An invasion percolation (IP) model was used to illustrate the effects of gravity on DNAPL migration into a horizontal water saturated fracture. While gravity is typically neglected in the conventional approach, this work demonstrated that gravity should often be included when modelling DNAPL invasion in water saturated fractures and provides an equation estimating the difference in invasion pattern between simulations including or neglecting gravity. The IP model was further utilized to examine the invasion of DNAPL saturated fractures by water. These simulated experiments focus on cases where covariance (COV), the ratio of the mean of the aperture field to the standard deviation of the aperture field) as well as when the fracture is inclined or declined from horizontal. Results show that when COV is greater than 0.1, then DNAPL will always remain in the fracture after waterflooding. Furthermore, fracture angles below -15 degrees permit the complete removal of DNAPL, while fractures oriented at higher angles do not. In order to study the transport of particles in water saturated fractures, physical experiments measuring the transport of 0.046 um and 0.55 um microspheres were undertaken on fractures where the geometry could be imported into a computer for comparative simulation analysis. Results demonstrated that during advection, particles generally travel at less than the velocity of the surrounding fluid. As well, hydrodynamic effects such as shear were shown to influence the effluent concentrations by increasing dispersion. Finally, the physical geometry of the fracture was shown to influence the particle pathway during transport and can limit the chances of particles adhering to a fracture wall, thus reducing dispersion and increasing peak concentration. The combined results of these studies show that fracture geometry has a significant effect on the mechanisms of transport in saturated fractures. / Thesis / Doctor of Philosophy (PhD) / This thesis describes the transport of contaminants in rock fractures in the environment. Specifically, the transport of denser than water liquids that are immiscible in water and particles are modelled and analysed. This work used experiments in order to calibrate these models for analysis. It was found that the local geometry of the fracture walls heavily influences the invasion pattern of immiscible dense fluids as well as the retention of the fluids after waterflooding (a first step in remediation). Particle transport was found to be heavily affected by the local geometry in the fracture, specifically lowering the likelihood of attachment to fracture walls limiting the filtration effects, and thus allowing greater contaminants to exit the fracture. Ultimately, these results lead to a greater understanding of the mechanisms of transport in fractured media.

A numerical model for subsurface solute transport is developed and applied to a contaminated field site. The model is capable of depicting multiple species transport in a three-dimensional, anisotropic, heterogeneous domain as influenced by advection, dispersion, adsorption, and biodegradation. Various hydrocarbon contaminants are simulated as electron donors for microbial growth, with electron acceptors utilized in the following sequence: oxygen, nitrate, Mn(IV), Fe(III), sulfate, and CO₂. In addition, the model accounts for products of biodegradation such as Mn (II), Fe(II), H₂S, and CH₄. Biodegradation of each hydrocarbon substrate follows Monod kinetics, modified to include the effects of electron acceptor and nutrient availability. Inhibition functions permit any electron acceptor to inhibit utilization of all other electron acceptors that provide less Gibbs free energy to the microbes. The model assumes that Fe(III) and Mn(IV) occur as solid phase ions, while the other electron acceptors are dissolved in the aqueous phase. Microbial biomass is simulated as independent groups of heterotrophic bacteria that exist as scattered microcolonies attached to the porous medium. Diffusional limitations to microbial growth are assumed to be negligible. In order to verify the accuracy of the computer code, the model was applied to simple, hypothetical test cases, and the results were compared to analytical solutions. In addition, a sensitivity analysis showed that variations in model inputs caused logical changes in output. Finally, the capabilities of the model were tested by comparing model output to observed concentrations of hydrocarbons, electron acceptors, and endproducts at a leaking UST site. The model was calibrated using historical site data, and predictive capabilities of the model were tested against subsequent sets of field data. The model was used to examine the effect of porous media heterogeneities on contaminant transport and biodegradation. The turning bands method was used to produce hypothetical, yet realistic heterogeneous fields describing hydraulic conductivity, initial biomass concentration, and the maximum rate of substrate utilization. When the available electron acceptor concentrations were small compared to the hydrocarbon concentration, the overall rate of hydrocarbon mass loss increased with time, even as hydrocarbon concentrations decreased. This trend is the opposite of what would be predicted by a first order decay model. / Ph. D.

