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.     

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.     

Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

Retardation capacity of organophilic bentonite for anionic fission products

Sorption and diffusivity of iodide and pertechnetate (I- and TcO4-) on MX-80 bentonite with different hexadecylpyridinium (HDPy+) loadings were studied using equilibrium solutions of different ionic strengths. In HDPy(+)-modified bentonite, iodide and pertechnetate ions exhibited increasing sorption (characterized by the distribution ratio, Rd), while Cs+ and Sr2+ showed decreasing sorption with increasing organophilicity. In case of medium-loading levels, the simultaneous sorption of anions (I- and TcO4-) and cations (Cs+ and Sr2+) was observed. Sorption of ions was influenced by the composition of the electrolytes employed. It decreased gradually with increasing ionic strength of the electrolyte solutions. The experiments revealed the general tendency that the diffusivity (Da [cm2.s-1]) for iodide and pertechnetate decreases with increasing organophilicity and increases with increasing ionic strength of the equilibrium solutions, confirming the results of the sorption experiments. Additionally, some mineralogical and chemical investigations, like IR spectral analysis of the organo-bentonite samples and exchange behavior of HDPy+, were performed. On the basis of these analyses, it was concluded that the alkylammonium ions are sorbed as (1) HDPy+ cations, (2) HDPyCl molecules and (3) micelles with decreasing binding intensities in this order.     

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.     

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.     

Diffusivity measurement of heavy ions in Wyoming montmorillonite gels by X-ray computed tomography

Medical X-ray computed tomography (CT) was applied to the measurement of the diffusion coefficients of heavy ions in an artificial barrier material for the disposal of nuclear wastes. Cs(+), Sr(2+), I(-), and Br(-) are the heavy ions measured and the barrier used is the water-rich gel of Wyoming montmorillonite (86.5-100 wt.% H(2)O). X-ray CT yields an inevitable artifact (beam-hardening) in the obtained images. Before the diffusion experiments, the polychromatic primary X-ray spectrum of the CT scanner was measured by a CdZnTe detector, and the effects of the artifact were examined for an aqueous CsCl solution sample. The results show that the beam-hardening artifact derived from the polychromatic photon energy distribution can be suppressed by applying a special image reconstruction method assuming the chemical composition of samples. The transient one-dimensional diffusion of heavy ions in a plastic container filled with the gel was imaged nondestructively by the X-ray CT scanner with an in-plane resolution of 0.31 mm and slice thickness of 2 mm. The results show that diffusivities decrease with increasing clay weight fraction. The degree of the diffusivity decrease was high for cations (Cs(+) and Sr(2+)) and low for anions (I(-) and Br(-)). The quantitative decomposition of the contribution of the geometrical tortuosity and of the sorption to the diffusivity was performed by subtracting the diffusivity of nonsorbing I(-) from the measured diffusivities. The results show that the contribution of the sorption is large for Cs(+), Sr(2+) and small for Br(-). Because X-ray CT allows nondestructive and quick measurements of diffusivities, the technique would be useful particularly for measuring the diffusive migration of harmful radioactive elements.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Simultaneous estimation of effective and apparent diffusion coefficients in compacted bentonite

Effective diffusion coefficients (D(e)) are usually measured by means of "through-diffusion" experiments in which steady state is reached, and the "time-lag" methods are used to estimate the apparent diffusion coefficient (D(a)). For sorbing radionuclides (as caesium), the time needed to reach steady-state conditions is very large, and the precision in D(a) determinations is not satisfactory. In this paper, a method that allows determining simultaneously effective and apparent diffusion coefficients in compacted bentonite without reaching steady-state conditions is described. Basically, this method consists of an "in-diffusion" experiment in which the concentration profile in the bentonite sample is used to estimate D(a), and the temporal evolution of the solute concentration in the reservoir is used to estimate D(e). This method has several advantages over the typical "through-diffusion" experiments, in particular: (a) experiment duration is significantly shorter, (b) D(a) values are measured with greater precision and (c) it is not necessary to maintain a constant solute concentration in the reservoir. This new method has been used to estimate the effective and apparent diffusion coefficients for caesium in FEBEX bentonite and in order to validate it, the results have been compared with results previously obtained with standard methods. Experimental results have been satisfactorily modelled using a simple model of diffusion in porewater and the measured value of D(e)(Cs) is very similar to D(e)(HTO) in the same bentonite. There is no evidence of "surface diffusion" in FEBEX bentonite for caesium.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

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.     

