Yukio Tachi

Diffusion and sorption of neptunium(V) in compacted montmorillonite: effects of carbonate and salinity

Abstract Diffusion and sorption of radionuclides in compacted bentonite/montmorillonite are key processes in the safe geological disposal of radioactive waste. In this study, the effects of carbonate and salinity on neptunium(V) diffusion and sorption in compacted sodium montmorillonite were investigated by experimental and modeling approaches. Effective diffusion coefficients (De) and distribution coefficients (Kd) of 237Np(V) in sodium montmorillonite compacted to a dry density of 800 kg m−3 were measured under four chemical conditions with different salinities (0.05/0.5 M NaCl) and carbonate concentrations (0/0.01 M NaHCO3). De values for carbonate-free conditions were of the order of 10−10–10−11 m2 s−1 and decreased as salinity increased, and those for carbonate conditions were of the order of 10−11–10−12 m2 s−1 and showed the opposite dependence. Diffusion-derived Kd values for carbonate-free conditions were higher by one order of magnitude than those for carbonate conditions. Diffusion and sorption behaviors were interpreted based on mechanistic models by coupling thermodynamic aqueous speciation, thermodynamic sorption model (TSM) based on ion exchange, and surface complexation reactions, and a diffusion model based on electrical double layer (EDL) theory in homogeneous narrow pores. The model predicted the experimentally observed tendency of De and Kd qualitatively, as a result of the following mechanisms; 1) the dominant aqueous species are NpO2+ and NpO2CO3− for carbonate-free and carbonate conditions, respectively, 2) the effects of cation excess and anion exclusion result in opposite tendencies of De for salinity, 3) higher carbonate in solution inhibits sorption due to the formation of carbonate complexes.

Comparative modeling of an in situ diffusion experiment in granite at the Grimsel Test Site

An in situ diffusion experiment was performed at the Grimsel Test Site (Switzerland). Several tracers ((3)H as HTO, (22)Na(+), (134)Cs(+), (131)I(-) with stable I(-) as carrier) were continuously circulated through a packed-off borehole and the decrease in tracer concentrations in the liquid phase was monitored for a period of about 2years. Subsequently, the borehole section was overcored and the tracer profiles in the rock analyzed ((3)H, (22)Na(+), (134)Cs(+)). (3)H and (22)Na(+) showed a similar decrease in activity in the circulation system (slightly larger drop for (3)H). The drop in activity for (134)Cs(+) was much more pronounced. Transport distances in the rock were about 20cm for (3)H, 10cm for (22)Na(+), and 1cm for (134)Cs(+). The dataset (except for (131)I(-) because of complete decay at the end of the experiment) was analyzed with different diffusion-sorption models by different teams (IDAEA-CSIC, UJV-Rez, JAEA) using different codes, with the goal of obtaining effective diffusion coefficients (De) and porosity (ϕ) or rock capacity (α) values. From the activity measurements in the rock, it was observed that it was not possible to recover the full tracer activity in the rock (no activity balance when adding the activities in the rock and in the fluid circulation system). A Borehole Disturbed Zone (BDZ) had to be taken into account to fit the experimental observations. The extension of the BDZ (1-2mm) is about the same magnitude than the mean grain size of the quartz and feldspar grains. IDAEA-CSIC and UJV-Rez tried directly to match the results of the in situ experiment, without forcing any laboratory-based parameter values into the models. JAEA conducted a predictive modeling based on laboratory diffusion data and their scaling to in situ conditions. The results from the different codes have been compared, also with results from small-scale laboratory experiments. Outstanding issues to be resolved are the need for a very large capacity factor in the BDZ for (3)H and the difference between apparent diffusion coefficients (Da) from the in situ experiment and out-leaching laboratory tests.

Integrated sorption and diffusion model for bentonite. Part 2: porewater chemistry, sorption and diffusion modeling in compacted systems

It is important to understand the coupled processes of sorption and diffusion of radionuclides (RNs) in compacted bentonite, and to develop mechanistic models that can aid in the prediction of the long-term performance of geological disposal systems of radioactive waste. The integrated sorption and diffusion (ISD) model was developed based on the consistent combination of clay–water interaction, sorption and diffusion models. The diffusion model based on the electrical double layer theory describing relative ionic concentrations and viscoelectric effects at the negatively charged clay surface was coupled with porewater chemistry and sorption models. This ISD model was successfully tested for various actinides with a complex chemistry (Np(V), Am(III), U(VI) under conditions where variably charged carbonate complexes are formed) considered in Part 1, by using published diffusion and sorption data (Da, De, Kd) as a function of partial montmorillonite density. Quantitative agreements were observed by considering uncertainty in porewater chemistry and dominant aqueous species. It can therefore be concluded that the ISD model developed here is able to adequately explain the sorption and diffusion behavior of various RNs with a complex chemistry in compacted bentonites. The performed modeling indicates that uncertainties are mainly related to porewater chemistry and RN speciation and that these parameters need to be carefully evaluated.

