Push-pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination

Naturally occurring radon in groundwater can be used as an in situ partitioning tracer for locating and quantifying non-aqueous phase liquid (NAPL) contamination in the subsurface. When combined with the single-well, push-pull test, this methodology has the potential to provide a low-cost alternative to inter-well partitioning tracer tests. During a push-pull test, a known volume of test solution (radon-free water containing a conservative tracer) is first injected ("pushed") into a well; flow is then reversed and the test solution/groundwater mixture is extracted ("pulled") from the same well. In the presence of NAPL radon transport is retarded relative to the conservative tracer. Assuming linear equilibrium partitioning, retardation factors for radon can be used to estimate NAPL saturations. The utility of this methodology was evaluated in laboratory and field settings. Laboratory push-pull tests were conducted in both non-contaminated and trichloroethene NAPL (TCE)-contaminated sediment. The methodology was then applied in wells located in non-contaminated and light non-aqueous phase liquid (LNAPL)-contaminated portions of an aquifer at a former petroleum refinery. The method of temporal moments and an approximate analytical solution to the governing transport equations were used to interpret breakthrough curves and estimate radon retardation factors; estimated retardation factors were then used to calculate TCE saturations. Numerical simulations were used to further investigate the behavior of the breakthrough curves. The laboratory and field push-pull tests demonstrated that radon retardation does occur in the presence of TCE and LNAPL and that radon retardation can be used to calculate TCE saturations. Laboratory injection-phase test results in TCE-contaminated sediment yielded radon retardation factors ranging from 1.1 to 1.5, resulting in calculated TCE saturations ranging from 0.2 to 0.9%. Laboratory extraction-phase test results in the same sediment yielded a radon retardation factor of 5.0, with a calculated TCE saturation of 6.5%. Numerical simulation breakthrough curves provided reasonably good matches to the approximate analytical solution breakthrough curves. However, non-equilibrium radon partitioning and heterogeneous TCE distributions may affect the retardation factors and TCE saturation estimates.     

Diffusive partitioning tracer test for the quantification of nonaqueous phase liquid (NAPL) in the vadose zone: Performance evaluation for heterogeneous NAPL distribution

A partitioning tracer test based on gas-phase diffusion in the vadose zone yields estimates of the residual nonaqueous phase liquid (NAPL) saturation. The present paper investigates this technique further by studying diffusive tracer breakthrough curves in the vadose zone for a heterogeneous NAPL distribution. Tracer experiments were performed in a lysimeter with a horizontal layer of artificial kerosene embedded in unsaturated sand. Tracer disappearance curves at the injection point and tracer breakthrough curves at some distance from the injection point were measured inside and outside of the NAPL layer. A numerical code was used to generate independent model predictions based on the physicochemical sand, NAPL, and tracer properties. The measured and modeled tracer breakthrough curves were in good agreement confirming the validity of important modeling assumptions such as negligible sorption of chlorofluorocarbon (CFC) tracers to the uncontaminated sand and their fast reversible partitioning between the soil air and the NAPL phase. Subsequently, the model was used to investigate different configurations of NAPL contamination. The experimental and model results show that the tracer disappearance curves of a single-well diffusive partitioning tracer test (DPTT) are dominated by the near-field presence of NAPL around the tip of the soil gas probe. In contrast, breakthrough curves of inter-well tracer tests reflect the NAPL saturation in between the probes, although there is no unique interpretation of the tracer signals if the NAPL distribution is heterogeneous. Numerical modeling is useful for the planning of a DPTT application. Simulations suggest that several cubic meters of soil can be investigated with a single inter-well partitioning tracer test of 24-hour duration by placing the injection point in the center of the investigated soil volume and probes at up to 1 m distance for the monitoring of gaseous tracers.     

