The assessment of electromigration as a new technique to study diffusion of radionuclides in clayey soils

For the performance assessment study of a geological disposal of High Level Waste (HLW) in clayey formations, migration studies are essential. For low permeability soils (clays), classical diffusion studies take a very long time. In order to reduce the experimental time, we propose an electrical field as driving force to accelerate the migration of ionic species. This paper reports the assessment of the electromigration technique as a powerful new and fast technique for migration studies. The apparent molecular diffusion coefficient can be derived by two independent methods using the migration parameters obtained from an electromigration experiment, namely the apparent dispersion coefficient and the apparent convection velocity. First, it can be calculated from the velocity of the migrating species by the Einstein relation. But, corrections are necessary for electroosmotic flow. The apparent electroosmotic mobility is experimentally determined as 2.2·10⁻⁹ m²/Vs. Second, it can be calculated from the relation between the apparent dispersion coefficient and the total apparent convection velocity. But it is necessary to know the dispersion length of the medium. The dispersion length for Boom Clay is experimentally determined as 8·10⁻⁵ m. Because of the serious reduction in time, it becomes possible to run series of experiments at different electrical fields to obtain averaged values for the apparent molecular diffusion coefficient according to the two methods. Experiments at different electrical fields have another advantage: the intercept of the linear relationship between the total apparent convection velocity and the apparent dispersion coefficient gives the apparent molecular diffusion coefficient. The apparent molecular diffusion coefficients obtained for ⁸⁵Sr, ¹³¹I and HTO are respectively 0.8·10⁻¹¹, 15·10⁻¹¹, and 24·10⁻¹¹ m²/s. These values are confirmed by pure diffusion experiments. The excellent agreement with the apparent molecular diffusion coefficients obtained by classical diffusion tests clearly demonstrates the feasibility of the electromigration technique for the determination of diffusion coefficients.     

Quantitative imaging of contaminant distributions in heterogeneous porous media laboratory experiments

Intermediate-scale laboratory experiments on heterogeneous porous media have been increasingly used for the study of saturated and unsaturated ground water systems. While the ability to reproduce field-scale heterogeneity in these experiments has advanced, the use of visualization or image analysis methods to characterize the spatial distribution of solute concentrations has largely remained at the homogeneous media level. To advance these imaging techniques we developed a generic image analysis package that, for the first time, automatically segments regions in photographic images that require unique concentration calibration curves due to varying porous media properties or lighting nonuniformities. As a robust test, our image analysis package was applied to an intermediate-scale flow tank experiment characterized by a correlated random permeability field with unprecedented resolution. Twenty-five distinct classes of porous media were developed and binned to the synthetic permeability field, creating an experimental field of 3456 rectangular cells and thereby ensuring the emplaced field closely matched the statistics of the original continuous distribution. Concentration distributions were determined for an experimental tracer run and the corresponding dispersion parameters were calculated. The closeness of the experimental, image-processed longitudinal dispersivity (4.6 x 10(-2) m) to that obtained from the field statistics (9.1 x 10(-2) m) verifies our image analysis technique.     

Experiments on vertical transverse mixing in a large-scale heterogeneous model aquifer

Vertical transverse mixing is known to be a controlling factor in natural attenuation of extended biodegradable plumes originating from continuously emitting sources. We perform conservative and reactive tracer tests in a quasi two-dimensional 14 m long sand box in order to quantify vertical mixing in heterogeneous media. The filling mimics natural sediments including a distribution of different hydro-facies, made of different sand mixtures, and micro-structures within the sand lenses. We quantify the concentration distribution of the conservative tracer by the analysis of digital images taken at steady state during the tracer-dye experiment. Heterogeneity causes plume meandering, leading to distorted concentration profiles. Without knowledge about the velocity distribution, it is not possible to determine meaningful vertical dispersion coefficients from the concentration profiles. Using the stream-line pattern resulting from an inverse model of previous experiments in the sand box, we can correct for the plume meandering. The resulting vertical dispersion coefficient is approximately approximately 4 x 10(-)(9) m(2)/s. We observe no distinct increase in the vertical dispersion coefficient with increasing travel distance, indicating that heterogeneity has hardly any impact on vertical transverse mixing. In the reactive tracer test, we continuously inject an alkaline solution over a certain height into the domain that is occupied otherwise by an acidic solution. The outline of the alkaline plume is visualized by adding a pH indicator into both solutions. From the height and length of the reactive plume, we estimate a transverse dispersion coefficient of approximately 3 x 10(-)(9) m(2)/s. Overall, the vertical transverse dispersion coefficients are less than an order of magnitude larger than pore diffusion coefficients and hardly increase due to heterogeneity. Thus, we conclude for the assessment of natural attenuation that reactive plumes might become very large if they are controlled by vertical dispersive mixing.     

