Mass-removal and mass-flux-reduction behavior for idealized source zones with hydraulically poorly-accessible immiscible liquid

A series of flow-cell experiments was conducted to investigate aqueous dissolution and mass-removal behavior for systems wherein immiscible liquid was non-uniformly distributed in physically heterogeneous source zones. The study focused specifically on characterizing the relationship between mass flux reduction and mass removal for systems for which immiscible liquid is poorly accessible to flowing water. Two idealized scenarios were examined, one wherein immiscible liquid at residual saturation exists within a lower-permeability unit residing in a higher-permeability matrix, and one wherein immiscible liquid at higher saturation (a pool) exists within a higher-permeability unit adjacent to a lower-permeability unit. The results showed that significant reductions in mass flux occurred at relatively moderate mass-removal fractions for all systems. Conversely, minimal mass flux reduction occurred until a relatively large fraction of mass (>80%) was removed for the control experiment, which was designed to exhibit ideal mass removal. In general, mass flux reduction was observed to follow an approximately one-to-one relationship with mass removal. Two methods for estimating mass-flux-reduction/mass-removal behavior, one based on system-indicator parameters (ganglia-to-pool ratio) and the other a simple mass-removal function, were used to evaluate the measured data. The results of this study illustrate the impact of poorly accessible immiscible liquid on mass-removal and mass-flux processes, and the difficulties posed for estimating mass-flux-reduction/mass-removal behavior.     

Nonideal transport of reactive contaminants in heterogeneous porous media: 7. distributed-domain model incorporating immiscible-liquid dissolution and rate-limited sorption/desorption

The purpose of this work is to present a distributed-domain mathematical model incorporating the primary mass-transfer processes that mediate the transport of immiscible organic liquid constituents in water-saturated, locally heterogeneous porous media. Specifically, the impact of grain/pore-scale heterogeneity on immiscible-liquid dissolution and sorption/desorption is represented in the model by describing the system as comprising a continuous distribution of mass-transfer domains. With this conceptualization, the distributions of the initial dissolution rate coefficient and the sorption/desorption rate coefficient are represented as probability density functions. Several sets of numerical experiments are conducted to examine the effects of heterogeneous dissolution and sorption/desorption on contaminant transport and elution. Four scenarios with different combinations of uniform/heterogeneous rate-limited dissolution and uniform/heterogeneous rate-limited sorption/desorption are evaluated. The results show that both heterogeneous rate-limited sorption/desorption and heterogeneous rate-limited dissolution can significantly increase the time or pore volumes required to elute immiscible-liquid constituents from a contaminated porous medium. However, sorption/desorption has minimal influence on elution behavior until essentially all of the immiscible liquid has been removed. For typical immiscible-liquid constituents that have relatively low sorption, the asymptotic elution tailing produced by heterogeneous rate-limited sorption/desorption begins at effluent concentrations that are several orders of magnitude below the initial steady-state concentrations associated with dissolution of the immiscible liquid. Conversely, the enhanced elution tailing associated with heterogeneous rate-limited dissolution begins at concentrations that are approximately one-tenth of the initial steady-state concentrations. Hence, dissolution may generally control elution behavior of immiscible-liquid constituents in cases wherein grain/pore-scale heterogeneity significantly influences both dissolution and sorption/desorption.     

Evaporative mass transfer behavior of a complex immiscible liquid

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.     

Source-zone characterization of a chlorinated-solvent contaminated Superfund site in Tucson, AZ

An extensive site-characterization project was conducted at a large chlorinated-solvent contaminated Superfund site in Tucson, AZ. The project consisted of several components, including traditional site-characterization activities, tracer tests, laboratory experiments conducted with core material collected from the site, and mathematical modeling. The primary focus of the work presented herein is the analysis of induced-gradient contaminant elution tests conducted in a source zone at the site, investigation of the potential occurrence of immiscible liquid in the saturated zone, characterization of the relationship between mass flux reduction and mass removal, and evaluation of the impact of source-zone management on site remediation. The results of the present study, along with those of prior work, indicate that immiscible liquid is likely present in the saturated zone at the site source zones. Extensive tailing and rebound was observed for the contaminant-elution tests, indicating nonideal transport and mass-transfer behavior. The elution data were analyzed with a source-zone-scale mathematical model, and the results indicated that nonideal immiscible-liquid dissolution was the primary cause of the observed behavior. The time-continuous relationship between mass flux reduction and mass removal associated with the plume-scale pump-and-treat operation exhibited an initial large drop in mass flux with minimal mass removed, followed by a period of minimal mass flux reduction and a second period of large reduction. This behavior reflects the impact of both source-zone and aqueous-plume mass removal dynamics. Ultimately, a greater than 90% reduction in mass flux was achieved for a mass removal of approximately 50%. The influence of source-zone management on site remediation was evaluated by conducting two predictive simulations, one for which the source zones were controlled and one for which they were not. A plume-scale model was used to simulate the composite contaminant concentrations associated with groundwater extracted with the pump-and-treat system, which were compared to measured data. The information generated from this study was used to enhance the site conceptual model, help optimize operation of the pump-and-treat system, and evaluate the utility of source-zone remediation.     