Tracer test for the measurement of gas diffusion and non-aqueous phase liquid (NAPL) saturation in soil

During soil bioremediation, the diffusion of oxygen into the soil is an important prerequisite for aerobic biodegradation, and the decrease of petroleum products is the ultimate goal. Both processes need to be monitored. The aim of this work was to develop a gas tracer test that yields information on both, gas diffusion and residual saturation with non-aqueous phase liquids (NAPLs) in unsaturated soil heaps. One conservative tracer (methane) and 4 partitioning gas tracers (diethylether, methyl tert-butyl ether, chloroform and n-heptane) were injected as vapors into laboratory columns filled with unsaturated sand with increasing NAPL saturation. Breakthrough curves of gaseous compounds were measured at two points and compared to analytical solutions of an analytical diffusive-reactive transport equation. By fitting of methane data, robust results for effective diffusivity (tortuosity) were obtained. NAPL saturation was most accurately measured by the moderately water soluble tracers (ethers and chloroform). The hydrophobic tracer n-heptane did not partition into water-immersed NAPL. An easy and accurate way to assess air-NAPL partitioning constants from gas chromatography retention times is furthermore reported. It is concluded that gas tracer tests have the potential for measuring two important properties in soil bioremediation systems easily and quickly.     

Numerical simulations of radon as an in situ partitioning tracer for quantifying NAPL contamination using push-pull tests

Presented here is a reanalysis of results previously presented by [Davis, B.M., Istok, J.D., Semprini, L., 2002. Push-pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination. J. Contam. Hydrol. 58, 129-146] of push-pull tests using radon as a naturally occurring partitioning tracer for evaluating NAPL contamination. In a push-pull test where radon-free water and bromide are injected, the presence of NAPL is manifested in greater dispersion of the radon breakthrough curve (BTC) relative to the bromide BTC during the extraction phase as a result of radon partitioning into the NAPL. Laboratory push-pull tests in a dense or DNAPL-contaminated physical aquifer model (PAM) indicated that the previously used modeling approach resulted in an overestimation of the DNAPL (trichloroethene) saturation (S(n)). The numerical simulations presented here investigated the influence of (1) initial radon concentrations, which vary as a function of S(n), and (2) heterogeneity in S(n) distribution within the radius of influence of the push-pull test. The simulations showed that these factors influence radon BTCs and resulting estimates of S(n). A revised method of interpreting radon BTCs is presented here, which takes into account initial radon concentrations and uses non-normalized radon BTCs. This revised method produces greater radon BTC sensitivity at small values of S(n) and was used to re-analyze the results from the PAM push-pull tests reported by Davis et al. The re-analysis resulted in a more accurate estimate of S(n) (1.8%) compared with the previously estimated value (7.4%). The revised method was then applied to results from a push-pull test conducted in a light or LNAPL-contaminated aquifer at a field site, resulting in a more accurate estimate of S(n) (4.1%) compared with a previously estimated value (13.6%). The revised method improves upon the efficacy of the radon push-pull test to estimate NAPL saturations. A limitation of the revised method is that 'background' radon concentrations from a non-contaminated well in the NAPL-contaminated aquifer are needed to accurately estimate NAPL saturation. The method has potential as a means of monitoring the progress of NAPL remediation.     

Controlled release,blind tests of DNAPL characterization using partitioning tracers

The partitioning tracer technique for dense nonaqueous phase liquid (DNAPL) characterization was evaluated in an isolated test cell, in which controlled releases of perchloroethylene (PCE) had occurred. Four partitioning tracer tests were conducted, two using an inverted, double five-spot pumping pattern, and two using vertical circulation wells. Two of the four tests were conducted prior to remedial activities, and two were conducted after. Each test was conducted as a "blind test" where researchers conducting the partitioning tracer tests had no knowledge of the volume, method of release, nor resulting spatial distribution of DNAPL. Multiple partitioning tracers were used in each test, and the DNAPL volume estimates varied significantly within each test based on the different partitioning tracers. The tracers with large partitioning coefficients generally predicted a smaller volume of PCE than that expected based on the actual release volume. However, these predictions were made for low DNAPL saturations (average saturation was approximately 0.003), under conditions near the limits of the method's application. Furthermore, there were several factors that may have hindered prediction accuracy, including tracer degradation and remedial fluid interference.     

