Irreversible sorption of benzene in sandy aquifer materials

Hydrocarbon compounds in aquifers are generally known to show a retardation effect due to sorption onto the surfaces of solid particles. In this study, we investigated the effect of sorption on the transport of benzene in sandy aquifer materials by conducting batch and column tests for both sandy aquifer materials and sandy materials to which had been added 0·5% powdered activated carbon. The batch test was conducted by equilibrating dry materials with benzene solutions of various initial concentrations, and by analysing the concentrations of benzene in the initial and equilibrated solutions using high‐performance liquid chromatography (HPLC). The column test was performed to monitor the concentrations of effluent versus time, known as a breakthrough curve (BTC). We injected KCl and benzene solutions as tracers into the inlet boundary as two different types of square pulse and step, and monitored the effluent concentrations at the exit boundary under a steady‐state condition using an electrical conductivity meter and HPLC. Simulation of benzene transport was performed using the convective–dispersive equation model with the distribution coefficients obtained from the batch test and the transport parameters of the conservative solute KCl from the column test. The observed BTCs of KCl and benzene for pulse injection showed that the arrival times of the peaks of both tracers coincided well, but the relative peak concentration of benzene was much lower than that of KCl. Comparison of the simulated and observed BTCs showed a great discrepancy for all cases of injection mode and material texture, indicating the absence of retardation effect. These results reveal that the predominant process affecting the benzene transport in the sandy aquifer materials is an irreversible sorption rather than retardation. This tentative conclusion was verified by simulation of benzene transport using an irreversible sorption parameter that led to a good agreement between the simulated and observed BTCs. Copyright © 2002 John Wiley & Sons, Ltd.     

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.     

Numerical Modeling of Emulsified Oil Distribution in Heterogeneous Aquifers

In situ anaerobic bioremediation using edible oil emulsions will be most effective if the oil droplets can be brought into close contact with the contaminant to be treated. However, uniformly distributing oil in heterogeneous aquifers can be difficult. The impact of injection conditions on emulsion distribution in a three-dimensional heterogeneous aquifer is examined using MODFLOW and RT3D. Emulsion retention is simulated using a rate-limited Langmuir isotherm. Volume and flow contact efficiency are shown to be functions of mass of oil injected, injection fluid volume, well spacing, and injection sequence. Regression equations are developed relating dimensionless scaling factors to expected contact efficiency for area treatment and barriers. Cleanup time for uncontacted zones is estimated using a mobile-immobile zone modeling approach.     

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.     

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.     

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.     

Temporal-moment matching for truncated breakthrough curves for step or step-pulse injection

The method of temporal moments is an efficient approach for analyzing breakthrough curves (BTCs). By matching the moments of the BTCs computed through parametric transfer-function models or one-dimensional transport models to those of the data, one can estimate the parameters characterizing the transfer function or apparent transport parameters. The classical method of moments presumes infinite duration. However, the measurement of BTCs is usually terminated prematurely, before the concentration has reached zero. Unless this truncation of the BTCs has been taken into account, the estimates of the parameters may be in error. Truncated measured BTCs are sometimes extrapolated assuming exponential decay. In this study, we use the concept of moments of the truncated impulse–response function [Jawitz JW. Moments of truncated continuous univariate distributions. Adv Water Res 2004;27:269–81] in the analysis of truncated BTCs corresponding to the commonly encountered step and step-pulse injection modes. The method is straightforward, based on the relation, which we derive, between truncated moments of the impulse–response function and the measured BTC. It is practical to apply and does not require the extrapolation of the measured BTC. The method is also accurate. In a numerical study we discuss how short a step-pulse injection may be so that we can approximate it as instantaneous. Finally, we apply the method to the analysis of a field-scale tracer test.     

Bioremediation in Fractured Rock: 1. Modeling to Inform Design,Monitoring, and Expectations

