Analytical Solutions for Free-Hydrocarbon Recovery Using Skimmer and Dual-Pump wells

Accidental release of petroleum hydrocarbons to the subsurface may occur through spills around refineries, leaking pipelines, storage tanks, or other sources. If the spill is large, the hydrocarbon liquids may eventually reach a water table and spread laterally in a pancake-like lens. Hydrocarbons that exist as a separate phase are termed light nonaqueous phase liquids (LNAPLs). The portion of the LNAPL that is mobile, not entrapped as residual saturation, is termed "free product."
This paper presents new analytical solutions for the design of long-term free-product recovery from aquifers with skimmer, single- and dual-pump wells. The solutions are for steady-state flow, based on the assumption of vertical equilibrium, and include the effect of coning of LNAPL, air, and water on flow. The solutions are valid for soils of large hydraulic conductivity where the effect of capillary pressure on coning is small.
The results show how to estimate the maximum rate of inflow of LNAPL for skimmer wells, i.e., wells in which LNAPL is recovered with little or no water production. The paper also shows how to calculate the increase in LNAPL recovery when water is pumped by single- or dual-pump wells. A simple equation is given that can be used to adjust the water rate to avoid smearing of the LNAPL below the water table.     

Relationship between P- and S-wave velocities and geological properties of near-surface sediments of the continental slope of the Barents Sea

Seismic velocities ( V _p and V _s) of compressional (P-) and shear (S-) waves are important parameters for the characterization of marine sediments with respect to their sedimentological and geotechnical properties. P- and S-wave velocity data of near-surface marine sediments (upper 9 m) of the continental slope of the Barents Sea are analysed and correlated to sedimentological and geotechnical properties. The results show that the S-wave velocity is much more sensitive to changes in lithology and mechanical properties than the P-wave velocity, which is characterized by a narrow range of values. The correlation coefficients between S-wave velocity and silt and clay content, wet bulk density, porosity, water content and shear strength are higher than 0.5 while the correlation coefficients of P-wave velocity and the same parameters are always lower than 0.4. Although the relationship between V _s and clay content has been widely described, the data show that V _s is better correlated with silt content than with clay content for the sediments of the area investigated. However, they show different trends. While V _s increases with increasing clay content, it decreases with increasing silt content.     

Investigation and Remediation of a 1,2-Dichloroethane Spill Part II: Documentation of Natural Attenuation

A release of 1,2-dichloroethane. also known as ethylene dichloride (EDC), resulted in shallow subsurface freephase contamination of a Gulf Coast site in the southern United States. The site stratigraphy consists primarily of a low permeability, surficial peat. silt, and clay zone underlain by fractured clay; a confined 12 in deep sand ground water flow zone; a confined 21 m deep fine sand zone of limited ground water flow, followed by a deep aquitard. The Gumbo clay and sandy clay aquitard below the release area overlies and protects the 61 m deep Upper Chicot Aquifer, which is a confined regional aquifer. An ongoing recovery and hydraulic containment program from the primary impacted and laterally and vertically restricted shallow 40-foot sand zone has effectively recovered dense nonaqueous phase liquid (DNAPL) and contained dissolved phase EDC.
Natural attenuation of EDC was demonstrated through (1) a laboratory microcosm study substantiating the ability of the native microbial population in the deeper aquifer lo degrade EDC under anaerobic environmental conditions found at the site. (2) field investigations showing reductions in EDC concentrations over time in many of the wells on site, and (3) an evaluation of the ground water for EDC and its degradation products and oilier geo-chemical parameters such as dissolved oxygen, redox potential, and pH. Degradation products of EDC found in the field investigations included 2-chloroeihanol, ethanol. ethene, and ethane. Dissolved EDC concentrations in selected wells between the first recorded samples and the fourth quarter of 1997 ranged from greater than 4% to 99% reductions. First-order exponential decay half-lives ranged from 0.21 to 4.2 years for wells showing decreases in FDC concentrations over time. Elevated methane concentrations indicated carbon dioxide to be the major terminal electron acceptor.     

