Radial reactive solute transport in an aquifer–aquitard system

Radial reactive transport is investigated in an aquifer–aquitard system considering the important processes such as advection, radial and vertical dispersions for the aquifer, vertical advection and dispersion for the aquitards, and first-order biodegradation or radioactive decay. We solved the coupled governing equations of transport in the aquifer and the aquitards by honoring the continuity of concentration and mass flux across the aquifer–aquitard interfaces and recognizing the concentration variation along the aquifer thickness. This effort improved the averaged-approximation (AA) model, which dealt with radial dispersion in an aquifer–aquitard system by excluding the aquitard advection. To compare with our new solution, we expanded the AA model by including the aquitard advection. The expanded AA model considerably overestimated the mass in the upper aquitard when an upward advection existed there. The rates of mass change in the upper aquitard from the new solution and the AA model solution increased with time following sub-linear fashions. The times corresponding to the peak values of the residence time distributions for the AA model, the expanded AA model, and the new model were almost the same. The residence time distributions seemed to follow the Maxwell–Boltzmann distribution closely when plotting the time in logarithmic scale. In addition, we developed a finite-element COMSOL Multiphysics simulation of the problem, and found that the COMSOL solution agreed with the new solution well.     

Continuous time random walks for non-local radial solute transport

This study formulates and analyzes continuous time random walk (CTRW) models in radial flow geometries for the quantification of non-local solute transport induced by heterogeneous flow distributions and by mobile–immobile mass transfer processes. To this end we derive a general CTRW framework in radial coordinates starting from the random walk equations for radial particle positions and times. The particle density, or solute concentration is governed by a non-local radial advection–dispersion equation (ADE). Unlike in CTRWs for uniform flow scenarios, particle transition times here depend on the radial particle position, which renders the CTRW non-stationary. As a consequence, the memory kernel characterizing the non-local ADE, is radially dependent. Based on this general formulation, we derive radial CTRW implementations that (i) emulate non-local radial transport due to heterogeneous advection, (ii) model multirate mass transfer (MRMT) between mobile and immobile continua, and (iii) quantify both heterogeneous advection in a mobile region and mass transfer between mobile and immobile regions. The expected solute breakthrough behavior is studied using numerical random walk particle tracking simulations. This behavior is analyzed by explicit analytical expressions for the asymptotic solute breakthrough curves. We observe clear power-law tails of the solute breakthrough for broad (power-law) distributions of particle transit times (heterogeneous advection) and particle trapping times (MRMT model). The combined model displays two distinct time regimes. An intermediate regime, in which the solute breakthrough is dominated by the particle transit times in the mobile zones, and a late time regime that is governed by the distribution of particle trapping times in immobile zones. These radial CTRW formulations allow for the identification of heterogeneous advection and mobile-immobile processes as drivers of anomalous transport, under conditions relevant for field tracer tests.     

Exposure concentration statistics in the subsurface transport

The concentration fluctuations resulting from hazardous releases in the subsurface are modeled through the concentration moments. The local solute exposure concentration, resulting from the heterogeneous velocity field and pore scale dispersion in the subsurface, is a random function characterized by its statistical moments. The approximate solution to the exact equation that describes the evolution of concentration standard moments in the aquifer transport is proposed in a recursive form. The expressions for concentration second, third and fourth central moments are derived and evaluated for various flow and transport conditions. The solutions are sought by starting from the exact upper bound solution with the zero pore scale dispersion and introducing the physically based approximation that allows the inclusion of the pore scale dispersion resulting in simple closed-form expressions for the concentration statistical moments. The concentration moments are also analyzed in the relative and absolute frame of reference indicating their combined importance in the practical cases of the subsurface contaminant plume migration. The influence of pore scale dispersion with different source sizes and orientations are analyzed and discussed with respect to common cases in the environmental risk assessment problems. The results are also compared with the concentration measurements of the conservative tracer collected in the field experiments at Cape Cod and Borden Site.     