Modelling of silica diffusion experiments with 32Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are etaR, the product of the diffusion accessible porosity eta and the retardation factor R, and the apparent diffusion coefficient D(app) of dissolved silica in clay. For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of 32Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible. Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests. Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K(d) is in the range 25-75 cm(3) g(-1). The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2 x 10(-13) and 7 x 10(-13) m(2) s(-1). The pore diffusion coefficient is in the range from 6 x 10(-11) to 1 x 10(-10) m(2) s(-1).     

城市污泥填埋气集气井收集系统的优化研究

对城市污泥填埋场填埋气集气井收集系统进行了优化研究,考察了城市污泥水平方向的渗透系数(以下简称污泥渗透系数)对集气井影响半径的影响、集气井抽气负压随填埋时间的变化规律、填埋气的经济收集年限。结果表明,当抽气负压为25000～30000Pa时,污泥渗透系数分别取1.04×10-7、2.60×10-8、1.04×10-8m2/(Pa.s)时,集气井的影响半径分别为10.0～11.0、6.0～7.0、5.0～5.5m,过小的污泥渗透系数会严重影响集气井的集气效率,因此污泥渗透系数最好不应小于1.00×10-8m2/(Pa.s);随城市污泥填埋时间的增加,集气井抽气负压总体呈指数型降低趋势,从第8年起,抽气负压由起初的25000Pa降低到5000Pa以下,此时CH4产率约为2kg/(m3.a),到第20年时CH4产率接近于零,故从城市污泥填埋后第8年起,对填埋气继续进行收集的意义已经不大。     

Application of a combined measurement and modeling method to quantify windblown dust emissions from the exposed playa at Mono Lake, California

Particulate matter < or =10 microm (PM10) emissions due to wind erosion can vary dramatically with changing surface conditions. Crust formation, mechanical disturbance, soil texture, moisture, and chemical content of the soil can affect the amount of dust emitted during a wind event. A refined method of quantifying windblown dust emissions was applied at Mono Lake, CA, to account for changing surface conditions. This method used a combination of real-time sand flux monitoring, ambient PM10 monitoring, and dispersion modeling to estimate dust emissions and their downwind impact. The method identified periods with high emissions and periods when the surface was stable (no sand flux), even though winds may have been high. A network of 25 Cox sand catchers (CSCs) was used to measure the mass of saltating particles to estimate sand flux rates across a 2-km2 area. Two electronic sensors (Sensits) were used to time-resolve the CSC sand mass to estimate hourly sand flux rates, and a perimeter tapered element oscillating microbalance (TEOM) monitor measured hourly PM10 concentrations. Hourly sand flux rates were related by dispersion modeling to hourly PM10 concentrations to back-calculate the ratio of vertical PM10 flux to horizontal sand flux (K-factors). Geometric mean K-factor values (K(f)) were found to change seasonally, ranging from 1.3 x 10(-5) to 5.1 x 10(-5) for sand flux measured at 15 cm above the surface (q15). Hourly PM10 emissions, F, were calculated by applying seasonal K-factors to sand flux measurements (F = K(f) x q15). The maximum hourly PM10 emission rate from the study area was 76 g/m2 x hr (10-m wind speed = 23.5 m/sec). Maximum daily PM10 emissions were estimated at 450 g/m2 x day, and annual emissions at 1095 g/m2 x yr. Hourly PM10 emissions were used by the U.S. Environmental Protection Agency (EPA) guideline AERMOD dispersion model to estimate downwind ambient impacts. Model predictions compared well with monitor concentrations, with hourly PM10 ranging from 16 to over 60,000 microg/m3 (slope = 0.89, R2 = 0.77).     

Determination of spatially-resolved porosity, tracer distributions and diffusion coefficients in porous media using MRI measurements and numerical simulations

This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.     

