Experimental Investigation of Surfactant-Enhanced Dissolution of Residual NAPL in Saturated Soil

Nonaqueous phase liquid (NAPL) is a long-term source of ground water contamination as the pollutant slowly partitions into the air and water phases. The objective of this work was to study the efficacy of aqueous surfactant solution to enhance the dissolution of a residual NAPL below the capillary fringe, hence reducing the time needed for aquifer restoration. An analytical technique was developed to measure the concentration of NAPL in a nonionic surfactant. Soil column experiments simulated conditions in the saturated soil where a NAPL may become trapped as a discontinuous immobile phase. Experimental results indicate that dissolution was a rate-limited process, approaching equilibrium concentrations after 24 hours. The relative permeability of the aqueous phase initially decreased as surfactant was injected, but increased over time as the saturation of residual NAPL was reduced through mass transfer into the surfactant-enhanced aqueous phase. These findings suggest that enhancing the aqueous phase with a nonionic surfactant may significantly enhance the in situ recovery or residual NAPL.     

Transport and fate of nonaqueous phase liquid (NAPL) in variably saturated porous media with evolving scales of heterogeneity

 A stochastic simulation is performed to study multiphase flow and contaminant transport in fractal porous media with evolving scales of heterogeneity. Numerical simulations of residual NAPL mass transfer and subsequent transport of dissolved and/or volatilized NAPL mass in variably saturated media are carried out in conjunction with Monte Carlo techniques. The impact of fractal dimension, plume scale and anisotropy (stratification) of fractal media on relative dispersivities is investigated and discussed. The results indicate the significance of evolving scale of porous media heterogeneity to the NAPL transport in the subsurface. In general, the fractal porous media enhance the dispersivities of NAPL mass plume transport in both the water phase and the gas phase while the influence on the water phase is more significant. The porous media with larger fractal dimension have larger relative dispersivities. The aqueous horizontal dispersivity exhibits a most significant increase against the plume scale.     

Pore-scale simulation of entrapped non-aqueous phase liquid dissolution

We investigated the dissolution of non-aqueous phase liquids (NAPLs) in a three-dimensional random sphere-pack medium using a pore-scale modeling approach to advance fundamental understanding and connect rigorously to microscale processes. Residual NAPL distributions were generated using a morphological approach and the entrapped non-wetting phase was quantitatively characterized by calculating volume, orientation, interfacial area, and shape of isolated NAPL regions. With a detailed aqueous-phase flow field obtained by a multiple-relaxation time lattice Boltzmann approach, we solved the advective–diffusive equation in the pore space using a high-resolution, adaptive-stencil finite-volume scheme and an operator-splitting algorithm. We show good agreement between the mass transfer rates predicted in the computational approach and previously published experimental observations. The pore-scale simulations presented in this work provide the first three-dimensional comparison to the considerable experimental work that has been performed to derive constitutive relations to quantify mass transfer from a residual NAPL to a flowing aqueous phase.     

Effect of NAPL film stability on the dissolution of residual wetting NAPL in porous media: A pore-scale modeling study

Wettability profoundly affects not only the initial distribution of residual NAPL contaminants in natural soils, but also their subsequent dissolution in a flowing aqueous phase. Under conditions of preferential NAPL wettability, the residual NAPL phase is found within the smaller pores and in the form of continuous corner filaments and thick films on pore walls. Such films expose a much greater interfacial area for mass transfer than would be exposed by the same amount of non-wetting NAPL. Importantly, capillary and hydraulic continuity of NAPL filaments and thick films is essential for sustaining NAPL–water counterflow during the course of NAPL dissolution in flowing groundwater—a mechanism which maintains and even increases the interfacial area for mass transfer. Continued dissolution results in gradual thinning of the NAPL films, which may become unstable and rupture causing disconnection of the residual NAPL in the form of clusters. Using a pore network simulator, we demonstrate that NAPL film instability drastically modifies the microscopic configuration of residual NAPL, and hence the local hydrodynamic conditions and interfacial area for mass transfer, with concomitant effects on macroscopically observable quantities, such as the aqueous effluent concentration and the fractional NAPL recovery with time. These results strongly suggest that the disjoining pressure of NAPL films may exert an important, and hitherto unaccounted, control on the dissolution behaviour of a residual NAPL phase in oil wet systems.     