Hot water flushing for immiscible displacement of a viscous NAPL

Thermal remediation techniques, such as hot water flooding, are emerging technologies that have been proposed for the removal of nonaqueous phase liquids (NAPLs) from the subsurface. In this study a combined laboratory and modeling investigation was conducted to determine if hot water flooding techniques would improve NAPL mass removal compared to ambient temperature water flushing. Two experiments were conducted in a bench scale two-dimensional sandbox (55 cmx45 cmx1.3 cm) and NAPL saturations were quantified using a light transmission apparatus. In these immiscible displacement experiments the aqueous phase, at 22 degrees C and 50 degrees C, displaced a zone with initial NAPL saturations on the order of 85%. The interfacial tension and viscosity of the selected light NAPL, Voltesso 35, are strongly temperature-dependent. Experimental results suggest that hot water flooding reduced the size of the high NAPL saturation zone, in comparison to the cold water flood, and yielded greater NAPL mass recovery (75% NAPL removal vs. 64%). Hot water flooding did not, however, result in lower residual NAPL saturations. A numerical simulator was modified to include simultaneous flow of water and organic phases, energy transport, temperature and pressure. Model predictions of mass removal and NAPL saturation profiles compared well with observed behavior. A sensitivity analysis indicates that the utility of hot water flooding improves with the increasing temperature dependence of NAPL hydraulic properties.     

Kinetic limitations on tracer partitioning in ganglia dominated source zones

Quantification of the relationship between dense nonaqueous phase liquid (DNAPL) source strength, source longevity and spatial distribution is increasingly recognized as important for effective remedial design. Partitioning tracers are one tool that may permit interrogation of DNAPL architecture. Tracer data are commonly analyzed under the assumption of linear, equilibrium partitioning, although the appropriateness of these assumptions has not been fully explored. Here we focus on elucidating the nonlinear and nonequilibrium partitioning behavior of three selected alcohol tracers - 1-pentanol, 1-hexanol and 2-octanol in a series of batch and column experiments. Liquid-liquid equilibria for systems comprising water, TCE and the selected alcohol illustrate the nonlinear distribution of alcohol between the aqueous and organic phases. Complete quantification of these equilibria facilitates delineation of the limits of applicability of the linear partitioning assumption, and assessment of potential inaccuracies associated with measurement of partition coefficients at a single concentration. Column experiments were conducted under conditions of non-equilibrium to evaluate the kinetics of the reversible absorption of the selected tracers in a sandy medium containing a uniform entrapped saturation of TCE-DNAPL. Experimental tracer breakthrough data were used, in conjunction with mathematical models and batch measurements, to evaluate alternative hypotheses for observed deviations from linear equilibrium partitioning behavior. Analyses suggest that, although all tracers accumulate at the TCE-DNAPL/aqueous interface, surface accumulation does not influence transport at concentrations typically employed for tracer tests. Moreover, results reveal that the kinetics of the reversible absorption process are well described using existing mass transfer correlations originally developed to model aqueous boundary layer resistance for pure-component NAPL dissolution.     

A constitutive model for air-NAPL-water flow in the vadose zone accounting for immobile, non-occluded (residual) NAPL in strongly water-wet porous media

A hysteretic constitutive model describing relations among relative permeabilities, saturations, and pressures in fluid systems consisting of air, nonaqueous-phase liquid (NAPL), and water is modified to account for NAPL that is postulated to be immobile in small pores and pore wedges and as films or lenses on water surfaces. A direct outcome of the model is prediction of the NAPL saturation that remains in the vadose zone after long drainage periods (residual NAPL). Using the modified model, water and NAPL (free, entrapped by water, and residual) saturations can be predicted from the capillary pressures and the water and total-liquid saturation-path histories. Relations between relative permeabilities and saturations are modified to account for the residual NAPL by adjusting the limits of integration in the integral expression used for predicting the NAPL relative permeability. When all of the NAPL is either residual or entrapped (i.e., no free NAPL), then the NAPL relative permeability will be zero. We model residual NAPL using concepts similar to those used to model residual water. As an initial test of the constitutive model, we compare predictions to published measurements of residual NAPL. Furthermore, we present results using the modified constitutive theory for a scenario involving NAPL imbibition and drainage.     