Investigation of Small‐Scale Preferential Flow with a Forced‐Gradient Tracer Test

A new tracer experiment (referred to as MADE‐5) was conducted at the well‐known Macrodispersion Experiment (MADE) site to investigate the influence of small‐scale mass‐transfer and dispersion processes on well‐to‐well transport. The test was performed under dipole forced‐gradient flow conditions and concentrations were monitored in an extraction well and in two multilevel sampler (MLS) wells located at 6, 1.5, and 3.75 m from the source, respectively. The shape of the breakthrough curve (BTC) measured at the extraction well is strongly asymmetric showing a rapidly arriving peak and an extensive late‐time tail. The BTCs measured at seven different depths in the two MLSs are radically different from one another in terms of shape, arrival times, and magnitude of the concentration peaks. All of these characteristics indicate the presence of a complex network of preferential flow pathways controlling solute transport at the test site. Field‐experimental data were also used to evaluate two transport models: a stochastic advection‐dispersion model (ADM) based on conditional multivariate Gaussian realizations of the hydraulic conductivity field and a dual‐domain single‐rate (DDSR) mass‐transfer model based on a deterministic reconstruction of the aquifer heterogeneity. Unlike the stochastic ADM realizations, the DDSR accurately predicted the magnitude of the concentration peak and its arrival time (within a 1.5% error). For the multilevel BTCs between the injection and extraction wells, neither model reproduced the observed values, indicating that a high‐resolution characterization of the aquifer heterogeneity at the subdecimeter scale would be needed to fully capture 3D transport details.     

Characterizing hyporheic transport processes — Interpretation of electrical geophysical data in coupled stream–hyporheic zone systems during solute tracer studies

Quantifying hyporheic solute dynamics has been limited by our ability to assess the magnitude and extent of stream interactions with multiple domains: mobile subsurface storage (MSS, e.g., freely flowing pore water) and immobile subsurface storage (ISS, e.g., poorly connected pore water). Stream-tracer experiments coupled with solute transport modeling are frequently used to characterize lumped MSS and ISS dynamics, but are limited by the ability to sample only “mobile” water and by window of detection issues. Here, we couple simulations of near-surface electrical resistivity (ER) methods with conservative solute transport to directly compare solute transport with ER interpretations, and to determine the ability of ER to predict spatial and temporal trends of solute distribution and transport in stream–hyporheic systems. Results show that temporal moments from both ER and solute transport data are well correlated for locations where advection is not the dominant solute transport process. Mean arrival time and variance are especially well-predicted by ER interpretation, providing the potential to estimate rate-limited mass transport (i.e. diffusive) parameters from these data in a distributed domain, substantially increasing our knowledge of the fate and transport of subsurface solutes.     

Transport of nonsorbing solutes in a streambed with periodic bedforms

Previous studies of hyporheic zone focused largely on the net mass transfer of solutes between stream and streambed. Solute transport within the bed has attracted less attention. In this study, we combined flume experiments and numerical simulations to examine solute transport processes in a streambed with periodic bedforms. Solute originating from the stream was subjected to advective transport driven by pore water circulation due to current–bedform interactions as well as hydrodynamic dispersion in the porous bed. The experimental and numerical results showed that advection played a dominant role at the early stage of solute transport, which took place in the hyporheic zone. Downward solute transfer to the deep ambient flow zone was controlled by transverse dispersion at the later stage when the elapsed time exceeded the advective transport characteristic time t_c (= L/u_c with L being the bedform length and u_c the characteristic pore water velocity). The advection-based pumping exchange model was found to predict reasonably well solute transfer between the overlying water and streambed at the early stage but its performance deteriorated at the later stage. With dispersion neglected, the pumping exchange model underestimated the long-term rate and total mass of solute transfer from the overlying water to the bed. Therefore both advective and dispersive transport components are essential for quantification of hyporheic exchange processes.     

