Activated carbons have been modif fed using reactive chemicals to produce adsorbents of enhanced hydrophobic character which will also be resistant to surface oxidation that results from exposure to humid air ("ageing"). The intention was that modification would not disrupt the carbon pore structure. The adsorptive properties of the modified carbons have been investigated using probe molecules Including nitrogen, water, hexane, and chloropicrin, and the ageing characteristics of the carbons, and the factors controlling the adsorption of a model hydrophobic vapour from high humidity air have been studied. Directly fluorinated carbons were unstable, probably due to weakly adsorbed fluorine. Treatment of these adsorbents with other chemicals indicated the potential of the technique for Introducing specific functional groups onto the carbon surface. Carbons modified using selective fluorinating reagents (hexafluoropropene and 1,1-difluoroethene) were more hydrophobic, and adsorbed hydrophobic vapours more efficiently from humid air in comparison to controls. These adsorbents aged, but at a reduced rate in comparison to control carbon. Carbons modified using chlorinating reagents (carbonyl chloride and chlorine) and treated with solvents to remove adsorbed reagent and/or reaction products were of improved hydrophobic character, and adsorbed hydrophobic vapours from humid air at least as efficiently as the control samples. More importantly, these carbons offered resistance to ageing effects. A study of the factors controlling the efficiency with which hydrophobic vapours; are adsorbed from humid air revealed that the surface chemistry of the carbon is important, but that under typical conditions of use, filter performance was limited by the rate at which water displaced by the organic vapour could be carried away by the airstream. The results illustrate that filters containing chemically modified activated carbon offer advantages when volatile hydrophobic contaminant vapours are present, and where ageing effects are an important mechanism by which filtration efficiency is degraded.

Hydraulic fracturing is used to extract oil and natural gas from low permeability formations. The potential of fluids migrating from depth through adjacent wellbores and through the production wellbore was investigated using statistical modeling and predic-tive classifiers. The probability of a hydraulic fracturing well becoming hydraulically connected to an adjacent well in the Marcellus shale of New York was determined to be between 0.00% and 3.45% at the time of the study. This means that the chance of an in-duced fracture from hydraulic fracturing intersecting an existing well is highly dependent on the area of increased permeability caused by fracturing. The chance of intersecting an existing well does not mean that fluid will flow upwards; for upward migration to occur, a pathway must exist and a pressure gradient is required to drive flow, with the exception of gas flow caused by buoyancy. Predictive classifiers were employed on a dataset of wells in Alberta Canada to identify well characteristics most associated to fluid migration along the production well. The models, specifically a random forest, were able to identify pathways better than random guessing with 78% of wells in the data set identified cor-rectly. Magnetic resonance imaging (MRI) was used to visualize and quantify contami-nant transport in a soil column using a full body scanner. T1 quantification was used to determine the concentration of a contaminant surrogate in the form of Magnevist, an MRI contrast agent. Imaging showed a strong impact from density driven convection when the density difference between the two fluids was small (0.3%). MRI also identified a buildup of contrast agent concentration at the interface between a low permeability ground silica and higher permeability AFS 50-70 testing sand when density driven con-vection was eliminated.

