Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.     

Sorption of hydrophobic organic pollutants in saturated soil systems

Sorption equilibria and rates were characterized for a matrix of four aquifer sands and two slightly to moderately hydrophobic organic solutes (nitrobenzene and lindane), and the effects of sorption on the behavior of these solutes in saturated systems of the soils were determined. Experimental data were used to test and evaluate a variety of mathematical models for predicting contaminant fate and transport in groundwater systems.Observed equilibrium relationships between soil and solution phase solute concentrations were found to be described best by the nonlinear Freundlich isotherm model. It was further determined that the sorption process in the systems tested is rate controlled, requiring several days to approach equilibrium in completely mixed batch reactors. Subsequent modeling of solute transport in continuous flow soil column reactors was found to be most successful when rate-controlled models were used, the best results were obtained with a dual-resistance model incorporating the coupled mass transport steps of boundary-layer and intraparticle diffusion.     

In situ modification of an aquifer material by a cationic surfactant to enhance retardation of organic contaminants

Sorption of hexadecyltrimethylammonium chloride (HDTMA), a cationic surfactant, on aquifer material from Columbus AFB, Mississippi, U.S.A., was examined. Transport studies using flow-through columns and a box model aquifer showed that an almost stationary zone of HDTMA-modified aquifer material could be produced in situ without a significant decrease in hydraulic conductivity.Perchloroethylene (PCE) and naphthalene sorption isotherms on the HDTMA-modified aquifer material were linear, and sorption coefficients were increased by over two orders of magnitude relative to the unmodified material. The retardation of PCE by insitu emplaced HDTMA zones within a column was examined. Agreement between batch- and column-derived sorption coefficients and breakthrough curve symmetry indicates that local equilibrium was attained. Significant retardation of a naphthalene plume by an in situ emplaced surfactant zone was demonstrated in the box model aquifer system.The experimental results indicate that it is feasible to create in situ a sorbent zone within an aquifer using cationic surfactants. In most situations, the sorbent zone concept needs to be coupled with contaminant degradation processes for sorbent emplacement to be a practical tool in the remediation of groundwater contamination sites. Sorbent zones may be of benefit in the engineering of suitable environments for microbial or abiotic degradation reactions and by providing time slow reactions to occur.     

Assessing the impacts of partial mass depletion in DNAPL source zones I. Analytical modeling of source strength functions and plume response

Analytical solutions are developed for approximating the time-dependent contaminant discharge from DNAPL source zones undergoing dissolution and other decay processes. The source functions assume a power relationship between source mass and chemical discharge and can consider partial DNAPL source remediation (depletion) at any time after the initial DNAPL release. The source functions are used as a time-dependent boundary condition in an idealized chemical transport model to develop leading order approximations of the plume response to DNAPL source removal. The results suggest that partial DNAPL remediation does not tend to have a dramatic impact on the maximum extent of the plume if very low concentration values are used to define the plume boundaries. However, the solutions show that partial DNAPL removal from the source zone is likely to lead to large reductions in plume concentrations and mass, and it reduces the longevity of the plume. When the mass discharge from the source zone is linearly related to the DNAPL mass, it is shown that partial DNAPL depletion leads to linearly proportional reductions in the plume mass and concentrations.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

Numerical experiments and field results on the size of steady state plumes

Contaminated groundwater poses a serious risk for drinking water supplies. Under certain conditions, however, groundwater contamination remains restricted to a tolerable extent because of natural attenuation processes. We present an innovative approach to evaluate the size of these so-called steady-state plumes by 2-D and 1-D modelling in homogeneous aquifers. If longitudinal mixing is negligible, scenarios can be modelled in a simplified way using a 1-D domain vertical to the direction of flow. We analysed the sensitivity of the plume length with respect to biodegradation kinetics, flow velocity, transverse vertical dispersivity alphat, the source and aquifer geometry and reaction stoichiometry. Our findings indicate that for many readily biodegradable compounds transverse-dispersive mixing rather than reaction kinetics is the limiting factor for natural attenuation. Therefore, if alphat, aquifer and source geometry and concentrations of electron acceptors and donors are known, the length of the steady state contaminant plume can be predicted. The approach is validated under field conditions for an ammonium plume at a former landfill site in SW Germany.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

Travel time and trajectory moments of conservative solutes in two-dimensional convergent flows