Performance assessment of NAPL remediation in heterogeneous alluvium

Over the last few years, more than 40 partitioning interwell tracer tests (PITTs) have been conducted at many different sites to measure nonaqueous phase liquid (NAPL) saturations in the subsurface. While the main goal of these PITTs was to estimate the NAPL volume in the subsurface, some were specifically conducted to assess the performance of remedial actions involving NAPL removal. In this paper, we present a quantitative approach to assess the performance of remedial actions to recover NAPL that can be used to assess any NAPL removal technology. It combines the use of PITTs (to estimate the NAPL volume in the swept pore volume between injection and extraction wells of a test area) with the use of several cores to determine the vertical NAPL distribution in the subsurface. We illustrate the effectiveness of such an approach by assessing the performance of a surfactant/foam flood conducted at Hill Air Force Base, UT, to remove a TCE-rich NAPL from alluvium with permeability contrasts as high as one order of magnitude. In addition, we compare the NAPL volumes determined by the PITTs with volumes estimated through geostatistical interpolation of aquifer sediment core data collected with a vertical frequency of 5-10 cm and a lateral borehole spacing of 0.15 m. We demonstrate the use of several innovations including the explicit estimation of not only the errors associated with NAPL volumes and saturations derived from PITTs but also the heterogeneity of the aquifer sediments based upon permeability estimates. Most importantly, we demonstrate the reliability of the     

Characterization of pore scale NAPL morphology in homogeneous sands as a function of grain size and NAPL dissolution

In this study, we investigate pore scale morphology of nonaqueous phase liquids (NAPLs) trapped in different pore sizes using tracer techniques. Specific interfacial area and saturation of NAPL trapped in homogeneous sands were measured using the interfacial and partitioning tracer techniques. The observed NAPL-water interfacial areas increased in a log-linear fashion with decreasing sand grain size, but showed no clear trend with residual NAPL saturation formed in the various grain sizes. The measured values were used to calculate the NAPL morphology index, which characterizes the spatial NAPL distribution within the pore space. The NAPL morphology indices, increased exponentially with decreasing grain size, indicating that the NAPL becomes smaller, but more blobs. For a fixed grain size, the specific interfacial area and saturation of the NAPL were measured following changes caused by dissolution using alcohol. The observed interfacial areas showed a decrease linearly as a function of the NAPL saturation.     

Influence of residual surfactants on DNAPL characterization using partitioning tracers

The partitioning tracer technique is among the DNAPL source-zone characterization methods being evaluated, while surfactant in-situ flushing is receiving attention as an innovative technology for enhanced source-zone cleanup. Here, we examine in batch and column experiments the magnitude of artifacts introduced in estimating DNAPL content when residual surfactants are present. The batch equilibrium tests, using residual surfactants ranging from 0.05 to 0.5 wt.%, showed that as the surfactant concentrations increased, the tracer partition coefficients decreased linearly for sodium hexadecyl diphenyl oxide disulfonate (DowFax 8390), increased linearly for polyoxyethylene (10) oleyl ether (Brij 97), and decreased slightly or exhibited no observable trend for sodium dihexyl sulfosuccinate (AMA 80). Results from column tests using clean sand with residual DowFax 8390 and Tetrachloroethylene (PCE) were consistent with those of batch tests. In the presence of DowFax 8390 (less than 0.5 wt.%), the PCE saturations were underestimated by up to 20%. Adsorbed surfactants on a loamy sand with positively charged oxides showed false indications of PCE saturation based on partitioning tracers in the absence of PCE. Using no surfactant (background soil) gave a false PCE saturation of 0.0004, while soil contacted by AMA 80, Brij 97, and DowFax 8390 gave false PCE saturations of 0.0024, 0.043, and 0.23, respectively.     

