Effects Of Matrix Diffusion Research Articles

Impact of matrix diffusion on the migration of groundwater plumes for Perfluoroalkyl acids (PFAAs) and other non-degradable compounds

Groundwater fate and transport modeling results demonstrate that matrix diffusion plays a role in attenuating the expansion of groundwater plumes of “non-degrading” or highly recalcitrant compounds. This is especially significant for systems where preferred destructive attenuation processes, such as biological and abiotic degradation, are weak or ineffective for plume control. Under these conditions, models of nondestructive physical attenuation processes, traditionally dispersion or sorption, do not demonstrate sufficient plume control unless matrix diffusion is considered. Matrix diffusion has been shown to be a notable emergent impact of geological heterogeneity, typically associated with back diffusion and extending remediation timeframes through concentration tailing of the trailing edge of a plume. However, less attention has been placed on evaluating how matrix diffusion can serve as an attenuation mechanism for the leading edge of a plume of non-degrading compounds like perfluoroalkyl acids (PFAAs), including perfluorooctane sulfonate (PFOS).In this study, the REMChlor-MD model was parametrically applied to a generic unconsolidated and heterogeneous geologic site with a constant PFOS source and no degradation of PFOS in the downgradient edge of the plume. Low levels of mechanical dispersion and retardation were used in the model for three different geologic heterogeneity cases ranging from no matrix diffusion (e.g., sand only) to considerable matrix diffusion using low permeability (“low-k”) layers/lenses and/or aquitards. Our analysis shows that, in theory, many non-degrading plumes may expand for significant time periods before dispersion alone would eventually stabilize the plume; however, matrix diffusion can significantly slow the rate and degree of this migration.For one 100-year travel time scenario, consideration of matrix diffusion results in a simulated PFOS plume length that is over 80% shorter than the plume length simulated without matrix diffusion. Although many non-degrading plumes may continue to slowly expand over time, matrix diffusion resulted in lower concentrations and smaller plume footprints. Modeling multiple hydrogeologic settings showed that the effect of matrix diffusion is more significant in transmissive zones containing multiple low-k lenses/layers than transmissive zones underlain and overlain by low-k aquitards. This study found that at sites with significant matrix diffusion, groundwater plumes will be shorter, will expand more slowly, and may be amenable to a physical, retention-based, Monitored Natural Attenuation (MNA) paradigm. In this case, a small “Plume Assimilative Capacity Zone” in front of the existing plume could be reserved for slow, de minimus, future expansion of a non-degrading plume. If potential receptors are protected in this scenario, then this approach is similar to allowances for expanding plumes under some existing environmental regulatory programs. Accounting for matrix diffusion may support new strategic approaches and alternative paradigms for remediation even for sites and conditions with “non-degrading” constituents such as PFAAs, metals/metalloids, and radionuclides.

Modeling of solute transport in a fracture-matrix system with a three-dimensional discrete fracture network

Understanding the fluid flow and solute transport mechanisms in fractured rocks is essential for many geoengineering applications. In this study, the fluid flow and solute transport in a fracture-matrix system with a three-dimensional (3-D) discrete fracture network (DFN) are modelled through an efficient numerical simulation workflow. The simulation approach is used to systematically investigate the effects of the rock matrix on the transport behaviors in a fracture-matrix system. The results show that the mass exchange between the DFN and the rock matrix can be accurately evaluated based on the conforming mesh at the interface between the fractures (using triangular elements) and the rock matrix (using tetrahedral elements). The complementary cumulative distribution function curves (CCDFs) for the physical processes that consider sorption and decay exhibit significant long tail characteristics, which suggests that the sorption and decay processes play an important role in retarding the migration of solutes in fractured rocks. It is also found that a larger matrix porosity enhances the mass exchange at the interface between the DFN and the rock matrix, which consequently promotes the matrix diffusion effects. The distribution of the concentration plumes in the matrix demonstrates in fracture-matrix systems with larger fracture densities could result in a better connection between the fracture networks and the larger interface (specific wetting) areas, which therefore, promotes the mass exchange. These findings are critical to understanding the migration behavior of radioactive nuclides in far field areas and for the deep geological disposal of nuclear waste.

Field, Laboratory and Modeling Evidence for Strong Attenuation of a Cr(VI) Plume in a Mudstone Aquifer Due to Matrix Diffusion and Reaction Processes.

