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.     

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.     

Cleaning oiled shores: laboratory experiments testing the potential use of vegetable oil biodiesels

A series of laboratory experiments were carried out to test the potential of vegetable oil biodiesel for the cleaning of oiled shorelines. In batch experiments, biodiesel was shown to have a considerable capacity to dissolve crude oil, which appears to be dependent on the type of biodiesel used. Pure vegetable oil biodiesels (rapeseed and soybean) were significantly more effective in the cleanup of oiled sands (up to 96%) than recycled waste cooking oil biodiesel (70%).In microcosm and mesocosm experiments, oiled sediments were sprayed with biodiesel and subjected to simulated tides. Microcosm experiments revealed that, of those tested, the highest ratio of biodiesel to crude oil, had the highest effectiveness for cleaning fine sands, with ratios of 2:1 (biodiesel:crude oil) giving the best results. In the mesocosm experiments a ratio 1:1 of soybean biodiesel to crude oil removed 80% of the oil in cobbles and fine sands, 50% in coarse sand and 30% in gravel. Most of the oil was removed with the surface water, with only a small amount being flushed through the sediments. Particle size and pore size were important determinants in the cleanup and mobility of crude oil in the sediments in these static systems. It is expected that the biodiesel effectiveness should improve in the natural environment particularly in exposed beaches with strong wave action. However, more laboratory and field trials are required to confirm the operational use of biodiesel as a shoreline cleaner.     

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.     

A set of constitutive relationships accounting for residual NAPL in the unsaturated zone

Although laboratory experiments show that non-aqueous phase liquid (NAPL) is retained in the unsaturated zone, no existing multiphase flow model has been developed to account for residual NAPL after NAPL drainage in the unsaturated zone. We developed a static constitutive set of saturation-capillary pressure relationships for water, NAPL and air that accounts for both this residual NAPL and entrapped NAPL. The set of constitutive relationships is formulated similarly to the set of scaled relationships that is frequently applied in continuum models. The new set consists of three fluid-phase systems: a three-phase system and a two-phase system, that both comply with the original constitutive model, and a newly introduced residual NAPL system. The new system can be added relatively easily to the original two- and three-phase systems. Entrapment is included in the model. The constitutive relationships of the non-drainable residual NAPL system are based on qualitative fluid behavior derived from a pore scale model. The pore scale model reveals that the amount of residual NAPL depends on the spreading coefficient and the water saturation. Furthermore, residual NAPL is history-dependent. At the continuum scale, a critical NAPL pressure head defines the transition from free, mobile NAPL to residual NAPL. Although the Pc-S relationships for water and total liquid are not independent in case of residual NAPL, two two-phase Pc-S relations can represent a three-phase residual system of Pc-S relations. A newly introduced parameter, referred to as the residual oil pressure head, reflects the mutual dependency of water and oil. Example calculations show consistent behavior of the constitutive model. Entrapment and retention in the unsaturated zone cooperate to retain NAPL. Moreover, the results of our constitutive model are in agreement with experimental observations.     

Impact of nonaqueous phase liquid (NAPL) source zone architecture on mass removal mechanisms in strongly layered heterogeneous porous media during soil vapor extraction

An existing multiphase flow simulator was modified in order to determine the effects of four mechanisms on NAPL mass removal in a strongly layered heterogeneous vadose zone during soil vapor extraction (SVE): a) NAPL flow, b) diffusion and dispersion from low permeability zones, c) slow desorption from sediment grains, and d) rate-limited dissolution of trapped NAPL. The impacts of water and NAPL saturation distribution, NAPL-type (i.e., free, residual, or trapped) distribution, and spatial heterogeneity of the permeability field on these mechanisms were evaluated. Two different initial source zone architectures (one with and one without trapped NAPL) were considered and these architectures were used to evaluate seven different SVE scenarios. For all runs, slow diffusion from low permeability zones that gas flow bypassed was a dominant factor for diminished SVE effectiveness at later times. This effect was more significant at high water saturation due to the decrease of gas-phase relative permeability. Transverse dispersion contributed to fast NAPL mass removal from the low permeability layer in both source zone architectures, but longitudinal dispersion did not affect overall mass removal time. Both slow desorption from sediment grains and rate-limited mass transfer from trapped NAPL only marginally affected removal times. However, mass transfer from trapped NAPL did affect mass removal at later time, as well as the NAPL distribution. NAPL flow from low to high permeability zones contributed to faster mass removal from the low permeability layer, and this effect increased when water infiltration was eliminated. These simulations indicate that if trapped NAPL exists in heterogeneous porous media, mass transfer can be improved by delivering gas directly to zones with trapped NAPL and by lowering the water content, which increases the gas relative permeability and changes trapped NAPL to free NAPL.     

