As áreas contaminadas por NAPL (Non-Aqueous Phase-Liquids ou fase líquida não aquosa ou ainda fase livre) podem causar riscos à saúde humana e aos ecossistemas, restrições para o desenvolvimento urbano e diminuição do valor imobiliário das propriedades. Este trabalho utilizou o gás radônio como um indicador para a análise de gás subsuperficial do solo, uma vez que este gás nobre apresenta boa solubilidade em uma ampla gama de NAPL, sendo parcialmente retido na contaminação NAPL. Portanto, uma diminuição da atividade de gás radônio no solo contaminado pode ser esperada, devido à elevada capacidade de particionamento do radônio em NAPL, o que permite que o NAPL retenha uma parte do radônio anteriormente disponível nos poros do solo. O levantamento foi realizado em uma indústria abandonada, contaminada por NAPL pouco volátil, localizada na zona sudeste da cidade de São Paulo, entre junho de 2014 e maio de 2015. A concentração de radônio foi avaliada pela metodologia de detecção passiva com detectores sólidos de traços nucleares (SSNTD) tipo CR-39 em dez estações de monitoramento instaladas na área contaminada investigada e nomeadas de A até J. A média das concentrações de atividade de radônio para as oito estações de monitoramento em locais supostamente não contaminados variou de (22 ± 4) kBq.m-3 a (39 ± 4) kBq.m-3. Para as duas estações de monitoramento supostas como locais contaminados, as concentrações de radônio foram (1,4 ± 0,4) kBq.m-3 e (13 ± 9) kBq.m-3. Os resultados demonstraram que o método utilizado foi consistente com as técnicas convencionais de investigação ambiental para a maioria das estações de monitoramento em diferentes estações do ano. Resultados obtidos com CR-39 variam ao longo dos períodos de exposição, devido à sazonalidade. Não foi observada relação entre as oscilações das concentrações de atividade de radônio e o volume de chuva acumulada nos diferentes períodos de exposição dos detectores CR-39. As menores concentrações de atividade do 222Rn ocorreram nas estações de monitoramento G e H e verificou-se por espectrometria gama, que a baixa atividade não está relacionada à concentração de atividade de seu pai 226Ra na série do decaimento radioativo do 238U, reforçando a teoria de retenção do gás radônio nos locais contaminados por NAPL. Resultados da etapa de remediação comprovaram que a técnica utilizada neste trabalho foi mais eficiente que as técnicas convencionais de investigação ambiental, especialmente para as estações de monitoramento D e G na área contaminada investigada. / Contaminated sites by NAPL (Non-Aqueous Phase-Liquids) may lead to safety risks to human health and to ecosystems, restrictions to urban development and decrease of real estate value. This work used the radon gas as an indicator for the analysis of subsurface soil gas, once this noble gas presents good solubility in a wide range of NAPL, being partially retained in the NAPL contamination. Therefore, a decrease of the activity of radon in the contaminated soil gas can be expected, due to the high capacity of partitioning of radon in NAPL, which allows that the NAPL retain part of the radon previously available in the soil pores. The survey was carried out at a disused industry, contaminated by low volatile NAPL, located at southeast of São Paulo city, from June/14 to May/15. Radon was evaluated by passive detection methodology with CR-39 solid state nuclear track detectors (SSNTD) in ten monitoring stations installed in the contaminated area investigated and named \"A\" to \"J\". Radon concentrations average for the eight monitoring stations at non-contaminated locations varied from (22 ± 4) kBq.m-3 to (39 ± 4) kBq.m-3. For the two monitoring stations assumed as contaminated locations, radon concentrations average were (1.4 ± 0.4) kBq.m-3 and (13 ± 9) kBq.m-3. The results have shown good agreement between the used method and the conventional environmental investigation techniques, for the majority of the monitoring stations in different seasons. Results obtained with CR-39 detectors varied over the exposure time due to the different seasons. No relation was observed between radon activity concentrations and rain volume accumulated over the different CR-39 exposure times. The lowest 222Rn activity concentrations occurred in G and H monitoring stations, also verifying by gamma-ray spectrometry, that the low activities are not related to the activity concentration of its father 226Ra from the 238U decay chain, reinforcing the theory that radon gas is retained in sites where NAPL contamination is present. Results obtained during environmental remediation proved that the methodology employed in this study was more efficient than the conventional investigation techniques, specially for the D and G monitoring stations to the investigated site.