Pulsed Air Sparging in Aquifers Contaminated with Dense Nonaqueous Phase Liquids

Air sparging was evaluated for remediation of tetrachloroethylene (PCE) present as dense nonaqueous phase liquid (DNAPL) in aquifers. A two-dimensional laboratory tank with a transparent front wall allowed for visual observation of DNAPL mobilization. A DNAPL zone 50 cm high was created, with a PCE pool accumulating on an aquitard. Detailed process control and analysis yielded accurate mass balances and insight into the mass-transfer limitations during air sparging. Initial PCE recovery rates were high, corresponding to fast removal of residual DNAPL within the zone influenced directly by air channels. The vadose zone DNAPL was removed within a few days, and the recovery in the extracted soil vapors decreased to low values. Increasing the sparge rate and pulsing the air injection led to improved mass recovery, as the pulsing induced water circulation and increased the DNAPL dissolution rate. Dissolved PCE concentrations both within and outside the zone of air channels were affected by the pulsing. Inside the sparge zone, aqueous concentrations decreased rapidly, matching the declining effluent PCE flux. Outside the sparge zone, PCE concentrations increased because highly contaminated water was pushed away from the air injection point. This overall circulation of water may lead to limited spreading of the contaminant, but accelerated the time-weighted average mass removal by 40% to 600%, depending on the aggressiveness of the pulsing. For field applications, pulsing with a daily or diurnal cycling time may increase the average mass removal rate, thus reducing the treatment time and saving in the order of 40% to 80% of the energy cost used to run the blowers. However, air sparging will always fail to remove DNAPL pools located below the sparge point because the air will rise upward from the top of a screen, unless very localized geological layers force the air to migrate horizontally. Unrecognized presence of DNAPL at chlorinated solvent sites residual and pools could potentially hamper success of air sparging cleanups, since the presence of small DNAPL pools, ganglia or droplets can greatly extend the treatment time.     

A physical model for shear-wave velocity prediction1

The clay-sand mixture model of Xu and White is shown to simulate observed relationships between S-wave velocity (or transit time), porosity and clay content. In general, neither S-wave velocity nor S-wave transit time is a linear function of porosity and clay content. For practical purposes, clay content is approximated by shale volume in well-log applications. In principle, the model can predict S-wave velocity from lithology and any pair of P-wave velocity, porosity and shale volume. Although the predictions should be the same if all measurements are error free, comparison of predictions with laboratory and logging measurements show that predictions using P-wave velocity are the most reliable. The robust relationship between S- and P-wave velocities is due to the fact that both are similarly affected by porosity, clay content and lithology. Moreover, errors in the measured P-wave velocity are normally smaller than those in porosity and shale volume, both of which are subject to errors introduced by imperfect models and imperfect parameters when estimated from logs. Because the model evaluates the bulk and shear moduli of the dry rock frame by a combination of Kuster and Toksöz’ theory and differential effective medium theory, using pore aspect ratios to characterize the compliances of the sand and clay components, the relationship between P- and S-wave velocities is explicit and consistent. Consequently the model sidesteps problems and assumptions that arise from the lack of knowledge of these moduli when applying Gassmann's theory to this relationship, making it a very flexible tool for investigating how the v_P-v_s relationship is affected by lithology, porosity, clay content and water saturation. Numerical results from the model are confirmed by laboratory and logging data and demonstrate, for example, how the presence of gas has a more pronounced effect on P-wave velocity in shaly sands than in less compliant cleaner sandstones.     

The Effects of Hydrophilic Polymer and Soil Salinity on Corn Growth in Sandy and Loamy Soils