Field characterization of a trichloroethene (TCE) source area in fractured mudstones produced a detailed understanding of the geology, contaminant distribution in fractures and the rock matrix, and hydraulic and transport properties. Groundwater flow and chemical transport modeling that synthesized the field characterization information proved critical for designing bioremediation of the source area. The planned bioremediation involved injecting emulsified vegetable oil and bacteria to enhance the naturally occurring biodegradation of TCE. The flow and transport modeling showed that injection will spread amendments widely over a zone of lower‐permeability fractures, with long residence times expected because of small velocities after injection and sorption of emulsified vegetable oil onto solids. Amendments transported out of this zone will be diluted by groundwater flux from other areas, limiting bioremediation effectiveness downgradient. At nearby pumping wells, further dilution is expected to make bioremediation effects undetectable in the pumped water. The results emphasize that in fracture‐dominated flow regimes, the extent of injected amendments cannot be conceptualized using simple homogeneous models of groundwater flow commonly adopted to design injections in unconsolidated porous media (e.g., radial diverging or dipole flow regimes). Instead, it is important to synthesize site characterization information using a groundwater flow model that includes discrete features representing high‐ and low‐permeability fractures. This type of model accounts for the highly heterogeneous hydraulic conductivity and groundwater fluxes in fractured‐rock aquifers, and facilitates designing injection strategies that target specific volumes of the aquifer and maximize the distribution of amendments over these volumes.     

Travel-time based model of bioremediation using circulation wells

Vertical circulation wells can efficiently provide microorganisms with substrates needed for enhanced bioremediation. We present a travel-time based approach for modeling bioreactive transport in a flow field caused by a series of circulation wells. Mixing within the aquifer is due to the differences in sorption behavior of the reactants. Neglecting local dispersion, transport simplifies to a single one-dimensional problem with constant coefficients for each well. Recirculation is characterized by the discharge densities over travel time. We apply the model to the stimulation of cometabolic dechlorination of trichloroethene (TCE) by alternate injection of oxygen and toluene into the circulation wells. Mixing within the wells can be minimized by interposing sufficiently long breaks between the oxygen and toluene pulses. In our simulation, the proposed injection scheme stimulates biomass growth without risking biofouling of the aquifer.     

Estimating Travel Time in Bank Filtration Systems from a Numerical Model Based on DTS Measurements

An approach is presented to determine the seasonal variations in travel time in a bank filtration system using a passive heat tracer test. The temperature in the aquifer varies seasonally because of temperature variations of the infiltrating surface water and at the soil surface. Temperature was measured with distributed temperature sensing along fiber optic cables that were inserted vertically into the aquifer with direct push equipment. The approach was applied to a bank filtration system consisting of a sequence of alternating, elongated recharge basins and rows of recovery wells. A SEAWAT model was developed to simulate coupled flow and heat transport. The model of a two‐dimensional vertical cross section is able to simulate the temperature of the water at the well and the measured vertical temperature profiles reasonably well. MODPATH was used to compute flowpaths and the travel time distribution. At the study site, temporal variation of the pumping discharge was the dominant factor influencing the travel time distribution. For an equivalent system with a constant pumping rate, variations in the travel time distribution are caused by variations in the temperature‐dependent viscosity. As a result, travel times increase in the winter, when a larger fraction of the water travels through the warmer, lower part of the aquifer, and decrease in the summer, when the upper part of the aquifer is warmer.     

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.     

Encapsulated Cell Bioremediation: Evaluation on the Basis of Particle Tracer Tests

Microencapsulation of degradative organisms enhances microorganism survivability (Stormo and Crawford 1994). The use of encapsulated cell microbeads for in situ biodegradation depends not only on microorganism survival but also on microbead transport characteristics. Two forced-gradient, recirculating-loop tracer experiments were conducted to evaluate the feasibility of encapsulated cell transport and bioremediation on the basis of polystyrene microsphere transport results. The tracer tests were conducted in a shallow, confined, unconsolidated, heterogeneous, sedimentary aquifer using bromide ion and 2 μm, 5 μn, and 15 μm microsphere tracers. Significant differences were observed in the transport of bromide solute and polystyrene microspheres. Microspheres reached peak concentrations in monitoring wells before bromide, which was thought to reflect the influence of aquifer heterogeneity. Greater decreases in microsphere C/C_o ratios were observed with distance from the injection wells than in bromide C/C_o ratios, which was attributed to particle filtration and/or settling. Several methods might be considered for introducing encapsulated cell microbeads into a subsurface environment, including direct injection into a contaminated aquifer zone, injection through a recirculating ground water flow system, or emplacement in a subsurface microbial curtain in advance of a plume. However, the in situ use of encapsulated cells in an aquifer is probably limited to aquifers containing sufficiently large pore spaces, allowing passage of at least some encapsulated cells. The use of encapsulated cells may also be limited by differences in solute and microbead transport patterns and flowpath clogging by larger encapsulated cell microbeads.     

Biodegradation and transport of benzene,toluene, and xylenes in a simulated aquifer: comparison of modelled and experimental results

Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.     