Effective distribution of emulsified edible oil for enhanced anaerobic bioremediation

Recent laboratory and field studies have shown that injection of emulsified edible oils can provide an effective, low-cost alternative for stimulating anaerobic biodegradation processes. A pilot-scale permeable reactive bio-barrier (PRBB) was installed at a perchlorate and chlorinated solvent impacted site by injecting 380 L of commercially available emulsion (EOS) containing emulsified soybean oil, food-grade surfactants, lactate, and yeast extract through ten direct push injection wells over a two day period. Soil cores collected six months after emulsion injection indicate the oil was distributed up to 5 m downgradient of the injection wells. A previously developed emulsion transport model was used to simulate emulsion transport and retention using independently estimated model parameters. While there was considerable variability in the soil sampling results, the model simulations generally agreed with the observed oil distribution at the field site. Model sensitivity analyses indicate that increasing the injection flow rate or diluting the oil with more water will have little effect on final oil distribution in the aquifer. The only effective approach for enhancing the spread of emulsified oil away from the injection well appears to be injecting a greater mass of oil.     

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.     

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.     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

Comparative study of microbial dechlorination of chlorinated ethenes in an aquifer and a clayey aquitard

In order to determine whether natural attenuation of chlorinated ethenes by microbial activity occurs in aquitards, sediments at a site contaminated with tetrachloroethene were vertically studied by drilling. The distribution of microbes (Dehalococcoides group and anaerobic hydrogen producers) and the ability of the sediments to sustain microbial dechlorination were determined in an aquitard as well as in an aquifer. Close-spaced sampling revealed the existence of large populations of Dehalococcoides and H(2)-producing bacteria, especially in the organic-rich clayey aquitard rather than in the aquifer. The vinyl chloride reductase gene was also detected in the clay layer. Furthermore, incubation experiments indicated that the clay sediment could sustain transformations of tetrachloroethene at least to vinyl chloride. In contrast, no significant transformation was observed in the aquifer sand. Our results indicate that dechlorination of tetrachloroethene by bacteria can take place in an organic-rich clayey aquitard, and that organic-rich clay may also be important in the natural attenuation in an adjacent aquifer, possibly supplying a carbon source or an electron donor.     

Effects of source zone heterogeneity on surfactant-enhanced NAPL dissolution and resulting remediation end-points

The effectiveness of removal of nonaqueous phase liquids (NAPLs) from the entrapment source zone of the subsurface has been limited by soil heterogeneity and the inability to locate all entrapped sources. The goal of this study was to demonstrate the uncertainty of degree of source removal associated with aquifer heterogeneity. In this demonstration, source zone NAPL removal using surfactant-enhanced dissolution was considered. Model components that simulate the processes of natural dissolution in aqueous phase and surfactant-enhanced dissolution were incorporated into an existing code of contaminant transport. The dissolution modules of the simulator used previously developed Gilland-Sherwood type phenomenological models of NAPL dissolution to estimate mass transfer coefficients that are upscaleable to multidimensional flow conditions found at field sites. The model was used to simulate the mass removal from 10 NAPL entrapment zone configurations based on previously conducted two-dimensional tank experiments. These entrapment zones represent the NAPL distribution in spatially correlated random fields of aquifer hydraulic conductivity. The numerical simulations representing two-dimensional conditions show that effectiveness of mass removal depends on the aquifer heterogeneity that controls the NAPL entrapment and delivery of the surfactant to the locations of entrapped NAPLs. Flow bypassing resulting from heterogeneity and the reduction of relative permeability due to NAPL entrapment reduces the delivery efficiency of the surfactant, thus prolonging the remediation time to achieve desired end-point NAPL saturations and downstream dissolved concentrations. In some extreme cases, the injected surfactant completely bypassed the NAPL source zones. It was also found that mass depletion rates for different NAPL source configurations vary significantly. The study shows that heterogeneity result in uncertainties in the mass removal and achievable end-points that are directly related to dissolved contaminant plume development downstream of the NAPL entrapment zone.     