Estimation of local scale dispersion from local breakthrough curves during a tracer test in a heterogeneous aquifer: the Lagrangian approach

The local scale dispersion tensor, Dd, is a controlling parameter for the dilution of concentrations in a solute plume that is displaced by groundwater flow in a heterogeneous aquifer. In this paper, we estimate the local scale dispersion from time series or breakthrough curves, BTCs, of Br concentrations that were measured at several points in a fluvial aquifer during a natural gradient tracer test at Krauthausen. Locally measured BTCs were characterized by equivalent convection dispersion parameters: equivalent velocity, v(eq)(x) and expected equivalent dispersivity, [lambda(eq)(x)]. A Lagrangian framework was used to approximately predict these equivalent parameters in terms of the spatial covariance of log(e) transformed conductivity and the local scale dispersion coefficient. The approximate Lagrangian theory illustrates that [lambda(eq)(x)] increases with increasing travel distance and is much larger than the local scale dispersivity, lambda(d). A sensitivity analysis indicates that [lambda(eq)(x)] is predominantly determined by the transverse component of the local scale dispersion and by the correlation scale of the hydraulic conductivity in the transverse to flow direction whereas it is relatively insensitive to the longitudinal component of the local scale dispersion. By comparing predicted [lambda(eq)(x)] for a range of Dd values with [lambda(eq)(x)] obtained from locally measured BTCs, the transverse component of Dd, DdT, was estimated. The estimated transverse local scale dispersivity, lambda(dT) = DdT/U1 (U1 = mean advection velocity) is in the order of 10(1)-10(2) mm, which is relatively large but realistic for the fluvial gravel sediments at Krauthausen.     

An analytical model for the interpretation of pulse injection experiments performed for testing the spatial variability of clay formations

This paper presents an analytical model to describe pulse injection experiments. This model solves the advection-diffusion equation while taking into account back diffusion from the clay core to the inlet and from the outlet to the clay core. In most analytical models, back diffusion is neglected. For sufficiently high Péclet numbers, this is a good approximation. However, in experiments where the Péclet number is low, back diffusion is important and must be taken into account. An additional advantage of the present model is that both concentration and flux are conserved at the inlet and at the outlet of the clay core. This model is used to fit pulse injection experiments with iodide and tritiated water (HTO) in clay cores. The (new) model is required for fitting the experimental results since in clay layers advection is very slow leading to a low Péclet number. The experiments are performed on clay cores taken from different depths from the Boom Clay and the Ypres Clay layer under the site of the nuclear power plant of Doel (Belgium). The quality of all fits is excellent and the obtained parameter values are coherent. For HTO, the fitted value for the diffusion accessible porosity is consistent with measurements of the water content in Ypres Clay cores. In both types of clays, the apparent diffusion coefficient at zero flow is between 10(-10) and 2 x 10(-10) m(2)/s for iodide and between 2 x 10(-10) and 3 x 10(-10) m(2)/s for HTO. The dispersion length is in the order of 10(-3) m. The average value for the diffusion accessible porosity is between 0.35 and 0.4 for HTO and between 0.2 and 0.25 for iodide.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

Transport of Escherichia coli in 25 m quartz sand columns

To help improve the prediction of bacteria travel distances in aquifers laboratory experiments were conducted to measure the distant dependent sticking efficiencies of two low attaching Escherichia coli strains (UCFL-94 and UCFL-131). The experimental set up consisted of a 25 m long helical column with a diameter of 3.2 cm packed with 99.1% pure-quartz sand saturated with a solution of magnesium sulfate and calcium chloride. Bacteria mass breakthrough at sampling distances ranging from 6 to 25.65 m were observed to quantify bacteria attachment over total transport distances (α(L)) and sticking efficiencies at large intra-column segments (α(i)) (>5m). Fractions of cells retained (F(i)) in a column segment as a function of α(i) were fitted with a power-law distribution from which the minimum sticking efficiency defined as the sticking efficiency of 0.001% bacteria fraction of the total input mass retained that results in a 5 log removal were extrapolated. Low values of α(L) in the order 10(-4) and 10(-3) were obtained for UCFL-94 and UCFL-131 respectively, while α(i)-values ranged between 10(-6) to 10(-3) for UCFL-94 and 10(-5) to 10(-4) for UCFL-131. In addition, both α(L) and α(i) reduced with increasing transport distance, and high coefficients of determination (0.99) were obtained for power-law distributions ofα(i) for the two strains. Minimum sticking efficiencies extrapolated were 10(-7) and 10(-8) for UCFL-94 and UCFL-131, respectively. Fractions of cells exiting the column were 0.19 and 0.87 for UCFL-94 and UCL-131, respectively. We concluded that environmentally realistic sticking efficiency values in the order of 10(-4) and 10(-3) and much lower sticking efficiencies in the order 10(-5) are measurable in the laboratory, Also power-law distributions in sticking efficiencies commonly observed for limited intra-column distances (<2m) are applicable at large transport distances(>6m) in columns packed with quartz grains. High fractions of bacteria populations may possess the so-called minimum sticking efficiency, thus expressing their ability to be transported over distances longer than what might be predicted using measured sticking efficiencies from experiments with both short (<1m) and long columns (>25 m). Also variable values of sticking efficiencies within and among the strains show heterogeneities possibly due to variations in cell surface characteristics of the strains. The low sticking efficiency values measured express the importance of the long columns used in the experiments and the lower values of extrapolated minimum sticking efficiencies makes the method a valuable tool in delineating protection areas in real-world scenarios.     