Visualization experiments of biodegradation in porous media and calculation of the biodegradation rate

Biodegradation in porous media is studied with carefully controlled and well-characterized experiments in model porous media constructed of etched glass. Porous media of this type allow visual observation of the phenomena that take place at pore scale. An aqueous solution of five organic pollutants (toluene, phenol, o-cresol, naphthalene and 1,2,3-trimethylbenzene) was used as a model NAPL (representing creosote). The bacteria used were Pseudomonas fluorescens, which are indigenous (even predominant) in many contaminated soils. The maximum aqueous concentrations of the specific organic substances, below which biodegradation becomes possible, were determined as a function of temperature from toxicity experiments. Visualization experiments were made under various flow velocities and organic loadings to study the morphology and thickness of the biofilm as a function of the pore size and the distance from the entrance, and the efficiency of biodegradation. The efficiency of biodegradation decreased as the aqueous concentration of NAPL at the inlet increased and/or as the flow velocity increased. The thickness of biofilm decreased as the distance from the inlet increased and/or the pore diameter decreased. A quasi-steady-state theoretical model of biodegradation was used to calculate the values of the mesoscopic biochemical rates and to predict the profile of NAPL concentration in the porous medium and the thickness of biofilm in pores. The agreement between experimental data and model predictions is quite satisfactory.     

Theoretical estimation of free and entrapped nonwetting–wetting fluid interfacial areas in porous media

Fluid–fluid interfacial areas play important roles in numerous subsurface processes such as dissolution, volatilization, and adsorption. Integral expressions have been derived to estimate both entrapped (discontinuous) and free (continuous) nonwetting fluid–wetting fluid specific interfacial areas in porous media. The expressions, compatible with widely used capillary head-saturation and entrapment models, require information on capillary head-saturation relation parameters, porosity, and fluid-pair interfacial tension. In addition, information on the maximum entrapped nonwetting fluid saturation as well as the main drainage branch reversal point for water and total liquid saturations is necessary to estimate entrapped fluid interfacial areas. Implementation of the interfacial area equations in continuum-based multifluid flow simulators is straightforward since no additional parameters are needed than those required by the simulators to complete the multifluid flow computations. A limited sensitivity analysis, based on experimentally obtained parameter values, showed that imposed variations resulted in logical and consistent changes in predicted specific interfacial areas for both entrapped and free nonwetting fluid–wetting fluid systems. A direct comparison with published experimental work to test the derived expressions was limited to free air–water systems and yielded reasonable results. Such comparisons are often not possible because of the lack of information given on retention parameters, and variables used to determine nonwetting fluid entrapment. This contribution is dedicated to John W. Cary.     

Impact of NAPL architecture on interphase mass transfer: A pore network study

Interphase mass transfer in porous media is commonly modeled using Sherwood number expressions that are developed in terms of fluid and porous medium properties averaged over some representative elementary volume (REV). In this work the influence of sub-grid scale properties on interphase mass transfer was investigated using a two-dimensional pore network model. The focus was on assessing the impact of (i) NAPL saturation, (ii) interfacial area (iii) NAPL spatial distribution at the pore scale, (iv) grain size heterogeneity, (v) REV or domain size and (vi) pore scale heterogeneity of the porous media on interphase mass transfer. Variability of both the mass transfer coefficient that explicitly accounts for the interfacial area and the mass transfer coefficient that lumps the interfacial area was examined. It was shown that pore scale NAPL distribution and its orientation relative to the flow direction have significant impact on flow bypassing and the interphase mass transfer coefficient. This results in a complex non-linear relationship between interfacial area and the REV-based interphase mass transfer rate. Hence, explicitly accounting for the interfacial area does not eliminate the uncertainty of the mass transfer coefficient. It was also shown that, even for explicitly defined flow patterns, changing the domain size over which the mass transfer process is defined influences the extent of NAPL bypassing and dilution and, consequently, the interphase mass transfer. It was also demonstrated that the spatial variability of pore scale parameters such as pore throat diameters may result in different rates of interphase mass transfer even for the same pore size distribution index.     

Pore Water Characteristics Following a Release of Neat Ethanol onto Pre-existing NAPL

Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous-flow, sand-packed aquifer tank (8.2 m³) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench-scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench- and pilot-scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near-source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre-existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.     

