Geological Repositories For Radioactive Waste Research Articles

Predicting bentonite swelling pressure: optimized XGBoost versus neural networks

The swelling pressure of bentonite and bentonite mixtures is critical in designing barrier systems for deep geological radioactive waste repositories. Accurately predicting the maximum swelling pressure is essential for ensuring these systems' long-term stability and sealing characteristics. In this study, we developed a constrained machine learning model based on the extreme gradient boosting (XGBoost) algorithm tuned with grey wolf optimization (GWO) to determine the maximum swelling pressure of bentonite and bentonite mixtures. A dataset containing 305 experimental data points was compiled, including relevant soil properties such as montmorillonite content, liquid limit, plastic limit, plasticity index, initial water content, and soil dry density. The GWO-XGBoost model, incorporating a penalty term in the loss function, achieved an R2 value of 0.9832 and an RMSE of 0.5248 MPa in the testing phase, outperforming feed-forward and cascade-forward neural network models. The feature importance analysis revealed that dry density and montmorillonite content were the most influential factors in predicting maximum swelling pressure. While the developed model demonstrates high accuracy and reliability, it may have limitations in capturing extreme values due to the complex nature of bentonite swelling behavior. The proposed approach provides a valuable tool for predicting the maximum swelling pressure of bentonite-based materials under various conditions, supporting the design and analysis of effective barrier systems in geotechnical engineering applications.

A CSS surface based THM bounding constitutive model for volumetric behavior of bentonite

Development of the constitutive model for bentonite under coupled thermo-hydro-mechanical (THM) condition is of great significance for the construction and safety assessment of deep geological disposal repositories for high-level radioactive waste (HLW). In this work, a new temperature-suction-mean net stress (T-s-p) space with the conception of critical saturated state (CSS) surface was defined to represent the actual stress state of bentonite under coupled THM condition. Then, based on the CSS surface, a THM constitutive model was proposed for describing the volumetric behavior of compacted bentonite. Under the THM model framework, two bounding surfaces were proposed to describe the elastoplastic volume changes induced by mechanical response of skeleton and hydration of montmorillonite, respectively. The model responses upon some typical THM paths were simulated and discussed to reveal the performance of the proposed constitutive model for bentonite. Finally, the proposed model was validated by simulating by several volume change tests carried out on different bentonites. The results confirmed that the proposed model shows more advantages in describing the THM volumetric behavior.

Differences and implications of strontium distribution coefficient on various granite compositional materials.

The distribution coefficient (Kd) of radionuclides is a crucial parameter in assessing the safety of high-level radioactive waste (HLW) geological repository. It is determined in the laboratory through batch and column experiments. However, differences in obtained Kd values from distinct experiments have not been thoroughly assessed and compared. This study evaluated strontium (Sr) sorption on different granite materials using static batch and dynamic experiments (column and core-flooding experiments). The results from batch sorption experiments showed higher Sr sorption on granite under acidic and strongly alkaline conditions, low solid-liquid ratios, and low ionic strength. In column experiments, a two-site sorption model was used to simulate Sr transport in crushed granite and mixed pure minerals. The sorption of Sr on crushed granite exhibited a higher affinity than that of mixed pure minerals. The dual-porosity transport model was employed to investigate Sr transport behavior in fractured granite in the core-flooding experiment. Kd obtained from batch sorption experiments are four to twenty times higher than those from column experiments, and two to three orders of magnitude higher than that from a core-flooding experiment. The results of this study provide valuable insights into safety assessment for the HLW geological repository.

The plastic behavior and compression of bentonite clay under heating effect

The bentonite material is currently used in a variety of applications ranging from hydraulic barriers and waste-buffer protection to other special uses in industry and underground disposal of high-level nuclear waste. In the deep geological repository for high-level radioactive waste, the clay acting as a buffer material between the host rock and the canister is subjected to thermal load, which could impact its geotechnical properties. Thus this study is aimed at investigating the swell and compressibility of bentonite subjected to heating at 200 °C, 400 °C, and 600 °C. The impact of heating on the index properties, the swell and compression and hydraulic conductivity is explored. The change in temperature due to weather fluctuations was found to have a minor effect on physical behavior, but this effect is found to be significant when the temperature is raised to high levels in the order of 200 °C–600 °C (Celsius). The rate at which swell and hydraulic conductivity is developed is presented in this study. The result indicated an elimination of the swellable clay minerals effect in the bentonite clay upon exposure to a temperature of 600 °C. This study introduces useful information and data for modeling the behavior of bentonite when subjected to elevated temperatures for use in application for deep geological repository for high-level radioactive waste storage and other applications.

