Endocrine disruption and high occurrences of intersex have been observed in wild fish associated with wastewater treatment plant (WWTP) effluents in the urbanized reaches of the Grand River watershed located in southern Ontario, Canada. WWTP effluent is a complex matrix with diverse aquatic environmental contaminants and stressors. This study aimed to: (1) characterize the spatio-temporal distribution and fate of antiandrogenic personal care products (triclosan, chlorophene, and dichlorophene), along with selected pharmaceuticals (carbamazepine, ibuprofen, naproxen, and venlafaxine) and the herbicide, atrazine in the Grand River watershed and (2) model the behaviour of these contaminants in the aquatic environment. Water sampling of 29 sites which covered six municipal WWTPs and ~100 km of river length was completed during summer low flows (July 2012). Monthly samples were also collected immediately upstream and downstream of a major WWTP (Kitchener) from August to November 2012. Many of the target pharmaceuticals and triclosan were detected in WWTP effluents in the Grand River watershed, especially those that did not nitrify (minimal treatment with high ammonia). Chlorophene was either undetected or was only found at trace levels in the effluents. Under low flow conditions, triclosan and several other pharmaceuticals exhibited a spatial pattern where concentrations increased directly downstream of the WWTPs, then decreased with distance downstream (dilution and/or degradation). Chlorophene, in contrast, was not found downstream of most of the WWTP outfalls but was first detected at a site 5 km upstream of a WWTP and then continued with relatively constant concentrations for approximately 29 km downstream. It was also only found during the summer sampling period. Atrazine was consistently found in all sampling locations which reflected the agricultural non-point source nature of this compound. The WASP 7.5 model (US Environmental Protection Agency) was adapted and calibrated to a reach of the Grand River associated with the Kitchener WWTP. The simulation of the fate and transport of the target compounds revealed that flow-driven transport processes (advection and dispersion) greatly influence their behaviour in the aquatic environment. However, fate mechanisms such as biodegradation and photolysis also potentially play an important role in the attenuation of most compounds. The exception was carbamazepine where it was shown to act as a conservative tracer compound for wastewater specific contaminants in the water phase. The fate model developed can be applied in the future to predict the fate of a wide variety of contaminants of emerging concern across the watershed to help define the exposure of these biologically active chemicals to sensitive ecosystems.

Endocrine disruption and high occurrences of intersex have been observed in wild fish associated with wastewater treatment plant (WWTP) effluents in the urbanized reaches of the Grand River watershed located in southern Ontario, Canada. WWTP effluent is a complex matrix with diverse aquatic environmental contaminants and stressors. This study aimed to: (1) characterize the spatio-temporal distribution and fate of antiandrogenic personal care products (triclosan, chlorophene, and dichlorophene), along with selected pharmaceuticals (carbamazepine, ibuprofen, naproxen, and venlafaxine) and the herbicide, atrazine in the Grand River watershed and (2) model the behaviour of these contaminants in the aquatic environment. Water sampling of 29 sites which covered six municipal WWTPs and ~100 km of river length was completed during summer low flows (July 2012). Monthly samples were also collected immediately upstream and downstream of a major WWTP (Kitchener) from August to November 2012. Many of the target pharmaceuticals and triclosan were detected in WWTP effluents in the Grand River watershed, especially those that did not nitrify (minimal treatment with high ammonia). Chlorophene was either undetected or was only found at trace levels in the effluents. Under low flow conditions, triclosan and several other pharmaceuticals exhibited a spatial pattern where concentrations increased directly downstream of the WWTPs, then decreased with distance downstream (dilution and/or degradation). Chlorophene, in contrast, was not found downstream of most of the WWTP outfalls but was first detected at a site 5 km upstream of a WWTP and then continued with relatively constant concentrations for approximately 29 km downstream. It was also only found during the summer sampling period. Atrazine was consistently found in all sampling locations which reflected the agricultural non-point source nature of this compound. The WASP 7.5 model (US Environmental Protection Agency) was adapted and calibrated to a reach of the Grand River associated with the Kitchener WWTP. The simulation of the fate and transport of the target compounds revealed that flow-driven transport processes (advection and dispersion) greatly influence their behaviour in the aquatic environment. However, fate mechanisms such as biodegradation and photolysis also potentially play an important role in the attenuation of most compounds. The exception was carbamazepine where it was shown to act as a conservative tracer compound for wastewater specific contaminants in the water phase. The fate model developed can be applied in the future to predict the fate of a wide variety of contaminants of emerging concern across the watershed to help define the exposure of these biologically active chemicals to sensitive ecosystems.