Applicability of the Dual‐Domain Model to Nonaggregated Porous Media

More theoretical analysis is needed to investigate why a dual‐domain model often works better than the classical advection‐dispersion (AD) model in reproducing observed breakthrough curves for relatively homogeneous porous media, which do not contain distinct dual domains. Pore‐scale numerical experiments presented here reveal that hydrodynamics create preferential flow paths that occupy a small part of the domain but where most of the flow takes place. This creates a flow‐dependent configuration, where the total domain consists of a mobile and an immobile domain. Mass transfer limitations may result in nonequilibrium, or significant differences in concentration, between the apparent mobile and immobile zones. When the advection timescale is smaller than the diffusion timescale, the dual‐domain mass transfer (DDMT) model better captures the tailing in the breakthrough curve. Moreover, the model parameters (mobile porosity, mean solute velocity, dispersivity, and mass transfer coefficient) demonstrate nonlinear dependency on mean fluid velocity. The studied case also shows that when the Peclet number, Pe, is large enough, the mobile porosity approaches a constant, and the mass transfer coefficient can be approximated as proportional to mean fluid velocity. Based on detailed analysis at the pore scale, this paper provides a physical explanation why these model parameters vary in certain ways with Pe. In addition, to improve prediction in practical applications, we recommend conducting experiments for parameterization of the DDMT model at a velocity close to that of the relevant field sites, or over a range of velocities that may allow a better parameterization.     

Analytical solutions for solute transport in saturated porous media with semi-infinite or finite thickness

Three-dimensional analytical solutions for solute transport in saturated, homogeneous porous media are developed. The models account for three-dimensional dispersion in a uniform flow field, first-order decay of aqueous phase and sorbed solutes with different decay rates, and nonequilibrium solute sorption onto the solid matrix of the porous formation. The governing solute transport equations are solved analytically by employing Laplace, Fourier and finite Fourier cosine transform techniques. Porous media with either semi-infinite or finite thickness are considered. Furthermore, continuous as well as periodic source loadings from either a point or an elliptic source geometry are examined. The effect of aquifer boundary conditions as well as the source geometry on solute transport in subsurface porous formations is investigated.     

Modeling plume behavior for nonlinearly sorbing solutes in saturated homogeneous porous media

Transport of a sorbing solute in a two-dimensional steady and uniform flow field is modeled using a particle tracking random walk method. The solute is initially introduced from an instantaneous point source. Cases of linear and nonlinear sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. The numerical simulation of solute particle transport yields the large scale behavior of the solute plume. Behavior of the plume is quantified in terms of the center-of-mass displacement distance, relative velocity of the center-of-mass, mass breakthrough curves, spread variance, and longitudinal skewness. The nonlinear sorption isotherm affects the plume behavior in the following way relative to the linear isotherm: (1) the plume velocity decreases exponentially with time; (2) the longitudinal variance increases nonlinearly with time; (3) the solute front is steepened and tailing is enhanced     

Implications of rate-limited mass transfer for aquifer storage and recovery

Pressure to decrease reliance on surface water storage has led to increased interest in aquifer storage and recovery (ASR) systems. Recovery efficiency, which is the ratio of the volume of recovered water that meets a predefined standard to total volume of injected fluid, is a common criterion of ASR viability. Recovery efficiency can be degraded by a number of physical and geochemical processes, including rate-limited mass transfer (RLMT), which describes the exchange of solutes between mobile and immobile pore fluids. RLMT may control transport behavior that cannot be explained by advection and dispersion. We present data from a pilot-scale ASR study in Charleston, South Carolina, and develop a three-dimensional finite-difference model to evaluate the impact of RLMT processes on ASR efficiency. The modeling shows that RLMT can explain a rebound in salinity during fresh water storage in a brackish aquifer. Multicycle model results show low efficiencies over one to three ASR cycles due to RLMT degrading water quality during storage; efficiencies can evolve and improve markedly, however, over multiple cycles, even exceeding efficiencies generated by advection-dispersion only models. For an idealized ASR model where RLMT is active, our simulations show a discrete range of diffusive length scales over which the viability of ASR schemes in brackish aquifers would be hindered.     

Transport of variable-density solute plumes in beach aquifers in response to oceanic forcing

A comprehensive numerical study was undertaken to investigate transport of a variable-density, conservative solute plume in an unconfined coastal aquifer subject to high and low frequency oceanic forcing. The model combined variable-density saturated flow for groundwater and solute transport, and wave hydrodynamics from a 2D Navier–Stokes solver. A sinusoidal tidal signal was specified by implementing time-varying heads at the seaward boundary. The solute plume behavior was investigated under different oceanic forcing conditions: no forcing, waves, tide, and combined waves and tide. For each forcing condition, four different injected solute densities (freshwater, brackish water, seawater, brine) were used to investigate the effects of density on the transport of the injected plume beneath and across the beach face. The plume’s low-order spatial moments were computed, viz., mass, centroid, variance and aspect ratio. The results confirmed that both tide- and wave-forcing produce an upper saline plume beneath the beach face in addition to the classical saltwater wedge. For the no-forcing and tide-only cases (during rising tides), an additional small circulation cell below the beach face was observed. Oceanic forcing affects strongly the solute plume’s flow path, residence time and discharge rate across the beach face, as well as its spreading. For the same oceanic forcing, solute plumes with different densities follow different trajectories from the source to the discharge location (beach face). The residence time and plume spreading increased with plume density. It was concluded that simulations that neglect the effect of waves or tides cannot reproduce accurately solute plume dispersion and also, in the case of coasts with small waves or tides, the solute residence time in the aquifer.     