The aim of this present research is to improve the containment properties of clayey soil by the use of bentonite and polymers as the additives. Clayey soils are generally used for the control of soil and water pollutions as they are inexpensive material. However, their applications are limited when it comes to durability of such liners in the field condition. Addition of additives to increase their efficiency by reducing the hydraulic conductivity can overcome this limitation. Generally, bentonite is used as the effective barrier additives because of their ability to render high swell and reduced hydraulic conductivity to the soil-bentonite mixtures. Due to high specific surface area and large cation exchange capacity, bentonite is always preferred for containment application. Despite their wide applicability in containment barrier, the problem with bentonite is its reduction of swell when the contaminant of interest consists of multivalent ions. Higher valency ions attach to the exchange site of bentonite and thus reduce its efficiency. To overcome these constraints the bentonite has, polymers are being used for containment applications. Normally, anionic polymers are used for such containment applications which help in increase negative charge concentration of the clayey soils. Previous studies have also proved the effectiveness of polymer in increasing the retardation factor of the soil which is due to the adsorption of contaminants to the negatively charged surface of clay. Hence attempt is also made in this thesis to study the effectiveness of super absorbent polymers when used as additive to the clayey soil. In this thesis, effectiveness of the local Bangalore soil for its use as barrier material is studied. Tests are done on the compacted sample to determine its contaminant transport properties. Because of their low hydraulic conductivities, advective flux through the barriers is negligible. In such cases, contaminant migration takes place due to the difference in concentration and this transport mechanism is known as diffusion. Laboratory test have been done to determine the diffusion coefficient of soil when the soil is saturated. For barriers and liner systems which are not fully saturated, suction adds to the hydraulic head. For unsaturated samples, although the liquid phase diffusion have been found to be nominal, head difference caused due to suction facilitates the migration of contaminants. Hence, effects of initial degree of saturation and density in contaminant transport process through soils have been examined. An attempt has been made to study unsaturated transport properties by using saturated transport parameters and unsaturated soil parameters obtained from soil-water characteristics curve. Another focus of this thesis has been towards enhancing the containment property of local soil by using additives. Effects of addition of bentonite and polymer on contaminant transport parameters of the soil have been studied. An attempt has been made to reduce the hydraulic conductivity of soil by using additives like bentonite. In addition, use of super-absorbent polymer as a novel material for barrier application has been studied to determine its suitability for local conditions. Experiments have been conducted to determine free swell, hydraulic conductivity and diffusion coefficient of soil-bentonite and soil-polymer mixes and compare them to those of local soil. To determine the effectiveness of soil-bentonite and soil-polymer mixes under the attack of concentrated solution over a long duration, chemical compatibility tests have been carried out. Micro-structural changes in the soil on addition of bentonite and polymer have been studied with the help of scanning electron microscope (SEM) images. Mineralogical changes occurring in the soil due to the additives have been studied using X-Ray Diffraction (XRD) plots. Effects of salt solution on soil-bentonite and soil-polymer mixes have also been studied by the help of SEM images and XRD plots. The final section of this thesis is on analysis of barrier performance for different conditions of densities, compaction and saturation by using numerical software CODE_BRIGHT. Transport parameters obtained from the experiments conducted in previous sections have been used as input for the analysis. A field condition of Bingipura landfill site in South Bangalore, Bangalore city has been simulated as a case study for this thesis. Time taken for contaminants to migrate from landfill to the nearby water body which is at a distance of about 122 meters is calculated for no barrier case. When barrier is provided, concentration variations of contaminant through the barrier with time are plotted and the results are compared for soil barrier, soil-bentonite barrier and soil-polymer barrier. v

Accurate modeling of contaminant transport and sorption processes in the soil and landfill liners is a prerequisite for realistic model simulations of contaminant fate and transport in the environment. These studies are also important for the remediation of soil and groundwater contamination. Modeling of contaminant transport through soils and landfill liners consists of either solving the direct/forward problem or the inverse problem. In this thesis, an automated time-stepping implicit procedure is developed from the convergence and error studies of explicit and implicit finite-difference solutions for the advection-dispersion transport of contaminants through soil with different sorption mechanisms. This study is further extended for transient through-diffusion (TTD) transport of contaminant in landfills by considering linear sorption mechanism. To validate the numerical solution and also to study the behavior of finite-difference numerical solutions for TTD transport problem, closed-form analytical solution is derived. Further, a new interface condition is proposed based on the finite-volume procedure for stratified soil or landfill liner system. Solvers are developed for the parameter estimation of inverse problem by integrating the developed procedures for the above forward problem with different optimization procedures. Solvers based on Simulated Annealing (SA) and Genetic Algorithm (GA) are developed for TTD transport in the landfill liners and verified with the existing methods of parameter estimation. Novel swarm intelligence based solver is developed for the first time for parameter estimation in contaminant transport inverse problem to overcome some of the limitations of the classical optimization methods and evolutionary methods such as GA. Additionally, the proposed swarm intelligence based algorithms and a new variant is applied to solve ill-posed problem of contaminant source characterization. The presented work in this dissertation can be unswervingly applied for modeling the contaminant transport in laboratory through-diffusion tests and contaminant transport through landfill liners where the transport is usually considered to be one-dimensional and also diffusion-dominated. Similarly, the advection-dispersion transport through laboratory soil columns can also be modeled with the developed, fast, automated, implicit numerical procedure with very good accuracy. The present study can be applied further for contaminant transport through stratified soil/liner system using fast converging numerical algorithms. Finally, the problems of design parameter estimation and source characterization can be handled accurately by the use of developed automated nature-inspired solvers.