Using groundwater age distributions to estimate the effective parameters of Fickian and non-Fickian models of solute transport

Groundwater age distributions are used to estimate the parameters of Fickian, and non-Fickian, effective models of solute transport. Based on the similarities between the transport and age equations, we develop a deconvolution based approach that describes transport between two monitoring wells. We show that the proposed method gives exact estimates of the travel time distribution between two wells when the domain is stationary and that the method still provides useful information on transport when the domain is non-stationary. The method is demonstrated using idealized uniform and layered 2-D aquifers. Homogeneous transport is determined exactly and non-Fickian transport in a layered aquifer was also approximated very well, even though this example problem is shown to be scale-dependent. This work introduces a method that addresses a significant limitation of tracer tests and non-Fickian transport modeling which is the difficulty in determining the effective parameters of the transport model.     

Multidimensional analytical models for isotope ratios in groundwater pollutant plumes of organic contaminants undergoing different biodegradation kinetics

This work presents analytical models which are able to predict contours of concentrations and isotope ratios of organic pollutants in homogeneous aquifers. Four analytical solutions of the advective–dispersive transport equation for reactive transport from the literature differing in assumptions regarding biodegradation kinetics were used. Stable isotope ratios are computed after modelling the individual reactive transport of isotopic species in the aquifer, which respond differently to fractionation by biodegradation or sorption. The main finding of this study is that the isotope ratios in the plumes are very sensitive to the assumptions underlying the biodegradation kinetics in the models. When biodegradation occurs throughout the core of the plume as first-order reaction, the transversal gradients in isotope ratios are smooth. When biodegradation occurs in a bi-molecular reaction with an electron acceptor (modelled by double-Monod kinetics), steep transversal isotope gradients are predicted. When the reaction rates approach instantaneous reaction along the plume fringes, isotope shifts in the core of the plume disappear. A model incorporating plume and fringe degradation produces the most plausible predictions of isotope ratios in this study. It is shown furthermore that isotope fractionation by sorption causes an even different pattern of isotope ratios, with positive shifts restricted to near the forerunning front of an expanding plume. The models developed in this work can serve for the validation of numerical models and may be incorporated in natural attenuation support systems such as e.g. BIOSCREEN.     

Push‐Pull Tests for Estimating RDX and TNT Degradation Rates in Groundwater

In situ bioremediation is being considered to optimize an existing pump‐and‐treat remedy for treatment of explosives‐contaminated groundwater at the Umatilla Chemical Depot. Push‐pull tests were conducted using a phased approach to measure in situ hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and 2,4,6‐trinitrotoluene (TNT) degradation rates associated with various carbon substrates. Phase I included short‐duration transport tests conducted in each well to determine dilution rates and retardation factors for RDX and TNT. Phase II included aquifer “feedings” conducted by injecting 150 gallons of treated site groundwater amended with ethanol, corn syrup, lactose or emulsified oil (concentrations 10, 25 and 27 mM, respectively; 12% by volume for emulsified oil). Wells received up to 6 substrate “feedings” over the course of 3 months followed by monitoring dissolved oxygen, nitrate, Fe(II), and sulfate to gauge in situ redox conditions as indicators of anaerobic microbial activity. Phase III included push‐pull tests conducted by injecting 150 gallons of site groundwater amended with approximately 1000 µg/L RDX, 350 µg/L TNT, carbon substrate and a conservative tracer, followed by sampling over 8 d. Corn syrup resulted in the best RDX removal (82% on average) and the largest RDX degradation rate coefficient (1.4 ± 1.1 d^?1). Emulsified oil resulted in the best TNT removal (99%) and largest TNT degradation rate coefficient (5.7 × 10^?2 d^?1). These results will be used to simulate full‐scale in situ bioremediation scenarios at Umatilla and will support a go/no‐go decision to initiate full‐scale bioremediation remedy optimization.     