This study uses a combination of conventional and high resolution field and laboratory methods to investigate processes causing attenuation of a hexavalent chromium (Cr(VI)) plume in sedimentary bedrock at a former industrial facility. Groundwater plume Cr(VI) concentrations decline by more than three orders of magnitude over a 900 m distance down gradient from the site. Internal plume concentrations generally exhibit stable to declining trends due to diffusive and reactive transport in the low permeability matrix as fluxes from the contamination source dissipate due to natural depletion processes and active remediation efforts. The strong attenuation is attributed to diffusion from mobile groundwater in fractures to immobile porewater in the rock matrix, and reactions causing transformation of aqueous Cr(VI) to low-solubility Cr(III) precipitates, confirmed by high spatial resolution rock matrix contaminant concentrations and comparisons with groundwater concentrations from multi-level sampling within the plume. Field characterization data for the fracture network and matrix properties were used to inform 2-D discrete-fracture matrix (DFM) numerical model simulations that quantify attenuation due to diffusion and reaction processes, which show consistency with field datasets, and provide insights regarding future plume conditions. The combination of field, laboratory and modeling evidence demonstrates effects of matrix diffusion and reaction processes causing strong attenuation of a Cr(VI) plume in a sedimentary bedrock aquifer. This approach has important implications for characterization of sites with Cr(VI) contamination for improved site conceptual models and remediation decision-making.

Analytical and Numerical Methods for a Preliminary Assessment of the Remediation Time of Pump and Treat Systems

Several remediation technologies are currently used to address groundwater pollution. “Pump and treat” (P&T) is probably one of the most widely applied, being a process where contaminated groundwater is extracted from the subsurface by pumping and then treated before it is discharged or reinjected into the aquifer. Despite being a very adaptable technology, groundwater remediation is often achieved in long and unsustainable times because of limitations due to the hydrogeological setting and contaminant properties. Therefore, the cost–benefit analysis over time results in an inefficient system and a preliminary evaluation of the clean-up time is crucial. The aim of the paper is to compare, in an integrated manner, the application of some models to estimate the time to compliance of a P&T system in relation to the specific hydrogeological condition. Analytical solutions are analyzed and applied to an industrial site and to a synthetic case. For both cases, batch flushing and the advection-dispersion-retardation (ADR) model underestimate remediation times comparing the results to real or simulated monitoring data, whereas the Square Root model provided more reliable remediation times. Finally, for the synthetic case, the reliability of analytical approaches and the effects of matrix diffusion are tested on the basis of a numerical groundwater transport model specifically implemented, which confirm the results of the analytical methods and the strong influence of the matrix diffusion on the results.

Borehole‐scale testing of matrix diffusion for contaminated‐rock aquifers

AbstractA new method was developed to assess the effect of matrix diffusion on contaminant transport and remediation of groundwater in fractured rock. This method utilizes monitoring wells constructed of open boreholes in the fractured rock to conduct backward diffusion experiments on chlorinated volatile organic compounds (CVOCs) in groundwater. The experiments are performed on relatively unfractured zones (called test zones) of the open boreholes over short intervals (approximately 1 meter) by physical isolation using straddle packers. The test zones were identified with a combination of borehole geophysical logging and chemical profiling of CVOCs with passive samplers in the open boreholes. To confirm the test zones are within inactive flow zones, they are subjected to a series of hydraulic tests. Afterward, the test zones are air sparged with argon to volatilize the CVOCs from aqueous to air phase. Backward diffusion is then measured by periodic passive‐sampling of water in the test zone to identify rebound. The passive (nonhydraulically stressed) sampling negates the need to extract water and potentially dewater the test zone. The authors also monitor active flowing zones of the borehole to assess trends in concentrations in other parts of the fractured rock by purge and passive sampling methods. The testing was performed at the former Pease Air Force Base (PAFB) in Portsmouth, New Hampshire. Bedrock at the former PAFB consists of fractured metasedimentary rocks where the authors investigated back diffusion of cis‐1,2‐dichloroethylene (cis‐1,2‐DCE), a CVOC. Postsparging concentrations of cis‐1,2‐DCE showed initial rebounding followed by declines, excluding an episodic spike in concentrations from a groundwater recharge event. The authors theorize that there are three processes that controlled concentration responses in the test zones postsparging. First, the limited back diffusion of CVOCs from a halo or thin zone of rock around the borehole contributes to the initial rebounding. Second, aerobic degradation of cis‐1,2‐DCE occurred causing declines in concentrations in the test zone. Third, microflow from microfractures contributed to the episodic spike in concentrations following the groundwater recharge event. In active flow zones, the latter two processes are not measurable due to equilibration from groundwater transport between the borehole and active flowing fractures.