The interaction effects of different applied ratios of a hydrophilic polymer (Superab A200) (0, 0.2, 0.6% w/w) under various soil salinity levels (initial salinity, 4 and 8 ms/cm) were evaluated on available water content (AWC), biomass, and water use efficiency for corn grown in loamy sand and sandy clay loam soils. The results showed that the highest AWC was measured at the lowest soil salinity. The application of 0.6% w/w of the polymer at the lowest salinity level increased the AWC by 2.2 and 1.2 times greater than those of control in the loamy sand and sandy clay loam soils, respectively. The analysis of variance of data showed that the effect of salinity was significant on biomass and water use efficiency of corn in the loamy sand and sandy clay loam soils. The highest amounts of these traits were measured in soils with the lowest salinity level. Application of polymer at the rate of 0.6% in the loamy sand soil and at the rate of 0.2% in the sandy clay loam soil resulted in the highest aerial and root biomass and water use efficiency for corn. At these polymer rates the amounts of water use efficiency for corn were 2.6 and 1.7 times greater than those of control in the loamy sand and sandy clay loam soils, respectively. Thus, the use of hydrophilic polymer in soils especially in the sandy soils increases soil water holding capacity, yield, and water use efficiency of plant. On the other hand, decreases the negative effect of soil salinity on plant and helps for irrigation projects to succeed in arid and semi‐arid areas.     

A Mass Balance Approach to Resolving LNAPL Stability

This article explores the hypothesis that natural losses of light nonaqueous phase liquids (LNAPLs) through dissolution and evaporation can control the overall extent of LNAPL bodies and LNAPL fluxes observed within LNAPL bodies. First, a proof‐of‐concept sand tank experiment is presented. An LNAPL (methyl tert‐butyl ether) was injected into a sand tank at five constant injection rates that were increased stepwise. Initially, for each injection rate the LNAPL bodies expanded quickly. With time the rate of expansion of the LNAPL bodies slowed and at extended times the extent of the LNAPL became constant. Attainment of a stable LNAPL extent is attributed to rates of LNAPL addition being equal to rates of LNAPL losses through dissolution and evaporation. Secondly, analytical solutions are developed to extrapolate the processes observed in the proof‐of‐concept experiment to dimensions and time frames that are consistent with field‐scale LNAPL bodies. Three LNAPL body geometries that are representative of common field conditions are considered including one‐dimensional, circular, and oblong shapes. Using idealized conditions, the solutions describe volumetric LNAPL fluxes as a function of position in LNAPL bodies and the overall extent of LNAPL bodies as a function of time. Results from both the proof‐of‐concept experiment and the mathematical developments illustrate that natural losses of LNAPL can play an important role in governing LNAPL fluxes within LNAPL bodies and the overall extent of LNAPL bodies.     

Integrity of Clay Till Aquitards to DNAPL Migration: Assessment Using Current and Emerging Characterization Tools

Field investigations were carried out to determine the occurrence of tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL), the source zone architecture and the aquitard integrity at a 30‐ to 50‐year old DNAPL release site. The DNAPL source zone is located in the clay till unit overlying a limestone aquifer. The DNAPL source zone architecture was investigated through a multiple‐lines‐of‐evidence approach using various characterization tools; the most favorable combination of tools for the DNAPL characterization was geophysical investigations, membrane interface probe, core subsampling with quantification of chlorinated solvents, hydrophobic dye test with Sudan IV, and Flexible Liner Underground Technologies (FLUTe) NAPL liners with activated carbon felt (FACT). While the occurrence of DNAPL was best determined by quantification of chlorinated solvents in soil samples supported by the hydrophobic dye tests (Sudan IV and NAPL FLUTe), the conceptual understanding of source zone architecture was greatly assisted by the indirect continuous characterization tools. Although mobile or high residual DNAPL (S _t > 1%) only occurred in 11% of the source zone samples (intact cores), they comprised 86% of the total PCE mass. The dataset, and associated data analysis, supported vertical migration of DNAPL through fractures in the upper part of the clay till, horizontal migration along high permeability features around the redox boundary in the clay till, and to some extent vertical migration through the fractures in the reduced part of the clay till aquitard to the underlying limestone aquifer. The aquitard integrity to DNAPL migration was found to be compromised at a thickness of reduced clay till of less than 2 m.     