Investigation of surfactant-enhanced mass removal and flux reduction in 3D correlated permeability fields using magnetic resonance imaging

Magnetic resonance imaging (MRI) was used to visualize the NAPL source zone architecture before and after surfactant-enhanced NAPL dissolution in three-dimensional (3D) heterogeneously packed flowcells characterized by different longitudinal correlation lengths: 2.1 cm (aquifer 1) and 1.1 cm (aquifer 2). Surfactant flowpaths were determined by imaging the breakthrough of a paramagnetic tracer (MnCl(2)) analyzed by the method of moments. In both experimental aquifers, preferential flow occurred in high permeability materials with low NAPL saturations, and NAPL was preferentially removed from the top of the aquifers with low saturation. Alternate flushing with water and two surfactant pulses (5-6 pore volumes each) resulted in approximately 63% of NAPL mass removal from both aquifers. However, overall reduction in mass flux (Mass Flux 1) exiting the flowcell was lower in aquifer 2 (68%) than in aquifer 1 (81%), and local effluent concentrations were found to increase by as high as 120 times at local sampling ports from aquifer 2 after surfactant flushing. 3D MRI images of NAPL revealed that NAPL migrated downward and created additional NAPL source zones in previously uncontaminated areas at the bottom of the aquifers. The additional NAPL source zones were created in the direction transverse to flow in aquifer 2, which explains the higher mass flux relative to aquifer 1. Analysis using a total trapping number indicates that mobilization of NAPL trapped in the two coarsest sand fractions is possible when saturation is below 0.5 and 0.4, respectively. Results from this study highlight the potential impacts of porous media heterogeneity and NAPL source zone architecture on advanced in-situ flushing technologies.     

Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers

The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the "radon method" under field conditions.     

Secondary imbibition in NAPL-invaded mixed-wet sediments

A previously developed pore network model is used here to study the spontaneous and forced secondary imbibition of a NAPL-invaded sediment, as in the displacement of NAPL by waterflooding a mixed-wet soil. We use a 3D disordered pore network with a realistic representation of pore geometry and connectivity, and a quasi-static displacement model that fully describes the pore-scale physics. After primary drainage (NAPL displacing water) up to a maximum capillary pressure, we simulate secondary imbibition (water displacing NAPL). We conduct a parametric study of imbibition by varying systematically the controlling parameters: the advancing contact angles, the fraction of NAPL-wet pores, the interfacial tension, and the initial water saturation. Once the secondary imbibition is completed, the controlling displacement mechanisms, capillary pressures, relative permeabilities, and trapped NAPL saturations are reported. It is assumed that NAPL migrates into an initially strongly water-wet sediment, i.e., the receding contact angles are very small. However, depending on the surface mineralogy and chemical compositions of the immiscible fluid phases, the wettability of pore interiors is altered while the neighborhoods of pore corners remain strongly water-wet-resulting in a mixed-wet sediment. Here, we compare three different levels of wettability alteration: water-wet (advancing contact angles (20 degrees to 55 degrees), intermediate-wet (55 degrees to 120 degrees), and NAPL-wet (120 degrees to 155 degrees). The range of advancing contact angles and the fraction of NAPL-wet pores have dramatic effects on the NAPL-water capillary pressures and relative permeabilities. The spatially inhomogeneous interfacial tension has a minor impact on the trapped NAPL saturation and relative permeability to NAPL, and a slight effect on the relative permeability to water. The initial water saturation has a slight effect on the two-phase flow characteristics of water-wet sediments; however, with more NAPL-wet pores in the sediment, it starts to have a profound effect on the water and NAPL relative permeabilities.     

