Nonaqueous Phase Liquid Source Research Articles

Wettability hysteresis and its implications for DNAPL source zone distribution

Subsurface heterogeneity at sites contaminated with nonaqueous phase liquids (NAPLs) reduces the effectiveness of traditional remediation measures. One cause may be the increased proportion of NAPL that is hydraulically isolated due to capillary trapping in heterogeneously-wetted materials. This study examines the wettability of ten materials, ranging from minerals, such as calcite and dolomite, to carbonaceous materials, such shale and coal, in air and water, NAPL and air, and NAPL and water systems. The wettability differed depending on which phase the solid material was initially immersed in: the less crystalline solids, if initially contacted by water were water-wet, but if initially contacted by NAPL were NAPL-wet. This difference, termed here wettability hysteresis, was observed for a suite of halogenated NAPLs and was independent of equilibration time. The degree of wettability hysteresis was greatest in the NAPL and water systems, with the magnitude of the difference increasing with the carbonaceous materials. Since the degree of capillary trapping in subsurface materials is related to wettability, the phenomenon of wettability hysteresis suggests that system history is a factor that may increase the heterogeneity of NAPL source zones.

Microbial activity and distribution during enhanced contaminant dissolution from a NAPL source zone

Laboratory experiments were conducted to assess microbial reductive dechlorination in one-dimensional sand columns containing a 10 cm long source zone of uniformly distributed residual tetrachloroethene (PCE) nonaqueous phase liquid (NAPL), a 10 cm long transition zone directly down-gradient of the source zone containing some nonuniformly distributed NAPL ganglia, and a 40 cm long plume region down-gradient of the transition zone. The activity and distribution of S ulfurospirillum multivorans, a PCE-to-1,2- cis-dichloroethene ( cis-DCE) dechlorinating bacterium, was evaluated in columns containing either a mixed-NAPL (0.25 mol/mol PCE in hexadecane) or pure PCE-NAPL. Significant dechlorination of PCE to cis-DCE was observed in the mixed-NAPL column, resulting in 53% PCE-NAPL mass recovery in the effluent with PCE-NAPL dissolution enhanced by up to 13.6-fold (maximum) and 4.6-fold (cumulative) relative to abiotic dissolution. Quantitative real-time PCR targeting pceA, the PCE reductive dehalogenase gene of S. multivorans, revealed that S. multivorans cells were present in the NAPL source zone, and increased in numbers (i.e., grew) throughout the source and transition zones. In contrast, minimal reductive dechlorination and microbial growth were observed in the column containing pure PCE-NAPL, where aqueous-phase PCE concentrations reached saturation. These results demonstrate that microbial growth within NAPL source zones is possible, provided that contaminant concentrations remain below levels toxic to the dechlorinating organisms, and that microbial growth can result in significant bioenhanced NAPL dissolution.

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~ 0.01 m/day, and a gas phase that covers greater than ~ 10% of the pool surface area and is located within ~ 0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.

Biodegradation of Residual Dense Nonaqueous-Phase Liquid Tetrachloroethene: Effects on Mass Transfer

ABSTRACT The mass emissions rate of contaminants from nonaqueous-phase liquids (NAPLs) is a driving factor in remediation efforts, whether those efforts are designed to remove, transform, or stabilize the entrapped NAPL or down-gradient aqueous concentrations. Enhancement of mass flux from NAPL source zones has been previously reported in the presence of microbial reductive dechlorination activity in systems containing NAPL with a low proportion of tetrachloroethene (PCE) or a low residual saturation (e.g., 2%). The results reported here demonstrate reductive dechlorination of PCE at residual saturations of 35%, obtained under two different column flow velocities and NAPL configurations. Mass flux in biotic columns was approximately 45% greater than that in uninoculated columns, due to both the presence of daughter products and higher concentrations of PCE in the effluent from biotic columns. Daughter product concentrations were greater in columns with NAPL emplaced only in the lower quarter compared to those with NAPL throughout, and in columns run at the slower velocity. The elevated PCE concentrations in biotic column effluents suggest the influence of microbially generated surfactants, which was supported by surface tension measurements. These results demonstrate the potential significance of bioactivity within NAPL source zones on NAPL longevity and down-gradient aqueous concentrations.