<p>This Master Thesis presents TMVOC simulations of a NAPL-spill (non-aqueous phase liquid) and following pumping remediation. TMVOC is a simulation program for three-phase non-isothermal multicomponent flow in saturated-unsaturated heterogeneous media. The models presented are based on an actual remediation project. The aim of the thesis was to study if the historical development of the NAPL-spill could be simulated and how long time the pumping remediation would take. A 3D-model and a radially symmetric cylindrical model were created.</p><p>A large effort of the work done was in taking the complex TMVOC model in use and modifying it for the problem at hand. Therefore, the numerical results of the simulations should be considered as preliminary and as forming basis for future studies.</p><p>The results from the spill simulation and historical pumping simulation indicated that the spill volume could be less than the estimated 1400 m³, perhaps around 700 m³, assuming a leakage time of 30 years.</p><p>The historical pumping simulation of a 700 m³ diesel spill showed good agreement with measured values for some wells, but overestimated the recovery in other wells. The overestimation could be due to the fact that the 3D-model did not take seasonal changes in the groundwater level into consideration. Also, the model did not account for any heterogeneity or compartmentalization in soil material properties that could explain the differences between the wells. </p><p>Assuming the same spill of 700 m³, future pumping was simulated. The results from these simulations indicated the remediation time to be long due to fast decreasing mobility of the NAPL phase. The NAPL flow rate to the wells was halved in a couple of years. Much of the NAPL was distributed over a large area at near residual saturation with the highest NAPL saturation found at the opposite side of the pumping wells in the model.</p><p> </p><p>Future simulation studies should address the effect of discretization as well as the effect of uncertainties in material properties e.g. conductivity, residual NAPL saturation and soil heterogeneity.</p>

This Master Thesis presents TMVOC simulations of a NAPL-spill (non-aqueous phase liquid) and following pumping remediation. TMVOC is a simulation program for three-phase non-isothermal multicomponent flow in saturated-unsaturated heterogeneous media. The models presented are based on an actual remediation project. The aim of the thesis was to study if the historical development of the NAPL-spill could be simulated and how long time the pumping remediation would take. A 3D-model and a radially symmetric cylindrical model were created. A large effort of the work done was in taking the complex TMVOC model in use and modifying it for the problem at hand. Therefore, the numerical results of the simulations should be considered as preliminary and as forming basis for future studies. The results from the spill simulation and historical pumping simulation indicated that the spill volume could be less than the estimated 1400 m3, perhaps around 700 m3, assuming a leakage time of 30 years. The historical pumping simulation of a 700 m3 diesel spill showed good agreement with measured values for some wells, but overestimated the recovery in other wells. The overestimation could be due to the fact that the 3D-model did not take seasonal changes in the groundwater level into consideration. Also, the model did not account for any heterogeneity or compartmentalization in soil material properties that could explain the differences between the wells.  Assuming the same spill of 700 m3, future pumping was simulated. The results from these simulations indicated the remediation time to be long due to fast decreasing mobility of the NAPL phase. The NAPL flow rate to the wells was halved in a couple of years. Much of the NAPL was distributed over a large area at near residual saturation with the highest NAPL saturation found at the opposite side of the pumping wells in the model.   Future simulation studies should address the effect of discretization as well as the effect of uncertainties in material properties e.g. conductivity, residual NAPL saturation and soil heterogeneity.