Concurrent bioremediation of perchlorate and 1,1,1-trichloroethane in an emulsified oil barrier

A detailed field pilot test was conducted to evaluate the use of edible oil emulsions for enhanced in situ biodegradation of perchlorate and chlorinated solvents in groundwater. Edible oil substrate (EOS) was injected into a line of ten direct push injection wells over a 2-day period to form a 15-m-long biologically active permeable reactive barrier (bio-barrier). Field monitoring results over a 2.5-year period indicate the oil injection generated strongly reducing conditions in the oil-treated zone with depletion of dissolved oxygen, nitrate, and sulfate, and increases in dissolved iron, manganese and methane. Perchlorate was degraded from 3100 to 20,000 microg/L to below detection (<4 microg/L) in the injection and nearby monitor wells within 5 days following the injection. Two years after the single emulsion injection, perchlorate was less than 6 microg/L in every downgradient well compared to an average upgradient concentration of 13,100 microg/L. Immediately after emulsion injection, there were large shifts in concentrations of chlorinated solvents and degradation products due to injection of clean water, sorption to the oil and adaptation of the in situ microbial community. Approximately 4 months after emulsion injection, concentrations of 1,1,1-trichloroethane (TCA), perchloroethene (PCE), trichloroethene (TCE) and their degradation products appeared to reach a quasi steady-state condition. During the period from 4 to 18 months, TCA was reduced from 30-70 microM to 0.2-4 microM during passage through the bio-barrier. However, 1-9 microM 1,1-dichloroethane (DCA) and 8-14 microM of chloroethane (CA) remained indicating significant amounts of incompletely degraded TCA were discharging from the oil-treated zone. During this same period, PCE and TCE were reduced with concurrent production of 1,2-cis-dichloroethene (cis-DCE). However, very little VC or ethene was produced indicating reductive dechlorination slowed or stopped at cis-DCE. The incomplete removal of TCA, PCE and TCE is likely associated with the short (5-20 days) hydraulic retention time of contaminants in the oil-treated zone. The permeability of the injection wells declined by 39-91% (average=68%) presumably due to biomass growth and/or gas production. However, non-reactive tracer tests and detailed monitoring of the perchlorate plume demonstrated that the permeability loss did not result in excessive flow bypassing around the bio-barrier. Contaminant transport and degradation within the bio-barrier was simulated using an advection-dispersion-reaction model where biodegradation rate was assumed to be linearly proportional to the residual oil concentration (Soil) and the contaminant concentration. Using this approach, the calibrated model was able to closely match the observed contaminant distribution. The calibrated model was then used to design a full-scale barrier to treat both ClO4 and chlorinated solvents.     

Inherent mineralization of 2,6-dichlorobenzamide (BAM) in unsaturated zone and aquifers--effect of initial concentrations and adaptation

The dichlobenil metabolite BAM (2,6-dichlorobenzamide) is frequently detected in aquifers e.g. in Denmark despite the mother compound dichlobenil was banned here since 1997. BAM mineralization was investigated at environmentally relevant concentrations in sediment samples. Undisturbed sediment cores with known dichlobenil application were collected from topsoil to 8.5 m below surface resulting in 57 samples hereof 4 aquifer samples. Mineralization was only substantial (>10%) in the uppermost meter of the unsaturated zone. Microbial adaptation, observed as faster mineralization in pre-exposed than in pristine sediments from the same location, was only evident in sandy sediment where dichlobenil was still present, but not in clayey sediments. Higher initial concentrations (1-5000 μg/kg) did not stimulate mineralization in pristine clayey or sandy sediments, or in pre-exposed sand. However, in pre-exposed clay mineralization was stimulated at high concentrations. Furthermore BAM was for the first time mineralized in aerobic aquifer sediments from different BAM-contaminated groundwater locations.     