Study on anisotropy of effective diffusion coefficient and activation energy for deuterated water in compacted sodium bentonite

To quantify the effects of temperature on the diffusivity of deuterated water (HDO) in compacted sodium bentonite, through-diffusion experiments were conducted at elevated temperatures ranging from 298 to 333 K. Kunipia F (Na-montmorillonite content>98 wt.%; Kunimine Industries) was compacted to a dry density of 0.9 or 1.35 Mg/m(3). As montmorillonite particles were oriented perpendicular to the direction of compaction, the anisotropy of diffusivity was investigated both parallel and normal to the preferred orientation of the montmorillonite. The effective diffusion coefficient D(e) of HDO was larger when the diffusional direction was parallel as opposed to normal to the preferred orientation for both dry densities. The magnitude of D(e) and the anisotropy for HDO were in good accordance with previously reported results for tritiated water at room temperature. Activation energies of D(e) were isotropic and increased with increasing dry density over the range of 19-25 kJ/mol. This relationship was considered to be due to both pore structure development and the high activation energy of water near the montmorillonite surface.     

Diffusive transport through compacted Na- and Ca-bentonite

The effect of exchangeable cation — Na⁺ and Ca ²⁺ — on the diffusive transport of I⁻, Sr ²⁺ and ³H (as HTO) in compacted bentonite was examined using a through-diffusion method. Total intrinsic diffusion coefficients, D_i, were determined from the steady-state flux of the diffusants through the clays, and apparent diffusion coefficients, D_a, were obtained from the time lag technique. The clays were compacted to a dry bulk density of 1.3 Mg/m³, and Na-bentonite was saturated with a solution of 100 mol NaCl/m3 and Ca-bentonite with one of 50 mol CaCl₂/m³. The D_i values for all diffusants are 2 to 6 times higher in the Ca- than Na-clay. We attribute this to the larger quasicrystal, or particle, size of Ca- compared to Na-bentonite. Hence, Ca-bentonite has a greater proportion of relatively large pores; this was confirmed by Hg intrusion porosimetry. This means the diffusion pathways in Ca-bentonite are less tortuous than those in Na-bentonite. Moreover, in some cases the effective porosity, or the porosity available for diffusive transport, may be greater in Ca-bentonite. The D_a values are inversely proportional to the distribution coefficients of the diffusants with the clays.     

Improved interpretation of in-diffusion measurements with confined swelling clays

Diffusion is considered the principal transport mechanism of radio-nuclides and other low-molecular-weight pollutants in compacted clays used as barriers at various disposal and storage sites, for example, at projected deep repositories for radioactive waste. Porous filters are routinely used to confine swelling clays in diffusion studies of radio-tracers. The presence of the filter gives rise to considerable mass-transfer limitations at the clay boundary that result in erroneous diffusion parameters. We have solved the problem of in-diffusion with due account for this phenomenon by means of Fourier transforms. By using literature data on the in-diffusion of traces of radioactive cesium in an argillaceous rock (Opalinus clay) and a compacted bentonite (FEBEX bentonite), we have demonstrated that taking into account the mass-transfer limitations considerably improves the quality of the theoretical fit of the time evolution of radio-tracer concentration in the reservoir. Besides that, we have shown that ignoring the mass-transfer limitations leads to a noticeable underestimation of both the effective diffusion coefficient and the specific sorption capacity of the clay.     

Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.     

Translocation studies of 137Cs and 90Sr in bean plants (Phaseolus vulgaris): simulation of fallout

In case of an accident at a nuclear power plant with liberation of radioactive material into the atmosphere, knowledge about the behavior of plant species when in contact with radionuclides is indispensable for safety reasons. The leaf-fruit translocation is an important route through which agricultural products are contaminated by radionuclides. To quantify the leaf-fruit translocation factors for 137Cs and 90Sr in common beans (Phaseolus vulgaris) an experiment was carried out in a greenhouse with a randomized block design. 137Cs activity was determined by gamma-ray spectrometry, while chemical separation followed by beta counting of 90Y was used for 90Sr determination. The model applied for translocation indicated functional dependence between the moment of tracer application and the physiological development of the bean plant. Translocation factors obtained for 137Cs and 90Sr were 0.16 and less than 0.005, respectively.     

A cation exchange model to describe Cs+ sorption at high ionic strength in subsurface sediments at Hanford site, USA

A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.     

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).     

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO(2)(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO(3)(-) and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions.