Field Tracer Tests to Evaluate Transport Properties of Tryptophan and Humic Acid in Karst

The monitoring of water quality, especially of karst springs, requires methods for rapidly estimating and quantifying parameters that indicate contamination. In the last few years, fluorescence-based measurements of tryptophan and humic acid have become a promising tool to assess water quality in near real-time. In this study, we conducted comparative tracer tests in a karst experimental site to investigate the transport properties and behavior of tryptophan and humic acid in a natural karst aquifer. These two tracers were compared with the conservative tracer uranine. Fluorescence measurements were conducted with an online field fluorometer and in the laboratory. The obtained breakthrough curves (BTCs) and the modeling results demonstrate that (1) the online field fluorometer is suitable for real-time fluorescence measurements of all three tracers; (2) the transport parameters obtained for uranine, tryptophan, and humic acid are comparable in the fast flow areas of the karst system; (3) the transport velocities of humic acid are slower and the resulting residence times are accordingly higher, compared to uranine and tryptophan, in the slower and longer flow paths; (4) the obtained BTCs reveal additional information about the investigated karst system. As a conclusion, the experiments show that the transport properties of tryptophan are similar to those of uranine while humic acid is partly transported slower and with retardation. These findings allow a better and quantitative interpretation of the results when these substances are used as natural fecal and contamination indicators.     

Estimating Reaction Rate Coefficients Within a Travel‐Time Modeling Framework

A generalized, efficient, and practical approach based on the travel‐time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel‐time distribution from the injection point to the observation point. For advection‐dominant reactive transport with well‐mixed reactive species and a constant travel‐time distribution, the reactive BTC is obtained by integrating the solutions to advective‐reactive transport over the entire travel‐time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero‐, first‐, nth‐order, and Michaelis‐Menten reactions. The proposed approach is validated by a reactive transport case in a two‐dimensional synthetic heterogeneous aquifer and a field‐scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)‐bioremediation is better approximated by zero‐order reaction kinetics than first‐order reaction kinetics.     

Solute and colloid transport in karst conduits under low- and high-flow conditions

Solute and colloid transport in karst aquifers under low and high flows was investigated by tracer tests using fluorescent dyes (uranine) and microspheres of the size of pathogenic bacteria (1 microm) and Cryptosporidium cysts (5 microm), which were injected into a cave stream and sampled at a spring 2.5 km away. The two types of microspheres were analyzed using an epifluorescence microscope or a novel fluorescence particle counter, respectively. Uranine breakthrough curves (BTCs) were regular shaped and recovery approached 100%. Microsphere recoveries ranged between 27% and 75%. During low flow, the 1-microm spheres displayed an irregular BTC preceding the uranine peak. Only a very few 5-microm spheres were recovered. During high flow, the 1-microm-sphere BTC was regular and more similar to the uranine curve. BTCs were modeled analytically with CXTFIT using a conventional advection dispersion model (ADM) and a two-region nonequilibrium model (2RNE). The results show that (1) colloids travel at higher velocities than solutes during low flow; (2) colloids and solutes travel at similar velocities during high flow; (3) higher maximum concentrations occur during high flow; and (4) the 2RNE achieves a better fit, while the ADM is more robust, as it requires less parameters.     

Influence of injection conditions on field tracer experiments

Calibration of ground water transport models is often performed using results of field tracer experiments. However, little attention is usually paid to the influence, on resulting breakthrough curves, of injection conditions and well-aquifer interactions, more particularly of the influence of the possible trapping of the tracer in the injection wellbore. Recently, a new mathematical and numerical approach has been developed to model injection conditions and well-aquifer interactions in a very accurate way. Using an analytical solution derived from this model, a detailed analysis is made of the evolution of the tracer input function in the aquifer. By varying injection conditions from one simulation to another, synthetic breakthrough curves are generated with the SUFT3D ground water flow and transport finite-element simulator. These tests show clearly that the shape of the breakthrough curves can be dramatically affected by injection conditions. Using generated breakthrough curves as "actual" field results, a calibration of hydrodispersive parameters is performed, neglecting the influence of injection conditions. This shows that neglecting the influence of actual injection conditions can lead to (1) errors on fitted parameters and (2) misleading identification of the active transport processes. Conclusions and guidelines are drawn in terms of proposed methodologies for better controlling the tracer injection in the field, in order to minimize risk of misinterpretation of results.     

Determination of longitudinal dispersivity in an unconfined sandy aquifer

Study of the mobility of contaminants in an aquifer is an important issue for the proper remediation of contaminated groundwater. Determination of associated solute transport parameters therefore is essential for investigation of the extent to which groundwater can be contaminated. This study aimed at determining solute transport parameters for an unconfined sandy aquifer at a laboratory scale through various tracer tests using a conservative solute as a tracer. Tracer tests consisted of both well‐tracer tests (single and double wells) and an aquifer tracer test using a plume‐capturing device such as time domain reflectometry (TDR). The results showed that longitudinal dispersivities estimated from the single and double well‐tracer tests were 2·2 cm and 13·5 cm for a travel distance of 9·3 cm and 13·5 cm from the injection point respectively. These results agreed reasonably well with the results of the aquifer tracer test. The solute transport parameters obtained at multiple points in the aquifer through the aquifer tracer test revealed that the dispersivity length was proportional to the travel distance by a factor of 0·3, which was moderately higher than the value of 0·1 given in the literature. Copyright © 2002 John Wiley & Sons, Ltd.     

Numerical methods for reactive transport on rectangular and streamline-oriented grids

Coupling advection-dominated transport to reactive processes leads to additional requirements and limitations for numerical simulation beyond those for non-reactive transport. Particularly, both monotonicity avoiding the occurence of negative concentrations, and high-order accuracy suppressing artificial diffusion, are necessary to study accurately the reactive interactions of compounds transported in groundwater. These requirements are met by non-linear Eulerian methods. Two cell-centered Finite Volume schemes are presented for the simulation of advection-dominated reactive transport. The first scheme is based on rectangular grids, whereas the second scheme requires streamline-oriented grids the generation of which is explained in an accompanying paper. Although excellent results for conservative transport are obtained by the scheme for rectangular grids, some artificial transverse mixing occurs in the case of multi-component transport. This may lead to erroneous reaction rates if the compounds interact. The transport scheme for streamline-oriented grids, on the other hand, avoids artificial transverse mixing. A quantitative comparison is given by two test cases. A conservative tracer simulation for a five-spot configuration in a heterogeneous aquifer shows a high coincidence of the breakthrough curves obtained for the two methods, whereas a test case of two reacting compounds shows significant differences. In this test case, a rate of convergence with respect to the overall reaction rates lower than first-order is calculated for the rectangular grid.     

Lattice Boltzmann Models for Flow and Transport in Saturated Karst

Flow and transport simulation in karst aquifers remains a significant challenge for the ground water modeling community. Darcy's law–based models cannot simulate the inertial flows characteristic of many karst aquifers. Eddies in these flows can strongly affect solute transport. The simple two-region conduit/matrix paradigm is inadequate for many purposes because it considers only a capacitance rather than a physical domain. Relatively new lattice Boltzmann methods (LBMs) are capable of solving inertial flows and associated solute transport in geometrically complex domains involving karst conduits and heterogeneous matrix rock. LBMs for flow and transport in heterogeneous porous media, which are needed to make the models applicable to large-scale problems, are still under development. Here we explore aspects of these future LBMs, present simple examples illustrating some of the processes that can be simulated, and compare the results with available analytical solutions. Simulations are contrived to mimic simple capacitance-based two-region models involving conduit (mobile) and matrix (immobile) regions and are compared against the analytical solution. There is a high correlation between LBM simulations and the analytical solution for two different mobile region fractions. In more realistic conduit/matrix simulation, the breakthrough curve showed classic features and the two-region model fit slightly better than the advection-dispersion equation (ADE). An LBM-based anisotropic dispersion solver is applied to simulate breakthrough curves from a heterogeneous porous medium, which fit the ADE solution. Finally, breakthrough from a karst-like system consisting of a conduit with inertial regime flow in a heterogeneous aquifer is compared with the advection-dispersion and two-region analytical solutions.     