Three-dimensional visualization and quantification of non-aqueous phase liquid volumes in natural porous media using a medical X-ray Computed Tomography scanner

This study demonstrates the capabilities of a typical medical X-ray Computed Tomography (CT) scanner to non-destructively quantify non-aqueous phase liquid (NAPL) volumes, saturation levels, and three-dimensional spatial distributions in packed soil columns. Columns packed with homogeneous sand, heterogeneous sand, or natural soil, were saturated with water and injected with known quantities of gasoline or tetrachloroethene and scanned. A methodology based on image subtraction was implemented for computing soil porosity and NAPL volumes in each 0.35 mm x 0.35 mm x 1 mm voxel of the columns. Elimination of sample positioning errors and instrument drift artifacts was essential for obtaining reliable estimates of above parameters. The CT data-derived total NAPL volume was in agreement with the measured NAPL volumes injected into the columns. CT data-derived NAPL volume is subject to a 2.6% error for PCE and a 15.5% error for gasoline, at average NAPL saturations as low as 5%, and is mainly due to instrument noise. Non-uniform distributions of NAPL due to preferential flow, and accumulation of NAPL above finer-grained layers could be observed from the data on 3-D distributions of NAPL volume fractions.     

Magnetic resonance imaging of nonaqueous phase liquid during soil vapor extraction in heterogeneous porous media

Soil vapor extraction (SVE) is commonly used to remediate nonaqueous phase liquids (NAPLs) from the vadose zone. This paper aims to determine the effect of grain size heterogeneity on the removal of NAPL in porous media during SVE. Magnetic resonance imaging (MRI) was used to observe and quantify the amount and location of NAPL in flow-through columns filled with silica gel grains. MRI is unique because it is nondestructive, allowing three-dimensional images to be taken of the phases as a function of space and time. Columns were packed with silica gel in three ways: coarse grains (250-550 microm) only, fine grains (32-63 microm) only, and a core of fine grains surrounded by a shell of coarse grains. Columns saturated with water were drained under a constant suction head, contaminated with decane, and then drained to different decane saturations. Each column was then continuously purged with water-saturated nitrogen gas and images were taken intermittently. Results showed that at residual saturation, a sharp volatilization front moved through the columns filled with either coarse-grain or fine-grain silica gel. In the heterogeneous columns, the volatilization front in the core lagged just behind the shell because gas flow was greater through the shell and decane in the core diffused outward to the shell. When decane saturation in the core was above residual saturation, decane volatilization occurred near the inlet, the relative decane saturation throughout the core dropped uniformly, and decane in the core flowed in the liquid phase to the shell to replenish volatilized decane. These results indicate that NAPL trapped in low-permeability zones can flow to replenish areas where NAPL is lost due to SVE. However, when residual NAPL saturation is reached, NAPL flow no longer occurs and diffusion limits removal from low-permeability zones.     

Flow behavior and residual saturation formation of liquid carbon tetrachloride in unsaturated heterogeneous porous media

The formation of residual, discontinuous nonaqueous phase liquids (NAPLs) in the vadose zone is a process that is not well understood. To obtain data that can be used to study the development of a residual NAPL saturation in the vadose zone and to test current corresponding models, detailed transient experiments were conducted in intermediate-scale columns and flow cell. The column experiments were conducted to determine residual carbon tetrachloride (CCl(4)) saturations of two sands and to evaluate the effect of CCl(4) vapors on the water distribution. In the intermediate-scale flow cell experiment, a rectangular zone of the fine-grained sand was packed in an otherwise medium-grained matrix. A limited amount of CCl(4) was injected from a small source and allowed to redistribute until a pseudo steady state situation had developed. A dual-energy gamma radiation system was used to determine fluid saturations at numerous locations. The experiments clearly demonstrated the formation of residual CCl(4) saturations in both sands. Simulations with an established multifluid flow simulator show the shortcomings of current relative permeability-saturation-capillary pressure (k-S-P) models. The results indicate that nonspreading behavior of NAPLs should be implemented in simulators to account for the formation of residual saturations.     