Two-dimensional laboratory simulation of LNAPL infiltration and redistribution in the vadose zone

A quantitative two-dimensional laboratory experiment was conducted to investigate the immiscible flow of a light non-aqueous phase liquid (LNAPL) in the vadose zone. An image analysis technique was used to determine the two-dimensional saturation distribution of LNAPL, water and air during LNAPL infiltration and redistribution. Vertical water saturation variations were also continuously monitored with miniature resistivity probes. LNAPL and water pressures were measured using hydrophobic and hydrophilic tensiometers. This study is limited to homogeneous geological conditions, but the unique experimental methods developed will be used to examine more complex systems. The pressure measurements and the quantification of the saturation distribution of all the fluids in the entire flow domain under transient conditions provide quantitative data essential for testing the predictive capability of numerical models. The data are used to examine the adequacy of the constitutive pressure-saturation relations that are used in multiphase flow models. The results indicate that refinement of these commonly used hydraulic relations is needed for accurate model prediction. It is noted in particular that, in three-fluid phase systems, models should account for the existence of a residual NAPL saturation occurring after NAPL drainage. This is of notable importance because residual NAPL can act as a non negligible persistent source of contamination.     

Assessing performance and closure for soil vapor extraction: integrating vapor discharge and impact to groundwater quality

Soil vapor extraction (SVE) is typically effective for removal of volatile contaminants from higher-permeability portions of the vadose zone. However, contamination in lower-permeability zones can persist due to mass transfer processes that limit the removal effectiveness. After SVE has been operated for a period of time and the remaining contamination is primarily located in lower-permeability zones, the remedy performance needs to be evaluated to determine whether the SVE system should be optimized, terminated, or transitioned to another technology to replace or augment SVE. Numerical modeling of vapor-phase contaminant transport was used to investigate the correlation between measured vapor-phase mass discharge, MF(r), from a persistent, vadose-zone contaminant source and the resulting groundwater contaminant concentrations. This relationship was shown to be linear, and was used to directly assess SVE remediation progress over time and to determine the level of remediation in the vadose zone necessary to protect groundwater. Although site properties and source characteristics must be specified to establish a unique relation between MF(r) and the groundwater contaminant concentration, this correlation provides insight into SVE performance and support for decisions to optimize or terminate the SVE operation or to transition to another type of treatment.     

Simulation of organic liquid flow in porous media using estimated and measured transport properties

Many numerical models which describe the movement of a separate organic liquid phase in the subsurface require information about the relationships between capillary pressure and saturation, and between relative permeability and saturation. An evaluation of the information available for these relationships suggests that substantial discrepancies may be introduced into simulations if estimated, rather than measured, data are employed. The purpose of this study was to quantify these deviations. Two-phase displacement simulations were performed in one and two dimensions for several organic liquid-water systems. Both constant-head and constant-flux boundary conditions were employed at a variety of flow rates and time scales, using both measurements and estimates of capillary pressure and relative permeability for a sandy aquifer material. The results demonstrate that the use of estimated transport relationships produces significantly different predictions of organic liquid migration. The magnitude of the deviations between predictions may be as high as 25% or more after relatively short displacement periods, depending on the boundary conditions of the simulated scenario, as well as on the physical characteristics of the two-phase system. For the systems examined, most of the deviations resulted from the estimates for relative permeability to the organic liquid. Thus, improved methods for the estimation of the relative permeability to the organic liquid are needed to reduce the uncertainty in displacement simulations.     

Simplified contaminant source depletion models as analogs of multiphase simulators

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.     

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.     

A functional relation for field-scale nonaqueous phase liquid dissolution developed using a pore network model

A pore network model with cubic chambers and rectangular tubes was used to estimate the nonaqueous phase liquid (NAPL) dissolution rate coefficient, Kdissai, and NAPL/water total specific interfacial area, ai. Kdissai was computed as a function of modified Peclet number (Pe') for various NAPL saturations (SN) and ai during drainage and imbibition and during dissolution without displacement. The largest contributor to ai was the interfacial area in the water-filled corners of chambers and tubes containing NAPL. When Kdissai was divided by ai, the resulting curves of dissolution coefficient, Kdiss versus Pe' suggested that an approximate value of Kdiss could be obtained as a weak function of hysteresis or SN. Spatially and temporally variable maps of Kdissai calculated using the network model were used in field-scale simulations of NAPL dissolution. These simulations were compared to simulations using a constant value of Kdissai and the empirical correlation of Powers et al. [Water Resour. Res. 30(2) (1994b) 321]. Overall, a methodology was developed for incorporating pore-scale processes into field-scale prediction of NAPL dissolution.     