Assessment of radionuclide transport uncertainty in the unsaturated zone of Yucca Mountain

The present study assesses the uncertainty of flow and radionuclide transport in the unsaturated zone at Yucca Mountain using a Monte Carlo method. Matrix permeability, porosity, and sorption coefficient are considered random. Different from previous studies that assume distributions of the parameters, the distributions are determined in this study by applying comprehensive transformations and rigorous statistics to on-site measurements of the parameters. The distribution of permeability is further adjusted based on model calibration results. Correlation between matrix permeability and porosity is incorporated using the Latin Hypercube Sampling method. After conducting 200 Monte Carlo simulations of three-dimensional unsaturated flow and radionuclide transport for conservative and reactive tracers, the mean, variances, and 5th, 50th, and 95th percentiles for quantities of interest (e.g., matrix liquid saturation and water potential) are evaluated. The mean and 50th percentile are used as the mean predictions, and their associated predictive uncertainties are measured by the variances and the 5th and 95th percentiles (also known as uncertainty bounds). The mean predictions of matrix liquid saturation and water potential are in reasonable agreement with corresponding measurements. The uncertainty bounds include a large portion of the measurements, suggesting that the data variability can be partially explained by parameter uncertainty. The study illustrates propagation of predictive uncertainty of percolation flux, increasing downward from repository horizon to water table. Statistics from the breakthrough curves indicate that transport of the reactive tracer is delayed significantly by the sorption process, and prediction on the reactive tracer is of greater uncertainty than on the conservative tracer because randomness in the sorption coefficient increases the prediction uncertainty. Uncertainty in radionuclide transport is related to uncertainty in the percolation flux, suggesting that reducing the former entails reduction in the latter.     

Diffusive mass exchange of non‐reactive substances in dual‐porosity porous systems – column experiments under saturated conditions

Diffusive mass exchange into immobile water regions within heterogeneous porous aquifers influences the fate of solutes. The percentage of immobile water is often unidentified in natural aquifers though. Hence, the mathematical prediction of solute transport in such heterogeneous aquifers remains challenging. The objective of this study was to find a simple analytical model approach that allows quantifying properties of mobile and immobile water regions and the portion of immobile water in a porous system. Therefore, the Single Fissure Dispersion Model (SFDM), which takes into account diffusive mass exchange between mobile and immobile water zones, was applied to model transport in well‐defined saturated dual‐porosity column experiments. Direct and indirect model validation was performed by running experiments at different flow velocities and using conservative tracer with different molecular diffusion coefficients. In another column setup, immobile water regions were randomly distributed to test the model applicability and to determine the portion of immobile water. In all setups, the tracer concentration curves showed differences in normalized maximum peak concentration, tailing and mass recovery according to their diffusion coefficients. These findings were more pronounced at lower flow rates (larger flow times) indicating the dependency of diffusive mass exchange into immobile water regions on tracers' molecular diffusion coefficients. The SFDM simulated all data with high model efficiency. Successful model validation supported the physical meaning of fitted model parameters. This study showed that the SFDM, developed for fissured aquifers, is applicable in porous media and can be used to determine porosity and volume of regions with immobile water. Copyright © 2015 John Wiley & Sons, Ltd.     