In situ diffusion experiment in granite: phase I

A program of in situ experiments, supported by laboratory studies, was initiated to study diffusion in sparsely fractured rock (SFR), with a goal of developing an understanding of diffusion processes within intact crystalline rock. Phase I of the in situ diffusion experiment was started in 1996, with the purpose of developing a methodology for estimating diffusion parameter values. Four in situ diffusion experiments, using a conservative iodide tracer, were performed in highly stressed SFR at a depth of 450 m in the Underground Research Laboratory (URL). The experiments, performed over a 2 year period, yielded rock permeability estimates of 2 x 10(-21) m(2) and effective diffusion coefficients varying from 2.1 x 10(-14) to 1.9 x 10(-13) m(2)/s, which were estimated using the MOTIF code. The in situ diffusion profiles reveal a characteristic "dog leg" pattern, with iodide concentrations decreasing rapidly within a centimeter of the open borehole wall. It is hypothesized that this is an artifact of local stress redistribution and creation of a zone of increased constrictivity close to the borehole wall. A comparison of estimated in situ and laboratory diffusivities and permeabilities provides evidence that the physical properties of rock samples removed from high-stress regimes change. As a result of the lessons learnt during Phase I, a Phase II in situ program has been initiated to improve our general understanding of diffusion in SFR.     

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.     

In situ anion diffusion experiments using radiotracers

Diffusion experiments in compacted bentonite have been carried out in situ using the borehole laboratory CHEMLAB. The "ordinary" anion iodide and the redox-sensitive pertechnetate ion have been investigated. In spite of strongly reducing groundwater conditions, technetium was found to diffuse mostly unreduced as TcO4-, although in some spots in the compacted clay, the activity was significantly higher, which may be explained by reduction of some TcO4- by iron-containing minerals in the bentonite. The measured concentration profiles in the clay cannot be accommodated by assuming one single diffusion process. The experimental data are modeled assuming two diffusion paths, intralamellar diffusion and diffusion in external water. The apparent diffusivity for the intralamellar diffusion was found to be 8.6 x 10(-11) m2 s(-1) for iodide with a capacity factor of 0.1, while the apparent diffusivity for the diffusion in external water was found to be 5 x 10(-14) m2 s(-1) with alpha=2.26. The corresponding values for Tc were found to be Da= 6 x 10(-11) m2 s(-1), alpha=0.1 and Da= 1 x 10(-13) m2 s(-1), alpha=0.46, respectively. The diffusion constants and capacity factors obtained in this study are in accordance with data from laboratory experiments.     

Use of tracer tests to investigate changes in flow and transport properties due to bioclogging of porous media

Tracer tests were conducted in three laboratory columns to study changes in the hydraulic properties of a porous medium due to bioclogging. About 30 breakthrough curves (BTCs) for each column were obtained. The BTCs were analyzed using analytical equilibrium and dual-porosity models, and estimates of the hydrodynamic dispersion and mass transfer coefficients were obtained by curve fitting. The change in transport properties developed in three stages: an initial phase (I) with no significant changes in transport properties, phase II with growth of biomass near the inlet of the columns causing changes in dispersivity, and phase III with added growth of micro-colonies deeper in the columns causing mass transfer of solutes from the water phase to the biophase. Tracer transport changed from being uniform to more non-uniform with increase in mass transfer of the tracer between the mobile phase and the immobile biomass. An increase in the bulk dispersivity value of up to one order of magnitude was observed. Numerical simulations suggest that local dispersivity values may be as much as 40 times higher in the more severe clogged areas inside the column. The bulk hydraulic conductivities of the columns decreased by up to three orders of magnitude. The hydraulic conductivity and dispersivity parameters were almost recovered after disinfection of the columns. Different models relating the changes of the hydraulic conductivity to the changes in the mobile porosity due to bioclogging were reviewed, and the micro-colony relation of Thullner et al. [Thullner, M., Zeyer, J., Kinzelbach, W., 2002. Influence of microbial growth on hydraulic properties of pore networks, Transport in Porous Media, 49, 99-122.] was found to best describe the relation between the bulk hydraulic parameters.     