LNAPL Volume Calculation: Parameter Estimation by Nonlinear Regression of Saturation Profiles

An estimation of the volume of light nonaqueous phase liquids (LNAPL) is often required during site assessment, remedial design, or litigation. LNAPL volume can be estimated by a strictly empirical approach whereby core samples, distributed throughout the vertical and lateral extent of LNAPL, are analyzed for LNAPL content, and these data are then integrated to compute a volume. Alternatively, if the LNAPL has obtained vertical equilibrium, the thickness of LNAPL in monitoring wells can be used to calculate of LNAPL in monitoring wells can be used to calculate LNAPL volume at the well locations if appropriate soil and LNAPL properties can be estimated.
A method is described for estimating key soil and LNAPL properties by nonlinear regression of vertical profiles of LNAPL saturation. The methods is relatively fast, cost effective, and amenable to quantitative analysis of uncertainty. Optionally, the method allows statistical determination of best-fit values for the Van Genuchten capillary parameters (n, α_oil-water and α_oil-air), residual water saturation and ANAPL density. The sensitivity of the method was investigated by fitting field LNAPL saturation profiles and then determining the variation in misfit (mean square residual) as a function of parameter value for each parameter. Using field data from a sandy aquifer, the fitting statistics were found to be highly sensitive to LNAPL density, α_oil-water and α_oil-air moderately sensitive to the Van Genuchten n value, and weakly sensitive to residual water saturation. The regression analysis also provides information that can be used to estimate uncertainty in the estimated parameters, which can then be used to estimate uncertainty in calculated values of specific volume.     

Cryogenic Core Collection (C3) from Unconsolidated Subsurface Media

We evaluated tools and methods for in situ freezing of cores in unconsolidated subsurface media. Our approach, referred to as cryogenic core collection (C₃), has key aspects that include downhole circulation of liquid nitrogen (LN) via a cooling system, strategic use of thermal insulation to focus cooling into the core, and controlling LN back pressure to optimize cooling. Two cooling systems (copper coil and dual‐wall cylinder) are described. For both systems, the time to freeze a single 2.5‐foot (76‐cm) long by 2.5‐inch (63‐mm) diameter core is 5 to 7 min. Frozen core collection rates of about 30 feet/day (10 m/day) were achieved at two field sites, one impacted by petroleum‐based light nonaqueous phase liquids (LNAPLs) and the other by chlorinated solvents. Merits of C₃ include (1) improved core recovery, (2) potential control of flowing sand, and (3) improved preservation of critical sediment attributes. Development of the C₃ method creates novel opportunities to characterize sediment with respect to physical, chemical, and biological properties. For example, we were able to resolve water, LNAPL, and gas saturations above and below the water table. By eliminating drainage of water, gas and LNAPL saturations in the range of 6 to 23% and 1 to 3% of pore space, respectively, were measured in LNAPL‐impacted intervals below the water table.     

DNAPL accumulation in wells and DNAPL recovery from wells: Model development and application to a laboratory study

Dense nonaqueous phase liquid (DNAPL) accumulation and recovery from wells cannot be accurately modeled through typical pressure or flux boundary conditions due to gravity segregation of water and DNAPL in the wellbore, the effects of wellbore storage, and variations of wellbore inflow and outflow rates with depth, particularly in heterogeneous formations. A discrete wellbore formulation is presented for numerical modeling of DNAPL accumulation in observation wells and DNAPL removal from recovery wells. The formulation includes fluid segregation, changing water and DNAPL levels in the well and the corresponding changes in fluid storage in the wellbore. The method was added to a three-dimensional finite difference model (CompSim) for three phase (water, gas, DNAPL) flow. The model predictions are compared to three-dimensional pilot scale experiments of DNAPL (benzyl alcohol) infiltration, redistribution, recovery, and water flushing. Model predictions match experimental results well, indicating the appropriateness of the model formulation. Characterization of mixing in the extraction well is important for predicting removal of highly soluble organic compounds like benzyl alcohol. A sensitivity analysis shows that the incorporation of hysteresis is critical for accurate prediction. Among the multiphase flow and transport parameters required for modeling, results are most sensitive to soil intrinsic permeability.     