Improved Method for Estimating Reaction Rates During Push-Pull Tests

The breakthrough curve obtained from a single-well push-pull test can be adjusted to account for dilution of the injection fluid in the aquifer fluid. The dilution-adjusted breakthrough curve can be analyzed to estimate the reaction rate of a solute. The conventional dilution-adjusted method assumes that the ratios of the concentrations of the nonreactive and reactive solutes in the injection fluid vs. the aquifer fluid are equal. If this assumption is invalid, the conventional method will generate inaccurate breakthrough curves and may lead to erroneous conclusions regarding the reactivity of a solute. In this study, a new method that generates a dilution-adjusted breakthrough curve was theoretically developed to account for any possible combination of nonreactive and reactive solute concentrations in the injection and aquifer fluids. The newly developed method was applied to a field-based data set and was shown to generate more accurate dilution-adjusted breakthrough curves. The improved dilution-adjusted method presented here is simple, makes no assumptions regarding the concentrations of the nonreactive and reactive solutes in the injection and aquifer fluids, and easily allows for estimating reaction rates during push-pull tests.     

Combining 3D Hydraulic Tomography with Tracer Tests for Improved Transport Characterization

Hydraulic tomography (HT) is a method for resolving the spatial distribution of hydraulic parameters to some extent, but many details important for solute transport usually remain unresolved. We present a methodology to improve solute transport predictions by combining data from HT with the breakthrough curve (BTC) of a single forced‐gradient tracer test. We estimated the three dimensional (3D) hydraulic‐conductivity field in an alluvial aquifer by inverting tomographic pumping tests performed at the Hydrogeological Research Site Lauswiesen close to Tübingen, Germany, using a regularized pilot‐point method. We compared the estimated parameter field to available profiles of hydraulic‐conductivity variations from direct‐push injection logging (DPIL), and validated the hydraulic‐conductivity field with hydraulic‐head measurements of tests not used in the inversion. After validation, spatially uniform parameters for dual‐domain transport were estimated by fitting tracer data collected during a forced‐gradient tracer test. The dual‐domain assumption was used to parameterize effects of the unresolved heterogeneity of the aquifer and deemed necessary to fit the shape of the BTC using reasonable parameter values. The estimated hydraulic‐conductivity field and transport parameters were subsequently used to successfully predict a second independent tracer test. Our work provides an efficient and practical approach to predict solute transport in heterogeneous aquifers without performing elaborate field tracer tests with a tomographic layout.     

A Method for Conducting Simultaneous Convergent Tracer Tests in Multilayered Aquifers

Forced gradient tracer tests between two boreholes can be used to study contaminant transport processes at the small field scale or investigate the transport properties of an aquifer. Full depth tests, in which tracer samples are collected just from the discharge of the abstraction borehole, often give rise to breakthrough curves with multiple peaks that are usually attributed to different flow paths through the aquifer that can rarely be identified from the test results alone. Tests in selected levels of the aquifer, such as those between packer‐isolated sections of the boreholes, are time consuming, expensive; and the identification of major transport pathways is not guaranteed. We present a method for simultaneously conducting multiple tracer tests covering the full depth of the boreholes, in which tracer sampling and monitoring is carried out by a novel multilevel sampling system allowing high frequency and cumulative sampling options. The method is applied to a tracer test using fluorescein conducted in the multilayered sandstone aquifer beneath the city of Birmingham, UK, producing six well‐defined tracer breakthrough curves.     

Comparison of approaches for predicting solute transport: sandbox experiments

The main purpose of this paper was to compare three approaches for predicting solute transport. The approaches include: (1) an effective parameter/macrodispersion approach (Gelhar and Axness 1983); (2) a heterogeneous approach using ordinary kriging based on core samples; and (3) a heterogeneous approach based on hydraulic tomography. We conducted our comparison in a heterogeneous sandbox aquifer. The aquifer was first characterized by taking 48 core samples to obtain local-scale hydraulic conductivity (K). The spatial statistics of these K values were then used to calculate the effective parameters. These K values and their statistics were also used for kriging to obtain a heterogeneous K field. In parallel, we performed a hydraulic tomography survey using hydraulic tests conducted in a dipole fashion with the drawdown data analyzed using the sequential successive linear estimator code (Yeh and Liu 2000) to obtain a K distribution (or K tomogram). The effective parameters and the heterogeneous K fields from kriging and hydraulic tomography were used in forward simulations of a dipole conservative tracer test. The simulated and observed breakthrough curves and their temporal moments were compared. Results show an improvement in predictions of drawdown behavior and tracer transport when the K tomogram from hydraulic tomography was used. This suggests that the high-resolution prediction of solute transport is possible without collecting a large number of small-scale samples to estimate flow and transport properties that are costly to obtain at the field scale.     