No description available.

Despite indications that they are potential contaminant transport systems and threats to groundwater quality, very little effort has been invested in comparing contaminant transport behavior of natural environmental nanocolloids and their corresponding macrocolloid fractions in the presence of As, Se, Pb, and Cu contaminants. This study involved physico-chemical, mineralogical, stability and contaminant-transport characterizations of nano- (< 100 nm) and macro-colloids (100-2000 nm) fractionated from three Kentucky soils and one biosolid waste. Particle size was investigated with SEM/TEM and dynamic light scattering. Surface reactivity was estimated using CEC and zeta potential. Mineralogical composition was determined by XRD, FTIR, and thermogravimetric analyses. Sorption isotherms assessed affinities for Cu2+, Pb2+, AsO3-, and SeO4-2 contaminants, while settling kinetics experiments of suspensions at 0, 2 and 10 mg/L contaminants determined stability and transportability potential. Undisturbed 18x30 cm KY Ashton Loam soil monoliths were also used for transport experiments, involving infusion of 50 mg L-1 colloid suspensions spiked with 2 mg L-1 mixed contaminant loads in unsaturated, steady state, unit gradient downward percolation experiments. Overall, nanocolloids exhibited greater stability over corresponding macrocolloids in the presence and absence of contaminants following specific mineralogy trends. Physicochemical characterizations indicated that extensive organic carbon surface coatings and higher Al/Fe:Si ratios may have induced higher stability in the nanocolloid fractions, in spite of some hindrance by nano-aggregation phenomena. In the transport experiments, nanocolloids eluted significantly higher concentrations of colloids, total, and colloid-bound metals than corresponding macrocolloids. Contaminant elutions varied by colloid type, mineralogy and contaminant, with the following sequences: soil-colloids>bio-colloids, smectitic>mixed≥kaolinitic>biosolid, and Se>Pb/Cu≥As. Our findings demonstrate that even though they behave more like nano-aggregates rather than individual nano-particles, nanocolloids may exhibit significantly higher mobility and contaminant transport potential over great distances in subsoil environments than their corresponding macrocolloid fractions.