Dependence of lumped mass transfer coefficient on scale and reactions kinetics for biologically enhanced NAPL dissolution

Residual dense non-aqueous liquids (NAPLs) in aquifers constitute a great challenge for groundwater cleanup. Active engineered treatment of regions that contain residual NAPLs is often required to shorten the long-term impact of NAPLs on groundwater quality. Enhanced residual NAPL cleanup can be achieved by promoting biodegradation of NAPL components in the aqueous phase, thereby increasing contaminant fluxes from the NAPL phase. Reaction-enhanced NAPL dissolution is often mathematically simulated under the assumption that lumped mass transfer coefficients, used to describe the dissolution behavior of the NAPL phase, are independent of the reactions. However, this assumption is not warranted because reactions occurring near the water–NAPL interface can reduce characteristic mass transfer lengths, which tend to enhance mass transfer over the no-reaction case.In this study, we mathematically investigated the connections between lumped mass transfer coefficients and reaction kinetics over an idealized residual NAPL domain. Since mass transfer is frequently a scale-dependent process, we also examined the influence of system extent on mass transfer coefficients. For our idealized domain with an assumed first-order decay reaction, the results show that lumped mass transfer coefficients depend on reaction kinetics and system scale. The mass transfer coefficient derived from the non-reactive case cannot properly represent the mass transfer process under the reactive conditions. When the advection time scale is long in comparison to the transverse dispersion time scale in the system, a fast reaction can increase significantly the lumped mass transfer coefficient. The mass transfer coefficient used for simulation was also found to be affected by the nature of the numerical scheme used.     

Dissolution of residual non-aqueous phase liquids in porous media: pore-scale mechanisms and mass transfer rates

Experiments designed to elucidate the pore-scale mechanisms of the dissolution of a residual non-aqueous phase liquid (NAPL), trapped in the form of ganglia within a porous medium, are discussed. These experiments were conducted using transparent glass micromodels with controlled pore geometry, so that the evolution of the size and shape of individual NAPL ganglia and, hence, the pore-scale mass transfer rates and mass transfer coefficients could be determined by image analysis. The micromodel design permitted reasonably accurate control of the pore water velocity, so that the mass transfer coefficients could be correlated in terms of a local (pore-scale) Peclet number. A simple mathematical model, incorporating convection and diffusion in a slit geometry was developed and used successfully to predict the observed mass transfer rates. For the case of non-wetting NAPL ganglia, water flow through the corners in the pore walls was seen to control the rate of NAPL dissolution, as recently postulated by Dillard and Blunt [Water Resour. Res. 36 (2000) 439–454]. Break-up of doublet non-wetting phase ganglia into singlet ganglia by snap-off in pore throats was also observed, confirming the interplay between capillarity and mass transfer. Additionally, the effect of wettability on dissolution mass transfer was demonstrated. Under conditions of preferential NAPL wettability, mass transfer from NAPL films covering the solid surfaces was seen to control the dissolution process. Supply of NAPL from the trapped ganglia to these films by capillary flow along pore corners was observed to result in a sequence of pore drainage events that increase the interfacial area for mass transfer. These observations provide new experimental evidence for the role of capillarity, wettability and corner flow on NAPL ganglia dissolution.     

The influence of wettability on NAPL dissolution fingering

Laboratory experiments and numerical simulations in homogeneous porous media were used to investigate the influence of porous medium wettability on the formation and growth of preferential dissolution pathways, dissolution fingers, during nonaqueous phase liquid (NAPL) dissolution. As the porous medium became increasingly NAPL-wet, dissolution fingers grew wider and slower. This result was observed in physical experiments with 0% and 100% NAPL-wet conditions and confirmed with numerical simulations at these and intermediate wettabilities. A previously derived expression for an upscaled mass transfer rate coefficient that accounts for the growth of dissolution fingers was used to quantify the effect of fingering on overall NAPL removal rates. For the test cases evaluated, NAPL dissolution fingering controlled the overall rate of NAPL dissolution after the dissolution front moved 4 cm in 0% NAPL-wet conditions and 18 cm in 100% NAPL-wet conditions. Thus, even in completely NAPL-wet media dissolution fingering may control the overall rate of NAPL dissolution after relatively short travel distances. The importance of NAPL dissolution fingering in heterogeneous systems with spatially varying NAPL saturations, though, remains an important question for future work.     

