residence periods enable the indigenous microbes to have increased contact time with the TEA which will be preferentially utilized to degrade the contaminants.   A reducing zone enriched with TEA in the anaerobic aquifer was established following consecutive injections of remedial test solution. A cumulative mass of 4 kg of NO3- was added to the target aquifer during the course of the remedial injections. Evidence demonstrating NO3- utilized as a terminal electron acceptor in the bioremediation of the petroleum-contaminated aquifer include: laboratory microcosm study confirming local indigenous microbial population’s ability to degrade hydrocarbons using NO3- as the TEA in addition to observed decrease in NO3- relative to a conservative Br- tracer and generation of nitrite, an intermediate product in denitrification in the pilot-scale operation. Contaminant mass removal likely occurred as Br- tracer evidence indicates that NO3- was utilized in the study area based on the inference of denitrification rates. Post-injection groundwater sampling indicate declining concentrations of toluene, however long term monitoring is recommended in order to evaluate the success of the remediation activity and assess the potential for rebound. Post-injection soil core results are unable to demonstrate the reduction in individual toluene, let alone BTEXTMB hydrocarbon levels, as a result of insufficient quantities of nitrate delivered to the target zone relative to the significant but heterogeneously distributed residual mass in the subsurface.

[pt] O presente trabalho apresenta o desenvolvimento de uma ferramenta para o estudo de problemas de transporte de contaminantes na água subterrânea. No desenvolvimento desta ferramenta foram utilizados métodos de estabilização na solução da equação de transporte e o método dos gradientes conjugados. Os métodos de estabilização buscam superar as limitações impostas pelo número de Peclet. O método dos Gradientes Conjugados, por sua vez, tem como objetivo melhorar a eficiência da solução do sistema de equações decorrente da utilização do método dos elementos finitos na solução do problema de transporte. Desenvolveu-se um modelo de reação química que fosse capaz de lidar com compostos que possuem propriedades de transporte diferentes. O desenvolvimento deste modelo levou à idealização de uma metodologia que abrange outros modelos químicos de uma forma única. Para descrever essa metodologia foi utilizado o paradigma de Orientação a Objetos que deu origem a uma hierarquia de classes capaz de suportar o desenvolvimento de modelos químicos das mais variadas formas. Por fim utilizou-se a ferramenta desenvolvida para avaliar alguns problemas decorrentes da contaminação por HCH da Cidade dos Meninos no município de Duque de Caxias, estado de Rio de Janeiro, e a avaliação da técnica de barreiras reativas como alternativa de remediação de águas subterrâneas contaminadas. / [en] This work presents the development of a tool to study the water contamination problem. This tool involves the utilization of stabilization methods and the utilization of the Conjugate Gradient method. The stabilization methods aims at overcoming the limitations imposed by the grid Peclet number. The Conjugate Gradient method aims at providing an eficient method to solve the system of equations which arises from the application of the finite element method in the solution of the contamination problem. As part of this work a chemical model was developed to simulate the interaction among chemical species involved in the transport process. These species sometimes have different physical properties that have to be taken under consideration by the chemical model. Taking advantage of the Object Oriented paradigm, we proposed a class hierarchy (OOP) to support the development of a chemical model. Finally the developed program was used to study a contamination problem with HCH at Cidade dos Meninos city in Duque de Caxias township, Rio de Janeiro, and to evaluate the reactive barrier design as a remediation method. / [es] Este trabajo presenta el desarrollo de una herramienta para el estudio de problemas de transporte de contaminantes en el agua subterránea. En el desarrollo de esta herramienta se utilizaron métodos de estabilización en la solución de la ecuación de transporte y el método del gradiente conjugado. Los métodos de estabilización intentan superar las limitaciones impuestas por el número de Peclet. El método del Gradiente Conjugados, por su vez, tiene como objetivo mejorar la eficiencia de la solución del sistema de ecuaciones que resulta de utilizar el método de los elementos finitos en la solución del problema de transporte. Se dearrolló un modelo de reacción química para compuestos que poseen propriedades de transporte diferentes. El desarrollo de este modelo tiene como resultado a formulación de una metodología que contiene otros modelos químicos de una forma única. Para describir esa metodología fue utilizado el paradigma de Orientación a Objetos que dió origen a una jerarquía de clases capaz de soportar el desarrollo de modelos químicos de las más variadas formas. Se utilizó la herramienta desarrollada para evaluar algunos problemas provocados por la contaminación por HCH de la Ciudad de los Meninos en el municipio de Duque de Caxias, estado de Rio de Janeiro, y la evaluación de la técnica de barreras reactivas como alternativas de remediación de aguas subterráneas contaminadas.