Contaminant transport in fractured chalk: laboratory and field experiments

Laboratory experiments were performed on chalk samples from Denmark and Israel to determine diffusion and distribution coefficients. Batch tests were used to define sorption isotherms for naphthalene and o-xylene. Linear sorption isotherms were observed and described with Henry-isotherms. Because of the high purity and low contents of clay minerals and organic carbon, Danish and white Israeli chalk generally have low retardation capacities. Contrarily, gray Israeli chalk, with organic carbon fractions as high as 1.092%, remarkably retards organic contaminants. The K(OC) concept is not applicable to predicting distribution coefficients based on the organic carbon content in the chalk samples. Effective diffusivities of o-xylene, naphthalene, and several artificial tracers were determined using through-diffusion experiments. Based on measured diffusion coefficients and available literature values, a chalk specific exponent of 2.36 for Archie's law was derived, allowing a satisfactory estimate of relative diffusivities in chalk. A field-scale tracer test with uranine and lithium was performed in the Negev desert (Israel) to examine the transferability of diffusivities determined on small rock samples in the laboratory. Due to low recovery rates of the tracer, a modified single fissure dispersion model was used for inverse modeling of the breakthrough curves. Resulting diffusivities deviate insignificantly from the laboratory values, which are considered to be representative for the investigated part of the aquifer and applicable in transport models.     

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.     

Key features of artificial aquifers for use in modeling contaminant transport

Two large-scale (9.5 m long, 4.7 m wide, 2.6 m deep), three-dimensional artificial aquifers were constructed to investigate the influence of spatial variations in aquifer properties on contaminant transport. One aquifer was uniformly filled with coarse sand media (0.6 to 2.0 mm) and the other was constructed as a heterogeneous aquifer using blocks of fine, medium, and coarse sands. The key features of these artificial aquifers are described. An innovative deaeration tower was constructed to overcome a problem of the aquifers becoming blocked with excess air from the ground water source. A series of tracer injection experiments were conducted to test the homogeneity of the first aquifer that was purposely built as a homogeneous aquifer and to calculate values of aquifer parameters. Experimental data show that the aquifer is slightly heterogeneous, and hydraulic conductivity values are significantly higher down one side of the aquifer compared to the mean value. There was very good agreement in estimated dispersivity values between the plume area ratio methods and the curve fitting of tracer breakthrough curves. Dispersivity estimates from a full areal source injection (12.2 m2) experiment using a 1D analytical model were higher than estimates from a limited source injection (0.2 m2) experiment using a 3D model, possibly because the 1D model does not take account of the heterogeneity of hydraulic conductivity in the aquifer, thus overestimating dispersivity. Transverse and vertical dispersivity values were about five times less than the longitudinal dispersivity. There was slight sorption of Rhodamine WT onto the aquifer media.     