Use of LIF for Real-Time In-Situ Mixed NAPL Source Zone Detection

The site characterization and analysis cone penetrometer system (SCAPS), equipped with realtime fluorophore detection capabilities, was used to delineate subsurface contaminant releases in an area where plating shop waste was temporarily stored. Records indicated that various nonaqueous phase liquids (NAPLs) were released at the site. The investigators advanced the SCAPS laser-induced fluorescence (LIF) sensor to depths beneath the water table of the principal water-bearing zone. The water table was located approximately 6 feet (1.8 m) below ground surface (bgs) across the site. Fluorescence, attributed to fuel compounds commingled with chlorinated solvents, was observed at depths ranging from 4.0 to 11.5 feet (1.2 to 3.5 m) bgs. Fluorescence, attributed to naturally occurring organic materials (by process of elimination and spectral characteristics) commingled with chlorinated solvent constituents, was observed at depths ranging from approximately 13 to 40 feet (4.0 to 12.2 m) bgs. Fluorescence responses from compounds confirmed to be commingled with chlorinated solvents indicates that the SCAPS fluorophore detection system is capable of indirectly delineating vadose zone and subaqueous chlorinated solvents and other dense nonaqueous phase liquids (DNAPLs) at contaminant release sites. This confirmation effort represents the first documented account of the successful application of LIF to identify a mixed DNAPL/LNAPL source zone.     

Numerical examination of the factors controlling DNAPL migration through a single fracture

The migration of five dense nonaqueous phase liquids (DNAPLs) through a single fracture in a clay aquitard was numerically simulated with the use of a compositional simulator. The effects of fracture aperture, fracture dip, matrix porosity, and matrix organic carbon content on the migration of chlorobenzene, 1,2-dichloroethylene, trichloroethylene, tetra-chloroethylene, and 1,2-dibromoethane were examined. Boundary conditions were chosen such that DNAPL entry into the system was allowed to vary according to the stresses applied. The aperture is the most important factor of those studied controlling the migration rate of DNAPL through a single fracture embedded in a clay matrix. Loss of mass to the matrix through diffusion does not significantly retard the migration rate of the DNAPL, particularly in larger aperture fractures (e.g., 50 microm). With time, the ratio of diffusive loss to the matrix to DNAPL flux into the fracture approaches an asymptotic value lower than unity. The implication is that matrix diffusion cannot arrest the migration of DNAPL in a single fracture. The complex relationships between density, viscosity, and solubility that, to some extent, govern the migration of DNAPL through these systems prevent accurate predictions without the use of numerical models. The contamination potential of the migrating DNAPL is significantly increased through the transfer of mass to the matrix. The occurrence of opposite concentration gradients within the matrix can cause dissolved phase contamination to exist in the system for more than 1000 years after the DNAPL has been completely removed from the fracture.     

Multifluid flow in bedded porous media: laboratory experiments and numerical simulations

Understanding light nonaqueous-phase liquid (LNAPL) movement in heterogeneous vadose environments is important for effective remediation design. We investigated LNAPL movement near a sloping fine- over coarse-grained textural interface, forming a capillary barrier. LNAPL flow experiments were performed in a glass chamber (50 cm×60 cm×1.0 cm) using two silica sands (12/20 and 30/40 sieve sizes). Variable water saturations near the textural interface were generated by applying water uniformly to the sand surface at various flow rates. A model LNAPL (Soltrol® 220) was subsequently released at two locations at the sand surface. Visible light transmission was used to quantitatively determine water saturations prior to LNAPL release and to observe LNAPL flow paths. Numerical simulations were performed using the Subsurface Transport Over Multiple Phases (STOMP) simulator, employing two nonhysteretic relative permeability–saturation–pressure (k–S–P) models. LNAPL movement strongly depended on the water saturation in the fine-grained sand layer above the textural interface. In general, reasonable agreement was found between observed and predicted water saturations near the textural interface and LNAPL flow paths. Discrepancies between predictions based on the van Genuchten/Mualem (VGM) and Brooks–Corey/Burdine (BCB) k–S–P models existed in the migration speed of the simulated LNAPL plume and the LNAPL flow patterns at high water saturation above the textural interface. In both instances, predictions based on the BCB model agreed better with experimental observations than predictions based on the VGM model. The results confirm the critical role water saturation plays in determining LNAPL movement in heterogeneous vadose zone environments and that accurate prediction of LNAPL flow paths depends on the careful selection of an appropriate k–S–P model.     