Matrix diffusion and sorption of Cs+, Na+, I– and HTO in granodiorite: Laboratory-scale results and their extrapolation to the in situ condition

Matrix diffusion and sorption are important processes controlling radionuclide transport in crystalline rocks. Such processes are typically studied in the laboratory using borehole core samples however there is still much uncertainty on the changes to rock transport properties during coring and decompression. It is therefore important to show how such laboratory-based results compare with in situ conditions. This paper focuses on laboratory-scale mechanistic understanding and how this can be extrapolated to in situ conditions as part of the Long Term Diffusion (LTD) project at the Grimsel Test Site, Switzerland. Diffusion and sorption of (137)Cs(+), (22)Na(+), (125)I(-) and tritiated water (HTO) in Grimsel granodiorite were studied using through-diffusion and batch sorption experiments. Effective diffusivities (De) of these tracers showed typical cation excess and anion exclusion effects and their salinity dependence, although the extent of these effects varied due to the heterogeneous pore networks in the crystalline rock samples. Rock capacity factors (α) and distribution coefficients (Kd) for Cs(+) and Na(+) were found to be sensitive to porewater salinity. Through-diffusion experiments indicated dual depth profiles for Cs(+) and Na(+) which could be explained by a near-surface Kd increment. A microscopic analysis indicated that this is caused by high porosity and sorption capacities in disturbed biotite minerals on the surface of the samples. The Kd values derived from the dual profiles are likely to correspond to Kd dependence on the grain sizes of crushed samples in the batch sorption experiments. The results of the in situ LTD experiments were interpreted reasonably well by using transport parameters derived from laboratory data and extrapolating them to in situ conditions. These comparative experimental and modelling studies provided a way to extrapolate from laboratory scale to in situ condition. It is well known that the difference in porosity between laboratory and in situ conditions is a key factor to scale laboratory-derived De to in situ conditions. We also show that cation excess diffusion is likely to be a key mechanism in crystalline rocks and that high Kd in the disturbed surfaces is critically important to evaluate transport in both laboratory and in situ tests.

Integrated sorption and diffusion model for bentonite. Part 1: clay–water interaction and sorption modeling in dispersed systems

To predict the long-term migration of radionuclides (RNs) under variable conditions within the framework of safety analyses for geological disposal, thermodynamic sorption models are very powerful tools. The integrated sorption and diffusion (ISD) model for compacted bentonite was developed to achieve a consistent combination of clay–water interaction, sorption, and diffusion models. The basic premise considered in the ISD model was to consistently use the same simple surface model design and parameters for describing RNs sorption/diffusion as well as clay surface and porewater chemistry. A simple 1-site non-electrostatic surface complexation model in combination with a 1-site ion exchange model was selected to keep sorption model characteristics relatively robust for compacted systems. Fundamental parameters for the proposed model were evaluated from surface titration data for purified montmorillonite. The resulting basic model was then parameterized on the basis of selected published sorption data-sets for Np(V), Am(III), and U(VI) in dispersed systems, which cover a range of key geochemical conditions such as pH, ionic strength, and carbonate concentration. The sorption trends for these RNs can be quantitatively described by the model considering a full suite of surface species including hydrolytic and carbonate species. The application of these models to the description of diffusive-sorptive transport in compacted bentonites is presented in Part 2.

Sorption and diffusion of Eu in sedimentary rock in the presence of humic substance

Abstract Sorption and diffusion behaviors of Eu in sedimentary rock in the presence of humic substance were investigated. The sedimentary rock collected from 500 m depth of HDB-6 bore hole at horonobe URL site of Japan and Aldrich humic acid (HA) were used in the present study. Sorption behaviors of Eu and the HA on the sedimentary rocks with and without the rock organic matter (ROM) were elucidated as a function of HA concentration. The HA reduced the sorption of Eu on the rock with the increase of HA. Eu and HA sorption on the rock with the ROM was larger than on the rock after removing the ROM, indicating that the ROM plays an important role on the sorption of Eu and HA. The diffusion of Eu in the presence of HA was examined as a function of HA concentration and molecular weight of the HA (∼150 kDa or below 10 kDa) by means of a reservoir depletion test method with the intact rock core of the sedimentary rock. Depletion of Eu concentration in the reservoir was reduced with the increase of HA concentration. On the other hand, slight depletion of HA concentration in the reservoir was observed, indicating that the larger HA molecule diffused less into the rock. From the depletion curve and in-diffusion profile of Eu in the rock, the effective diffusion coefficient, De, and distribution coefficient, Kd, in the intact system were estimated based on the profile fitting of the diffusion data with the conventional simple diffusion-sorption model. It was elucidated that the HA reduced the Kd and De of Eu in the intact system with the increase of HA. The contribution of the HA with smaller molecular weight to both the Eu sorption and diffusion was examined.