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.     

Simple screening models of NAPL dissolution in the subsurface

Three simple screening models of nonaqueous phase liquid (NAPL) dissolution in the subsurface are proposed based on the NAPL mass conservation and the assumption of proportionality between the residual NAPL source zone concentration and the remaining residual NAPL mass. The purpose of the proposed models is to predict the solute concentration in the zone of the residual NAPL as a result of dissolution. The predicted source zone concentration decrease is used to simulate and account for the decrease of dissolution rate with time. The proposed simple NAPL dissolution models enable the pseudo-equilibrium formulation to be used and therefore the numerical simulations for field application problems can be simplified compared to the non-equilibrium counterpart. With proper choice of empirical parameters, the proposed simple screening models can work as well as more complex dissolution rate correlation models, such as that of Imhoff et al. [Water Resour. Res. 30 (1994) 307-320]. It is found that the proposed models are very good for quantifying non-equilibrium dissolution, which is characterized by tailing of breakthrough curves. The models are especially useful for situations of small residual NAPL saturation, which are typical for many field applications.     

The influence of field-scale heterogeneity on the infiltration and entrapment of dense nonaqueous phase liquids in saturated formations

Numerical simulations are used for the systematic exploration of the migration and entrapment of dense nonaqueous phase liquids (DNAPLs) in heterogeneous formations. Ensembles of realizations of random, spatially correlated permeability fields are generated and employed in model simulations of a spill event. Statistical techniques are then used to quantify the sensitivity of model predictions to input parameters, thereby identifying the parameters or processes that may be of primary importance in the determination of organic liquid distributions in heterogeneous systems. Results of the study indicate that the most critical factors in modeling organic entrapment include the spill release rate, reliable estimates of the mean, variance, and vertical correlation scale of the formation permeability, and an accurate representation of the correlation between the capillary pressure–saturation function and the permeability. In contrast, the hydraulic gradient and cross-correlation of residual saturations with permeabilities are found to have only minor influence on organic liquid distributions in such heterogeneous formations.     

Investigation of surfactant-enhanced dissolution of entrapped nonaqueous phase liquid chemicals in a two-dimensional groundwater flow field.

Because of their low solubility, waste chemicals in the form of nonaqueous phase liquids (NAPLs) that are entrapped in subsurface formations act as long-term sources of groundwater contamination. In the design of remediation schemes that use surfactants, it is necessary to estimate the mass transfer rate coefficients under multi-dimensional flow fields that exit at field sites. In this study, we investigate mass transfer under a two-dimensional flow field to obtain an understanding of the basic mechanisms of surfactant-enhanced dissolution and to quantify the mass transfer rates. Enhanced dissolution experiments in a two-dimensional test cell were conducted to measure rates of mass depletion from entrapped NAPLs to a flowing aqueous phase containing a surfactant. In situ measurement of transient saturation changes using a gamma attenuation system revealed dissolution patterns that are affected by the dimensionality of the groundwater flow field. Numerical modeling of local flow fields that changed with time, due to depletion of NAPL sources, enabled the examination of the basic mechanisms of NAPL dissolution in complex groundwater systems. Through nonlinear regression analysis, mass transfer rates were correlated to porous media properties, NAPL saturation and aqueous phase velocity. Results from the experiments and numerical analyses were used to identify deficiencies in existing methods of analysis that uses assumptions of one-dimensional flow, homogeneity of aquifer properties, local equilibrium and idealized transient mass transfer.     

Relationship between mass-flux reduction and source-zone mass removal: analysis of field data