<p>Certain types of waste, e.g. bottom ash originating from municipal solid waste incineration (MSWI bottom ash) can be used as road construction materials. A potential problem is the possibility of substances leaching out of the road and spreading in the surrounding groundwater.</p><p>The aim of this master’s thesis is to conclude whether hydrogeological type settings can be employed to, based on local conditions, provide an estimate of the probable spreading of these substances in the surrounding groundwater, and whether certain types of soils can be identified as being less suitable for the localization of a MSWI bottom ash road. A hydrogeological type setting is defined as a mappable unit with similar hydrogeological properties. An advantage of this approach would be that mainly existing maps and surveys could form the basis for the assessment.</p><p>The work has been performed by placing a hypothetical road construction in different hydrogeological type settings. The expected patterns of spreading has then been evaluated using theoretical reasoning and analytical and numerical models.</p><p>The method can be used. In the report various type settings are defined. In several cases further information will be required to render possible a more exact estimate of the spreading. By locating the road on less permeable soils to reduce the local spreading of substances in groundwater, a greater proportion of the water will be drained as surface water. Thus it becomes important to take into account surface water transport aswell. In the report a procedure to estimate the maximum concentrations in groundwater at locations situated downstream the road is presented. This estimate could be used as basis for a more balanced valuation of appropriateness, e.g. by relating the estimated concentrations to background values.</p> / <p>Vissa typer av avfall, exempelvis slaggrus (sorterad bottenaska från avfallsförbränning), kan användas som vägbyggnadsmaterial. Ett potentiellt problem är möjligheten att ämnen lakas ut ur vägen och sprids i omgivande grundvatten.</p><p>Syftet med detta examensarbete är att avgöra om hydrogeologiska typmiljöer kan användas för att, utifrån omgivningens förutsättningar, ge en bild av hur den vidare spridningen av dessa ämnen i omgivande grundvatten sannolikt ser ut, och om vissa typer av mark kan pekas ut som mindre lämpade för lokalisering av en slaggrusväg. En hydrogeologisk typmiljö definieras som ett område möjligt att avgränsa med avseende på karakteristiska hydrogeologiska förhållanden. En fördel med angreppssättet skulle vara att underlagsmaterialet till bedömningen då kan utgöras av i huvudsak befintligt kartmaterial.</p><p>Studien har utförts genom att en hypotetisk vägkonstruktion placerats in i olika hydrogeologiska typmiljöer. De troliga spridningsscenarierna har sedan utvärderats genom teoretiska resonemang, samt genom användande av analytiska och numeriska modeller.</p><p>Metodiken går att använda och i rapporten definieras olika typmiljöer. I flera fall kommer platsspecifik kunskap behöva inhämtas för en närmare beskrivning av spridningsbilden. Genom placering av vägen på tätare mark för att minska lokal spridning av ämnen i grundvatten kommer en större andel av vattnet att avledas som ytvatten. Därmed blir det viktigt att även inhämta kunskap om transport med ytvatten. I rapporten presenteras också en metod för uppskattning av maximala halter i grundvatten nedströms en väg. Denna metod kan användas som underlag för en mer nyanserad värdering av lämplighet, genom att de uppskattade halterna relateras till bakgrundsvärden eller lämpliga riktvärden.</p>