Simulating the dissolution of a complex dense nonaqueous phase liquid source zone: 2. Experimental validation of an interfacial area–based mass transfer model

A multiphase flow–aqueous phase transport numerical model (DNAPL3D‐MT) is developed to simulate the dissolution of complex source zones containing both pooled and residual dense nonaqueous phase liquids (DNAPLs). The multiphase flow model (DNAPL3D) is coupled to the aqueous species transport code (MT3D) via a flexible mass transfer function, which can employ the local equilibrium assumption or the single–boundary layer expression for rate‐limited dissolution either incorporating a lumped (correlation function) coefficient or explicitly accounting for the interfacial area (IFA) between the fluids. For the latter, this work employs the thermodynamically based Explicit IFA Submodel (Grant and Gerhard, 2007), which provides IFA as a function of saturation and saturation history. A bench‐scale experiment is presented involving the complete, natural dissolution of a DNAPL source zone emplaced by a point source release into heterogeneous porous media. DNAPL3D‐MT simulations of the experiment, involving no calibration to results, are compared with the observed evolution of both (1) measured downgradient dissolved phase concentrations and (2) DNAPL source zone configuration. The model, employing a mass transfer expression equipped with the Explicit IFA Submodel, simulates the experiment more accurately than when equipped with either a local equilibrium assumption or a published empirical correlation expression. Sensitivity simulations indicate that this model validation is sensitive to a number of the key assumptions in the Submodel derivation except one: the relationship between interfacial area and residual DNAPL saturations. The employed assumption of a single mass transfer coefficient value is supported by an analysis of the evolution of Peclet numbers throughout the DNAPL source zone, which reveals that the low hydraulic gradient employed resulted in diffusion‐dominated mass transfer conditions throughout the experiment. This study suggests that simulations of global mass flux from complex DNAPL source zones are sensitive to the interrelationship of rate‐limited mass transfer and groundwater velocity (and thus aqueous phase relative permeability and DNAPL saturation) at the local scale.

Intermediate‐Scale Investigation of Nonaqueous‐Phase Liquid Architecture on Partitioning Tracer Test Performance

Partitioning interwell tracer tests (PITTs) have been proposed as a tool to characterize source zones of waste sites with chemicals entrapped in the form of nonaqueous‐phase liquids (NAPLs). This technique has the potential to be applied to NAPL source characterization of both the vadose and saturated zones, but the recent applications have been primarily focused on dense NAPLs (DNAPLs) entrapped below the water table. This study presents an intermediate‐scale experiment to investigate the applicability of the technique to heterogeneous sites with complex NAPL entrapment architecture. Tracer experiments were conducted in an intermediate‐scale test tank (4.87 by 1.21 by 0.05 m) with heterogeneity defined using the geostatistical parameters of a spatially correlated random field. Tetrachloroethene (PCE), a DNAPL, was spilled into the heterogeneous packing and was allowed to distribute naturally, creating zones of both residual and pooled entrapment. The saturation distribution of the DNAPL was determined in situ using a gamma attenuation system. Once the saturation distribution was characterized, a set of tracer tests was conducted. Results of this study demonstrate how the inversion of the tracer breakthrough concentrations provided valuable information to establish the validity of the use of equilibrium partition coefficients in situations where tracer partitioning might be controlled by nonequilibrium behavior. While our previous work quantified the estimation error introduced by the assumption of equilibrium partitioning in tracer data analysis, this study demonstrated that more accurate NAPL estimates can be obtained using effective partition coefficients in combination with inverse modeling methods upscaled for more realistic heterogeneous settings.

