Apparent diffusion coefficients and chemical species of neptunium (V) in compacted Na-montmorillonite

Diffusion of neptunium (V) in compacted Na-montmorillonite was studied through the non-steady state diffusion method. In this study, two experimental attempts were carried out to understand the diffusion mechanism of neptunium. One was to establish the diffusion activation energy, which was then used to determine the diffusion process in the montmorillonite. The other was the measurement of the distribution of neptunium in the montmorillonite by a sequential batch extraction. The apparent diffusion coefficients of neptunium in the montmorillonite at a dry density of 1.0 Mg m-3 were from 3.7 x 10(-12) m2 s-1 at 288 K to 9.2 x 10(-12) m2 s-1 at 323 K. At a dry density of 1.6 Mg m-3, the apparent diffusion coefficients ranged between 1.5 x 10(-13) m2 s-1 at 288 K and 8.7 x 10(-13) m2 s-1 at 323 K. The activation energy for the diffusion of neptunium at a dry density of 1.0 Mg m-3 was 17.5 +/- 1.9 kJ mol-1. This value is similar to those reported for diffusion of other ions in free water, e.g., 18.4 and 17.4 kJ mol-1 for Na+ and Cl-, respectively. At a dry density of 1.6 Mg.m-3, the activation energy was 39.8 +/- 1.9 kJ mol-1. The change in the activation energy suggests that the diffusion process changes depending on the dry density of the compacted montmorillonite. A characteristic distribution profile was obtained by the sequential extraction procedure for neptunium diffused in compacted montmorillonite. The estimated fraction of neptunium in the pore water was between 3% and 11% at a dry density of 1.6 Mg m-3 and at a temperature of 313 K. The major fraction of the neptunium in the montmorillonite was identified as neptunyl ions sorbed on the outer surface of the montmorillonite. These findings suggested that the activation energy for diffusion and the distribution profile of the involved nuclides could become powerful parameters in understanding the diffusion mechanism.     

Diffusion mechanism of chloride ions in sodium montmorillonite

For safety assessment of geological disposal of HLW, it is necessary to understand the diffusion mechanism of radionuclides in compacted bentonite. In this study, the diffusion behavior of chloride ions in compacted montmorillonite was studied from the viewpoints of the activation energy for apparent diffusion and the basal spacing of the compacted montmorillonite. A unique change in the activation energy as a function of the dry density of the montmorillonite was found. The activation energy decreased from 17.4 to 13.5 kJ mol-1 as the dry density increased from 0.7 to 1.0 Mg m-3 and increased to 25.1 kJ mol-1 at dry densities above 1.0 Mg m-3. The basal spacing of 1.88 nm, corresponding to the three-water layer hydrate state, was not observed by X-ray diffraction (XRD) until the dry density increased to 1.0 Mg m-3, where the minimum activation energy was obtained. On the other hand, a basal spacing of 1.56 nm, corresponding to the two-water layer hydrate state, was observed at the dry densities of 1.4 Mg m-3 and above, where the activation energies were more than 22 kJ mol-1. These experimental results suggest that there are at least two additional diffusion processes that can raise or reduce the activation energy and are affected by water in the region adjacent to the montmorillonite surfaces. If the "Grahame model" can be introduced to describe the electrical double layer, surface diffusion will be considered the possible predominant diffusion process, even for anions like chloride ions.     

Effect of silica sand on activation energy for diffusion of sodium ions in montmorillonite and silica sand mixture

The effect of silica sand on the diffusion of sodium ions in mixtures of montmorillonite and silica sand was studied by measuring the apparent diffusion coefficients, activation energies for diffusion, and the basal spacing of the mixed samples. These diffusion experiments suggest that the apparent diffusion coefficients of sodium ions in the mixed samples were almost the same as those of pure montmorillonite samples having the same partial dry densities of montmorillonite. The activation energy dependence for diffusion of sodium ions on the partial dry density was different between the mixed samples and the pure montmorillonite samples. The activation energy increased by adding silica sand at the partial dry density of 1.0 Mg m(-3), and decreased by adding silica sand at the partial dry densities higher than 1.2 Mg m(-3). A change in the XRD profile was observed after adding silica sand at the partial dry density of 1.6 Mg m(-3). Here, a three-water-layer hydrate state of montmorillonite was found in the mixed sample whereas only a two-water-layer hydrate state was observed in the pure montmorillonite sample. These experimental results suggest that silica sand changed the montmorillonite microstructure in the mixed samples, which then altered the sodium-ion diffusion process.     