The magnitude of contaminant mass flux reduction associated with a specific amount of contaminant mass removed is a key consideration for evaluating the effectiveness of a source-zone remediation effort. Thus, there is great interest in characterizing, estimating and predicting relationships between mass flux reduction and mass removal. Intermediate-scale flow- cell experiments and published data for several field studies were examined to evaluate factors controlling the mass-flux-reduction/mass-removal relationship. Flow-cell experiments evaluated the impact of source-zone architecture and flow-field heterogeneity on mass-flux-reduction/mass-removal behavior. Significant reductions in mass flux occurred for systems wherein immiscible-liquid mass was present at both residual saturation and in high saturation pools. For a system with immiscible liquid present in multiple zones of different permeability, an increase in mass flux was observed for late stages of mass removal. Image analysis confirmed that the late stage increase in mass flux was attributed to changes in relative permeability. Early reductions in mass flux were also observed for systems wherein immiscible-liquid mass was poorly accessible to flowing water. End-point analysis, based on comparing masses and mass fluxes measured before and after a source-zone remediation effort, conducted for 21 field remediation projects ranged from slightly less than to slightly greater than one-to-one. Time-continuous analysis, based on continuous monitoring of mass removal and mass flux, performed for two sites illustrated the dependence of the mass-flux-reduction/mass-removal relationship on source-zone architecture and mass-transfer processes. Minimal mass flux reduction was observed for a system wherein mass removal was relatively efficient. Conversely, a significant degree of mass flux reduction was observed for a site wherein mass removal was inefficient. A simple mass-removal function was used to evaluate the measured data at both the intermediate and field scales. This function was unable to capture the complex behavior observed for some of the systems unless specific measurable system parameters were incorporated into the function. Finally, mathematical models of varying complexity used to simulate immiscible liquid dissolution illustrated the dependence of the calibrated dissolution rate coefficient on implicit and explicit consideration of larger-scale factors influencing immiscible liquid dissolution.

This research addresses a number of fundamental issues concerning convective mass transfer across fluid-fluid interfaces in porous media. Mass transfer to/from distributed sinks/sources is considered for i) the slow dissolution of liquid filaments of a wetting non-aqueous phase liquid (NAPL) held in the corners of angular pores or throats and ii) the fate of gas bubbles generated during the flow of a supersaturated aqueous phase in porous media. 1. Effects of the stability of NAPL films on wetting NAPL dissolution Wettability profoundly affects the distribution of residual NAPL contaminants in natural soils. Under conditions of preferential NAPL wettability, NAPL is retained within small pores and in the form of thick films (liquid filaments) along the corners and crevices of the pore walls. NAPL films in pore corners provide capillary continuity between NAPL-filled pores, dramatically influencing the behaviour of NAPL dissolution to the flowing aqueous phase by convection and diffusion. A pore network model is developed to explore the dissolution behaviour of wetting NAPL in porous media. The effects of initial NAPL distribution and NAPL film stability on dissolution behaviour are studied using the simulator. NAPL phase loses continuity and splits into disconnected clusters of NAPL-filled pores due to rupture of NAPL films. Quasi-state drainage and fingering of the aqueous phase into NAPL-filled pores is treated as an invasion percolation process and a stepwise procedure is adopted for the solution of flow and solute concentration fields. NAPL film stability is shown to critically affect the rate of mass transfer as such that stable NAPL films provide for more rapid dissolution. The network simulator reproduces the essential physics of wetting NAPL dissolution in porous media and explains the concentration-tailing behaviour observed in experiments, suggesting also new possibilities for experimental investigation. 