Combination of radon and stable isotope analysis as a tool for decision support concerning the remediation of NAPL-contaminated sites

The non-aqueous phase-liquid (NAPL)-contaminated aquifer at a major refinery site in Mexico was investigated. Owing to the depth of the contaminated aquifer section (NAPL source zone) of over 100 m below the surface, the actual aquifer material was not accessible for sampling. Information on the residual NAPL contamination of the aquifer could only be obtained indirectly by analysing groundwater samples from a few wells available at the site. To tackle the problem, an approach alternative to conventional groundwater analysis for dissolved NAPL was chosen. For evaluating the recent contamination and estimating its probable future development, the radioisotope radon-222 and the stable isotopes 13C, 34S and 18O were used as naturally occurring contamination tracers and process indicators. Radon was used as partitioning tracer for the approximate localization and semi-quantitative assessment of the NAPL source zone. The stable isotopes were used as indicators for naturally occurring biodegradation processes, which might potentially be implemented into future remediation schemes.

Hydraulic/partitioning tracer tomography for characterization of dense nonaqueous phase liquid source zones

A new technology, hydraulic/partitioning tracer tomography (HPTT), is proposed to survey spatial distributions of hydraulic properties and dense nonaqueous phase liquids (DNAPLs) in the subsurface. HPTT is nothing more than a set of multiple hydraulic/partitioning tracer tests and synthesis of all the tests to map the spatial distributions. It involves injection of water at one borehole in a source zone to create a steady state forced gradient flow field, then release of conservative/partitioning tracers at the same borehole, and monitoring heads and tracer breakthroughs at the others. The same operation is repeated using different boreholes for the water and the tracer injections. To analyze the head and tracer data obtained from the proposed tomographic survey, a joint stochastic estimator was developed. Numerical experiments were then conducted to evaluate the effectiveness of HPTT as well as the stochastic estimator. Results show that prior knowledge of hydraulic heterogeneity is critical for mapping the distribution of DNAPLs. In addition, the results suggest that the proposed HPTT in conjunction with the stochastic estimator is potentially a viable tool for high‐resolution characterization of subsurface heterogeneity and contamination.

Characterization of NAPL Source Zone Architecture and Dissolution Kinetics in Heterogeneous Porous Media Using Magnetic Resonance Imaging

A direct visualization method using magnetic resonance imaging (MRI) was developed to characterize sand grain size distribution, nonaqueous phase liquid (NAPL) source zone architecture, and aqueous flowpaths in a three-dimensional (3-D) flowcell (26.5 cm x 10.5 cm x 10.5 cm) packed with a heterogeneous distribution of five different sand fractions. All images were acquired at a resolution of 0.1875 cm x 0.1875 cm x 0.225 cm. A 1H image of pore water resolved the heterogeneous permeability field; grain size differences as small as 0.1 mm could be distinguished. A time series of 1H images of water doped with the paramagnetic tracer MnCl2 were acquired and used to obtain voxel-scale breakthrough curves. Water preferentially flowed through coarse sands before NAPL release. After NAPL release, the flow bypassed NAPLzones, and bypassing was more evident for high NAPL saturation zones. A time series of 19F images of NAPL were acquired and used to determine voxel-scale NAPL saturation (Sn) during dissolution. Results show that 93% of NAPL mass was in the coarsest sand, most NAPL was trapped as pools and not as residual ganglia, NAPL saturation increased with depth, and the NAPL dissolution front moved vertically from the top to the bottom of the flowcell during the first 170 pore volumes of waterflushed. NAPL component effluent concentrations initially increased due to the development of flow in zones with decreasing NAPL saturation. Flowpath images suggest that this occurs as NAPL transitions from pools (Sn > 0.15) to residual ganglia. The results highlight the importance of flow bypassing and provide the opportunity to develop more accurate NAPL dissolution models.

Determination of radon partition coefficients between water and organic liquids and their utilization for the assessment of subsurface NAPL contamination