The Horizontal Reactive Media Treatment Well (HRX Well®) for Passive In‐Situ Remediation

A new in‐situ remediation concept termed a Horizontal Reactive Media Treatment Well (HRX Well®) is presented that utilizes horizontal wells filled with reactive media to passively treat contaminated groundwater in‐situ. The approach involves the use of large‐diameter directionally drilled horizontal wells filled with granular reactive media generally installed parallel to the direction of groundwater flow. The design leverages natural “flow‐focusing” behavior induced by the high in‐well hydraulic conductivity of the reactive media relative to the aquifer hydraulic conductivity to passively capture and treat proportionally large volumes of groundwater within the well. Clean groundwater then exits the horizontal well along its downgradient sections. Many different types of solid granular reactive media are already available (e.g., zero valent iron, activated carbon, ion exchange resins, zeolite, apatite, chitin); therefore, this concept could be used to address a wide range of contaminants. Three‐dimensional flow and transport simulations were completed to assess the general hydraulic performance, capture zones, residence times, effects of aquifer heterogeneity, and treatment effectiveness of the concept. The results demonstrate that capture and treatment widths of up to tens of feet can be achieved for many aquifer settings, and that reductions in downgradient concentrations and contaminant mass flux are nearly immediate. For a representative example, the predicted treatment zone width for the HRX Well is approximately 27 to 44 feet, and contaminant concentrations immediately downgradient of the HRX Well decreased an order of magnitude within 10 days. A series of laboratory‐scale physical tests (i.e., tank tests) were completed that further demonstrate the concept and confirm model prediction performance. For example, the breakthrough time, peak concentration and total mass recovery of methylene blue (reactive tracer) was about 2, 35, and 20 times (respectively) less than chloride (conservative tracer) at the outlet of the tank‐scale HRX Well.     

Multiscale characterization of a heterogeneous aquifer using an ASR operation

Heterogeneity in the physical properties of an aquifer can significantly affect the viability of aquifer storage and recovery (ASR) by reducing the recoverable proportion of low-salinity water where the ambient ground water is brackish or saline. This study investigated the relationship between knowledge of heterogeneity and predictions of solute transport and recovery efficiency by combining permeability and ASR-based tracer testing with modeling. Multiscale permeability testing of a sandy limestone aquifer at an ASR trial site showed that small-scale core data give lower-bound estimates of aquifer hydraulic conductivity (K), intermediate-scale downhole flowmeter data offer valuable information on variations in K with depth, and large-scale pumping test data provide an integrated measure of the effective K that is useful to constrain ground water models. Chloride breakthrough and thermal profiling data measured during two cycles of ASR showed that the movement of injected water is predominantly within two stratigraphic layers identified from the flowmeter data. The behavior of the injectant was reasonably well simulated with a four-layer numerical model that required minimal calibration. Verification in the second cycle achieved acceptable results given the model's simplicity. Without accounting for the aquifer's layered structure, high precision could be achieved on either piezometer breakthrough or recovered water quality, but not both. This study demonstrates the merit of an integrated approach to characterizing aquifers targeted for ASR.     

The Dual-Domain Porosity Apparatus: Characterizing Dual Porosity at the Sediment/Water Interface

The characterization of pore-space connectivity in porous media at the sediment/water interface is critical in understanding contaminant transport and reactive biogeochemical processes in zones of groundwater and surface-water exchange. Previous in situ studies of dual-domain (i.e., mobile/less-mobile porosity) systems have been limited to solute tracer injections at scales of meters to hundreds of meters and subsequent numerical model parameterization using fluid concentration histories. Pairing fine-scale (e.g., sub-meter) geoelectrical measurements with fluid tracer data over time alleviates dependence on flowpath-scale experiments, enabling spatially targeted characterization of shallow sediment/water interface media where biogeochemical reactivity is often high. The Dual-Domain Porosity Apparatus is a field-tested device capable of variable rate-controlled downward flow experiments. The Dual-Domain Porosity Apparatus facilitates inference of dual-domain parameters, i.e., mobile/less-mobile exchange rate coefficient and the ratio of less mobile to mobile porosity. The Dual-Domain Porosity Apparatus experimental procedure uses water electrical conductivity as a conservative tracer of differential loading and flushing of pore spaces within the region of measurement. Variable injection rates permit the direct quantification of the flow-dependence of dual-domain parameters, which has been theorized for decades but remains challenging to assess using existing experimental methodologies.