This thesis compares different methods for risk assessment of a creosote contaminated site in Vansbro, Dalarna. In a complementary study the importance of using representative data for calibration and validation of stationary groundwater models is discussed. The time dependency between surface water levels and groundwater levels on the site in Vansbro is evaluated by step response analysis. The results show that the groundwater levels reflect only long-term variation in the surface water levels. Hence the use of such long-term means for calibration and validation of the stationary groundwater models is the only theoretically defendable alternative. As a first step in the comparison of risk assessment methods the degree of contamination is evaluated on the basis of generic guideline values for contaminated soils, developed by the Swedish Environmental Protection Agency. The guidelines specifically developed for contaminated petrol stations are also taken into consideration. Secondly, a site-specific evaluation is carried out. The transport of contaminants from the soil to the on-site groundwater and nearby surface water is calculated using the mathematical models behind the aforementioned guideline values. The calculated groundwater concentrations show a poor agreement with observed data and the thesis points out several possible explanations of this deviation. A sensitivity analysis is carried out and the influence of biodegradation during the transport in the aquifer is evaluated. The results indicate that the deviation between observed and calculated groundwater concentrations cannot be explained by the absence of biodegradation in the mathematical models, but rather by other simplifications and uncertainties in estimated model parameters. Finally, a risk assessment is made on the basis of observed groundwater concentrations instead of observed soil concentrations as in the assessments above. Observed groundwater concentrations are compared with guideline values for groundwater on contaminated sites. The risk of negative environmental effects in the surface water is evaluated based on the estimated inflow of contaminated groundwater and its concentration of contaminants. The inflow is estimated from the interpolation of observed groundwater levels as well as with two numerical groundwater models of varying hydrogeological complexity: a three-dimensional flow model developed in Visual MODFLOW and a two-dimensional flow model developed in TWODAN. The models are compared with respect to the calculated inflows of contaminated groundwater into the surface water body as well as their ability to reproduce observed groundwater levels. The results indicate that the differences between the models, with respect to the calculated inflows, are of lesser importance to the risk assessment in comparison with the uncertainties associated with other parameters. The choice to base the assessment on observed contaminant concentrations in either the soil or the groundwater is shown to be of crucial importance. / I detta examensarbete jämförs olika metoder att bedöma de hälsomässiga och miljömässiga risker som föreligger med ett kreosotförorenat markområde i Vansbro, Dalarna. I en kompletterande undersökning belyses vikten av att stationära grundvattenmodeller kalibreras och valideras mot tidskompatibla indata. Tidsberoendet mellan yt- och grundvattennivåer på området i Vansbro studeras genom stegsvarsanalys. Resultaten visar att grundvattennivåerna på området anpassar sig mycket långsamt efter rådande ytvattennivåer. Grundvattennivåerna återspeglar således medelvärden av ytvattennivåerna över en mycket lång tidsperiod. Därför är användandet av sådana medelvärden för kalibrering och validering av modellerna det enda teoretiskt försvarbara alternativet. Som ett första steg i jämförelsen mellan olika riskbedömningsmetoder utvärderas föroreningssituationen baserat på uppmätta föroreningskoncentrationer i jorden och med hjälp av Naturvårdsverkets generella samt branschspecifika riktvärden för förorenad mark. Därefter genomförs en platsspecifik riskbedömning. Föroreningstransporten från markområdet till grundvattnet samt till ett närbeläget ytvatten beräknas med de matematiska modeller som användes av Naturvårdsverket vid framtagandet av ovannämnda riktvärden. Beräknade grundvattenkoncentrationer jämförs med uppmätta koncentrationer och resultaten visar på stora avvikelser. En känslighetsanalys utförs och inverkan av biologisk nedbrytning i akviferen utvärderas. Resultaten tyder på att avvikelsen mellan uppmätta och beräknade grundvattenkoncentrationer ej förklaras av att biologisk nedbrytning inte beaktas i modellerna utan att avvikelsen härrör från andra förenklingar och från osäkerheter i indata. Slutligen genomförs en platsspecifik riskbedömning, motsvarande den ovan, men denna gång utifrån uppmätta föroreningskoncentrationer i grundvattnet. De uppmätta grundvattenkoncentrationerna jämförs direkt mot Naturvårdsverkets riktvärden för grundvatten på förorenade områden. Risken för negativa ekologiska effekter i ytvattnet utvärderas utifrån det beräknade inflödet av förorenat grundvatten samt dess koncentration. Inflödet beräknas överslagsmässigt utifrån interpolerade grundvattennivåer samt med två numeriska grundvattenmodeller av olika hydrogeologisk komplexitet: en tredimensionell flödesmodell uppbyggd i Visual MODFLOW och en tvådimensionell modell uppbyggd i TWODAN. Grundvattenmodellerna jämförs med avseende på det beräknade inflödet och med avseende på deras förmåga att beskriva observerade grundvattenförhållanden.Resultaten tyder på att skillnaden i det, med de olika metoderna, beräknade inflödet är av liten betydelse för riskbedömningen i förhållande till osäkerheter förknippade med övriga parametrar. Störst betydelse för riskbedömningen får valet att utgå från uppmätta föroreningskoncentrationer i antingen jorden eller grundvattnet.

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.

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

The investigation of environmental impacts of 16 different contaminants originating from the E18 Highway (17 000 AADT) were carried out over the first six months of the highway‘s operational life. Investigative methods used include electrical resistivity surveying, water chemistry analyses, soil analyses, distribution modelling and transportation modelling. The investigation shows conclusively a year round infiltration due to melting of the snowpack from road salt, and a strong preferential anthropogenic pathway due to in-creased hydraulic conductivities of the road building materials relative to the natural soils. The resistivity surveys show values well below the expected values for the highway materials, indicating increased ionic content of the unsaturated zone. Time lapse resistivity modelling shows a clear downwards spreading of contamination from the roadway to subsurface distances greater than 5 m. Elevated concentrations of nearly every contaminant relative to baseline values were observed, with many concentrations of metals in the snow pack averaging values in excess of Swedish EPA groundwater limitations. Distribution modelling demonstrated a potential offset of peak values from the road surface due to ploughing and splash transport processes, but otherwise conformed to established distribution patterns. One dimensional transport modelling demonstrated the importance of adsorption and other retentive factors to the migration of contaminants to the water table, and provided an estimate for potential long term contaminant concentrations.