Implementation of a Time-Domain Random-Walk Method into a Discrete Element Method to Simulate Nuclide Transport in Fractured Rock Masses

It is essential to study nuclide transport with underground water in fractured rock masses in order to evaluate potential radionuclide leakage in nuclear waste disposal. A time-domain random-walk (TDRW) method was firstly implemented into a discrete element method (DEM), that is, UDEC, in this paper to address the pressing challenges of modelling the nuclide transport in fractured rock masses such as massive fractures and coupled hydromechanical effect. The implementation was then validated against analytical solutions for nuclide transport in a single fracture and a simple fracture network. After that, the proposed implementation was applied to model the nuclide transport in a complex fracture network investigated in the DECOVALEX 2011 project to analyze the effect of matrix diffusion and stress on the nuclide transport in the fractured rock masses. It was concluded that the implementation of the TDRW method into UDEC provided a valuable tool to study the nuclide transport in the fractured rock masses. Moreover, it was found that the total travel time of the nuclide particles in the fractured rock masses with the matrix diffusion and external stress modelled was much longer than that without the matrix diffusion and external stress modelled.

Investigating the age distribution of fracture discharge using multiple environmental tracers, Bedrichov Tunnel, Czech Republic

The transit time distribution (TTD) of discharge collected from fractures in the Bedrichov Tunnel, Czech Republic, is investigated using lumped parameter models and multiple environmental tracers. We utilize time series of $$\delta ^{18}O$$ , $$\delta ^{2}$$ H and $$^3$$ H along with CFC measurements from individual fractures in the Bedrichov Tunnel of the Czech Republic to investigate the TTD, and the uncertainty in estimated mean travel time in several fracture networks of varying length and discharge. We compare several TTDs, including the dispersion distribution, the exponential distribution, and a developed TTD which includes the effects of matrix diffusion. The effect of seasonal recharge is explored by comparing several seasonal weighting functions to derive the historical recharge concentration. We identify best fit mean ages for each TTD by minimizing the error-weighted, multi-tracer $$\chi ^{2}$$ residual for each seasonal weighting function. We use this methodology to test the ability of each TTD and seasonal input function to fit the observed tracer concentrations, and the effect of choosing different TTD and seasonal recharge functions on the mean age estimation. We find that the estimated mean transit time is a function of both the assumed TTD and seasonal weighting function. Best fits as measured by the $$\chi ^2$$ value were achieved for the dispersion model using the seasonal input function developed here for two of the three modeled sites, while at the third site, equally good fits were achieved with the exponential model and the dispersion model and our seasonal input function. The average mean transit time for all TTDs and seasonal input functions converged to similar values at each location. The sensitivity of the estimated mean transit time to the seasonal weighting function was equal to that of the TTD. These results indicated that understanding seasonality of recharge is at least as important as the uncertainty in the flow path distribution in fracture networks and that unique identification of the TTD and mean transit time is difficult given the uncertainty in the recharge function. However, the mean transit time appears to be relatively robust to the structural model uncertainty. The results presented here should be applicable to other studies using environmental tracers to constrain flow and transport properties in fractured rock systems.

Gas Phase Measurements of Matrix Diffusion in Rock Samples from Olkiluoto Bedrock, Finland

The Finnish plan for the final deposition of nuclear waste is deposition deep in the crystalline bedrock. In the safety case of the final deposition, matrix diffusion, along with sorption, is considered the most important retarding factor for radionuclide transport in the geosphere. We set out to measure matrix diffusion in the gas phase for two 80 cm long drill-core samples from Olkiluoto, Finland. One sample consisted of veined gneiss and the other of pegmatitic granite. The measurements were taken in the laboratory with an advection–diffusion measurement setup that uses nitrogen as the carrier gas and helium as the tracer. The measured breakthrough curve for the veined gneiss sample could be interpreted with a homogeneous mathematical model, and the result for the effective diffusion coefficient (\(D_{\mathrm{e}}\)), \(4.2 \pm 0.9 \times 10^{-10}\,\frac{\mathrm {m}^2}{\mathrm {s}}\), agreed with previous results for veined gneiss from through-diffusion experiments in the gas phase. The breakthrough curve for the pegmatitic granite sample required a three-component model because of high variations in the local transport parameters (porosity, diffusion coefficient). The spatial distributions of porosities were characterized with the \(^{14}\)C-polymethylmethacrylate-autoradiography technique. The result, \(D_{\mathrm{e}} = \left( 32 \pm 7\right) \times 10^{-10}\,\frac{\mathrm {m}^2}{\mathrm {s}}\), for the most abundant component was also in accordance with the previous through-diffusion results. Comparison of the two measurements showed that diffusion phenomena can be very sensitive to the microstructure of rock even when macroscopic properties such as porosity remain the same. The retarding effect of matrix diffusion from flow was clearly observed for both samples, and knowledge of the sample structure, rock types, and mineralogy were concluded to be vital in analyzing and interpreting the results.