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.     

Geotechnical engineering properties of incinerator ash mixes

The incineration of solid waste produces large quantities of bottom and fly ash. Landfilling has been the primary mode of disposal of these waste materials. Shortage in landfill space and the high cost of treatment have, however, prompted the search for alternative uses of these waste materials. This study presents an experimental program that was conducted to determine the engineering properties of incinerator ash mixes for use as construction materials. Incinerator ash mixes were tested as received and around optimum compacted conditions. Compaction curves, shear strength, and permeability values of fly ash, bottom ash, and their various blends were investigated. Bottom ash tends to achieve maximum dry density at much lower water content than does fly ash. The mixes displayed a change in their cohesion and friction angle values when one of the two mix components was altered or as a result of the addition of water. The permeability of bottom ash is quite comparable to that of sand. The permeability of fly ash lies in the range of those values obtained for silts and clays. A 100% bottom ash compacted at the optimum water content has a lower density value and yields a higher friction angle and cohesion values than most construction fills. This would encourage the use of bottom ash as a fill or embankment material because free drainage of water will prevent the buildup of pore water pressures.     

Geotechnical Engineering Properties of Incinerator Ash Mixes

Abstract

The incineration of solid waste produces large quantities of bottom and fly ash. Landfilling has been the primary mode of disposal of these waste materials. Shortage in landfill space and the high cost of treatment have, however, prompted the search for alternative uses of these waste materials. This study presents an experimental program that was conducted to determine the engineering properties of incinerator ash mixes for use as construction materials. Incinerator ash mixes were tested as received and around optimum compacted conditions. Compaction curves, shear strength, and permeability values of fly ash, bottom ash, and their various blends were investigated. Bottom ash tends to achieve maximum dry density at much lower water content than does fly ash. The mixes displayed a change in their cohesion and friction angle values when one of the two mix components was altered or as a result of the addition of water. The permeability of bottom ash is quite comparable to that of sand. The permeability of fly ash lies in the range of those values obtained for silts and clays. A 100% bottom ash compacted at the optimum water content has a lower density value and yields a higher friction angle and cohesion values than most construction fills. This would encourage the use of bottom ash as a fill or embankment material because free drainage of water will prevent the buildup of pore water pressures.     

Hydraulic anisotropy characterization of pneumatic-fractured sediments using azimuthal self potential gradient

The pneumatic fracturing technique is used to enhance the permeability and porosity of tight unconsolidated soils (e.g. clays), thereby improving the effectiveness of remediation treatments. Azimuthal self potential gradient (ASPG) surveys were performed on a compacted, unconsolidated clay block in order to evaluate their potential to delineate contaminant migration pathways in a mechanically-induced fracture network. Azimuthal resistivity (ARS) measurements were also made for comparative purposes. Following similar procedures to those used in the field, compressed kaolinite sediments were pneumatically fractured and the resulting fracture geometry characterized from strike analysis of visible fractures combined with strike data from optical borehole televiewer (BHTV) imaging. We subsequently injected a simulated treatment (electrolyte/dye) into the fractures. Both ASPG and ARS data exhibit anisotropic geoelectric signatures resulting from the fracturing. Self potentials observed during injection of electrolyte are consistent with electrokinetic theory and previous laboratory results on a fracture block model. Visual (polar plot) analysis and linear regression of cross plots show ASPG lobes are correlated with azimuths of high fracture strike density, evidence that the ASPG anisotropy is a proxy measure of hydraulic anisotropy created by the pneumatic fracturing. However, ARS data are uncorrelated with fracture strike maxima and resistivity anisotropy is probably dominated by enhanced surface conduction along azimuths of weak ‘starter paths’ formed from pulverization of the clay and increases in interfacial surface area. We find the magnitude of electrokinetic SP scales with the applied N₂ gas pressure gradient (ΔPN₂) for any particular hydraulically-active fracture set and that the positive lobe of the ASPG anomaly indicates the flow direction within the fracture network. These findings demonstrate the use of ASPG in characterizing the effectiveness of (1) pneumatic fracturing and (2) defining likely flow directions of remedial treatments in unconsolidated sediments and rock.     