The inhomogeneous distribution of radon between water and non-aqueous phase liquid (NAPL) allows for utilizing naturally occurring radon as aqueous tracer for the assessment of residual NAPL contamination of aquifers ("NAPL source zones"). For the qualitative assessment (i.e. the localization) of NAPL source zones depleted radon concentrations that occur locally in the groundwater can be used as indicator. However, quantitative estimation of the NAPL saturation of the aquifer pore space requires the knowledge of the radon partition coefficient specific for the NAPL present. While radon partition coefficients are known for a wide range of pure substances, few reliable data is available on radon partitioning into complex NAPL mixtures. At the same time, widely used NAPL mixtures, such as diesel fuel, gasoline, and kerosene, have to be named as main contaminants at many NAPL contaminated sites. The paper presents radon partition coefficients for the three NAPL mixtures mentioned, achieved by application of an analytical method based on radon partitioning between air, water, and NAPL in a closed system, which is described in detail. Based on the experimental results a respective potential theoretical approach employing the regular-solution theory of Hildebrand and Scatchard is discussed and evaluated critically. Finally, the general practical applicability of naturally occurring radon as an indicator for the quantitative evaluation of NAPL source zones is assessed through laboratory experiments carried out in NAPL-contaminated sand columns. The distinct negative correlation between radon concentration and NAPL saturation of the pore space suggests the general applicability of radon for quantitative estimation of NAPL contamination of aquifers.

Radon distribution in a gasoline-contaminated aquifer

Naturally occurring radon-222 gas in groundwater was investigated as a partitioning tracer to detect non-aqueous phase liquid (NAPL) in a gasoline-contaminated aquifer. The radon-222 activity of groundwater decreased significantly from an average of 7.38 ± 1.68 Bq L - 1 measured in monitoring wells located upgradient in the uncontaminated zone to an average of 2.30 ± 0.60 Bq L - 1 measured in monitoring wells inside the NAPL source zone. Meanwhile, the radium-226 concentrations measured in aquifer matrix were virtually homogeneous at several locations both upgradient of and inside the NAPL source zone. Furthermore, the NAPL concentration obtained from the Radon Deficit Factor agrees reasonably with the results derived from direct sampling and chemical analysis of soil samples taken from the residual NAPL source zone. The field results of this study confirmed the general applicability of groundwater radon to detect residual NAPL source zone.

Inverse Characterization of NAPL Source Zones

This work presents a possible tool for inverse characterization of NAPL (nonaqueous phase liquid) source zones in terms of contaminant mass flux. A hybrid solution technique was applied that considers contaminant transport through a vertical flux plane. The hybrid solution technique takes advantage of the robust solution capabilities of simulated annealing (SA) and the uncertainty estimation capabilities of minimum relative entropy (MRE). The coupled technique (SA-MRE) provides probability density functions and confidence intervals that would not be available from an independent SA algorithm, and they are obtained more efficiently than if provided by an independent MRE algorithm. The SA-MRE method was used to characterize a NAPL source zone that was emplaced in a three-dimensional aquifer model. When dissolution experiments were complete, the aquifer model was excavated, and the distribution of NAPL zones was recorded using digital images of excavation grids. The excavation images were compiled into a three-dimensional representation of the source zone for comparison with and validation of modeling results.

Modeling the Impact of a Benzene Source Zone on the Transport Behavior of PAHs in Groundwater

Aquifers at industrial sites are commonly characterized by a multitude of contaminant source zones. Conceivably, dissolved contaminants originating from an up-gradient residual nonaqueous phase liquid (NAPL) source zone may be transported along the groundwater flow path into another residual NAPL source zone down-gradient. However, if and how contaminants from different zones may affect one another with regard to dissolution and transport has thus far been unknown. To identify and understand such potential interactions, the numerical model BIONAPL3D was applied to simulate the behavior of six dissolved polycyclic aromatic hydrocarbons (PAHs), stemming simultaneously from an up-gradient NAPL source zone, when they encounter a down-gradient NAPL source zone. The down-gradient NAPL source zone was assumed to be a residual benzene phase with a saturation of 10%. When the dissolved PAHs entered the benzene source zone, the aqueous PAH concentrations declined significantly due to their partitioning into the residual benzene phase. As benzene rapidly dissolved intothe aqueous phase,the PAHswere resolubilized with negligible impact due to benzene co-solvency. The degree of resolubilization was much smaller than the initial loss due to partitioning into the benzene phase. Thus, the PAHs formed a new residual NAPL phase that, over time, replaced the original benzene source zone. The new NAPL phase continued to grow even after all of the benzene was dissolved. Our modeling approach is the first theoretical demonstration of a significant interaction of contaminants emanating from multiple source zones. It should be regarded as a starting point to consider source zone interactions at polluted field sites.