2. Convective Mass Transfer across Fluid Interfaces in Straight Angular Pores Steady convective mass transfer to or from fluid interfaces in pores of angular cross-section is theoretically investigated. The model incorporates the essential physics of capillarity and solute mass transfer by convection and diffusion in corner fluid filaments. The geometry of the corner filaments, characterized by the fluid-fluid contact angle, the corner half-angle and the interface meniscus curvature, is accounted for. Boundary conditions of zero surface shear (???perfect-slip???) and infinite surface shear (???no-slip???) at the fluid-fluid interface are considered. The governing equations for laminar flow within the corner filament and convective diffusion to or from the fluid-fluid interface are solved using finite-element methods. Flow computations are verified by comparing the dimensionless resistance factor and hydraulic conductance of corner filaments against recent numerical solutions by Patzek and Kristensen [2001]. Novel results are obtained for the average effluent concentration as a function of flow geometry and pore-scale Peclet number. These results are correlated to a characteristic corner length and local pore-scale Peclet number using empirical equations appropriate for implementation in pore network models. Finally, a previously published ???2D-slit??? approximation to the problem at hand is checked and found to be in considerable error. 3. Bubble evolution driven by solute diffusion during the process of supersaturated carbonated water flooding In situ bubble growth in porous media is simulated using a pore network model that idealizes the pore space as a lattice of cubic chambers connected by square tubes. Evolution of the gas phase from nucleation sites is driven by the solute mass transfer from the flowing supersaturated water solution to the bubble clusters. Effects of viscous aqueous phase flow and convective diffusion in pore corners are explicitly accounted for. Growth of bubble clusters is characterised by a pattern of quasi-static drainage and fingering in the gas phase, an invasion percolation process controlled by capillary and gravitational forces. A stepwise solution procedure is followed to determine the aqueous flow field and the solute concentration field in the model by solving the conservation equations. Mobilization of bubbles driven by buoyancy forces is also studied. Results of bubble growth pattern, relative permeability and macroscopic mass transfer coefficient are obtained under different gas saturations and aqueous flow conditions.

NAPL (non-aqueous phase liquid) blob mobilization and solubilization models were developed to predict residual NAPL fate and describe flow dynamics of various displacing phases (water and surfactant foam). The models were achieved by pore-scale mass and force balances and were focused on the understanding of the physico-chemical interactions between NAPL blobs and the displacing phases. The pore-level mass balance indicated changes in NAPL saturation instead of mass reduction occurring with blob solubilization. The force balance was used to explain the complex flow configurations among NAPL blobs and the displacing phases. Some factors such as the wettability and the spreading/entering coefficients were useful in determining flow configurations. From the models developed in this study, dimensional analysis was performed to identify NAPL blob motion during water or surfactant foam flooding. In non-dimensionalized forms, a Trapping number employed as an indicator of blob displacement performance was modified to quantify the onset of blob mobilization. Its value for water flooding was nearly 2-3 orders of magnitude greater than that of surfactant foam flooding. Next, to investigate the blob flow regime in porous media, a blob velocity was computed. Regardless of the displacing phases, a blob’s velocity increased with increasing blob sizes after commencement of blob motion, and the velocity of DNAPL (dense non-aqueous phase liquid) blobs was greater than that of LNAPL (light non-aqueous phase liquid) blobs. From this investigation, it is expected that the pore-scale solubilization and mobilization models would provide better understanding leading to a predictive capability for the flow behavior of NAPL blobs removed by various displacing phases in a porous medium. Additionally, the models based on newly approached concepts and modified governing equations would be useful in conceptualization, as well as the model prediction of other immiscible or miscible fluids flowing through a porous medium. Further, the models developed in our study would be a useful contribution to the study of small-scale contaminants or substances such as particle and bacterial transport in porous media.