Electrical Resistance Heating of Clay Layers in Water‐Saturated Sand

Electrical resistance heating (ERH) experiments were performed in a two‐dimensional water‐saturated porous medium comprising an electrically conductive, low‐permeability clay lens embedded within a less electrically conductive, higher permeability silica sand. These were compared to experiments performed in homogeneous silica sand. All experiments were performed in the absence of a non‐aqueous phase liquid (NAPL) or dissolved volatile organic compound (VOC). Temperature monitoring showed preferential heating in the clay lens and higher overall heating rates throughout the test cell compared to the homogeneous case. Gas production was localized around the sand–clay interface due to high temperature and low capillary displacement pressure. Above the clay lens, unexpected temperature plateaus were observed, similar to those observed in previous experiments during NAPL–water co‐boiling. A conceptual model based on the consumption of thermal energy as latent heat of vaporization in the highly localized heating and gas production region adjacent to the clay lens is proposed to explain the temperature plateaus. Supporting data is drawn from images of the gas phase and electric current measurements. These results show that the use of co‐boiling plateaus as an indicator of NAPL–water co‐boiling could be misleading during applications of ERH at sites containing electrically conductive, low‐permeability clay lenses embedded within less electrically conductive, higher‐permeability sands.     

Effect of NAPL Source Morphology on Mass Transfer in the Vadose Zone

The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.     

Influence of mass transfer resistance on detection of nonaqueous phase liquids with partitioning tracer tests

Partitioning interwell tracer tests (PITTs) are a relatively new technique for measuring the amount of nonaqueous phase liquid (NAPL) within saturated porous media. In this work we examined the influence of mass transfer limitations on the accuracy of measured NAPL from PITTs. Two mathematical models were used along with laboratory column experiments to explore the influence of tracer partition coefficient, tracer detection limit, and injected tracer mass on NAPL measurements. When dimensionless mass transfer coefficients were small, NAPL measurement errors decreased with decreasing tracer partition coefficient, decreasing tracer detection limit, and increasing injected tracer mass. Extrapolating breakthrough curves exponentially reduced but did not eliminate systematic errors in NAPL measurement. Although transport in a single stream tube was used in the mathematical models and laboratory experiments, the results from this simplified domain were supported by data taken from a three-dimensional computational experiment, where the NAPL resided as large pool. Based on these results, we suggest guidelines for interpreting tracer breakthrough data to ascertain the importance of mass transfer limitations on NAPL measurements.     

A novel experimental procedure to investigate the biodegradation of NAPL under unsaturated conditions

Soils need to be thoroughly investigated regarding their potential for the natural attenuation of non-aqueous phase liquids (NAPL). Laboratory investigations truly representative of degradation processes in field conditions are difficult to implement for porous media partially saturated with water, NAPL and air. We propose an innovative protocol to investigate degradation processes under steady-state vadose zone conditions. Experiments are carried out in glass columns filled with a sand and, as bacteria source, a soil from a diesel-fuel-polluted site. Water and NAPL (n-hexadecane diluted in heptamethylnonane (HMN)) are added to the porous medium in a two-step procedure using ceramic membranes placed at the bottom of the column. This procedure results, for appropriate experimental conditions, in a uniform distribution of the two fluids (water and NAPL) throughout the column. In a biodegradation experiment non-biodegradable HMN is used to provide NAPL mass, while keeping biodegradable n-hexadecane small enough to monitor its rapid degradation. Biodegradation is followed as a function of time by measuring oxygen consumption, using a respirometer. Degradative activity is controlled by diffusive transfers in the porous network, of oxygen from the gas phase to the water phase and of n-hexadecane from the NAPL phase to the water phase.     

Sensitivity and moment analyses of head in variably saturated regimes

A numerical approach for approximating statistical moments of hydraulic heads of variably saturated flows in multi-dimensional porous media is developed. The approximation relies on a first-order Taylor series expansion of a finite element flow model and an adjoint state numerical method for variably saturated flows to evaluate sensitivities. This approach can be employed to analyze uncertainties associated with predictions of head of steady-state or transient flows in variably saturated porous media, with any type of boundary and initial conditions. Limitations of stochastic analytical methods such as spectral/perturbation approaches and the time-consuming Monte Carlo simulation technique are thus alleviated. An example is given to demonstrate the utility of the approach and to investigate the temporal evolution of head variances in a variably saturated flow regime. Results show that the fluctuation of the water table can have significant impacts on the propagation of the head variance.     