The Henry Aquifer in Gallatin County Illinois provides groundwater for municipal, irrigation, industrial, and household wells. The greatest annual withdrawal is by a water utility that serves over 40,000 persons in southeast Illinois. Buried coal refuse at a mine near the water utility has contaminated the groundwater. Remediation efforts, including source control wells on the border of the mine site and low permeability caps over refuse areas attempt to control the migration of contaminants offsite. Current mine land owners believe source control well pumping over 20 years has reduced contamination in the aquifer enough to stop pumping. However, some monitoring wells off the mine site have recently sampled high concentrations of contaminants. Previous studies failed to account for the elevated concentrations found offsite. The purpose of this research is to reevaluate contaminant transport in this region. Specific objectives include a new conceptual model of the hydrostratigraphy and hydrology, revised contaminant source locations and loading, and new groundwater models accurately calibrated to a comprehensive set of monitoring well data. The research included extensive review of prior studies and historical records from the past 50 years. Relevant information was combined in Quantum Geographic Information System (GIS) software for the conceptual and numerical models. A new groundwater modeling pre/post processor for MODFLOW and MT3DMS was ii created for Quantum GIS to calibrate the models and simulate future conditions for risk assessment. Observed hydraulic head and sulfate concentrations from 1984-2015 were used for calibration. In addition, modeled baseflow was compared with observed streamflow in 2017. The calibrated models were used for twelve unique scenarios that forecast contamination from 2017- 2068. The scenarios tested model sensitivity to changes in groundwater management and environmental conditions. The results show that groundwater quality about 300 meters west of the mine deteriorates in all scenarios, water utility wells near the mine are at risk in most scenarios, and that the location and discharge of wells have a commanding effect on the regional groundwater flow and transport systems. This research offers important questions for further study, valuable tools for groundwater management in the region, and shows that without active source control wells, negative impacts to water quality near the mine will likely occur.

A ocorrência de produtos farmacêuticos e de cuidados pessoais no meio ambiente tem levado a preocupações sobre seu impacto ambiental e à saúde pública. O sulfametoxazol (SMX) é um fármaco que tem sido encontrado amplamente no ambiente. Neste estudo foi verificada a eficácia de vários processos, a saber eletroquímico, eletroquímico foto assistido, fotoquímico, Fenton e foto-Fenton, para a degradação de SMX em solução aquosa. A degradação eletroquímica e eletroquímica foto assistida foram realizadas em uma célula de fluxo do tipo filtro-prensa, usando um ânodo dimensionalmente estável comercial com composição nominal Ti/Ru0,3Ti0,7O2. Durante ambos os processos, efeitos de diferentes parâmetros foram analisados, como a natureza do eletrólito, a concentração de eletrólito suporte (NaCl) e a densidade de corrente aplicada. Os experimentos fotoquímicos, Fenton e foto-Fenton foram realizados em um reator de vidro cilíndrico de compartimento único. O efeito das concentrações inicias de Fe2+ e de H2O2 foram estudados para os processos Fenton e foto-Fenton. Similarmente, o efeito do pH inicial, a concentração inicial do SMX e a temperatura foram investigados para todos os processos. A variação da concentração de SMX foi determinada por cromatografia líquida de alta eficiência (CLAE) e a quantidade de matéria orgânica foi monitorada por análise de carbono orgânico total (COT). Os resultados obtidos indicaram que o SMX foi completamente degradado, porém, o COT foi apenas parcialmente removido em todos os processos. No período de tempo de ensaio estabelecido o aumento da densidade de corrente e da concentração de NaCl mais eficiente para a degradação e remoção de COT nos processos eletroquímicos. A quantidade de Fe2+ e H2O2 aumenta a eficiência do processo Fenton e foto-Fenton, e meio ácido foi favorável para todos os processos. O consumo de energia elétrica, baseado no parâmetro EEO (energia por ordem) mostrou que os processos eletroquímicos são energeticamente mais eficientes do que os fotoquímicos. As degradações acompanhadas por CLAE acoplado à espectrometria de massas, permitiu que vários intermediários fossem identificados, sendo então proposta uma sequência reacional para a degradação do SMX. O radical hidroxila e o cloro ativo atacam os anéis benzílico e isoxazólico, tendo sido demonstrado que os