New Approach To Understanding the Experimental 133Cs NMR Chemical Shift of Clay Minerals via Machine Learning and DFT-GIPAW Calculations.

Structural determination of adsorbed atoms on layered structures such as clay minerals is a complex subject. Radioactive cesium (Cs) is an important element for environmental conservation, so it is vital to understand its adsorption structure on clay. The nuclear magnetic resonance (NMR) parameters of 133Cs, which can be determined from solid-state NMR experiments, are sensitive to the local neighboring structures of adsorbed Cs. However, determining the Cs positions from NMR data alone is difficult. This paper describes an approach for identifying the expected atomic positions on clay minerals by combining machine learning (ML) with experimentally observed chemical shifts. A linear ridge regression model for ML is constructed from the smooth overlap of atomic position descriptor and gauge-including projector augmented wave (GIPAW) ab initio data. The constructed ML model predicts the GIPAW data to within a 3 ppm root-mean-squared error. At this stage, the 133Cs chemical shifts can be instantaneously calculated from the Cs positions on any clay layers using ML. The inverse analysis, which derives the atomic positions from experimentally observed chemical shifts, is developed from the ML model. The input data for the inverse analysis are the layer structure and the experimentally observed chemical shifts. The Cs positions for the targeted chemical shifts are then output. Inverse analysis is applied to montmorillonite, and the resultant Cs positions are found to be consistent with previous results (Ohkubo, T.; et al. J. Phys. Chem. A 2018, 122, 9326-9337). The Cs positions on saponite clay are also clarified from experimentally observed chemical shifts and inverse analysis.

Selenide [Se(-II)] Immobilization in Anoxic, Fe(II)-Rich Environments: Coprecipitation and Behavior during Phase Transformations.

The radionuclide selenium-79 (Se-79) is predicted to be a key contributor to the long-term radiologic hazards associated with geological high-level waste (HLW) repositories; hence its release is of pertinent concern in the safety assessment of repositories. However, interactions of reduced Se species with aqueous Fe(II) species and solid phases arising from the corrosion of a steel overpack could play a role in mitigating its migration to the surrounding environment. In this study, we examined the immobilization mechanisms of Se(-II) during its interaction with aqueous Fe(II) and freshly precipitated Fe(OH)2 at circumneutral and alkaline conditions, respectively, its response to changes in pH, and its behavior during aging at 90 °C. Using microscopic and spectroscopic techniques, we observed ß-FeSe precipitation, regardless of whether Se(-II) reacts with aqueous species or solid phases, and that modifying the pH following initial immobilization did not remobilize Se(-II). These observations indicate that Se(-II) migration beyond the overpack can be effectively and rapidly retarded via interactions with Fe(II) species arising from overpack corrosion. Thermodynamic calculations, however, showed that iron selenides became metastable at alkaline conditions and will dissolve in the long term. Aging experiments at 90 °C showed that Se(-II) can be completely retained via the crystallization of ferroselite at circumneutral conditions, while it will be largely remobilized at alkaline conditions. Our results show that Se(-II) mobility can be significantly influenced by its interactions with the corrosion products of the steel overpack and that these behaviors will have to be considered in repository safety assessments.

Key factors controlling radiocesium sorption and fixation in river sediments around the Fukushima Daiichi Nuclear Power Plant. Part 1: Insights from sediment properties and radiocesium distributions.