Laplace transform solutions for solute transport in fissured aquifers

The main processes affecting the migration of a solute in a fissured aquifer will be advection and dispersion in the fissures, diffusion into the porous matrix; and adsorption. This paper considers solute transport in an idealized fissured aquifer consisting of slabs of saturated rock-matrix separated by equally spaced, planar fissures. The solution of the transport equations is developed as far as Laplace transforms of the solute concentrations in the fissure and matrix water. Numerical inversion of the transforms is used to investigate characteristic behaviour of the model for a number of special cases.     

Incorporating Super‐Diffusion due to Sub‐Grid Heterogeneity to Capture Non‐Fickian Transport

Numerical transport models based on the advection‐dispersion equation (ADE) are built on the assumption that sub‐grid cell transport is Fickian such that dispersive spreading around the average velocity is symmetric and without significant tailing on the front edge of a solute plume. However, anomalous diffusion in the form of super‐diffusion due to preferential pathways in an aquifer has been observed in field data, challenging the assumption of Fickian dispersion at the local scale. This study develops a fully Lagrangian method to simulate sub‐grid super‐diffusion in a multidimensional regional‐scale transport model by using a recent mathematical model allowing super‐diffusion along the flow direction given by the regional model. Here, the time randomizing procedure known as subordination is applied to flow field output from MODFLOW simulations. Numerical tests check the applicability of the novel method in mapping regional‐scale super‐diffusive transport conditioned on local properties of multidimensional heterogeneous media.     

Plume Detachment and Recession Times in Fractured Rock

The influence of source zone concentration reduction on solute plume detachment and recession times in fractured rock was investigated using new semianalytical solutions to transient solute transport in the presence of advection, dispersion, sorption, matrix diffusion, and first-order decay. Novel aspects of these solutions are: (1) the source zone concentration behavior is simulated using a constant concentration with the option for either an instantaneous reduction to zero concentration or an exponentially decaying source zone concentration initiated at some time (t^*) after the source is introduced, and (2) different biodegradation rates in the fracture and rock matrix. These solutions were applied for sandstone bedrock and revealed that biodegradation in the matrix, not the fracture, may be the most significant attenuation mechanism and therefore may dictate remediation time scales. Also, instantaneous and complete source concentration reduction in aged plumes may not be beneficial with respect to plume response because back-diffusion can sustain plume migration for long periods of time. Moderate source zone concentration reduction has a similar impact on the rate of advance of the leading edge of the plume as aggressive concentration reduction. If the source zone concentration reduction half-life is less than the plume decay half-life, then volatile organic compound (VOC) mass sequestered in the rock matrix will ultimately dictate plume persistence and not the presence of the source zone.     

Monte Carlo evaluation of microbial-mediated contaminant reactions in heterogeneous aquifers

Monte Carlo simulations are conducted to evaluate microbial-mediated contaminant reactions in an aquifer comprised of spatially variable microbial biomass concentrations, aquifer hydraulic conductivities, and initial electron donor/acceptor concentrations. A finite element simulation model is used that incorporates advection, dispersion, and Monod kinetic expressions to describe biological processes. Comparisons between Monte Carlo simulations of heterogeneous systems and simulations using homogeneous formulation of the same two-dimensional transport problem are presented. For the assumed set of parameters, physical aquifer heterogeneity is found to have a minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system; however, it noticeably changes the dispersion, skewness, and peakness of contaminant concentration distributions. Similarly, for low microbial growth rate, given favorable microbial growth characteristics, biological heterogeneity has minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system. On the other hand, when higher effective growth rates are assumed, biological heterogeneity and spatial heterogeneities in essential electron donor/acceptors reduce the efficiency of biotic contaminant reactions; consequently, model simulations derived from heterogeneous biomass distributions predict remediation time scales that are longer than those simulated for homogeneous systems. When correlations between physical aquifer and biological heterogeneities are considered, the assumed correlation affects predicted mean and variance of contaminant concentration and biomass distributions. For example, an assumed negative correlation between hydraulic conductivity and the initial biomass distribution produces a plume where less efficient biotic contaminant reactions occur at the leading edge of the plume; this is consistent with less degradation/transformation occurring over regions of higher groundwater velocities. However, the presence and absence of these correlations do not appear to affect the efficiency of microbial-mediated contaminant attenuation.     