compostos iniciais formados foram os compostos hidrolisados e clorados. Os íons inorgânicos, tais como: NO3-, NH4+ e SO42-, também foram identificados durante os processos de degradação. / The occurrence of pharmaceuticals and personal care products in the environment has raised concerns about their impact upon environmental and public health. Sulfamethoxazole (SMX) is a pharmaceutical that has been found widely in the environment. This study investigated the effectiveness of various processes such as electrochemical, photo assisted electrochemical, photochemical, Fenton photo-Fenton to SMX degradation in aqueous solution. The electrochemical and photo-assisted electrochemical degradations were performed in a filter press type flow cell using a dimensionally stable anode with nominal composition of Ti/Ru0.3Ti0.7O2. During both these processes the effects of different parameters were analyzed, such as, nature of the electrolyte concentration of the supporting electrolyte (NaCl) and the applied current density. The photochemical, Fenton and photo - Fenton experiments were carried out in a single compartment cylindrical glass reactor. The effects initial iron concentrations and H2O2 were studied for Fenton and photo-Fenton processes. Similarly the effect of initial pH, initial concentration of SMX and temperature were investigated for all processes. The variation of SMX concentration was determined by high performance liquid chromatography (HPLC) and the amount of organic matter was monitored by analysis of total organic carbon (TOC). The results indicated that SMX was completely degraded, but TOC was partially removed in all processes studied, during experimental period the increase of the current density and NaCl concentration enhanced the degradation and TOC removal in the electrochemical processes. The amount of iron and H2O2 increases the efficiency of Fenton and photo-Fenton processes and acidic media was favorable for all processes. The electrical energy consumption parameter based on EEO (energy per order) was also evaluated and it was observed that the electrochemical processes are more energetically efficient than the photochemical. The degradations followed by HPLC coupled with mass spectrometry, in which several intermediates were identified and proposed a reaction sequence for the degradation of SMX. The hydroxyl radical and active chlorine attack benzene and isoxazólico rings, and has been demonstrated that the initial compounds formed were hydrolyzed and chlorinated compounds. Inorganic ions such NO3-, NH4+ and SO42- were also identified during degradation processes.

Le but de cette thèse consiste à créer et développer un modèle de transport de suspension colloïdale en milieu poreux saturé qui sera capable de détecter et de prédire l'apparition de vitesses différentes entre l'eau et la suspension ; de distinguer les cas de l'accélération et de retard des particules colloïdales ainsi que de calculer les deux vitesses en utilisant l'information initiale des propriétés du milieu poreux et des particules. On a procédé de deux manières différentes. Premièrement, on a proposé une méthode analytique de calcul de facteur d'augmentation de la vitesse qu'on peut introduire dans le modèle monophasique classique du transport colloïdal. Deuxièmement, on a proposé un nouvelle approche mathématique phénoménologique pour décrire un transport colloïdal.Pour développer cette approche, on a utilisé le fait que les deux vitesses apparaissent automatiquement dans le modèle diphasique d'écoulement. Ainsi notre modèle doit être proche de celui diphasique. En conséquence, pour notre modèle mathématique, on a écarté l'approche traditionnelle qui suppose un transport d'un liquide monophasique / The aim of this PhD thesis is to create and to develop a colloid suspension transport model in the saturated porous media that will be able to detect and to predict the apparition of the difference between water and suspension velocity; to distinguish cases of acceleration and of deceleration of the colloidal particles and also to calculate the two velocities using the initial information on the properties of porous media and of particles. We are proceeded by two different manners. Firstly, we are proposed an analytical method of calculation of enhancement velocity factor that can be introduced in the classic colloid transport model that is single-phase one. Secondly, we are proposed a new phenomenological mathematical approach to describe a colloid transport. To develop this approach, we are used the fact that two velocities appear automatically in the two-phase transport model. Thus our model must be similar to two-phase one. Therefore, for our mathematical model we are refused the traditional approach that assumes a transport of a single-phase liquid