Diffusive flux and pore anisotropy in sedimentary rocks

Diffusion of dissolved contaminants into or from bedrock matrices can have a substantial impact on both the extent and longevity of dissolved contaminant plumes. For layered rocks, bedding orientation can have a significant impact on diffusion. A series of laboratory experiments was performed on minimally disturbed bedrock cores to measure the diffusive flux both parallel and normal to mineral bedding of four different anisotropic sedimentary rocks. Measured effective diffusion coefficients ranged from 4.9×10(-8) to 6.5×10(-7)cm(2)/s. Effective diffusion coefficients differed by as great as 10-folds when comparing diffusion normal versus parallel to bedding. Differences in the effective diffusion coefficients corresponded to differences in the "apparent" porosity in the orientation of diffusion (determined by determining the fraction of pore cross-sectional area measured using scanning electron microscopy), with the difference in apparent porosity between normal and parallel bedding orientations differing by greater than 2-folds for two of the rocks studied. Existing empirical models failed to provide accurate predictions of the effective diffusion coefficient in either bedding orientation for all four rock types studied, indicating that substantial uncertainty exists when attempting to predict diffusive flux through sedimentary rocks containing mineral bedding. A modified model based on the apparent porosity of the rocks provided a reasonable prediction of the experimental diffusion data.     

Diffusion of radionuclides in concrete and concrete-bentonite systems

Various construction materials are under consideration for nuclear waste repositories. Two important materials are concrete and bentonite clay, which will act as mechanical barriers and prevent convective water flow. These barriers will also retard transport (diffusion controlled) of dissolved radionuclides by a combination of mechanical constraints and chemical interactions with the solid.An important issue is the possible change of the initial sodium bentonite into the calcium form due to interaction with calcium from the concrete. The initial leaching of concrete was studied using radioactive spiked concrete in contact with compacted bentonite.Measurement were made of the diffusion of Cs, Am and Pu into 5 different types of concrete in contact with pore water. The diffusivity measured for Cs agrees reasonably well with data found in the literature. No movement could be measured for Am and Pu (< 0.2 mm), even though the contact times were extremely long (2.5 and 5 yr, respectively). The diffusion of Na, Ca and Cs from concrete into bentonite was also measured.     

An integrated sorption-diffusion model for the calculation of consistent distribution and diffusion coefficients in compacted bentonite

A thermodynamic sorption model and a diffusion model based on electric double layer (EDL) theory are integrated to yield a surface chemical model that treats porewater chemistry, surface reactions, and the influence of charged pore walls on diffusing ions in a consistent fashion. The relative contribution of Stern and diffuse layer to the compensation of the permanent surface charge represents a key parameter; it is optimized for the diffusion of Cs in Kunipia-F bentonite, at a dry density of 400 kg/m3. The model is then directly used to predict apparent diffusivities (Da) of Cs, Sr, Cl-, I- and TcO4- and corresponding distribution coefficients (Kd) of Cs and Sr in different bentonites as a function of dry density, without any further adjustment of surface chemical and EDL parameters. Effective diffusivities (De) for Cs, HTO, and TcO4- are also calculated. All calculated values (Da, De, Kd) are fully consistent with each other. A comparison with published, measured data shows that the present model allows a good prediction and consistent explanation of (i) apparent and effective diffusivities for cations, anions, and neutral species in compacted bentonite, and of (ii) Kd values in batch and compacted systems.     

Porewater chemistry in compacted re-saturated MX-80 bentonite

Bentonites of various types are being investigated in many countries as backfill materials in high-level radioactive waste disposal concepts. Being able to understand the chemistry of the porewater in compacted bentonite is very important since it is critical to predicting radionuclide solubilities and to the synthesis of sorption data bases, and hence to repository safety studies. In this paper, porewater compositions in compacted bentonites are calculated, taking into consideration such factors as montmorillonite swelling, semi-permeable membrane effects, very low "free water" volumes, and the highly effective buffering characteristics of the exchangeable cations and the amphoteric edge sites. The former buffer the cation concentrations and the latter fix the pH in the porewater of a re-saturated bentonite. The above considerations are used in conjunction with previously measured physico-chemical characterisation data on MX-80 powder to calculate porewater compositions in compacted bentonites. For the MX-80 material specified, the porewaters calculated for initial dry densities between 1200 and 1600 kg m(-3) had relatively high ionic strengths (I approximately 0.3 M), similar cation concentrations and a pH equal to 8.0. The porewaters changed from being Na(2)SO(4)-rich at 1200 kg m(-3) to a NaCl/Na(2)SO(4) type water at 1600 kg m(-3).     