Locally-calibrated light transmission visualization methods to quantify nonaqueous phase liquid mass in porous media

Five locally-calibrated light transmission visualization (LTV) methods were tested to quantify nonaqueous phase liquid (NAPL) mass and mass reduction in porous media. Tetrachloroethylene (PCE) was released into a two-dimensional laboratory flow chamber packed with water-saturated sand which was then flushed with a surfactant solution (2% Tween 80) until all of the PCE had been dissolved. In all the LTV methods employed here, the water phase was dyed, rather than the more common approach of dyeing the NAPL phase, such that the light adsorption characteristics of NAPL did not change as dissolution progressed. Also, none of the methods used here required the use of external calibration chambers. The five visualization approaches evaluated included three methods developed from previously published models, a binary method, and a novel multiple wavelength method that has the advantage of not requiring any assumptions about the intra-pore interface structure between the various phases (sand/water/NAPL). The new multiple wavelength method is also expected to be applicable to any translucent porous media containing two immiscible fluids (e.g., water-air, water-NAPL). Results from the sand-water-PCE system evaluated here showed that the model that assumes wetting media of uniform pore size (Model C of Niemet and Selker, 2001) and the multiple wavelength model with no interface structure assumptions were able to accurately quantify PCE mass reduction during surfactant flushing. The average mass recoveries from these two imaging methods were greater than 95% for domain-average NAPL saturations of approximately 2.6x10(-2), and were approximately 90% during seven cycles of surfactant flushing that sequentially reduced the average NAPL saturation to 7.5x10(-4).     

Multispectral image analysis method to determine dynamic fluid saturation distribution in two-dimensional three-fluid phase flow laboratory experiments

The need for measuring dynamic fluid saturation distribution in multi-dimensional three-fluid phase flow experiments is hampered by lack of appropriate techniques to monitor full field transient flow phenomena. There is no conventional technique able to measure dynamic three-fluid phase saturation at several array points of the flow field at the same time. A multispectral image analysis technique was developed to determine dynamic NAPL, water and air saturation distribution in two-dimensional three-fluid phase laboratory experiments. Using a digital near-infrared camera, images of sand samples with various degrees of NAPL, water and air saturation were taken, under constant lighting conditions and within three narrow spectral bands of the visible and near-infrared spectrum. It was shown that the optical density defined for the reflected luminous intensity was a linear function of the NAPL and the water saturation for each spectral band and for any two and three-fluid phase systems. This allowed the definition of dimensionless lump reflection coefficients for the NAPL and the water phase within each spectral band. Consequently, at any given time, two images taken within two different spectral bands provided two linear equations which could be solved for the water and the NAPL saturation. The method was applied to two-dimensional three-phase flow experiments, which were conducted to investigate the migration and the distribution of LNAPL in the vadose zone. The method was used to obtain continuous, quantitative and dynamic full field mapping of the NAPL saturation as well as the variation of the water and the air saturation during NAPL flow. The method provides a non-destructive and non-intrusive tool for studying multiphase flow for which rapid changes in fluid saturation in the entire flow domain is difficult to measure using conventional techniques.     

The impact of methanogenesis on flow and transport in coarse sand

The effects of biofilm growth and methane gas generation on water flow in porous media were investigated in an anaerobic two-dimensional sand-filled cell. Inoculation of the lower portion of the cell with a methanogenic culture and addition of methanol to the bottom of the cell led to biomass growth and formation of a gas phase. Biomass distributions in the water and on the sand in the cell were measured by protein analysis. The biofilm distribution on sand was observed by confocal laser scanning microscopy. The formation, migration, distribution and saturation of gases in the cell were visualized by the charge-coupled device (CCD) camera. The effects of biofilm and gas generation on water flow were separated by performing one tracer test in the presence of both biofilm and a gas phase and a second tracer test after removal of the gas phase through water flushing. The results of tracer tests demonstrated that flow and transport in the two-dimensional cell were significantly affected by both gas generation and biofilm growth. Gas generated at the bottom of the cell in the biologically active zone moved upwards in discrete fingers, so that gas phase saturations (gas-filled fraction of void space) in the biologically active zone at the bottom of the cell did not exceed 40-50%, while gas accumulation at the top of the cell produced gas phase saturations as high as 80%. The greatest reductions in water phase permeability, based on measurements of reductions in water phase saturations, occurred near the top of the box as a result of the gas accumulation. In contrast the greatest reductions in permeability due to biofilm growth, based on measurements of biofilm thickness, occurred in the most biologically active zone at the bottom of the cell, where gas phase saturations were approximately 40-50%, but permeability reductions due to biofilm growth were estimated to be 80-95%.