We address advective transport of a solute traveling toward a single pumping well in a two-dimensional randomly heterogeneous aquifer. The two random variables of interest are the trajectory followed by an individual particle from the injection point to the well location and the particle travel time under steady-state conditions. Our main objective is to derive the predictors of trajectory and travel time and the associated uncertainty, in terms of their first two statistical moments (mean and variance). We consider a solute that undergoes mass transfer between a mobile and an immobile zone. Based on Lawrence et al. [Lawrence, A.E., Sánchez-Vila, X., Rubin, Y., 2002. Conditional moments of the breakthrough curves of kinetically sorbing solute in heterogeneous porous media using multirate mass transfer models for sorption and desorption. Water Resour. Res. 38 (11), 1248, doi:10.1029/2001WR001006.], travel time moments can be written in terms of those of a conservative solute times a deterministic quantity. Moreover, the moments of solute particles trajectory do not depend on mass transfer processes. The resulting mean and variance of travel time and trajectory for a conservative species can be written as functions of the first, second moments and cross-moments of trajectory and velocity components. The equations are developed from a consistent second order expansion in sigmaY (standard deviation of the natural logarithm of hydraulic conductivity). Our solution can be completely integrated with the moment equations of groundwater flow of Guadagnini and Neuman [Guadagnini, A., Neuman, S.P., 1999a. Nonlocal and localized analyses of conditional mean steady state flow in bounded, randomly non uniform domains 1. Theory and computational approach. Water Resour. Res. 35(10), 2999-3018.,Guadagnini, A., Neuman, S.P., 1999b. Nonlocal and localized analyses of conditional mean steady state flow in bounded, randomly non uniform domains 2. Computational examples. Water Resour. Res. 35(10), 3019-3039.], it is free of distributional assumptions regarding the log conductivity field, and formally includes conditioning. We present analytical expressions for the unconditional case by making use of the results of Riva et al. [Riva, M., Guadagnini, A., Neuman, S.P., Franzetti, S., 2001. Radial flow in a bounded randomly heterogeneous aquifer. Transport in Porous Media 45, 139-193.]. The quality of the solution is supported by numerical Monte Carlo simulations. Potential uses of this work include the determination of aquifer reclamation time by means of a single pumping well, and the demarcation of the region potentially affected by the presence of a contaminant in the proximity of a well, whenever the aquifer is very thin and Dupuit-Forchheimer assumption holds.     

Assessing the natural attenuation of organic contaminants in aquifers using plume-scale electron and carbon balances: model development with analysis of uncertainty and parameter sensitivity

A quantitative methodology is described for the field-scale performance assessment of natural attenuation using plume-scale electron and carbon balances. This provides a practical framework for the calculation of global mass balances for contaminant plumes, using mass inputs from the plume source, background groundwater and plume residuals in a simplified box model. Biodegradation processes and reactions included in the analysis are identified from electron acceptors, electron donors and degradation products present in these inputs. Parameter values used in the model are obtained from data acquired during typical site investigation and groundwater monitoring studies for natural attenuation schemes. The approach is evaluated for a UK Permo-Triassic Sandstone aquifer contaminated with a plume of phenolic compounds. Uncertainty in the model predictions and sensitivity to parameter values was assessed by probabilistic modelling using Monte Carlo methods. Sensitivity analyses were compared for different input parameter probability distributions and a base case using fixed parameter values, using an identical conceptual model and data set. Results show that consumption of oxidants by biodegradation is approximately balanced by the production of CH4 and total dissolved inorganic carbon (TDIC) which is conserved in the plume. Under this condition, either the plume electron or carbon balance can be used to determine contaminant mass loss, which is equivalent to only 4% of the estimated source term. This corresponds to a first order, plume-averaged, half-life of > 800 years. The electron balance is particularly sensitive to uncertainty in the source term and dispersive inputs. Reliable historical information on contaminant spillages and detailed site investigation are necessary to accurately characterise the source term. The dispersive influx is sensitive to variability in the plume mixing zone width. Consumption of aqueous oxidants greatly exceeds that of mineral oxidants in the plume, but electron acceptor supply is insufficient to meet the electron donor demand and the plume will grow. The aquifer potential for degradation of these contaminants is limited by high contaminant concentrations and the supply of bioavailable electron acceptors. Natural attenuation will increase only after increased transport and dilution.     