Characterisation of hydraulic and hydrogeochemical processes in a reducing and alkalinity-producing system (RAPS) treating mine drainage, South Wales, UK

A series of tracer tests has been carried out in the compost and limestone Tan-y-Garn Reducing and Alkalinity-Producing System (RAPS), designed to treat iron-rich net acidic mine water (mean pH6.18, Fe=47mgL−1, alkalinity 1.70meqL−1 and mineral acidity 1.82meqL−1) in South Wales, UK. Conservative tracer breakthrough time in the RAPS basal effluent is approximately inversely related to throughflow rate. Repeat tracer tests indicate a long term decrease in hydraulic conductivity, but not in total porosity.A specific sodium chloride tracer test from June 2008 is reported, when 15kg salt was added to a raw mine water inflow rate of 0.87Ls−1. Electrical conductivity and major ion chemistry were monitored for a 170h period. Sodium exhibited a retardation of 1.15 to 1.2 in the RAPS medium relative to chloride, due to cation exchange. Simple 1-D advection-diffusion analytical modelling succeeded in simulating the early portion of tracer breakthrough in the RAPS effluent. More complex analytical modelling, accounting for (i) mixing and dilution effects in the supernatant water input signature and (ii) matrix diffusion effects, was found to be required to adequately simulate the later-stage tail of the breakthrough curve in the RAPS effluent.

The New Potential for Understanding Groundwater Contaminant Transport

The groundwater remediation field has been changing constantly since it first emerged in the 1970s. The remediation field has evolved from a dissolved-phase centric conceptual model to a DNAPL-dominated one, which is now being questioned due to a renewed appreciation of matrix diffusion effects on remediation. Detailed observations about contaminant transport have emerged from the remediation field, and challenge the validity of one of the mainstays of the groundwater solute transport modeling world: the concept of mechanical dispersion (Payne et al. 2008). We review and discuss how a new conceptual model of contaminant transport based on diffusion (the usurper) may topple the well-established position of mechanical dispersion (the status quo) that is commonly used in almost every groundwater contaminant transport model, and evaluate the status of existing models and modeling studies that were conducted using advection-dispersion models.

The New Potential for Understanding Groundwater Contaminant Transport

AbstractThe groundwater remediation field has been changing constantly since it first emerged in the 1970s. The remediation field has evolved from a dissolved‐phase centric conceptual model to a DNAPL‐dominated one, which is now being questioned due to a renewed appreciation of matrix diffusion effects on remediation. Detailed observations about contaminant transport have emerged from the remediation field, and challenge the validity of one of the mainstays of the groundwater solute transport modeling world: the concept of mechanical dispersion (Payne et al. 2008). We review and discuss how a new conceptual model of contaminant transport based on diffusion (the usurper) may topple the well‐established position of mechanical dispersion (the status quo) that is commonly used in almost every groundwater contaminant transport model, and evaluate the status of existing models and modeling studies that were conducted using advection‐dispersion models.

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

AbstractDetailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 1. Method Development

AbstractDespite the installation in the 1980s and 1990s of hydraulic containment systems around known source zones (four slurry walls and ten pump‐and‐treat systems), trichloroethene (TCE) plumes persist in the three uppermost groundwater‐bearing units at the Middlefield‐Ellis‐Whisman (MEW) Superfund Study Area in Mountain View, California. In analyzing TCE data from 15 recovery wells, the observed TCE mass discharge decreased less than an order of magnitude over a 10‐year period despite the removal of an average of 11 pore volumes of affected groundwater. Two groundwater models were applied to long‐term groundwater pump‐and‐treat data from 15 recovery wells to determine if matrix diffusion could explain the long‐term persistence of a TCE plume. The first model assumed that TCE concentrations in the plume are controlled only by advection, dispersion, and retardation (ADR model). The second model used a one‐dimensional diffusion equation in contact with two low‐permeability zones (i.e., upper and lower aquitard) to estimate the potential effects of matrix diffusion of TCE into and out of low‐permeability media in the plume. In all 15 wells, the matrix diffusion model fit the data much better than the ADR model (normalized root mean square error of 0.17 vs. 0.29; r2 of 0.99 vs. 0.19), indicating that matrix diffusion is a likely contributing factor to the persistence of the TCE plume in the non‐source‐capture zones of the MEW Study Area's groundwater‐extraction wells. © 2013 Wiley Periodicals, Inc.