[pt] O presente trabalho apresenta estudos de simulações dos processos de transporte e atenuação do derramamento de gasolina nas condições encontradas em postos de gasolina. Estas simulações são realizadas através da aplicação de métodos numéricos para análise de transporte de multicompostos em meios porosos. Na simulação são utilizados programas para análise tridimensional de fluxo e transporte de contaminantes, bem como um programa de pré- e pós-processamento gráfico utilizado na definição da geometria, geração da malha de diferenças finitas, definição dos parâmetros adotados e visualização dos resultados. Um estudo detalhado dos programas utilizados nas análises é realizado. Este estudo inclui um teste para validar os dados fornecidos pelo programa de análise de transporte de contaminantes, bem como, a implementação numérica de uma nova reação química (reação do BTEX com o reagente de Fenton). Como aplicação dos procedimentos estudados, foi utilizado um caso de derramamento de gasolina em um posto na cidade do Rio de Janeiro-RJ. Para representar este derramamento, a simulação foi dividida em três etapas. A primeira refere-se à tentativa de reproduzir as condições de fluxo e contaminação do BTEX, medidos no campo, até o instante de retirada dos tanques. A segunda etapa da simulação corresponde ao período após a substituição dos tanques. A última etapa da simulação, corresponde ao início da injeção de oxigênio usado para bioremediação da área contaminada. O trabalho apresenta uma descrição dos programas utilizados e sua formulação. Apresenta e comenta também os resultados das análises e implementação efetuada. / [en] The present work presents studies related to the simulation of transport and attenuation processes of gasoline spills in conditions normally encountered in petrol stations. These studies are carried out through the application of numerical methods for the analysis of transport of multicomponents in porous media. Computer programs for 3D analysis of flow and transport of contaminants were used as well as graphics routines for the visualization of results. A detailed study of the programs used was carried out. Validation tests were performed as well as an external implementation of a new routine to simulate a particular chemical reaction (reaction of BTEX with Fenton`s reagent) related to a special remediation technique. As application of the studied procedures, a case related to the gasoline spill in a petrol station located in the city of Rio de Janeiro-RJ was focused. In order to represent as close as possible the gasoline spill the simulation was divided into three stages. The first one, refers to an attempt to reproduce the flow and contamination conditions of BTEX compounds formed in situ until the removal of the underground tanks. The second stage corresponds to a period just after the replacement of the damaged tanks. Finally, the last stage consisted in the injection of oxygen used for bioremediation of the contaminated area. The present work describes the overall methodology used, the obtained results and pertinent comments. / [es] EL presente trabajo presenta estudios de simulación de los procesos de transporte y atenuación del derrame de gasolina en las condiciones encontradas en los puestos de gasolina. Estas simulaciones son realizadas aplicando métodos numéricos para el análisis de transporte de multicompuestos en medios porosos. En la simulación se utilizan programas par el análisis tridimensional de flujo y transporte de contaminantes, así como un programa de pré y postprocesamiento gráfico utilizado en la definición de la geometría, generación de la malla de diferencias finitas, definición de los parámetros adoptados y visualización de los resultados. Se incluye un detallado estudio de los programas utilizados en el análisis. Este estudio incluye una prueba para validar los datos suministrados por el programa de análisis de transporte de contaminantes, así como, la implementación numérica de una nueva reacción química (reacción del BTEX con el reagente de Fenton). Como aplicación de los procedimentos estudiados, fue utilizado un caso de derramamiento de gasolina en un puesto de la ciudad del Rio de Janeiro RJ. Para representar este derramamento, la simulación fue dividida en tres etapas. La primera intenta reproduzir las condiciones de flujo y contaminación del BTEX, medidos en el campo, hasta el instante de retirada de los tanques. La segunda etapa de la simulación corresponde al período después la substituición de los tanques. La última etapa, corresponde al início de la inyeción de oxígeno usado para biocuración de la área contaminada. EL trabajo presenta una descripción de los programas utilizados, de su formulación y los resultados del análisis son comentados.

[pt] Neste trabalho foi desenvolvido um programa para simulação numérica do fluxo bifásico em meios porosos com transferência de massa entre as duas fases e transporte dos solutos em cada fase. O programa calcula o aumento da mobilidade da fase não aquosa e da solubilidade de seus componentes na água como resultado da adição de um co- solvente. O objetivo foi simular problemas de contaminação no subsolo com líquidos imiscíveis com a água e a remediação através da técnica de injeção de co-solventes, assim como a contaminação a partir de vazamentos de gasolina acrescida de álcool em postos de abastecimento. Podem-se ainda resolver problemas de fluxo bifásico envolvendo uma fase gasosa. Foi desenvolvido e implementado um modelo para a transferência de massa durante o fluxo das duas fases. O cálculo das propriedades das duas fases ao longo do tempo é feito utilizando o diagrama ternário de fases. Para resolver as equações do fluxo e do transporte de solutos foi empregado o método de elementos finitos. / [en] A computer code was developed for numerical simulation of two-phase flow in porous media considering mass transfer between the phases involved and solute transport in each phase. Enhanced mobility of nonaqueous phase and enhanced aqueous solubility of its components as a result of cosolvent injection are calculated. The objective of this work was to simulate subsurface contamination by nonaqueous phase liquids and remediation utilizing cosolvent injection technique, and also contamination by gasoline with alcohol from fuel tanks. It is also possible to solve two-phase flow problems involving a gaseous phase. A model for mass transfer during two-phase flow was developed and implemented. Properties variation with time for both phases is calculated using ternary phase diagram. Finite element method was used to solve flow and solute transport equations.