Parameters that control the cleanup of fractured permeable aquifers

This study develops a modeling approach for simulating and evaluating entrapped light nonaqueous-phase liquid (light NAPL-LNAPL) dissolution and transport of the solute in a fractured permeable aquifer (FPA). The term FPA refers to an aquifer made of porous blocks of high permeability that embed fractures. The fracture network is part of the domain characterized by high permeability and negligible storage. Previous studies show that sandstone aquifers often represent FPAs. The basic model developed in this study is a two-dimensional (2-D) model of permeable blocks that embed oblique equidistant fractures with constant aperture and orientation. According to this model, two major parameters govern NAPL dissolution and transport of the solute. These parameters are: 1) the dimensionless interphase mass transfer coefficient, K(f0), and 2) the mobility number, N(M0). These parameters represent measures of heterogeneity affecting flow, NAPL dissolution, and transport of the solute in the domain. The parameter K(f0) refers to the rate at which organic mass is transferred from the NAPL into the water phase. The parameter N(M0) represents the ratio of flow through the porous blocks to flow through the fracture network in regions free of entrapped NAPL. It also provides a measure of groundwater flow bypassing regions contaminated by entrapped NAPL. In regions contaminated by entrapped NAPL our simulations have often indicated very low permeability of the porous blocks, enabling a significant increase of the fracture flow at the expense of the permeable block flow. Two types of constitutive relationships also affect the rate of FPA cleanup: 1) the relationship between the saturation of the entrapped NAPL and the permeability of the porous blocks, and 2) the relationships representing effects of the entrapped NAPL saturation and the permeable block flow velocity on rates of interphase mass transfer. This study provides basic tools for evaluating the characteristics of pump-and-treat cleanup of FPAs by referring to sets of parameters and constitutive relationships typical of FPAs. The numerical simulations carried out in this study show that at high initial saturation of the entrapped NAPL, during initial stages of the FPA cleanup the contaminant concentration increases, but later it decreases. This phenomenon originates from significant groundwater bypassing the NAPL entrapped in the permeable blocks via the fracture network.     

Effect of nonionic surfactant partitioning on the dissolution kinetics of residual perchloroethylene in a model porous medium

At concentrations above the critical micelle concentration, surfactants can significantly enhance the solubilization of residual nonaqueous phase liquids (NAPL) and, for this reason, are the focus of research on surfactant-enhanced aquifer remediation (SEAR). As a consequence of their amphiphilic nature, surfactants may also partition to various extents between the organic and aqueous phases, thereby affecting SEAR performance. We report here on the observation and analysis of the effect of surfactant partitioning on the dissolution kinetics of residual perchloroethylene (PCE) by aqueous solutions (1000 mg/L) of the non-ionic surfactant Triton X-100 in a model porous medium. For this fluid system, batch equilibration experiments showed that the surfactant partitions strongly into the NAPL (NAPL-water partition coefficient equal to 12.5). Dynamic interfacial tension (IFT) measurements were employed to study surfactant diffusion and interfacial adsorption. The dynamic IFT measurements were consistent with partitioning of the surfactant between the two liquid phases. PCE dissolution experiments, conducted in a transparent glass micromodel using an aqueous surfactant solution, were contrasted to experiments using clean water. Surfactant partitioning was observed to delay significantly the onset of micellar solubilization of PCE, an observation reproduced by a numerical model. This effect is attributed to the reduction of surfactant concentration in the immediate vicinity of the NAPL-water interface, which accompanies transport of the surfactant into the NAPL. Accordingly, it is suggested that both the rate and the extent of diffusion of the surfactant into the NAPL affect the onset of and the driving force for micellar solubilization. While many surfactants do not readily partition in NAPL, this possibility must be considered when selecting non-ionic surfactants for the enhanced solubilization of residual chlorinated solvents in porous media.     