Translation of field tracer-test results into bounding predictions of matrix diffusion in the shallow subsurface at Idaho National Laboratory, USA

Matrix-diffusion parameters deduced from an infiltration tracer test at Idaho National Laboratory (INL), USA, are combined with other site information in an analysis involving two dimensionless lumped parameters to assess the effects of matrix diffusion on contaminant transport at the INL over longer distance and time scales than were evaluated in the test. Matrix diffusion was interrogated in the test by comparing, in three different observation wells, the breakthrough curves of two simultaneously injected nonsorbing solutes that have different diffusion coefficients. The matrix-diffusion parameters deduced from the different breakthrough curves were in good agreement, suggesting that the parameters may be broadly applicable at the INL. With this in mind, the uncertainties in the individual parameters that make up the two lumped parameters were estimated, and the resulting ranges of parameter values were used to assess matrix diffusion over larger scales. Assessments of the effects of flow transients, spatial heterogeneity in transport parameters, and sorption on solute transport in the shallow subsurface flow system were also conducted. The methods presented here should be generally applicable to other settings for making bounding assessments of the effects of matrix diffusion while honoring the information obtained from tracer tests and other supporting data.

Regional channelized transport in fractured media with matrix diffusion and linear sorption

A regional‐scale solute transport model with long‐range flow channeling is used to study the effect of matrix diffusion and linear sorption on channelized transport. We start from a fracture‐network‐based block model to build up a large‐scale flow and transport model with regional flow channeling, and then incorporate the processes of matrix diffusion and linear sorption. Regional‐scale solute transport is then studied by applying the model to the fracture data set from Sellafield, England. The results demonstrate the significant impact that matrix diffusion has on regional‐scale solute travel times for different degrees of long‐range channeling. With no channeling, a relatively sharp and significantly delayed arrival can be observed, which is the well‐known retardation effect of matrix diffusion and linear sorption. However, with increasing regional channeling the delay becomes much smaller while the spread of transit times becomes much larger. The solute breakthrough curves obtained are analyzed with both the traditional advection‐dispersion equation (ADE) and a Continuous Time Random Walk (CTRW) method developed for non‐Fickian transport. The low β values obtained from the CTRW model indicate an extremely non‐Fickian transport, which is also confirmed by the low Peclet numbers (much less than 1) required for the best fit to the ADE model. In particular, the times for the first arrival of solute are much earlier when regional channeling occurs. In other words, the degree of large‐scale channeling is a crucial parameter for determining the first arrival of particles, and it becomes even more important when matrix diffusion and linear sorption are included in the model.

Retardation of mobile radionuclides in granitic rock fractures by matrix diffusion

Transport of iodide and sodium has been studied by means of block fracture and core column experiments to evaluate the simplified radionuclide transport concept. The objectives were to examine the processes causing retention in solute transport, especially matrix diffusion, and to estimate their importance during transport in different scales and flow conditions. Block experiments were performed using a Kuru Grey granite block having a horizontally planar natural fracture. Core columns were constructed from cores drilled orthogonal to the fracture of the granite block. Several tracer tests were performed using uranine, 131I and 22Na as tracers at water flow rates 0.7–50 μL min −1. Transport of tracers was modelled by applying the advection–dispersion model based on the generalized Taylor dispersion added with matrix diffusion. Scoping calculations were combined with experiments to test the model concepts. Two different experimental configurations could be modelled applying consistent transport processes and parameters. The processes, advection–dispersion and matrix diffusion, were conceptualized with sufficient accuracy to replicate the experimental results. The effects of matrix diffusion were demonstrated on the slightly sorbing sodium and mobile iodine breakthrough curves.