The magnitude of contaminant mass-flux reduction associated with a specific amount of contaminant mass removed is a key consideration for evaluating the effectiveness of a source-zone remediation effort. Thus, there is great interest in characterizing, estimating, and predicting relationships between mass-flux reduction and mass removal. Published data collected for several field studies were examined to evaluate relationships between mass-flux reduction and source-zone mass removal. The studies analyzed herein represent a variety of source-zone architectures, immiscible-liquid compositions, and implemented remediation technologies. There are two general approaches to characterizing the mass-flux-reduction/mass-removal relationship, end-point analysis and time-continuous analysis. End-point analysis, based on comparing masses and mass fluxes measured before and after a source-zone remediation effort, was conducted for 21 remediation projects. Mass removals were greater than 60% for all but three of the studies. Mass-flux reductions ranging from slightly less than to slightly greater than one-to-one were observed for the majority of the sites. However, these single-snapshot characterizations are limited in that the antecedent behavior is indeterminate. Time-continuous analysis, based on continuous monitoring of mass removal and mass flux, was performed for two sites, both for which data were obtained under water-flushing conditions. The reductions in mass flux were significantly different for the two sites (90% vs. approximately 8%) for similar mass removals ( approximately 40%). These results illustrate the dependence of the mass-flux-reduction/mass-removal relationship on source-zone architecture and associated mass-transfer processes. Minimal mass-flux reduction was observed for a system wherein mass removal was relatively efficient (ideal mass-transfer and displacement). Conversely, a significant degree of mass-flux reduction was observed for a site wherein mass removal was inefficient (non-ideal mass-transfer and displacement). The mass-flux-reduction/mass-removal relationship for the latter site exhibited a multi-step behavior, which cannot be predicted using some of the available simple estimation functions.     

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

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

Biodegradation during contaminant transport in porous media: 3. Apparent condition-dependency of growth-related coefficients

The biodegradation of organic contaminants in the subsurface has become a major focus of attention, in part, due to the tremendous interest in applying in situ biodegradation and natural attenuation approaches for site remediation. The biodegradation and transport of contaminants is influenced by a combination of microbial and physicochemical properties and processes. The purpose of this paper is to investigate the impact of hydrodynamic residence time, substrate concentration, and growth-related factors on the simulation of contaminant biodegradation and transport, with a specific focus on potentially condition-dependent growth coefficients. Two sets of data from miscible-displacement experiments, performed with different residence times and initial solute concentrations, were simulated using a transport model that includes biodegradation described by the Monod nonlinear equations and which incorporates microbial growth and oxygen limitation. Two variations of the model were used, one wherein metabolic lag and cell transport are explicitly accounted for, and one wherein they are not. The magnitude of the maximum specific growth rates obtained from calibration of the column-experiment results using the simpler model exhibits dependency on pore-water velocity and initial substrate concentration (C0) for most cases. Specifically, the magnitude of micron generally increases with increasing pore-water velocity for a specific C0, and increases with decreasing C0 for a specific pore-water velocity. Conversely, use of the model wherein observed lag and cell elution are explicitly accounted for produces growth coefficients that are similar, both to each other and to the batch-measured value. These results illustrate the potential condition-dependency of calibrated coefficients obtained from the use of models that do not account explicitly for all pertinent processes influencing transport of reactive solutes.     

Comparison of the solution behaviour of a pyrite-calcite mixture in batch and unsaturated sand column

A successful application of reaction transport algorithms to calculate the chemical evolution of natural systems requires accurate methods to compute the rates of mineral/fluid surface reactions. Regarding the transport of radio-nuclides in mining dumps the dissolution of minerals is of special importance. Using a kinetic rate law of the mineral dissolution verified for unsaturated conditions will allow a realistic modelling of the mineral weathering in the environment. Dissolution rates of minerals in an aqueous solution are determined by several characteristics. These are surface reaction rates, morphology of the mineral's surface and, in case it is the unsaturated zone, the degree of the water saturation. For this process, the quantity of the particle surfaces which are in contact with percolating water is most decisive. In order to study the differences of mineral dissolution under saturated and unsaturated conditions batch and column experiments were carried out with a pyrite-calcite mixture. The experimental results were verified by calculations. Comparing the dissolution in batch with those in the column experiment, which was performed with a water flow velocity of 0.64 cm/day and was analyzed in the region of a water saturation of 0.11, one can conclude that only a small portion of about 5% of the grain surface is chemically reactive in this unsaturated flow.     

DNAPL source depletion: linking architecture and flux response

The relationship between dense non-aqueous phase liquid (DNAPL) mass reduction and contaminant mass flux was investigated experimentally in four model source zones. The flow cell design for the experiments featured a segmented extraction well that allowed for analysis of spatially resolved flux information. This flux information was coupled with image analysis of the NAPL spatial distribution to investigate the relationship between flux and the up-gradient NAPL architecture. Results indicate that in the systems studied, the relationship between DNAPL mass reduction and contaminant mass flux was primarily controlled by the NAPL architecture. A specific definition of NAPL architecture was employed where the source zone is resolved into a collection of streamtubes with spatial variability in NAPL saturation along each streamtube integrated and transformed into an effective NAPL content for each streamtube. The distribution of NAPL contents among the streamtubes (NAPL architecture) controlled dissolution dynamics. Two simplified models, a streamtube model and an effective Damkohler number model, were investigated for their ability to simulate dissolution dynamics.