A adsorção de metais em solos tem sido estudada no escopo da geotecnia ambiental principalmente para prever formação de plumas, estudar viabilidade de técnicas de remediação e projetar revestimentos impermeabilizantes em sistemas de disposição de resíduos, entre outros. A consideração da adsorção como um fenômeno imediato e reversível é geralmente aceitável nessas aplicações, porém tem-se verificado que para solos tropicais o estudo da cinética pode melhorar as retroanálises de dados de campo e as interpretações de resultados experimentais. Este trabalho apresenta aspectos teóricos da cinética de adsorção, incluindo fatores que afetam a cinética de adsorção, modelos para determinar os mecanismos que controlam a cinética de adsorção e modelos de cinética de adsorção. A adsorção e a cinética de adsorção de cádmio e chumbo em um Latossolo roxo foram investigadas por meio de ensaios de adsorção tipo Batch. As concentrações iniciais nas soluções variaram de 2 mg/L até 2000 mg/L. OS tempos de contatos variaram de 5 minutos até 6 meses. Também foram realizados ensaios de extração e digestão química. A seguir, foram aplicados modelos para determinar os mecanismos que controlam a cinética de adsorção e também foram ajustados modelos de cinética de adsorção aos dados experimentais. Os resultados mostram que a adsorção pode ser representada por dois distintos comportamentos: curto prazo, até cerca de 8 horas, e longo prazo, para tempos superiores. A adsorção não específica aumenta com o aumento da concentração do contaminante na fase sólida no caso do cádmio, enquanto para o chumbo esta relação não ficou clara. Os modelos de cinética de adsorção testados representam apenas o comportamento de curto prazo e o ajuste desses modelos aos dados experimentais, mesmo para a adsorção de curto prazo, varia consideravelmente em função do método matemático utilizado. Finalmente, concluiu-se que a cinética de adsorção é bem representada por uma função tipo potência com expoente negativo. / Metal adsorption in soils has been studied in the scope of environmental geotechnics mainly to predict migration of contaminant plumes, to study feasibility of remediation techniques, and to design waste disposal sites. The consideration of adsorption as an immediate and reversible phenomenon is generally accepted in those applications; however, the study of adsorption kinetics in tropical soils may improve back-calculation of field data and interpretation of experimental results. This study presents theoretical aspects of adsorption kinetics, including factors that affect adsorption kinetics, models to determine mechanisms that control adsorption kinetics and adsorption kinetics models. Adsorption and adsorption kinetics of cadmium and lead in a Brazilian lateritic red clay were investigated by means of Batch adsorption tests on. Initial solutions concentrations varied from 2 mg/L to 2000 mg/L. Contact times varied from 5 minutes to 6 months. Chemical extraction and digestion tests were also performed. Models were then applied to experimental data to determine the mechanisms that control adsorption kinetics and adsorption kinetics models were also fitted to experimental data. The results show that adsorption can be represented by two different behaviors: a short time behavior, until circa 8 hours, and a long time behavior, for longer times. For cadmium, the importance of non specific adsorption increases as the contaminant concentration in the solid phase increases, while this relation is not clear for lead. The investigated adsorption kinetics models can only represent the short time behavior, and fitting of these models, even for short-time adsorption, depends considerably on the utilized mathematical method. Finally, adsorption kinetics can be well represented by a power function with negative exponent.