DNAPL to LNAPL Transitions During Horizontal Cosolvent Flooding

Cosolvent flooding is a technology with the potential to remove nonaqueous phase liquid (NAPL) sources from the subsurface. It can be used to initiate separate phase mobilization, which allows removal of NAPL within very few pore volumes. Mobilization may result in a sinking DNAPL bank during horizontal flooding of NAPLs denser than water. Reversal of phase density difference between aqueous and DNAPL phases could potentially avoid this downward migration of mobilized DNAPLs. We achieved phase density difference reversal and made DNAPLs float using two components in the cosolvent flooding solution. A low-density cosolvent partitions preferentially into the DNAPL and swells it, which causes a reduction in density of the DNAPL and reversal of the density difference between the NAPL and aqueous phases. A highdensity additive that remains in the aqueous phase allows the cosolvent flooding solution overall to have a density greater than that of water and permits control of the flooding instability. This study focused on tert-butanol as the swelling cosolvent and tetrachloroethylene as the contaminant. In batch tests with sucrose and glycerol as dense additives, phase density difference reversal occurred. To investigate the applicability of phase density difference reversal as a remediation technology, horizontal column and sandbox experiments were performed. These experiments demonstrated the occurrence of phase density difference reversal and effective remediation in horizontal cosolvent floods.     

Unifying NAPL Drawdown and Transmissivity Testing in Unconfined,Confined, Perched,and Fractured Settings using the Z-Factor and MH Principles

Light nonaqueous phase liquid (LNAPL) flow in in fractured rock is governed by the same physics as porous media, but LNAPL discharge to a well from fractured rock is subject to the unique geometry of the fractures within the rock and the degree of interconnectivity between the factures. Previous conceptualization and definition of drawdown of nonaqueous phase liquids (NAPL) has employed a single drawdown value to represent the entire vertical interval of mobile NAPL. Application of the single drawdown model may result in erroneous calculation of NAPL transmissivity in fractured rock settings. This work illustrates how drawdown in multiphase systems can be variable over the vertical interval of mobile NAPL. In settings with discrete fracture networks, it is clear that consistently applying a single drawdown value will not accurately represent the pressure gradients. This work presents the multiphase head (MH) model, which is proposed as a comprehensive methodology for evaluating NAPL drawdown in fractured rock, and unconsolidated porous media. The MH model utilizes fluid statics and physical principles to accurately represent pressure differences in the formation and convert those into NAPL drawdown for discrete elevations. This first principles approach to describing how drawdown varies with NAPL-production zone elevations and fluid levels, resulting in a more accurate representation of discharge vs. fluid elevation behavior. Application of the MH model to various scenarios has identified that dissimilar scenarios can represent similar behavior during recovery from a NAPL removal event or baildown test. The resulting understanding improves the selection of representative portions of baildown test data to use in NAPL transmissivity analysis. Proper conceptualization of drawdown in bedrock identifies an alternate analysis method, the Z-factor, to estimate NAPL transmissivity. The resulting drawdown calculations and transmissivity analysis method result in a comprehensive approach to calculating NAPL transmissivity in both bedrock and unconsolidated porous media.     

Predicting Soil-Water and Soil-Air Transport Properties and Their Effects on Soil-Vapor Extraction Efficiency

Accurate prediction of water and air Iran sport parameters in variably saturated soil is necessary for modeling of soil-vapor extraction (SVE) at soil sites contaminated with volatile organic chemicals (VOCs). An expression for predicting saturated water permeability (k_l,s) in undisturbed soils from the soil total porosity and the field capacity soil-water content was developed by fitting a tortuous-tube fluid flow model to measured water permeability and gas diffusivity data. The new k_l,s expression gave accurate predictions when tested against independent k_l,s data. The k_l,s expression was implemented in the Campbell relative water permeability model to yield a predictive model for water permeability in variably saturated, undisturbed soil. The water permeability model, together with recently developed predictive equations for gas permeability and gas diffusivity, was used in a two-dimensional numerical SVE model that also included non-equilibrium mass transfer of VOC from a separate phase (nonaqueous phase liquid [NAPL]) to the air phase. SVE: calculations showed that gas permeability is likely the most important factor controlling VOC migration and vapor extraction efficiency. Water permeability and gas diffusivity effects became significant at water contents near and above field capacity. The NAPL-air mass transfer coefficient also had large impacts on simulated vapor extraction efficiency. The calculations suggest that realistic SVE models need to include predictive expressions for both conveciive, diffusive. and phase-partitioning processes in natural, undisturbed soils.     

软件ABAQUS在饱和土体动力响应分析中的应用

研究表明:地震作用下土体的动力特性及变形特性与超静孔隙水压力的发展变化密切相关,因此,在土体动力分析过程中考虑孔隙水压的影响是非常必要的。本文通过对基本方程的推导,借助于大型有限元软件ABAQUS,进行了饱和土体在动力作用下孔隙水压变化的数值模拟。计算结果表明,ABAQUS完全适用于此类问题的数值模拟,并且稳定性和收敛性较好。