Evaluation of air permeability in layered unsaturated materials

Field estimation of air permeability is important in the design and operation of soil-vapor extraction systems. Previous models have examined airflow in homogenous soils, incorporating leakage through a low-permeability cap either as a correction to the airflow equation or as a boundary condition. The dual leakage model solution developed here improves upon the previous efforts by adding a leaky lower boundary condition, allowing for the examination of airflow in heterogeneous layered soils. The dual leakage model is applied to the evaluation of pump tests at a pilot soil-vapor extraction system at the Savannah River Site in South Carolina. A thick, low-permeability, stiff clay layer divides the stratigraphy at the site into two units for evaluation. A modified version of the previous model, using the water table as the impermeable lower boundary, is used to evaluate the permeability of the low-permeability stiff clay layer (3.2 x 10(-10) cm(2)) and permeable sand (7.2 x 10(-7) cm(2)) beneath it. The stiff clay permeability estimate is used in the evaluation of the shallow unit. Permeability estimates of the shallow sand (3.8 x 10(-7) cm(2)) and kaolin cap (1.5 x 10(-9)cm(2)) were obtained with the dual leakage model. The shallow unit was evaluated using the previous model for comparison. The effects of anisotropy were investigated with a series of model simulations based on the shallow unit solution. The anisotropy sensitivity analysis suggests that increased anisotropy ratio or decreased axial permeability has a significant impact on the velocity profile at the lower boundary, especially at high values of the anisotropy ratio. This result may increase estimates of SVE removal rates for contaminants located at the interface of the lower boundary, typical of chlorinated solvent contamination.     

Microbiological reduction of chromium(VI) in presence of pyrolusite-coated sand by Shewanella alga Simidu ATCC 55627 in laboratory column experiments

Hexavalent chromium (Cr(VI)) was reduced to non-toxic trivalent chromium (Cr(III)) by a dissimilatory metal reducing bacteria, Shewanella alga Simidu (BrY-MT) ATCC 55627. A series of dynamic column experiments were conducted to provide an understanding of Cr(VI) reduction by the facultative anaerobe BrY-MT in the presence of pyrolusite (beta-MnO(2)) coated sand and uncoated-quartz sand. All dynamic column experiments were conducted under growth conditions using Cr(VI) as the terminal electron acceptor and lactate as the electron donor and energy source. Reduction of Cr(VI) was rapid (within 8 h) in columns packed with uncoated quartz sand and BrY-MT, whereas Cr(VI) reduction by BrY-MT was delayed (57 h) in the presence of beta-MnO(2)-coated sand. The role of beta-MnO(2) in this study was to provide oxidation of trivalent chromium (Cr(III)). BrY-MT attachment was higher on beta-MnO(2)-coated sand than on uncoated quartz sand at 10, 60, and 85.5 h. Results have shown that this particular strain of Shewanella did not appreciably reduce Mn(IV) to Mn(II) species nor biosorbed Cr and Mn during its metabolic activities.     

In situ experiment to determine advective-diffusive controls on solute transport in a clay-rich aquitard

Solute transport in clay-rich aquitards is characterized as molecular diffusion- or advection-dominated based on the Péclet number (P(e)). However, few field-based measurements of the coefficient of molecular diffusion (D(e)) exist, and none with a range of advection- or diffusion-dominated conditions in the same aquitard. In this long-term field experiment, standing water in a recovering well was spiked with deuterium ((2)H), then water-level recovery and δ(2)H values were monitored as the well returned to static conditions over 1054 days. After a second (2)H spike, water levels and δ(2)H values were monitored to day 1644 while under near static conditions. Modeling of the second spike was used to define the D(e) of (2)H as (3-4)× 10(-10)m(2)s(-1) for an accessible porosity of 0.31. Reservoir concentrations from the initial spike were modeled to define the transition from advection- to diffusion-dominated transport. This occurred after 200 days, consistent with a transition in P(e) from <1 to >1 when the length term is taken as the radial extent of the tracer plume (normalized concentration <0.05). This study verifies plume extent as the characteristic length term in the calculation of P(e) and demonstrates the transition from advection- to diffusion-dominated transport as the value of P(e) decreases below unity.     

A technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.