Plume persistence due to aquitard back diffusion following dense nonaqueous phase liquid source removal or isolation

At an industrial site on a sand aquifer overlying a clayey silt aquitard in Connecticut, a zone of trichloroethylene dense nonaqueous phase liquid (DNAPL) at the aquifer bottom was isolated in late 1994 by installation of a steel sheet piling enclosure. In response to this DNAPL isolation, three aquifer monitoring wells located approximately 330 m downgradient exhibited strong TCE declines over the next 2–3 years, from trichloroethylene (TCE) concentrations between 5000 and 30,000 μg/L to values leveling off between 200 and 2000 μg/L. TCE concentrations from analysis of vertical cores from the aquitard below the plume and also from depth‐discrete multilevel systems in the aquifer sampled in 2000 were represented in a numerical model. This shows that vertical back diffusion from the aquitard combined with horizontal advection and vertical transverse dispersion account for the TCE distribution in the aquifer and that the aquifer TCE will remain much above the MCL for centuries.

Soil Sampling in NAPL Source Zones: Challenges to Representativeness

The physical and chemical characteristics of NAPL (nonaqueous phase liquid) source zones in the subsurface present substantial challenges to the representativeness of soil samples collected for the purpose of characterizing the NAPL source. The principal challenge to representativeness arises from the extreme small-scale spatial variation in contaminant concentrations expected in most NAPL source zones. This challenge can be overcome for characterization of small-scale properties of the source zone by careful selection of sampling locations based on soil stratigraphy and field screening, and for larger-scale properties of the source zone by the collection and analysis of large-quantity soil samples and composite samples.

Comparison of Bioenhancement of Nonaqueous Phase Liquid Pool Dissolution with First- and Zero-Order Biokinetics

Dissolution is one of the key physiochemical processes controlling subsurface remediation of nonaqueous phase liquid (NAPL) pools. One process that can accelerate NAPL pool dissolution is in situ biodegradation. The bioenhancement of NAPL pool dissolution has been studied previously using an analytical solution for the case of first-order biodegradation kinetics. However, data suggest that at typical NAPL source zone concentrations, mathematical description of dissolution bioenhancement may require biokinetic models ranging from first to zero order. In this work, it was determined that an nth-order approximation could be derived using the first-order case and bioenhancement was compared under first- and zero-order conditions. Two example scenarios demonstrate that predictions of the potential magnitude of the bioenhancement effect are erroneously high when the first- and zero-order cases are incorrectly applied.

Remediation of DNAPL Source Zones with Granular Iron: Laboratory and Field Tests

Degradation of dissolved chlorinated solvents using granular iron is an established in situ technology. This paper reports on investigations into mixing iron and bentonite with contaminated soil for in situ containment and degradation of dense nonaqueous phase liquid source zones. In the laboratory, hypovials containing soil, water, bentonite, iron, and free-phase trichloroethene (TCE) were assembled. Periodic measurement of TCE, chloride, and degradation products showed progressive degradation of TCE to nondetectable levels. Subsequently, a demonstration was conducted at Canadian Forces Base Borden near Alliston, Ontario, Canada, where, in 1991, a portion of the surficial aquifer was isolated and free-phase tetrachloroethene (PCE) was introduced. Using a drill rig equipped with large-diameter mixing blades, three mixed zones were prepared containing 0%, 5%, and 10% granular iron by volume. The bentonite was added to serve as a lubricant to facilitate injection of the iron and to isolate the contaminated zone. Analysis of core samples showed reasonably uniform distributions of iron through the mixed zones. Monitoring over a 13-month period following installation showed, relative to the control, a decline in PCE concentrations to virtually nondetectable values. Reaction rates in the laboratory tests were similar to those reported in the literature, while the rate in the field test was substantially lower. The lower rate may be a consequence of mass transfer limitations under the static conditions of the field test. Results indicate that mixing iron and bentonite into source zones may be an effective means of source-zone remediation, with the particular advantage of being relatively immune to effects of geologic heterogeneity.