Sorption of Eu3+ on Na-montmorillonite studied by time-resolved laser fluorescence spectroscopy and surface complexation modeling

The influence of pH and concentrations of Eu3+ and NaNO3 on the sorption of Eu3+ to Na-montmorillonite were investigated through batch sorption measurements and time-resolved laser fluorescence spectroscopy. The pH had little effect on the distribution coefficients (Kd) in the range of pH 4–7 at 0.01 M NaNO3, which indicates that the cation exchange reaction is a dominant sorption process. Meanwhile, the Kd strongly depended on pH at 1 M NaNO3, suggesting the formation of inner-sphere surface complexes. A cation exchange model combined with a one-site non-electrostatic surface complexation model was successfully applied to the measured Kd data. Linear free-energy relationship was used to estimate the formation constants of the surface species from those of the corresponding aqueous hydrolyzed species. The TRLFS spectra of Eu3+ sorbed on Na-montmorillonite were processed by parallel factor analysis, which provided the fluorescence spectra, decay lifetimes, and relative intensity profiles of three Eu3+ surface species. These species corresponded to one outer-sphere (factor A) and two inner-sphere (factors B and C) complexes. It turned out that factors A and B correspond to Eu3+ sorbed by ion exchange to permanent charge sites of Na-montmorillonite and inner-sphere complexation with surface hydroxyl groups of the edge faces. Factor C became dominant at relatively high pH and ionic strength and likely corresponded to the precipitation of Eu(OH)3 on the surface of Na-montmorillonite.

STABILITY OF MONTMORILLONITE EDGE FACES STUDIED USING FIRST-PRINCIPLES CALCULATIONS

The reactivity and stability of the edge faces of swelling clay minerals can be altered by layer charge and the stacking structure; however, these effects are poorly understood due to experimental limitations. The structure and stability of the montmorillonite {110}, {010}, {100}, and {130} edge faces with a layer charge of either y = 0.50 or y = 0.33 (e−/Si4O10) were investigated using first-principles calculations based on density functional theory. Stacked- and single-layer models were tested and compared to understand the effect of stacking on the stability of montmorillonite edge faces. Most stacked layers stabilize the edge faces by creating hydrogen bonds between the layers; therefore, the surface energy of the layers in the stacked-layer model is lower than in the single-layer model. This indicates that the estimates of edge face surface energy should consider the swelling conditions. Negative surface energies were calculated for these edge faces in the presence of chemisorbed water molecules. A high layer charge of 0.50 reduced the surface energy relative to that of the low layer charge of 0.33. The isomorphic substitution of Mg for Al increased the stability of interlayer Na ion positions, which were stable in the trigonal ring next to the Mg ions. The lowest surface energies of the {010} and {130} edge faces were characterized by the presence of Mg ions on edge faces, which had a strong cation adsorption site due to the local negative charge of the edges. The coordination numbers of O atoms around cations adsorbed to these edge faces were small in comparison to interlayers without water.

Diffusion Model Considering Multiple Pore Structures in Compacted Bentonite

Sorption and diffusion of radionuclides in compacted clays and argillaceous rocks are key processes in the safe geological disposal of radioactive waste. The integrated sorption and diffusion (ISD) model was developed to quantify radionuclide transport in compacted bentonite. The current ISD model is based on a simplified pore structure with averaged pore aperture and the Gouy-Chapman electric double layer (EDL) theory and can account quantitatively for the diffusion of monovalent cations and anions under different conditions (e.g. porewater salinity and bentonite density). In the present study a modified ISD model was developed which considers multiple pore structures, including interlayer and interparticle pores, particularly for anionic species, in order to improve the applicability of the existing model. The applicability of the modified ISD model to multiple pore structures was tested. The dual-pore model, which considers only interparticle pores and averaged interlayer pores, performed adequately as an heterogeneous pore model.

Clay-Based Modeling Approach to Diffusion and Sorption in the Argillaceous Rock from the Horonobe URL: Application to Ni(II), Am(III), and Se(IV)

Sorption and diffusion of radionuclides (RNs) in argillaceous rocks are key processes in the safe geological disposal of radioactive waste. Sorption and diffusion of Ni(II), Am(III), and Se(IV) in mudstone from the Horonobe Underground Research Laboratory were investigated using experimental and modeling approaches. Effective diffusivities obtained by means of through-diffusion experiments were in the following decreasing order: Csþ . Ni2þ HTO . I . Se (SeO3) . Am (Am(CO3)2) based on a comparison with the results of previous studies. The distribution coefficient values were consistent with those obtained using batch sorption tests. These results were interpreted using the clay-based modeling approach coupled with the thermodynamic sorption model by assuming key contributions of clays (smectite and illite), and the diffusion model by assuming the electric double layer theory and the simplified pore model with size distribution. This clay-based model can provide a reasonable account of observed trends for various RNs with complex chemistry, although some systematic gaps in the modeling results need to be evaluated further by considering uncertainties in both the experimental and the modeling approaches.