A field study of the coupled effects of aquifer stratification,fluid density,and groundwater fluctuations on dispersivity assessments

A number of experimental studies have tackled the issue of solute transport parameter assessments either in the laboratory or in the field. But yet, the behavior of a plume in the field under density driven forces, is not well known due to possible development of instabilities. Some field tracer tests on the fate of plumes denser than native groundwater such as those encountered under waste disposal facilities, have pointed out the processes of sinking and splitting at the early stage of migration. The process of dispersion was widely investigated, but the range of dispersivity values obtained from either experimental tests, or numerical and theoretical calculations is still very large, even for the same type of aquifers. These discrepancies were considered to be essentially caused by soil heterogeneities and scale effects. In the meantime, studies on the influence of sinking and fingering have remained more scarce. The objective of the work is to analyze how transport parameters such as dispersivities can be affected by unstable conditions, which lead to plume sinking and fingering. A series of tracer tests were carried out to study under natural conditions, the transport of a dense chloride solution injected in a shallow two-layered aquifer. Two types of experiments were performed: in the first type, source injection was such that the plume could travel downward from one layer to the other of higher pore velocity, and in the second one, the migration took place only in the faster layer. The results suggest some new insights in the processes occurring at the early stages of a dense plume migration moving in a stratified aquifer under groundwater fluctuations, which can be summarized through the following points: (i) Above a stability criterion threshold, a fingering process and a multi modal plume transport take place, but local dispersivities can be cautiously derived, using breakthrough curves matching. (ii) When water table is subject to some cycling or rising, the plume can be significantly distorted in the transverse direction, leading to unusual values of the ratio between longitudinal and transverse dispersivities. (iii) Under stable conditions, for example in the case of straightforward injection in the faster aquifer layer, longitudinal dispersivity is greater than the transverse component as usually encountered, and the obtained transport parameters are closed to macro dispersivity values, which reach their asymptotic limit at very short distances. (iv) The classical scale effect about the varying dispersivity at short distances could be a process mainly due to the distance required for a plume stabilization.     

Lessons Learned from 25 Years of Research at the MADE Site

Field studies at well‐instrumented research sites have provided extensive data sets and important insights essential for development and testing of transport theories and mathematical models. This paper provides an overview of over 25 years of research and lessons learned at one of such field research sites on the Columbus Air Force Base in Mississippi, commonly known as the Macrodispersion Experiment (MADE) site. Since the mid‐1980s, field data from the MADE site have been used extensively by researchers around the world to explore complex contaminant transport phenomena in highly heterogeneous porous media. Results from field investigations and modeling analyses suggested that connected networks of small‐scale preferential flow paths and relative flow barriers exert dominant control on solute transport processes. The classical advection‐dispersion model was shown to inadequately represent plume‐scale transport, while the dual‐domain mass transfer model was found to reproduce the primary observed plume characteristics. The MADE site has served as a valuable natural observatory for contaminant transport studies where new observations have led to better understanding and improved models have sprung out analysis of new data.     