Continuous and reliable monitoring of contaminants in drinking water, which adversely affect human health, is the main goal of the Broward County Well Field Protection Program. In this study the individual monitoring station locations were used in a yearly and quarterly spatiotemporal Ordinary Kriging interpolation to create a raster network of contaminant detections. In the final analysis, the raster spatiotemporal nitrate concentration trends were overlaid with a pollution vulnerability index to determine if the concentrations are influenced by a set of independent variables. The pollution vulnerability factors are depth to water, recharge, aquifer media, soil, impact to vadose zone, and conductivity. The creation of the nitrate raster dataset had an average RMS Standardized error close to 1 at 0.98. The greatest frequency of detections and the highest concentrations are found in the months of April, May, June, July, August, and September. An average of 76.4% of the nitrate intersected with cells of the pollution vulnerability index over 100.

The Oak Ridge National Laboratory, Tennessee, was the site for a number of US Government projects during the 1940s and 1950s including the development of thermonuclear weapons. Chemical processes conducted at the site as part of these projects resulted in contamination of certain building areas at the ORNL. The purpose of this study is to develop a hydraulic-hydrologic computer model via XPSWMM to determine surface water flow rates and water stages within the drainage system during rainfall events and introduce a conservative contaminant into the system to trace peak concentrations of contaminants. The model was calibrated by simulating actual rainfall events over the area of interest. The model results were compared to that of Outfall 211’s monitored data. Trial 1 was most successful, where the cumulative flow rates produced by the model and the monitored data varied only by 0.5 cfs. A sensitivity analysis was completed by varying Manning’s coefficient and infiltration parameters within the area of interest. The sensitivity analysis concluded that the model was responsive to the variations presented; however, only minor differences were determined for the selected range of parameters, indicating robustness of model predictions. A hypothetical conservative contaminant was entered into the system as constant and varied timeseries. The resulting pollutographs produced by XPSWMM aid in the assessment for potential mobilization of contaminants and provide insight to where peak concentrations and loads occur under present conditions. Probability exceedance and probability distribution methods were used to analyze the timeseries of flow and pollutant concentrations collected during this study. Probability exceedance curves determined the percentage of time flooding occurred within the system under various conditions. The flow rates and concentrations produced by the transport analysis were best described by the Generalized Extreme Value, while the loading rates were best described by Log-logistic distribution.