Per- and polyfluoroalkyl substances (PFASs) are a group of man-made organic chemicals that have been commercially used since the 1950s in many consumer products, including impregnated textiles, impregnated paper, nonstick products (e.g., Teflon), cleaning agents, and in firefighting foams. However, PFASs have in recent years received increasing public attention due to their persistence, bioaccumulative potential, and potentially toxic effects on humans and animals. Firefighting training sites have been identified as one of the most important sources for the spread of PFASs in the environment, due to the use of PFAS-containing firefighting foam of type AFFFs (aqueous film forming foams). This has resulted in contamination of both drinking water and groundwater in several municipalities in Sweden. At the former fire station in Åkersberga, AFFFs were handled and used during the fire-training exercises. WSP Environmental Sweden has performed a preliminary investigation on site and elevated levels of PFASs in both soil and groundwater were observed. Since the property is located next to a railroad track, there is a concern that PFASs will spread through the railroad track towards the nearby Åkers canal. The aim of this master’s thesis has therefore been to map the transport of PFASs in groundwater from this former fire station. A groundwater flow model was first constructed in the software program Visual MODFLOW. The groundwater model was then used as a basis for the construction of a transport model with MODPATH and MT3DMS. The transport of four PFAS homologues was modeled; perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), 6:2 Fluorotelomer sulfonate (6:2 FTS), and perfluoropentanoic acid (PFPeA). The result of the groundwater modelling showed that groundwater from the property flows towards the southwest and then further towards Åkers canal. The approximated velocity of a water molecule varied between 270 m/year and 400 m/year. The transport modelling showed that all four PFAS homologues traveled towards Åkers canal via the railroad track and that the short-chain PFAS homologues (6:2 FTS and PFPeA) traveled longer and faster than the long-chain PFAS homologues (PFOS and PFOA). The approximated velocity of the contaminant plume for the concentration 4.5 ·10−5 mg/L was 0.6 m/year for PFOS, 3 m/year for PFOA, 8 m/year for 6:2 FTS, and 16 m/year for PFPeA. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp av konstgjorda organiska kemikalier som sedan 1950-talet har kommersiellt använts i många konsumentprodukter, inklusive impregnerade textilier, impregnerat papper, nonstick-produkter (t.ex. Teflon), rengöringsmedel och brandsläckningsskum. PFAS har dock under senare år fått ökad allmän uppmärksamhet på grund av deras persistens, bioackumuleringspotential och potentiella toxiska effekter på människor och djur. Brandövningsplatser har identifierats som en av de största källorna för spridningen av PFAS i miljön, på grund av användningen av PFAS-innehållande brandsläckningsskum av typen AFFF (aqueous film forming foams). Detta har resulterat i förorening av både dricksvatten och grundvatten i flera kommuner i Sverige. På den tidigare brandstationen i Åkersberga har hantering och användning av AFFF ägt rum under släckningsövningarna. WSP Environmental Sverige har utfört förundersökning på plats och förhöjda halter PFAS i både jord och grundvatten observerades. Då fastigheten gränsar mot en banvall, finns det en oro att PFAS ska sprida via banvallen mot den närliggande Åkers kanalen. Syftet med detta examensarbete har därför varit att kartlägga transporten av PFAS i grundvatten från denna tidigare brandstation. En grundvattenflödesmodell konstruerades först i programvaran Visual MODFLOW. Grundvattenmodellen användes sedan som grund för konstruktionen av en transportmodell med MODPATH och MT3DMS. Transporten av fyra PFAS-homologer modellerades; perfluoroktansulfonat (PFOS), perfluorooktansyra (PFOA), 6:2 fluortelomersulfonat (6: 2 FTS) och perfluorpentansyra (PFPeA). Resultatet av grundvattenmodelleringen visade att grundvatten från fastigheten strömmar mot sydväst och sedan vidare mot Åkers kanal. Den approximerade hastigheten hos en vattenmolekyl varierade mellan 270 m/år och 400 m/år. Transportmodelleringen visade att alla fyra PFAS-homologerna spred mot Åkers kanal via banvallen och att de kortkedjiga PFAS-homologerna (6:2 FTS och PFPeA) spred längre och snabbare än de långkedjiga PFAS-homologerna (PFOS och PFOA). Ungefärlig hastighet av föroreningsplymen för koncentration 4.5 ·10−5 mg/L var 0,6 m/år för PFOS, 3 m/år för PFOA, 8 m/år för 6: 2 FTS och 16 m/år för PFPeA.