Determination of Matrix Diffusion Properties of Granite

AbstractRock–core column experiments were introduced to estimate the diffusion and sorption properties of Kuru Grey granite used in block–scale experiments. The objective was to examine the processes causing retention in solute transport through rock fractures, especially matrix diffusion used to estimate the importance of retention processes during transport in different scales and flow conditions. Rock–core columns were constructed from cores drilled into the fracture and were placed inside tubes to form flow channels in the 0.5 mm gap between the cores and the tube walls. Tracer experiments were performed using uranine, HTO, 36Cl, 131I, 22Na and 85Sr at flow rates of 1–50 µlmin-1. Rock matrix was characterized using 14C–PMMA method, scanning electron microscopy (SEM), energy dispersive X–ray micro analysis (EDX) and the B.E.T. method.Solute mass flux through a column was modelled by applying the assumption of a linear velocity profile and a molecular diffusion. Coupling of the advection and diffusion processes was based on the model of generalised Taylor dispersion in the linear velocity profile. Experiments could be modelled applying a consistent parameterization and transport processes. The results provide evidence that it is possible to investigate matrix diffusion at the laboratory scale. The effects of matrix diffusion were demonstrated on the slightly–sorbing tracer breakthrough curves. Based on scoping calculations matrix diffusion begins to be clearly observable for non–sorbing tracer when the flow rate is 0.1 μl×min-1. The experimental results presented here cannot be transferred directly to the spatial and temporal scales that prevail in an underground repository. However, the knowledge and understanding of transport and retention processes gained from this study is transferable to different scales from laboratory to in–situ conditions.

Measurements of groundwater velocity in discrete rock fractures

Estimating groundwater velocity in fracture networks using a Darcy or cubic law calculation is complicated by the wide distribution of fracture aperture often found in these systems and by the difficulty in measuring hydraulic head in discrete fracture features. Although difficult to conduct in a fractured rock setting, the point dilution method can be utilized to collect direct measurements of groundwater velocity in individual fractures. To compare measured against calculated velocities, more than 100 point dilution experiments were conducted within a 35 × 35 m area of a single fracture and in discrete fracture features within a fracture network at a larger scale. The dilution experiments were conducted by isolating a fracture feature in a borehole, measuring the hydraulic aperture, and measuring the decay of an injected tracer due to the advective groundwater flux across the fracture. Groundwater velocity was estimated using the hydraulic aperture and the rate of decay of the injected tracer. Estimates of the local hydraulic gradient were calculated via the cubic law using the velocity estimate and the hydraulic aperture. The results of the tests conducted in the single fracture show variable (1 to 33 m/day) but on average higher velocities in comparison to that measured during a natural gradient tracer experiment conducted previously (in which the effects of matrix diffusion were accounted for) and to that which would be calculated using the cubic law. Based on these results, it was determined that the best estimate of the average groundwater velocity, at the scale of the measurement area used for the cubic law calculations, could only be obtained using the largest apertures in the aperture distribution. Variability of the velocity measurements was also observed over time. Increases in velocity were attributed to the effect of rainfall although concurrent increases in hydraulic gradient were not detected (likely within the tolerance of the measuring devices). The groundwater velocities measured in the fracture network varied over a wider range than at the scale of the single fracture (from 2 to 388 m/day). No correlation, however, was observed between the size of the fracture aperture and measured velocity.

Vertical Cross Contamination of Trichloroethylene in a Borehole in Fractured Sandstone

Boreholes drilled through contaminated zones in fractured rock create the potential for vertical movement of contaminated ground water between fractures. The usual assumption is that purging eliminates cross contamination; however, the results of a field study conducted in a trichloroethylene (TCE) plume in fractured sandstone with a mean matrix porosity of 13% demonstrates that matrix-diffusion effects can be strong and persistent. A deep borehole was drilled to 110 m below ground surface (mbgs) near a shallow bedrock well containing high TCE concentrations. The borehole was cored continuously to collect closely spaced samples of rock for analysis of TCE concentrations. Geophysical logging and flowmetering were conducted in the open borehole, and a removable multilevel monitoring system was installed to provide hydraulic-head and ground water samples from discrete fracture zones. The borehole was later reamed to complete a well screened from 89 to 100 mbgs; persistent TCE concentrations at this depth ranged from 2100 to 33,000 microg/L. Rock-core analyses, combined with the other types of borehole information, show that nearly all of this deep contamination was due to the lingering effects of the downward flow of dissolved TCE from shallower depths during the few days of open-hole conditions that existed prior to installation of the multilevel system. This study demonstrates that transfer of contaminant mass to the matrix by diffusion can cause severe cross contamination effects in sedimentary rocks, but these effects generally are not identified from information normally obtained in fractured-rock investigations, resulting in potential misinterpretation of site conditions.

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: Effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.