Modeling Steady Sea Water Intrusion with Single‐Density Groundwater Codes

Steady interface flow in heterogeneous aquifer systems is simulated with single‐density groundwater codes by using transformed values for the hydraulic conductivity and thickness of the aquifers and aquitards. For example, unconfined interface flow may be simulated with a transformed model by setting the base of the aquifer to sea level and by multiplying the hydraulic conductivity with 41 (for sea water density of 1025 kg/m³). Similar transformations are derived for unconfined interface flow with a finite aquifer base and for confined multi‐aquifer interface flow. The head and flow distribution are identical in the transformed and original model domains. The location of the interface is obtained through application of the Ghyben‐Herzberg formula. The transformed problem may be solved with a single‐density code that is able to simulate unconfined flow where the saturated thickness is a linear function of the head and, depending on the boundary conditions, the code needs to be able to simulate dry cells where the saturated thickness is zero. For multi‐aquifer interface flow, an additional requirement is that the code must be able to handle vertical leakage in situations where flow in an aquifer is unconfined while there is also flow in the aquifer directly above it. Specific examples and limitations are discussed for the application of the approach with MODFLOW. Comparisons between exact interface flow solutions and MODFLOW solutions of the transformed model domain show good agreement. The presented approach is an efficient alternative to running transient sea water intrusion models until steady state is reached.     

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.     

Aquifer Vulnerability Assessment Based on Sequence Stratigraphic and 39Ar Transport Modeling

A large‐scale groundwater flow and transport model is developed for a deep‐seated (100 to 300 m below ground surface) sedimentary aquifer system. The model is based on a three‐dimensional (3D) hydrostratigraphic model, building on a sequence stratigraphic approach. The flow model is calibrated against observations of hydraulic head and stream discharge while the credibility of the transport model is evaluated against measurements of ³⁹Ar from deep wells using alternative parameterizations of dispersivity and effective porosity. The directly simulated 3D mean age distributions and vertical fluxes are used to visualize the two‐dimensional (2D)/3D age and flux distribution along transects and at the top plane of individual aquifers. The simulation results are used to assess the vulnerability of the aquifer system that generally has been assumed to be protected by thick overlaying clayey units and therefore proposed as future reservoirs for drinking water supply. The results indicate that on a regional scale these deep‐seated aquifers are not as protected from modern surface water contamination as expected because significant leakage to the deeper aquifers occurs. The complex distribution of local and intermediate groundwater flow systems controlled by the distribution of the river network as well as the topographical variation (Tóth 1963) provides the possibility for modern water to be found in even the deepest aquifers.     

Evaluating the transport and removal of chromate using pyrite and biotite columns

To remove chromate from a wastewater, a porous permeable reactive barrier system (PRBS), using pyrite and biotite, was adapted. This study included bench‐scale column experiments to evaluate the efficiency of the PRBS and investigate the reaction process. The total chromium concentration of the effluent from the biotite and pyrite columns reached the influent concentration of 0·10 mM after passing through more than 150 pore volumes (PVs) and 27 PVs respectively, and remained constant thereafter. The Cr^VI concentration in the effluent from the biotite column became constant at about 0·08 mM , accounting for approximately 80% of the influent concentration, after passing through 200 PVs. Moreover, in the pyrite column, the Cr^VI concentration remained at about 0·01 mM , 10% of the input level, after passing through 116 PVs. This shows that both columns maintained their levels of chromate reduction once the Cr^VI breakthrough curves (BTCs) had reached the steady state, though the steady‐state output concentration of total chromium had reached the influent level. The variances of the iron concentration closely followed those of the chromium. The observed data for both columns were fitted to the predicted BTCs calculated by CXTFIT, a program for estimating the solute transport parameters from experimental data. The degradation coefficient µ of the total chromium BTCs for both columns was zero, suggesting the mechanisms for the removal of chromate limit the µ of the Cr^VI BTCs. The Cr^VI degradation of the pyrite column (6·60) was much greater than that of the biotite column (0·27). In addition, the Cr^VI retardation coefficient R of the pyrite column (253) was also larger than that of the biotite column (125). The R values for the total chromium BTCs from both columns were smaller than those of the Cr^VI BTC. Whereas the total chromium BTC for the pyrite column showed little retardation (1·5), the biotite column showed considerable retardation (80). The results for the 900 °C heat‐treated biotite column were analogous to those of the control column (quartz sand). This suggests that the heat‐treated biotite played no role in the retardation and removal of hexavalent chromium. The parameters of the heat‐treated biotite were calculated to an R of 1·2 and µ of 0·01, and these values confirmed quantitatively that the heated biotite had little effect on the transport of Cr^VI. These solute transport parameters, calculated by CXTFIT from the data obtained from the column tests, can provide quantitative information for the evaluation of bench‐ or field‐scale columns as a removal technology for Cr^VI in wastewater or contaminated groundwater. Copyright © 2006 John Wiley & Sons, Ltd.