A adsorção de metais em solos tem sido estudada no escopo da geotecnia ambiental principalmente para prever formação de plumas, estudar viabilidade de técnicas de remediação e projetar revestimentos impermeabilizantes em sistemas de disposição de resíduos, entre outros. A consideração da adsorção como um fenômeno imediato e reversível é geralmente aceitável nessas aplicações, porém tem-se verificado que para solos tropicais o estudo da cinética pode melhorar as retroanálises de dados de campo e as interpretações de resultados experimentais. Este trabalho apresenta aspectos teóricos da cinética de adsorção, incluindo fatores que afetam a cinética de adsorção, modelos para determinar os mecanismos que controlam a cinética de adsorção e modelos de cinética de adsorção. A adsorção e a cinética de adsorção de cádmio e chumbo em um Latossolo roxo foram investigadas por meio de ensaios de adsorção tipo Batch. As concentrações iniciais nas soluções variaram de 2 mg/L até 2000 mg/L. OS tempos de contatos variaram de 5 minutos até 6 meses. Também foram realizados ensaios de extração e digestão química. A seguir, foram aplicados modelos para determinar os mecanismos que controlam a cinética de adsorção e também foram ajustados modelos de cinética de adsorção aos dados experimentais. Os resultados mostram que a adsorção pode ser representada por dois distintos comportamentos: curto prazo, até cerca de 8 horas, e longo prazo, para tempos superiores. A adsorção não específica aumenta com o aumento da concentração do contaminante na fase sólida no caso do cádmio, enquanto para o chumbo esta relação não ficou clara. Os modelos de cinética de adsorção testados representam apenas o comportamento de curto prazo e o ajuste desses modelos aos dados experimentais, mesmo para a adsorção de curto prazo, varia consideravelmente em função do método matemático utilizado. Finalmente, concluiu-se que a cinética de adsorção é bem representada por uma função tipo potência com expoente negativo. / Metal adsorption in soils has been studied in the scope of environmental geotechnics mainly to predict migration of contaminant plumes, to study feasibility of remediation techniques, and to design waste disposal sites. The consideration of adsorption as an immediate and reversible phenomenon is generally accepted in those applications; however, the study of adsorption kinetics in tropical soils may improve back-calculation of field data and interpretation of experimental results. This study presents theoretical aspects of adsorption kinetics, including factors that affect adsorption kinetics, models to determine mechanisms that control adsorption kinetics and adsorption kinetics models. Adsorption and adsorption kinetics of cadmium and lead in a Brazilian lateritic red clay were investigated by means of Batch adsorption tests on. Initial solutions concentrations varied from 2 mg/L to 2000 mg/L. Contact times varied from 5 minutes to 6 months. Chemical extraction and digestion tests were also performed. Models were then applied to experimental data to determine the mechanisms that control adsorption kinetics and adsorption kinetics models were also fitted to experimental data. The results show that adsorption can be represented by two different behaviors: a short time behavior, until circa 8 hours, and a long time behavior, for longer times. For cadmium, the importance of non specific adsorption increases as the contaminant concentration in the solid phase increases, while this relation is not clear for lead. The investigated adsorption kinetics models can only represent the short time behavior, and fitting of these models, even for short-time adsorption, depends considerably on the utilized mathematical method. Finally, adsorption kinetics can be well represented by a power function with negative exponent.

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.

Natural attenuation refers to the observed reduction in contaminant concentration via natural processes as contaminants migrate from the source into environmental media. Assessment of the dimensions of contaminant plumes and prediction of their fate requires predictions of the rate of dissolution of contaminants from residual non-aqueous-phase liquids (NAPLs) into the aquifer and the rate of contaminant removal through biodegradation. The available techniques to estimate these parameters do not characterize their confidence intervals by accounting for their relationships to uncertainty in source geometry and hydraulic conductivity distribution. The central idea in this thesis is to develop a flexible modeling approach for characterization of uncertainty in residual NAPL dissolution rate and first-order biodegradation rate by tailoring the estimation of these parameters to distributions of uncertainty in source size and hydraulic conductivity field. The first development in this thesis is related to a distance function approach that characterizes the uncertainty in the areal limits of the source zones. Implementation of the approach for a given monitoring well arrangement results in a unique uncertainty band that meets the requirements of unbiasedness and fairness of the calibrated probabilities. The second development in this thesis is related to a probabilistic model for characterization of uncertainty in the 3D localized distribution of residual NAPL in a real site. A categorical variable is defined based on the available CPT-UVIF data, while secondary data based on soil texture and groundwater table elevation are also incorporated into the model. A cross-validation study shows the importance of incorporation of secondary data in improving the prediction of contaminated and uncontaminated locations. The third development in this thesis is related to the implementation of a Monte Carlo type inverse modeling to develop a screening model used to characterize the confidence intervals in the NAPL dissolution rate and first-order biodegradation rate. The development of the model is based on sequential self-calibration approach, distance-function approach and a gradient-based optimization. It is shown that tailoring the estimation of the transport parameters to joint realizations of source geometry and transmissivity field can effectively reduce the uncertainties in the predicted state variables.