Low frequency complex conductivity measurements of microcrack properties

The frequency dependence of complex electrical conductivity in the IP frequency range (10^–3 to 10³ Hertz) has been investigated for a variety of microcracked rocks from the German continental deep drilling project (KTB), Northern Bavaria. The laboratory measurements were made with a computer controlled four-electrode system on plugs saturated with brine of different salinity. It has been found that the complex nature of the conductivity is caused solely by the capacitive behaviour of the interlayer region between the solid matrix and the electrolytic pore solution. The resulting main feature of the conductivity spectra is a constant phase angle over the investigated frequency range combined with a nearly identical power law frequency dependence of the real as well as the imaginary parts. The low-frequency exponent is in the order of about 0 to 0.05. It is related to common IP-parameters. The relationships between the frequency exponent and microcrack properties are of special interest. The results of the study show that the frequency exponent is (1) proportional to the surface area to porosity ratio, (2) inversely proportional to water salinity, and (3) dependent on water composition. Complex conductivity measurements allow an uncomplicated separation of electrical volume and interface effects. Moreover, the results suggest that determination of specific surface area of microcracked rocks directly from complex electrical measurements can be made.     

Investigation and Remediation of a 1,2–Dichloroethane Spill Part I: Short and Long-Term Remediation Strategies

Release of an estimated 150,000 gallons (568,000 L).of 1.2–dichloroethane (EDC) from a buried pipeline into a ditch and surrounding soil resulted in shallow subsurface contamination of a Gulf Coast site. Short-term remediation included removal of EDC DNAPI. (dense nonaqueous phase liquid) by dredging and vacuuming the ditch, and by dredging the river where the ditch discharged. EDC saturation in shallow impacted sediments located beneath the ditch was at or below residual saturation and these sediments were therefore left in place. The ditch was lined, backfilled, and capped. Long-term remediation includes EDC DNAPL recovery and hydraulic containment from the shallow zone with long-term monitoring of the shallow, intermediate, and deep (200 foot) aquifers. Ground water, DNAPL., and dissolved phase models were used to guide field investigations and the selection of an effective remedial action strategy. The DNAPL. modeling was conducted for a two-dimensional vertical cross section of the site, and included the three aquifers separated by two aquitards with microfractures. These aquitards were modeled using a dual porosity approach. Matrix and fracture properties of the aquitards used for DNAPL modeling were determined from small-scale laboratory properties. These properties were consistent with effective hydraulic conductivity determined from ground water flow modeling. A sensitivity analysis demonstrated that the vertical migration of EDC was attenuated by dissolution of EDC into the matrix of the upper aquitard. When the organic/water entry pressure of the aquitard matrix, or the solubility of EDC were decreased to unrealislically low values. EDC DNAPL. accumulated in the aquifer below the upper aquitard.
EDC DNALM, did not reach the regional (deepest) aquifer in any of the cases modeled. The limited extent of vertical EDC migration predicted is supported by ground water monitoring conducted over the four years since the spill.     

Identification and Assessment of Confined and Perched LNAPL Conditions

Although confined and perched light nonaqueous phase liquids (LNAPLs) have previously been recognized, the majority of technical LNAPL literature focuses on unconfined LNAPL. Little information exists regarding the appropriate use of LNAPL distribution and transmissivity data to distinguish between confined, perched, and unconfined LNAPL hydrogeological scenarios. This paper describes three case histories that illustrate how the observed behavior of LNAPL can be used to identify the hydrogeologic condition of LNAPL at a given site and improved methods for calculating LNAPL drawdown based on these hydrogeologic conditions. The assessment methodology uses routinely available data such as fluid gauging, boring lo, laser‐induced fluorescence, visual observations of soil cores, and LNAPL baildown testing. Identification of the correct LNAPL hydrogeologic condition results in more accurate LNAPL conceptual site models, improved estimates of LNAPL recovery rates and volumes, more appropriate technology applications, and improved accuracy of LNAPL remediation metrics such as LNAPL transmissivity.     