Simultaneous optimization of dense non-aqueous phase liquid (DNAPL) source and contaminant plume remediation

A framework is developed for simultaneous, optimal design of groundwater contaminant source removal and plume remediation strategies. The framework allows for varying degrees of effort and cost to be dedicated to source removal versus plume remediation. We have accounted for the presence of physical heterogeneity in the DNAPL source, since source heterogeneity controls mass release into the plume and the efficiency of source removal efforts. We considered high and low estimates of capital and operating costs for chemical flushing removal of the source, since these are expected to vary form site to site. Using the lower chemical flushing cost estimates, it is found that the optimal allocation of funds to source removal or plume remediation is sensitive to the degree of heterogeneity in the source. When the time elapsed between the source release and the implementation of remediation was varied, it was found that, except for the longest elapsed time (50,000 days), a combination of partial source removal and plume remediation was most efficient. When first-order, dissolved contaminant degradation was allowed, source removal was found to be unnecessary for the cases where the degradation rate exceeded intermediate values of the first-order rate constant. Finally, it was found that source removal became more necessary as the degree of aquifer heterogeneity increased.     

Role of back diffusion and biodegradation reactions in sustaining an MTBE/TBA plume in alluvial media

A methyl tert-butyl ether (MTBE) / tert-butyl alcohol (TBA) plume originating from a gasoline spill in late 1994 at Vandenberg Air Force Base (VAFB) persisted for over 15 years within 200 feet of the original spill source. The plume persisted until 2010 despite excavation of the tanks and piping within months after the spill and excavations of additional contaminated sediments from the source area in 2007 and 2008. The probable history of MTBE concentrations along the plume centerline at its source was estimated using a wide variety of available information, including published details about the original spill, excavations and monitoring by VAFB consultants, and our own research data. Two-dimensional reactive transport simulations of MTBE along the plume centerline were conducted for a 20-year period following the spill. These analyses suggest that MTBE diffused from the thin anaerobic aquifer into the adjacent anaerobic silts and transformed to TBA in both aquifer and silt layers. The model reproduces the observation that after 2004 TBA was the dominant solute, diffusing back out of the silts into the aquifer and sustaining plume concentrations much longer than would have been the case in the absence of such diffusive exchange. Simulations also suggest that aerobic degradation of MTBE or TBA at the water table in the overlying silt layer significantly affected concentrations of MTBE and TBA by limiting the chemical mass available for back diffusion to the aquifer.     

Progression of natural attenuation processes at a crude-oil spill site: I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.     

Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

A controlled field experiment on groundwater contamination by a multicomponent DNAPL: dissolved-plume retardation

A natural gradient emplaced-source (ES) controlled field experiment was conducted at the Borden aquifer research site, Ontario, to study the transport of dissolved plumes emanating from residual dense nonaqueous-phase liquid (DNAPL) source zones. The specific objective of the work presented here is to determine the effects of solute and co-solute concentrations on sorption and retardation of dissolved chlorinated solvent-contaminant plumes. The ES field experiment comprised a controlled emplacement of a residual multicomponent DNAPL below the groundwater table and intensive monitoring of dissolved-phase plumes of trichloromethane (TCM), trichloroethylene (TCE), and perchloroethylene (PCE) plumes continuously generated in the aquifer down gradient from gradual source dissolution. Estimates of plume retardation (and dispersion) were obtained from 3-D numerical simulations that incorporated transient source input and flow regimes monitored during the test. PCE, the most retarded solute, surprisingly exhibited a retardation factor approximately 3 times lower than observed in a previous Borden tracer test by Mackay et al. [Water Resour. Res. 22 (1986) 2017] conducted approximately 150 m away. Also, an absence of temporal trend in PCE retardation contrasted with the previous Borden test. Supporting laboratory studies on ES site core indicated that sorption was nonlinear and competitive, i.e. reduced sorption of PCE was observed in the presence of TCE. Consideration of the effects of relatively high co-solute (TCE) concentration (competitive sorption) in addition to PCE concentration effects (nonlinear sorption) was necessary to yield laboratory-based PCE retardation estimates consistent with the field plume values. Concentration- and co-solute-based sorption and retardation analysis was also applied to the previous low-concentration pulse injection test of Mackay et al. [Water Resour. Res. 22 (1986) 2017] and was able to successfully predict the temporal field retardation trends observed in that test. While it is acknowledged that other "nonideal transport" effects may contribute, our analysis predicts differences in the PCE retardation magnitude and trend between the two experiments that are consistent with field observations based on the marked solute concentration differences that resulted from contrasting source conditions. Solute and co-solute concentration effects have heretofore received little attention, but may have wide significance in aquifers contaminated by point-source pollutants because many plumes contain mixed solutes over wide concentration ranges in strata that are likely subject to nonlinear sorption.     