Organic aerosols in the Miami area, USA: temporal variability of atmospheric particles and wet/dry deposition

Atmospheric particulate matter and both wet and dry deposition was collected over a period of nine months at one location in the metropolitan area of Miami, Florida. Molecular distributions and concentrations of n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAHs) and hopanes were determined using weekly composite samples over this time period in order to determine temporal variability, and their possible dependence on climatic parameters such as temperature, rainfall and wind direction and frequency. Based on molecular distributions of the compounds studied, potential emission sources for the atmospheric particles were assessed and suggested to be mainly derived from automobile exhaust and natural sources. Although wet and dry deposition processes were observed to remove about equal amounts of organic aerosols from the Miami atmosphere, dry deposition was dominant in the removal of anthropogenically derived compounds such as PAHs and hopanes. Only very limited seasonal trends were observed, while wind direction and frequency was found to be the most important meteorological parameter controlling the temporal variability of the organic aerosols. This is the first detailed report of this nature for the Miami area.     

Simultaneous nitrification, denitrification, and phosphorus removal in single-tank low-dissolved-oxygen systems under cyclic aeration.

Simultaneous nitrification and denitrification (SND or SNdN) may occur at low dissolved oxygen concentrations. In this study, bench-scale (approximately 6 L) bioreactors treating a continuous feed of synthetic wastewater were used to evaluate the effects of solids retention time and low dissolved oxygen concentration, under cyclic aeration, on the removal of organics, nitrogen, and phosphorus. The cyclic aeration was carried out with repeated cycles of 1 hour at a higher dissolved oxygen concentration (HDO) and 30 minutes at a lower (or zero) dissolved oxygen concentration (LDO). Compared with aeration at constant dissolved oxygen concentrations, the cyclic aeration, when operated with proper combinations of HDO and LDO, produced better-settling sludge and more complete nitrogen and phosphorus removal. For nitrogen removal, the advantage resulted from the more readily available nitrate and nitrite (generated by nitrification during the HDO period) for denitrification (during the LDO period). For phosphorus removal, the advantage of cyclic aeration came from the development of a higher population of polyphosphate-accumulating organisms, as indicated by the higher phosphorus contents in the sludge solids of the cyclically aerated systems. Nitrite shunt was also observed to occur in the LDO systems. Higher ratios of nitrite to nitrate were found in the systems of lower HDO (and, to less dependency, higher LDO), suggesting that the nitrite shunt took place mainly because of the disrupted nitrification at lower HDO. The study results indicated that the HDO used should be kept reasonably high (approximately 0.8 mg/L) or the HDO period prolonged, to promote adequate nitrification, and the LDO kept low (< or =0.2 mg/L), to achieve more complete denitrification and higher phosphorus removal. The above findings in the laboratory systems find strong support from the results obtained in full-scale plant implementation. Two plant case studies using the cyclic low-dissolved-oxygen aeration for creating and maintaining SND are also presented.     

A hybrid plume model for local-scale atmospheric dispersion

This paper presents a local-scale dispersion model, based on atmospheric boundary layer scaling theory. In the vicinity of the source, Gaussian equations are used in both the horizontal and vertical directions. After a specified transition distance, gradient transfer theory is applied in the vertical direction, while the horizontal dispersion is still assumed to be Gaussian. The dispersion parameters and eddy diffusivity are modelled in a form, which facilitates the use of a meteorological pre-processor. We present a novel model of the vertical eddy diffusivity (K_z), which is a continuous function of height in various atmospheric scaling regions. The model also includes a treatment of the dry deposition of gases and particulate matter. The accuracy of the numerical model was analysed by comparing the model predictions with two analytical solutions; the numerical deviations from these solutions were less than 2% for the computational regime. The model has been tested against the Kincaid experimental field data. The agreement of the predictions and the data is good on the average, although the internal variation of the predictions versus data scatter plot is substantial.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.     