In order to elucidate the radiocesium transport behaviors in natural environment, we systematically investigated sediments from the highly contaminated rivers of Ukedo and Odaka around the Fukushima Daiichi Nuclear Power Plant. We focused on determining the key factors controlling the radiocesium sorption and fixation, such as variations in the particle size, clay mineralogy, and organic matter (OM). The distribution patterns of the 137Cs concentration and particle size fractions were found to be similar for the two rivers, indicating that both clay and silt fractions contributed almost equally to the Cs sorption. The clay mineralogical composition evaluated using X-ray diffraction analysis showed that the relative contents of micaceous minerals were higher in the Ukedo River samples, whereas the relative contents of smectite and kaolinite were higher in the Odaka River samples. This implies that the sediments in both rivers were likely at different weathering stages due to the different geological settings in both catchments. The effects of OM on the sediment properties were also investigated by comparing the cation exchange capacity (CEC) and the radiocesium interception potential (RIP) of the two samples both with and without OM present. The CEC values were controlled by both the clay minerals and OM, and the RIP values increased significantly in the absence of OM. Such trends were correlated to the total organic carbon values, which may be used to understand the direct and indirect roles of OM in the sorption and fixation of Cs. These key differences in river sediment were attributed to the differences in the geological settings and weathering stages. These properties may contribute to the different sorption and fixation behaviors of radiocesium. In the second part paper, we further examined these behaviors and identified key factors by investigating their relationship to the sediment properties of both rivers.

Key factors controlling radiocesium sorption and fixation in river sediments around the Fukushima Daiichi Nuclear Power Plant. Part 2: Sorption and fixation behaviors and their relationship to sediment properties.

We systematically investigated the sorption and fixation behaviors of radiocesium (137Cs) for sediments taken from the rivers of Ukedo and Odaka around the Fukushima Daiichi Nuclear Power Plant. By comparing the Cs sorption and sequential desorption results at various Cs concentrations, across a range of sediment properties, we were able to understand the different contributions at frayed edge sites (FESs) and regular exchange sites (RESs) of the clay minerals, and their relationships with the Cs concentrations and the contents of organic matter (OM). The Cs sorption and fixation were dominated by FESs at trace Cs concentrations, and by ion exchange at RES and the collapse of interlayers at higher Cs concentrations. The Cs sorption at lower Cs concentration was strongly related to radiocesium interception potential (RIP); however, Cs fixation was more related to clay mineralogy (i.e. contents of mica, vermiculite and hydroxy-interlayered vermiculite) rather than the RIP. The first-order kinetic constants for time-dependent Cs sorption at low Cs concentrations were correlated negatively to the ratio between the total organic carbon and RIP values. This implies that Cs access to FESs requires a relatively long duration that is dependent on the contents of the OM. From these results, the sorption and fixation mechanisms were confirmed to be significantly different at different Cs concentrations. Then, the prediction of Cs transport should be based on the key mechanisms that are dominant at the actual trace levels of Cs. A significant difference between the Cs fixation behaviors at the Ukedo River and Odaka River may be understood by considering the differences in their clay mineralogy, due to the different geological settings and weathering stages of both catchments.

New Insights into the Cs Adsorption on Montmorillonite Clay from 133Cs Solid-State NMR and Density Functional Theory Calculations.

The adsorption sites of Cs on montmorillonite clays were investigated by theoretical 133Cs chemical shift calculations, 133Cs magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and X-ray diffraction under controlled relative humidity. The theoretical calculations were carried out for structures with three stacking variations in the clay layers, where hexagonal cavities formed with Si-O bonds in the tetrahedral layers were aligned as monoclinic, parallel, alternated; with various d-spacings. After structural optimization, all Cs atoms were positioned around the center of hexagonal cavities in the upper or lower tetrahedral sheets. The calculated 133Cs chemical shifts were highly sensitive to the tetrahedral Al (AlT)-Cs distance and d-spacing, rather than to the Cs coordination number. Accordingly, three peaks observed in our theoretical spectra were interpreted to be adsorbed Cs around the center of hexagonal cavity with or without AlT and on the surface in the open nanospace. In a series of 133Cs MAS NMR spectral changes for partial Cs substituted samples, the Cs atoms are preferentially adsorbed at sites near AlT for low Cs substituted montmorillonites. The presence of nonhydrated Cs was also confirmed in partially Cs substituted samples, even after being hydrated under high relative humidity.

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.

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.