Progression of natural attenuation processes at a crude oil spill site: II. Controls on spatial distribution of microbial populations

A multidisciplinary study of a crude-oil contaminated aquifer shows that the distribution of microbial physiologic types is strongly controlled by the aquifer properties and crude oil location. The microbial populations of four physiologic types were analyzed together with permeability, pore-water chemistry, nonaqueous oil content, and extractable sediment iron. Microbial data from three vertical profiles through the anaerobic portion of the contaminated aquifer clearly show areas that have progressed from iron-reduction to methanogenesis. These locations contain lower numbers of iron reducers, and increased numbers of fermenters with detectable methanogens. Methanogenic conditions exist both in the area contaminated by nonaqueous oil and also below the oil where high hydrocarbon concentrations correspond to local increases in aquifer permeability. The results indicate that high contaminant flux either from local dissolution or by advective transport plays a key role in determining which areas first become methanogenic. Other factors besides flux that are important include the sediment Fe(II) content and proximity to the water table. In locations near a seasonally oscillating water table, methanogenic conditions exist only below the lowest typical water table elevation. During 20 years since the oil spill occurred, a laterally continuous methanogenic zone has developed along a narrow horizon extending from the source area to 50-60 m downgradient. A companion paper [J. Contam. Hydrol. 53, 369-386] documents how the growth of the methanogenic zone results in expansion of the aquifer volume contaminated with the highest concentrations of benzene, toluene, ethylbenzene, and xylenes.     

Geochemical interactions between process-affected water from oil sands tailings ponds and North Alberta surficial sediments

In Northern Alberta, the placement of out-of-pit oil sands tailings ponds atop natural buried sand channels is becoming increasingly common. Preliminary modeling of such a site suggests that process-affected (PA) pond water will infiltrate through the underlying clay till aquitard, reaching the sand channel. However, the impact of seepage upon native sediments and groundwater resources is not known. The goal of this study is to investigate the role of adsorption and ion exchange reactions in the clay till and their effect on the attenuation or release of inorganic species. This was evaluated using batch sorption experiments (traditional and a recent modification using less disturbed sediment samples) and geochemical modeling with PHREEQC. The results show that clay till sediments have the capacity to mitigate the high concentrations of ingressing sodium (600 mg L(-1)), with linear sorption partitioning coefficients (K(d)) of 0.45 L kg(-1). Ion exchange theory was required to account for all other cation behaviour, precluding the calculation of such coefficients for other species. Qualitative evidence suggests that chloride will behave conservatively, with high concentrations remaining in solution (375 mg L(-1)). As a whole, system behaviour was found to be controlled by a combination of competitive ion exchange, dissolution and precipitation reactions. Observations, supported by PHREEQC simulations, suggest that the influx of PA water will induce the dissolution of pre-existing sulphate salts. Sodium present in the process-affected water will exchange with sediment-bound calcium and magnesium, increasing the divalent ions' pore fluid concentrations, and leading to the precipitation of a calcium-magnesium carbonate mineral phase. Thus, in similar tailings pond settings, particularly if the glacial till coverage is thin or altogether absent, it is reasonable to expect that high concentrations of sodium and chloride will remain in solution, while sulphate concentrations will exceed those of the ingressing plume (150 mg L(-1)).     

Waste green sands as reactive media for the removal of zinc from water

Waste green sands are industrial byproducts of the gray iron foundry industry. These green sands are composed of fine silica sand, clay binder, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were performed to determine the feasibility of using green sands as a low cost reactive medium in permeable reactive barriers (PRBs). Serial batch kinetic tests and conventional batch sorption tests were conducted to determine the removal characteristics for zinc in aqueous solutions. Removal characteristics for zinc in the presence of green sands are comparable to those of Peerless iron, a common reactive medium used in PRBs. High removal capacities for zinc of green sands are attributed to clay, organic carbon, and residual iron particles, which are known sorptive media for heavy metals. Furthermore, high pH values in the presence of clay and residual iron particles enhanced sorption and precipitation of zinc.