An Approach for Passive Removal of Residual LNAPL from Groundwater

Light nonaqueous phase liquids (LNAPLs) are a problematic challenge for obtaining site closure or no further action remediation sites. The source of the LNAPLs varies from leaking underground petroleum storage tanks, to manufacturing facilities where oil leaks create LNAPL accumulations beneath factory floors. Active recovery using pumping or periodic vacuum recovery from wells or sumps is used for remediation, but usually has disappointing results when LNAPL reaccumulates to thicknesses exceeding the 0.01-foot action level recognized by many states. This paper presents a simple passive approach for recovering persistent LNAPL using nonwoven hydrophobic oil absorbing cloth. The method used laboratory trials to assess physical properties of the cloth. Parameters observed and assessed included sorptive capacity and rate, buoyancy, and LNAPL wicking. It was determined that the cloth could be rolled and secured with cable ties for placement in the wells/sumps. Two placement designs were developed, one where rolled sorbent freely floated on the well/sump fluid surface and a second where the sorbent roll was placed in the fluid column at a fixed depth. Sorbents were then used at two manufacturing facilities where LNAPLs persisted for decades. In both instances, many wells/sumps were reduced to thicknesses below the action level in less than 2 months. In most wells, LNAPL did not reaccumulate. Where it did reaccumulate, it was less than 50% of the original thickness. Using laboratory-derived recovery rates, cloth sorbents could be sized to minimize placement/recovery frequency while effectively recovering LNAPL.     

Mass Flux Analysis of Abiotic Tetrachloroethene Dense Nonaqueous Phase Liquid Pool Dissolution in a Heterogeneous Flow Environment

Porous aquifer materials are often characterized by layered heterogeneities that influence groundwater flow and present complexities in contaminant transport modeling. Such flow variations also have the potential to impact the dissolution flux from dense nonaqueous phase liquid (DNAPL) pools. This study examined how these heterogeneous flow conditions affected the dissolution of a tetrachloroethene (PCE) pool in a two-dimensional intermediate-scale flow cell containing coarse sand. A steady-state mass-balance approach was used to calculate the PCE dissolution rate at three different flow rates. As expected, aqueous PCE concentrations increased along the length of the PCE pool and higher flow rates decreased the aqueous PCE concentration in the effluent. Nonreactive tracer studies at two flow rates confirmed the presence of a vertical flow gradient, with the most rapid velocity located at the bottom of the tank. These results suggest that flow focusing occurred near the DNAPL pool. Effluent PCE concentrations and pool dissolution flux rates were compared to model predictions assuming local equilibrium (LE) conditions at the DNAPL pool/aqueous phase interface and a uniform distribution of flow. The LE model did not describe the data well, even over a wide range of PCE solubility and macroscopic transverse dispersivity values. Model predictions assuming nonequilibrium mass-transfer-limited conditions and accounting for vertical flow gradients, however, resulted in a better fit to the data. These results have important implications for evaluating DNAPL pool dissolution in the field where subsurface heterogeneities are likely to be present.     

Experimental Study of the Effects of DNAPL Distribution on Mass Rebound

The release of stored dissolved contaminants from low permeability zones contributes to plume persistence beyond the time when dense nonaqueous phase liquid (DNAPL) has completely dissolved. This is fundamental to successfully meeting acceptable low concentrations in groundwater that are driven by site‐specific cleanup goals. The study goals were to assess the role of DNAPL entrapment morphology on mass storage and plume longevity. As controlled field studies are not feasible, two‐dimensional (2D) test tanks were used to quantify the significance of mass loading processes from source dissolution and stored mass rebound. A simple two‐layer soil domain representing a high permeable formation sand overlying a zone of lower permeability sand was used in the tests. DNAPL mass depletion through dissolution was monitored via X‐ray photon attenuation, and effluent samples were used to monitor the plume. These data enabled analysis of the DNAPL distribution, the dissolved plume, and the dissolved phase distribution within the low permeability layer. Tests in an intermediate tank showed that mass storage contributes substantially to plume longevity. Detectable effluent concentrations persisted long after DNAPL depletion. The small tank results indicated that the DNAPL morphology influenced the flow field and caused distinctive transport mechanisms contributing to mass storage. Zones of high DNAPL saturation at the interface between the low and high permeability layers exhibited flow bypassing and diffusion dominated transport into the low permeability layer. In the absence of a highly saturated DNAPL zone near the soil interface the contaminant penetrated deeper into the low permeability layer caused by a combination of advection and diffusion.