Controlling steam flood migration using air injection wells

Plumes of contamination emanate from nonaqueous-phase liquid sources as its constituents slowly dissolve into passing groundwater. For a large, well-characterized source, an aggressive technology such as steam flooding can accelerate cleanup. Steam is injected through a series of wells within and around a source area, and the steam zone grows radially around each injection well. The steam front drives the contamination to a system of groundwater pumping wells in the saturated zone and soil vapor extraction wells in the vadose zone. The movement of steam in the subsurface is governed primarily by soil heterogeneity and gravity. Steam is buoyant in groundwater and tends to migrate upward unless injected below a continuous confining layer. Groundwater pumping rates and vacuums typical of steam flooding are generally low compared to the steam injection rate and pressure and have limited influence over the lateral growth of the steam zone. To overcome these limitations, a system of air injection wells can be used to direct the steam zone growth. This paper presents results of sand-box experiments using air injection to prevent the outward growth of a steam zone between extraction wells with a discontinuous confining layer limiting the upward migration of steam. These experiments were numerically modeled with the multiphase nonisothermal code T2VOC. When confined vertically, the experiments and modeling show that outward migration of the steam front can be effectively controlled by placing air injection wells opposite steam injection wells. This technique can direct steam zone growth toward difficult access sources and away from areas where steam is not desired. Control of a proposed full-scale steam flood of the M-Area settling basin at the Savannah River Site was modeled using this method and the results are presented in this paper.

Influence of hydraulic property correlation on predicted dense nonaqueous phase liquid source zone architecture, mass recovery and contaminant flux

Organic liquid saturation distributions resulting from a simulated tetrachloroethene (PCE) spill were generated with alternative models of spatially varying aquifer properties for a statistically homogeneous, nonuniform sand aquifer. The distributions were analyzed to quantify DNAPL source zone characteristics and then incorporated as initial conditions for simulated PCE recovery using surfactant‐enhanced aquifer remediation (SEAR). The predicted evolution of the spatial distribution of DNAPL saturations or source zone “architectures” and associated remediation efficiencies are strongly influenced by the spatial correlation of aquifer parameters and multiphase flow constitutive relationships. Model predictions suggest that removal of 60 to 99% of entrapped PCE can reduce dissolved contaminant concentration and mass flux under natural gradient conditions by approximately two orders of magnitude. Aqueous phase contaminant flux, however, does not vary consistently as a function of the percentage of DNAPL removed, and notable differences in flux evolution were observed for models incorporating correlated versus uncorrelated capillary entry pressure and permeability fields. Simulation results demonstrate that the application of alternative models of aquifer parameter spatial variability can influence predicted DNAPL infiltration, entrapment, and recovery, even for relatively homogeneous aquifers of the type investigated here. Results also demonstrate potential benefits, in the form of reduced mass flux, accruing from partial mass removal that may not be readily predicted from analyses relying on simplified conceptual models for DNAPL source zone architecture or aquifer flow fields.

Modeling the transport of dissolved contaminants originating from a nonaqueous phase liquid source containing polycyclic aromatic hydrocarbon compounds in groundwater

A three-dimensional mathematical model is developed for simulating the transport of dissolved contaminants originating from a well-defined, multicomponent nonaqueous phase liquid (NAPL) source containing polycyclic aromatic hydrocarbon (PAH) compounds in groundwater. The dissolution process for each NAPL component is envisioned to occur in a successive series of small dissolution intervals (or pulses). The equilibrium aqueous phase concentration of each component and the source dimensions are assumed to remain constant for the duration of each dissolution interval. The model accounts for possible solidification of PAH components as the NAPL source dissolves. Aqueous phase contaminant concentrations resulting from each dissolution interval are calculated using an existing analytical solution. A synthetic PAH-rich NAPL mixture consisting of benzene and eight PAH components is used for model simulations. The model is useful for evaluation and prediction of downstream aqueous phase contaminant concentrations resulting from dissolution of a PAH-rich NAPL source. Key words: contaminant transport, groundwater, nonaqueous phase liquid (NAPL), mathematical modeling, polycyclic aromatic hydrocarbons.