Microtopographical and hydrophysical controls on subsurface flow and solute transport: A continuous solute release experiment in a subarctic bog

Resource extraction and transportation activities in subarctic Canada can result in the unintentional release of contaminants into the surrounding peatlands. In the event of a release, a thorough understanding of solute transport within the saturated zone is necessary to predict plume fate and the potential impacts on peatland ecosystems. To better characterize contaminant transport in these systems, approximately 13,000 L/day of sodium chloride tracer (200 mg/L) was released into a bog in the James Bay Lowland. The tracer was pumped into a fully penetrating well (1.5 m) between July 5 and August 18, 2015. Horizontal and vertical plume development was measured via in situ specific conductance and water table depth from an adaptive monitoring network. Over the spill period, the bulk of the plume travelled a lateral distance of 100 m in the direction of the slight regional groundwater and topographical slope. The plume shape was irregular and followed the hollows, indicating preferential flow paths due to the site microtopography. Saturated transport of the tracer occurred primarily at ~25 cm below ground surface (bgs), and at a discontinuous high hydraulic conductivity layer ~125 cm bgs due to a complex and heterogeneous vertical hydraulic conductivity profile. Plume measurement was confounded by a large amount of precipitation (233 mm over the study period) that temporarily diluted the tracer in the highly conductive upper peat layer. Longitudinal solute advection can be approximated using local water table information (i.e., depth and gradient); microtopography; and meteorological conditions. Vertical distribution of solute within the peat profile is far more complex due to the heterogeneous subsurface; characterization would be aided by a detailed understanding of the site‐specific peat profile; the degree of decomposition; and the type of contaminant (e.g., reactive/nonreactive). The results of this research highlight the difficulty of tracking a contaminant spill in bogs and provide a benchmark for the characterization of the short‐term fate of a plume in these complex systems.     

Computational issues in the determination of solute discharge moments and implications for comparison to analytical solutions

Solute discharge moments (mean and variance) are computed using numerical modeling of flow and advective transport in two-dimensional heterogeneous aquifers and are compared to theoretical results. The solute discharge quantifies the temporal evolution of the total contaminant mass crossing a certain compliance boundary. In addition to analyzing the solute discharge moments within a classical absolute dispersion framework, we also analyze relative dispersion formulation, whereby plume meandering (deviation from mean flow path caused by velocity variations at scales larger than plume size) is removed. This study addresses some important issues related to the computation of solute discharge moments from random walk particle tracking experiments, and highlights some of the important differences between absolute and relative dispersion frameworks. Relative dispersion formulation produces maximum uncertainty that coincides with the peak mean discharge. Absolute dispersion, however, results in earlier arrival of the uncertainty peak as compared to the first moment peak. Simulations show that the standard deviation of solute discharge in a relative dispersion framework requires increasingly large temporal sampling windows to smooth out some of the large fluctuations in breakthrough curves associated with advective transport. Using smoothing techniques in particle tracking to distribute the particle mass over a volume rather than at a point significantly reduces the noise in the numerical simulations and removes the need to use large temporal windows. Same effect can be obtained by adding a local dispersion process to the particle tracking experiments used to model advective transport. The effect of the temporal sampling window bears some relevance and important consequences for evaluating risk-related parameters. The expected value of peak solute discharge and its standard deviation are very sensitive to this sampling window and so will be the risk distribution relying on such numerical models.     

Natural Gradient Tracer Test to Evaluate Natural Attenuation of MTBE Under Anaerobic Conditions

A natural gradient tracer test using perdeuterated MTBE was conducted in an anaerobic aquifer to determine the relative importance of dispersion and degradation in reducing MTBE concentrations in ground water. Preliminary ground water chemistry and hydraulic conductivity data were used to place the tracer within an existing dissolved MTBE plume at Port Hueneme, California. Following one year of transport, the tracer plume was characterized in detail.
Longitudinal dispersion was identified as the dominant mechanism for lowering the perdeuterated MTBE concentrations. The method of moments was used to determine the longitudinal and lateral dispersion coefficients (0.85 m²/day and 0.08 m²/day, respectively). A mass-balance analysis, carried out after one year of transport, accounted for 110% of the injected mass and indicated that no significant mass loss occurred. The plume structure created by zones of higher and lower hydraulic conductivity at the site was complex, consisting of several localized areas of high tracer concentration in a lower concentration plume. This is important because the aquifer has generally been characterized as exhibiting fairly minor heterogeneity. In addition, the tracer plume followed a curved flowpath that deviated from the more macroscopic direction of ground water flow inferred from local ground water elevation measurements and the behavior of the existing plume. Understanding the mass balance, plume structure, curvature of the tracer plume, and consequently natural attenuation behavior required the detailed sampling approach employed in this study. These data imply that a detailed understanding of site hydrogeology and an extensive sampling network may be critical for the correct interpretation of monitored natural attenuation of MTBE.