Variability of aquifer sorption properties in a field experiment on groundwater transport of organic solutes: Methods and preliminary results

Methods to characterize the organic solute sorption distribution coefficient, organic carbon content, and specific surface area of aquifer solids from the site of a field experiment on solute transport in groundwater were refined for application to small subsamples of 10-cm depth increments taken from 5-cm diameter cores. Initial results indicate that the average sorption characteristics of the Borden aquifer do not vary appreciably along the trajectory of the solute plumes. However, the sorption distribution coefficient of tetrachloroethylene varied over nearly an order of magnitude among 10-cm depth increments in one core sample. Preliminary evidence suggests that the sorption distribution coefficients for four halogenated organic solutes vary proportionally among core strata. However, the distribution coefficients for sorption of tetrachloroethylene on various depth increments are not well correlated with either organic carbon content or specific surface area, suggesting that as yet unidentified mineral phases may play a significant role in sorption of such solutes by the sandy aquifer solids.     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Optimal design of pump-and-treat systems under uncertain hydraulic conductivity and plume distribution

In this work, we present a stochastic optimal control framework for assisting the management of the cleanup by pump-and-treat of polluted shallow aquifers. In the problem being investigated, hydraulic conductivity distribution and dissolved contaminant plume location are considered as the uncertain variables. The framework considers the subdivision of the cleanup horizon in a number of stress periods over which the pumping policy implemented until that stage is dynamically adjusted based upon new information that has become available in the previous stages. In particular, by following a geostatistical approach, we study the idea of monitoring the cumulative contaminant mass extracted from the installed recovery wells, and using these measurements to generate conditional realizations of the hydraulic conductivity field. These realizations are thus used to obtain a more accurate evaluation of the initial plume distribution, and modify accordingly the design of the pump-and-treat system for the remainder of the remedial process. The study indicates that measurements of contaminant mass extracted from pumping wells retain valuable information about the plume location and the spatial heterogeneity characterizing the hydraulic conductivity field. However, such an information may prove quite soft, particularly in the instances where recovery wells are installed in regions where contaminant concentration is low or zero. On the other hand, integrated solute mass measurements may effectively allow for reducing parameter uncertainty and identifying the plume distribution if more recovery wells are available, in particular in the early stages of the cleanup process.     

Influence of rate-limited sorption on the cleanup of layered soils by vapor extraction

The conditions under which rate-limited sorption is important for cleanup of layered soils by vapor extraction are investigated. The investigation includes two steps: (a) the cleanup time is estimated for a number of scenario cases by means of a numerical model and (b) the numerical results are approximated using analytical solutions derived for simplified models. In this way, equations are derived, which give insight into the influence of different parameters characterizing the properties of the soil, the geometry of the formation, the mass transfer mechanisms in it, and the distribution of the contaminant mass in the different phases (gas phase, water phase and solid phase). The numerical model used is based on the advection-dispersion differential equations for Darcian isothermal airflow, local equilibrium contaminant mass transfer between gas phase and soil water and first-order kinetics for mass transfer between soil water and solid phase. The numerical results are approximated combining an analytical solution to estimate cleanup time in layered formations for local equilibrium sorption, which has been presented in a previous work (J. Contam. Hydrol., 36 (1999) 105). with an analytical solution based on the well-mixed reservoir model under consideration of rate-limited sorption. The analytical approximation of the cleanup time is in reasonable agreement with the numerical results and allows its estimation with small computational effort.     

Spatial and temporal features of density-dependent contaminant transport: Experimental investigation and numerical modeling

We investigate the spatial and temporal features of variable-density contaminant plumes migration in porous materials. Our analysis is supported by novel experimental results concerning concentration profiles inside a vertical column setup that has been conceived at CEA to this aim. The experimental method relies on X-ray spectrometry, which allows determining solute profiles as a function of time at several positions along the column. The salient outcomes of the measurements are elucidated, with focus on miscible fluids in homogeneous saturated media. The role of the injected solution molarity is evidenced. As molarity increases, the solutes plume transport progressively deviates from the usual Fickian behavior, and pollutants distribution becomes skewed in the direction dictated by gravity. By resorting to a finite elements approach, we numerically solve the nonlinear equations that rule the pollutants migration: a good agreement is found between the simulated profiles and the experimental data. At high molarity, a strong dependence on initial conditions is found. Finally, we qualitatively explore the (unstable) interfacial dynamics between the dense contaminant plume and the lighter resident fluid that saturates the column, and detail its evolution for finite-duration contaminant injections.