A composite medium approximation for unsaturated flow in layered sediments

Saturated-unsaturated flow in strictly layered sediments proceeds via conductors in parallel in the direction parallel to bedding, and via resistors in series in the direction perpendicular to bedding. On sufficiently small scales of space and time, flow in such media will be subject to approximate capillary equilibrium locally, which provides a basis for approximating the effective hydraulic conductivity of a composite multi-layer medium in terms of the conductivities of the individual layers. Equations for the hydraulic conductivity tensor in "composite medium approximation" (COMA) are given in a coordinate system aligned with bedding. Hydraulic conductivity parallel to bedding is generally larger than in the perpendicular direction. The anisotropy depends on the spread of the conductivity distribution, and tends to increase for dryer conditions. The COMA model was implemented in a multi-phase flow simulator and tested by comparison with high-resolution simulations in which all layering heterogeneity is resolved explicitly. Under favorable conditions, COMA is found to accurately represent sub-grid scale flow and transport processes, providing a practical method for simulating field-scale flow and transport in layered media. The approximation improves when layers are thinner, and when flow rates are smaller.     

Recovery of acetylcholine esterase activity of Drawida willsi (Oligochaeta) following application of three pesticides to soil

The recovery of acetylcholine esterase (AChE) activity of a dominant crop field earthworm (Drawida willsi, Michaelsen) was investigated under laboratory conditions following the application of two recommended agricultural (single and double) doses of butachlor (1.1 and 2.2 mga.i.kg(-1) dry soil), malathion (2.2 and 4.4 mga.i.kg(-1) dry soil) and carbofuran (1.1 and 2.2 mga.i.kg(-1) dry soil) to the soil. A sharp decline in the AChE activity of D. willsi was observed up to 9 and 12 days following treatment of carbofuran and malathion in both single and double doses, respectively, whereas very little inhibition was noticed in case of butachlor. D. willsi worms took 45 and 75 days to resume normal AChE activity after exposure to both single and double doses of malathion and carbofuran, respectively. Earlier [Soil Biol. Biochem. 31 (1999) 363-366], [Ph.D. thesis, Sambalpur University, Orissa, India, 2003] and [Pedobiologia (spl. issue), in press] reported that D. willsi takes 75-90 days and 90-105 days to resume normal growth and reproduction following application of both single and double agricultural doses of malathion and carbofuran, respectively. On the basis of the present and previous studies, we strongly suggest that the time gap between the first and second application of malathion, irrespective of single and double dosage, should be at least 90 days, whereas it should be at least 105 days for carbofuran. Butachlor was found to be very toxic, suppressing growth, sexual maturation and cocoon production of D. willsi at both single and double doses [Ph.D. thesis, Sambalpur University, Orissa, India, 2003]. We therefore suggest that application of organochlorine pesticides like butachlor should be avoided as far as possible to ensure maintenance of good soil health.     

The effects of scale and spatial heterogeneities on diffusion in volcanic breccias and basalts: Amchitka Island, Alaska

Knowledge of the factors that influence the diffusion of contaminants, such as the diffusivity and the connected porosity, is crucial to modeling the long-term fate and transport of contaminants in subsurface systems with small or negligible advective flow, such as in fractured crystalline rock. Fractured rock is naturally heterogeneous, and hence, understanding the diffusivity of a molecule through this material (or the formation factor of the medium) becomes a complex problem, with critical concerns about the scale of laboratory measurements and about the spatial variability of these measurements relative to the scale needed for fate and transport modeling. This study employed both electrical and tracer-based laboratory methods to investigate the effects of scale and pore system connectivity on the diffusivity for volcanic matrix rock derived from the study site, a former underground nuclear test site at Amchitka Island, Alaska. The results of these investigations indicate a relatively well-connected pore system with scale effects generally limited to approximately 6 cm lengths and well-correlated to observed heterogeneous features. An important conclusion resulting from this study, however, is that there is a potential for the estimated diffusivity to be misrepresented by an order of magnitude if multiple samples or longer sample lengths are not used. Given the relatively large number of measurements resulting from these investigations, an analysis of the probability density function (PDF) of the diffusivity was possible. The PDF of the diffusivity was shown to generally follow a normal distribution for individual geologic layers. However, when all of the geologic layers are considered together, the distribution of the subsurface as a whole was shown to follow a lognormal distribution due to the order of magnitude differences amongst the layers. An understanding of these distributions is essential for future stochastic modeling efforts.     

Experimental and modeling studies on sorption and diffusion of radium in bentonite

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.