Gas inFusion? is a novel remedial technology that dissolves CO₂ into water under pressure for NAPL recovery. As the supersaturated liquid flows through the porous medium gas evolution occurs in situ as the system returns to thermodynamic equilibrium. The evolution of gas bubbles leads to NAPL recovery by two mechanisms: 1) volatilization and 2) mobilization by the NAPL spreading in a film around the rising bubbles. Laboratory experiments by Li demonstrated that injecting the supersaturated water into a porous medium minimized the buoyancy driven flow of gas and the fingering phenomena that limit typical gas sparging. The distribution of carbon dioxide at partial pressures (p_CO2) above the applicable hydrostatic pressure and the evolved gas phase were determined in two field experiments conducted in the relatively homogeneous fine to medium sand at CFB Borden. First, CO₂-supersaturated water was injected into a single point located approximately 4 metres below ground surface. Then this injection was repeated with pumping of two nearby wells to see if the lateral distribution of CO₂ gas could be controlled hydraulically. Groundwater monitoring of p_CO2 above the hydrostatic pressure and geophysical surveys (neutron measurements, surface ground penetrating radar (GPR), and cross-borehole GPR) to find zones of induced gas content were supported by hydraulic monitoring and physical observations of gas bubble distribution at the water table. <br /><br /> Based on the results of these tests, enhanced CO₂ levels above the hydrostatic pressure were observed up to 5. 5-7. 0 m from the injection point and the gas phase up to ~5. 3 m. It was not possible to determine the impact hydraulic control had on the lateral distribution of CO₂ due to problems with the experiment. The distribution of the gas phase was heterogeneous with CO₂ gas pockets forming below low permeability layers, as evidenced by surface GPR, permeameter tests, and grain size analyses. These gas pockets accumulated until sufficient pressure built up to overcome the displacement pressure of these lower permeability layers. At this point there is evidence of CO₂ breakthrough in the cross-borehole GPR data and physical observations of gas bubbles at the water table. These observations are consistent with previous investigations, which indicate that although the Borden aquifer is homogeneous, distinct horizontal layering is present with sufficient variations in permeability/displacement pressure to trap and cause some lateral spreading of a gas phase. The evidence of channeling and the impact of heterogeneities on gas distribution are consistent with air sparging studies.

The behaviour of hydrocarbon fuels in contaminated groundwater systems is studied using a multicomponent reactive transport model. The simulated processes include residual NAPL dissolution, aerobic and anaerobic biodegradation with daughter-product transport, and transport of a reactive carrier with mixed equilibrium/kinetic sorption. The solution algorithm is based on a three-dimensional Galerkin finite element scheme with deformable brick elements and capacity for a free watertable search. Nonlinearities are handled through Picard iteration. Convergence is rapid for most applications and mass balance errors for all phases are minimal. The model is first applied to simulate a pilot scale diesel fuel dissolution experiment in which humic acid is used as a natural organic carrier to enhance dissolution and to promote biodegradation of the aqueous components. The pilot scale experiment is described by Lesage et al. (1995) and Van Stempvoort et al. (2000). The conceptual model includes 8 unique components dissolving from 500 mL of residual diesel fuel within a 3D saturated domain. Oxygen-limiting competitive aerobic biodegradation with a dynamic microbial population is also included. A mixed 2-site equilibrium/kinetic model for describing sorption of the carrier to the aquifer solids was adopted to reproduce the observed breakthrough of the humic acid and organic components. Most model parameters were obtained independently with minimal calibration. Batch sorption data were found to fit well at the pilot scale, however biodegradation and dissolution rates were not well known and had to be fitted. Simulations confirmed the observed 10-fold increase in effective solubility of trimethylnaphthalene, and increases on the order of 2-5 for methyl- and dimethylnaphthalene. The simulated plumes showed almost complete attenuation after 5 years, in excellent agreement with observed data. A sensitivity analysis showed the importance of carrier concentrations, binding coefficients, dissolution and biodegradation rates. Compared to a dissolution scenario assuming no carrier, the humic acid-enhanced dissolution case decreased the remediation time by a factor of about 5. The second application of the model involves simulating the effect of ethanol on the persistence of benzene in gasoline-impacted groundwater systems. The conceptual model includes a 4-component residual gasoline source which is dissolving at the watertable into a 3D aquifer. Comparisons are made between dissolved plumes from a gasoline spill and those from an otherwise equivalent gasohol spill. Simulations have shown that under some conditions, a 10% ethanol component in gasoline can extend the travel distance of a benzene plume by at least 150% relative to that from an equivalent ethanol-free gasoline spill. The increase is due to preferred consumption of oxygen by ethanol and a corresponding reduction in the biodegradation rate of benzene while the two plumes overlap. Because of differences in retardation however, the ethanol and benzene plumes gradually separate. The impact therefore becomes limited because oxygen rapidly disperses behind the ethanol plume and benzene degradation eventually resumes. A sensitivity analysis for two common spill scenarios showed that background oxygen concentrations, and benzene retardation had the most significant influence on benzene persistence. A continuous gasohol spill over 10 years was found to increase the benzene travel distance by over 120% and a pure ethanol spill into an existing gasoline plume increased benzene travel distance by 150% after 40 years. The results are highly relevant in light of the forthcoming ban of MTBE in California and its likely replacement by ethanol by the end of 2002.