As leveduras Dekkera/Brettanomyces estão envolvidas na deterioração de vinhos após o término das fermentações alcoólicas e maloláticas, tendo se apresentado como agente contaminante de processos contínuos de produção de etanol industrial. São caracterizadas pela morfologia celular típica (células alongadas e ogivais), alta produção de ácido e crescimento lento, porém de difícil identificação. Embora muitos trabalhos já tenham sido publicados acerca do seu papel na fermentação do vinho, pouco se conhece sobre o seu comportamento no processo de fermentação para produção de álcool combustível. Desta forma, este trabalho objetivou selecionar, identificar e caracterizar linhagens de Dekkera e Brettanomyces isoladas de processos fermentativos, através de testes de taxonomia clássica, moleculares (PCR e sequenciamento) e de biotipagem através do sistema killer, visando a avaliação de fermentações mistas de Saccharomyces cerevisiae e Dekkera bruxellensis, a última em níveis de contaminação variando de 101 a 103 células/mL, em meio de caldo de cana, em processo de fermentação em batelada com reciclo celular (14 ciclos de 12 horas) para produção de etanol. Os testes morfológicos e fisiológicos/bioquímicos de oito linhagens selecionadas pela alta produtividade de ácido a partir da glicose e morfologia celular característica, apontaram os gêneros Dekkera ou Brettanomyces, sem possibilidade de identificação em nível de espécie devido à ambigüidade dos resultados dos testes fisiológicos. O sequenciamento da região ITS (Internal transcribed spacer) do DNA ribossomal confirmou somente três linhagens como Dekkera bruxellensis, sendo as demais predominantemente pertencentes à espécie Pichia guillermondii. O tamanho da região ITS, incluindo o gene 5,8S, variou de 400 500 pb entre as três linhagens. A utilização do sistema killer como método de biotipagem para leveduras Dekkera mostrou-se inviável devido ao fenótipo predominantemente neutro apresentado pelas linhagens. Somente a levedura killer CCA510 (Kluyveromyces marxianus) apresentou atividade inibitória contra as três linhagens de D. bruxellensis. Os ensaios fermentativos realizados com a linhagem de D. bruxellensis (CCA059) em fermentações puras e mistas com S. cerevisiae (CCA193, PE-02), mostraram que a levedura contaminante foi capaz de crescer em meio de caldo de cana, independentemente do tamanho do seu inóculo inicial (101 a 103 células/mL), impactando negativamente a fermentação etanólica, causando a diminuição da viabilidade de S. cerevisiae, diminuindo o pH do meio, decréscimo na produção de etanol e eficiência fermentativa, possivelmente devido à produção de ácido acético a partir do ART do meio de fermentação. Extrapolando-se os resultados obtidos em escala de laboratório para a escala industrial de uma destilaria de médio porte, a contaminação por Dekkera bruxellensis acarretaria uma perda de 6 milhões a 15 milhões de litros de álcool na safra, que deixariam de ser produzidos, dependendo do nível de contaminação. / Dekkera/Brettanomyces yeasts are found to be either contaminants in wine after completion of alcoholic and malolactic fermentations and in continuous fermentations for fuel alcohol production. They are characterized by typical cell morphology (elongated and ogival cells), high acid production and slow growth, however not easily identified. Although their role in wine fermentations is well-defined, a little is known about their behavior during fermentation for ethanol production. This work aimed the screening, identification and characterization of Dekkera and Brettanomyces strains isolated from fermentative processes, through classical taxonomic tests, molecular analysis (PCR and DNA sequencing) and biotyping by killer system. Following fermentation essays were carried out to evaluate mixed fermentations of Saccharomyces cerevisiae and Dekkera bruxellensis, the last one in contamination levels varying from 101 to 103 cells/mL, in sugar cane medium, using batch fermentation process with cell recycle (fourteen 12-hour cycles) for fuel ethanol production. Morphological and physiological/biochemical tests involving eight strains selected for their high acid production from glucose and typical cell morphology, pointed out to the genera Dekkera or Brettanomyces, without possibility of species identification due to the variability and ambiguity of physiological tests. DNA sequencing of the ITS (Internal transcribed spacer) region belonging to ribosomal DNA confirmed only three strains as Dekkera bruxellensis, the others were predominantly Pichia guilliermondii. The ITS region, including the 5,8S gene, varied from 400 to 500 bp among the three strains. The use of killer system as a biotyping method for Dekkera strains might not be applied because the strains were predominantly neutral to killer toxins. Only the killer strain CCA510 (Kluyveromyces marxianus) showed to have inhibitory activity against the strains of D. bruxellensis. The fermentative essays using a strain of D. bruxellensis (CCA059) in mixed and pure fermentations with S. cerevisiae (CCA193, PE-02), have shown that the contaminant yeast was able to grown in sugar cane juice, regardless of the initial inoculum size ((101 to 103 cells/mL), impairing the bioethanol fermentation, causing diminished S. cerevisiae viability, pH decrease, lower ethanol production and fermentative efficiency, mainly due to the acetic acid production from reducing sugar present in fermentation medium. Extrapolation of the results obtained in laboratory scale to industrial scale in a medium-sized distillery, have revealed that contamination by Dekkera bruxellensis would result in a alcohol loss of 6 millions to 15 millions of liters, which would not be produced, depending on the contamination level.

abstract: Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has proved to be efficient in removing PFAS from water. There is a need to study the effectiveness of commercially available sorbents in PFAS removal at the pilot-scale with real PFAS contaminated water, which would aid in efficient full-scale plant design. Additionally, there is also a need to have validated bench-scale testing techniques to aid municipalities and researchers in selecting or comparing adsorbents to remove PFAS. Rapid Small-Scale Column Tests (RSSCTs) are bench-scale testing to assess media performance and operational life to remove trace organics but have not been validated for PFAS. Different design considerations exist for RSSCTs, which rely upon either proportional diffusivity (PD) or constant diffusivity (CD) dimensionless scaling relationships. This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2020

abstract: De facto potable reuse (DFR) occurs when surface water sources at drinking water treatment plants (DWTPs) contain treated effluents from upstream wastewater treatment plants (WWTPs). Contaminants of emerging concerns (CECs) originate from treated effluents (e.g., unregulated disinfection by-products, pathogenic microorganisms as Cryptosporidium oocyst, Giardia cyst, and Norovirus) can be present in surface water and pose human health risks linked to CECs. Previously developed De facto Reuse Incidence in our Nations Consumable Supply (DRINCS) model predicted DFR for the national largest DWTPs that serve >10,000 people (N = 2,056 SW intakes at 1,210 DWTPs). The dissertation aims to quantify DFR at all surface water intakes for smaller DWTPs serving ≤10,000 people across the United States and develop a programmed ArcGIS tool for proximity analysis between upstream WWTPs and DWTPs. The tested hypothesis is whether DWTPs serving ≤10,000 people are more likely to be impacted by DFR than larger systems serving > 10,000 people.The original DRINCS model was expanded to include all smaller DWTPs (N = 6,045 SW intakes at 3,984 DWTPs) in the U.S. First, results for Texas predicted that two-thirds of all SW intakes were impacted by at least one WWTP upstream. The level of DFR at SW intakes in Texas ranged between 1% to 20% under average flow and exceeded 90% during mild droughts. Smaller DWTPs in Texas had a higher frequency of DFR than larger systems while < 10% of these DWTPs employed advanced technology (AT) capable of removing CECs. Second, nationally over 40% of surface water intakes at all DWTPs were impacted by DFR under average flow (2,917 of 6,826). Smaller DWTPs had a higher frequency (1,504 and 1,413, respectively) of being impacted by upstream WWTP discharges than larger DWTPs. Third, the difference in DFR levels at smaller versus larger DWTPs was statistically unclear (t-test, p = 0.274). Smaller communities could have high risks to CECs as they rely on surface water from lower-order streams impacted by DFR. Furthermore, smaller DWTPs lack more than twice as advanced unit processes as larger DWTPs with 52.1% and 23%, respectively. DFR levels for DWTPs serving > 10,000 people were statistically higher on mid-size order streams (3, 5, and 8) than those for smaller DWTPs. Finally, DWTPs serving > 10,000 people could pose risks to a population impacted by DFR > 1% as 40 times as those served by smaller DWTPs with 71 million and 1.7 million people, respectively. The total exposed population to risks of CECs served by DWTPs impacted by upstream WWTP discharges (DFR >10%) was estimated at 12.3 million people in the United States. Future studies can use DRINCS results to conduct an epidemiological risk assessment for impacted communities and identify communities that would benefit from advanced technology to remove CECs. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

Groundwater is one of the main sources for drinking water and agricultural activities. Various activities of both humans and nature may lead to groundwater pollution. Very often, pollution, or contamination, of groundwater goes undetected for long periods of time until it begins to affect human health and/or the environment. Cleanup technologies used to remediate pollution can be costly and remediation processes are often protracted. A more practical and feasible way to manage groundwater contamination is to monitor and predict contamination and act as soon as there is risk to the population and the environment. Predicting groundwater contamination requires advanced numerical models of groundwater flow and solute transport. Such numerical modeling is increasingly becoming a reference criterion for water resources assessment and environmental protection. Subsurface numerical models are, however, subject to many sources of uncertainties from unknown parameters and approximate dynamics. This dissertation considers the sequential data assimilation approach and tackles the groundwater contamination problem at the port of Rotterdam in the Netherlands. Industrial concentration data are used to monitor and predict the fate of organic contaminants using a three dimensional coupled flow and reactive transport model. We propose a number of 5 novel assimilation techniques that address different challenges, including prohibitive computational burden, the nonlinearity and coupling of the subsurface dynamics, and the structural and parametric uncertainties. We also investigate the problem of optimal observational designs to optimize the location and the number of wells. The proposed new methods are based on the ensemble Kalman Filter (EnKF), which provides an efficient numerical solution to the Bayesian filtering problem. The dissertation first investigates in depth the popular joint and dual filtering formulations of the state-parameters estimation problem. New methodologies, algorithmically similar, but more efficient numerically, are then proposed based on a more consistent derivation with the Bayesian filtering approach. To reduce computational cost, I further extend the formulation of the hybrid EnKF-variational approach to the state parameter estimation problem and propose an adaptive scheme for the specification of the weights of the flow-dependent and static background covariance matrices. The new adaptive hybrid scheme is shown to provide much better results than the EnKF while using a fraction of the ensemble size. The new methods are implemented and successfully tested with a realistic coupled subsurface and transport-reaction model of the port of Rotterdam by assimilating industrial data on biodegradable chlorinated hydrocarbons. The observational design problem for placing hydrologic wells is subsequently considered and a new efficient solution is proposed that combines concepts from both information theory and data assimilation