Supersaturated water injection (SWI) is a novel remediation technology which is able to remove entrapped residual NAPLs from saturated porous media by both volatilization (partitioning of volatile contaminants into the gas phase) and mobilization (displacement of isolated NAPL residuals by gas clusters). The character of gas saturation evolution in-situ in saturated porous media during SWI results in high sweep efficiency. This work focuses on studying the recovery of entrapped residual NAPL by the mobilization mechanism during SWI, thus low-volatility NAPL residuals, kerosene and a kerosene-hexadecane mixture, are used as contaminants. A series of SWI recovery experiments are conducted to investigate the influence of grain size, low-permeability layering, and physical properties of the contaminants on the recovery behavior. For columns contaminated with kerosene, the residual saturation can be reduced to around 4% from an initial value of 16%, and over 70% of the residual kerosene is recovered by a combination of mobilization and volatilization in homogeneous sand packs. For columns contaminated with a kerosene-hexadecane mixture, the final residual saturation is 7.4% and the final NAPL recovery is lower than that in kerosene columns. Grain size has little influence on NAPL recovery, but low permeability layering has a significantly negative influence. Experiments designed to compare SWI to sparging, and water-gas co-injection showed that water-gas co-injection was able to effectively recovery residual NAPLs albeit not as efficiently as SWI, while steady gas sparging is completely ineffective at recovering residual NAPL by mobilization. Based on these experimental observations, a conceptual model, involving double displacements and NAPL bank formation, is purposed to explain the experimental observations.

Gas inFusion? is a novel remedial technology that dissolves CO₂ into water under pressure for NAPL recovery. As the supersaturated liquid flows through the porous medium gas evolution occurs in situ as the system returns to thermodynamic equilibrium. The evolution of gas bubbles leads to NAPL recovery by two mechanisms: 1) volatilization and 2) mobilization by the NAPL spreading in a film around the rising bubbles. Laboratory experiments by Li demonstrated that injecting the supersaturated water into a porous medium minimized the buoyancy driven flow of gas and the fingering phenomena that limit typical gas sparging. The distribution of carbon dioxide at partial pressures (p_CO2) above the applicable hydrostatic pressure and the evolved gas phase were determined in two field experiments conducted in the relatively homogeneous fine to medium sand at CFB Borden. First, CO₂-supersaturated water was injected into a single point located approximately 4 metres below ground surface. Then this injection was repeated with pumping of two nearby wells to see if the lateral distribution of CO₂ gas could be controlled hydraulically. Groundwater monitoring of p_CO2 above the hydrostatic pressure and geophysical surveys (neutron measurements, surface ground penetrating radar (GPR), and cross-borehole GPR) to find zones of induced gas content were supported by hydraulic monitoring and physical observations of gas bubble distribution at the water table. <br /><br /> Based on the results of these tests, enhanced CO₂ levels above the hydrostatic pressure were observed up to 5. 5-7. 0 m from the injection point and the gas phase up to ~5. 3 m. It was not possible to determine the impact hydraulic control had on the lateral distribution of CO₂ due to problems with the experiment. The distribution of the gas phase was heterogeneous with CO₂ gas pockets forming below low permeability layers, as evidenced by surface GPR, permeameter tests, and grain size analyses. These gas pockets accumulated until sufficient pressure built up to overcome the displacement pressure of these lower permeability layers. At this point there is evidence of CO₂ breakthrough in the cross-borehole GPR data and physical observations of gas bubbles at the water table. These observations are consistent with previous investigations, which indicate that although the Borden aquifer is homogeneous, distinct horizontal layering is present with sufficient variations in permeability/displacement pressure to trap and cause some lateral spreading of a gas phase. The evidence of channeling and the impact of heterogeneities on gas distribution are consistent with air sparging studies.