Development of thermal-hydraulic coupling model for deep-geological disposal of high-level radioactive wastes

The buffer plays an important role in a engineered barrier system for the deep geological repository of high-level radioactive waste (HLW). High temperature may result in degradation of buffer performance. It is crucial to investigate the buffer temperature behavior so that its peak temperature is not higher than the criterion of 100 °C. In the present work, the thermal-hydraulic (T-H) coupling model is developed to simulate the histories of temperature and saturation in the disposal repository. This model is validated with the previous simulation works in the DECOVALEX 2015 Task B2 in order to simulate the geological repository of HLW with confidence. The whole repository of HLW in the present works can be reasonably simplified as a single hole with the symmetric boundary conditions on its peripheral sides. Effects of tunnel spacing and hole spacing of repository on the histories of buffer peak temperature are considered since the layout with various spacing is strongly related to the peak temperature of buffer. Based on the comparison of simulation results from the T-H coupling model and T-only model for the different layout of whole HLW repository, the maximum value of peak temperature in the buffer predicted by the T-H coupling model is lower than that from the T-only model. In other words, less area is needed for the selection of repository, rendering that the present T-H coupling model can assist in the design of HLW repository.

Quantifying the impact of upscaled parameters on radionuclide transport in three-dimensional fracture-matrix systems

Assessing the long-term safety of geological repositories for high-level radioactive waste is critically dependent on understanding radionuclide transport in multi-scale fractured rocks. This study explores the influence of upscaled parameters on radionuclide movement within a three-dimensional fracture-matrix system using a discrete fracture-matrix (DFM) model. The developed numerical simulation workflow includes creating a random discrete fracture network, meshing of the fractures and matrix, assigning upscaled parameters, and conducting finite element simulations. We simulated the spatiotemporal evolution of radionuclide concentrations in the fractures and matrix over a century, revealing significant spatial heterogeneity driven by a heterogeneous seepage field. Employing geostatistics-based upscaling methods, we predicted the effective ranges of crucial solute transport parameters at the field scale. The matrix diffusion coefficient, matrix distribution coefficient, and longitudinal dispersivity were upscaled by factors of 2.0–3.0, 2.5–4.0, and 10–104, respectively, based on laboratory-scale measurements. Incorporating these upscaled parameters into the DFM model, we analyzed their impact on radionuclide transport. Our findings demonstrate that an upscaled matrix diffusion coefficient and matrix distribution coefficient result in a delayed transport of radionuclides in fractures by enhancing mass transfer between the fractures and rock matrix, while an upscaled longitudinal dispersivity accelerates transport by advancing the positions of concentration peaks. Sensitivity analysis revealed that the matrix distribution coefficient is the most impactful, followed by dispersivity and matrix diffusion coefficient. These insights are important for minimizing parameter uncertainties and enhancing the accuracy of predictions concerning radionuclide transport in multi-scale fractured rocks.

Multi-stage micrite diagenesis in the late Jurassic of the Eastern Paris Basin: petrophysical and mechanical properties for engineering purposes

Abstract The Calcaires du Barrois Formation is a succession of dominantly micritic limestone of Kimmeridgian to Tithonian age, outcropping in the eastern part of the Paris Basin. This is an active karstic aquifer of interest to Andra (French National Agency for Radioactive Waste Management), who are studying the feasibility of a deep geological repository of radioactive waste in an underground research laboratory located approximately 450 m below the surface. Surface installations of the Industrial Centre for Geological Disposal project are planned in the upstream recharge zone of the aquifer. It is of primary interest to characterize the Calcaires du Barrois Formation to provide guidelines for the planning and sizing of these facilities, to minimize the impact on the aquifer system. An integrated study was designed for this purpose, linking petrography (thin section and scanning electron microscopy), carbon and oxygen stable isotope geochemistry, X-ray diffraction, petrophysics and geomechanics. It is based on the analysis of three key cored wells penetrating the formation at different relative depths. The Calcaires du Barrois have undergone several stages of diagenesis that have defined the current properties. Unconformities associated with the Jurassic–Cretaceous transition led to prolonged early subaerial exposures during which freshwater flowed efficiently through the upper half of the formation. Through mineralogical stabilization, among other processes, microporosity was preserved in micrites in this interval consisting of clean limestone with thin marl layers. The lower half of the formation, more argillaceous, was not or was only slightly affected by this early meteoric diagenesis, and recrystallization and cementation of micrites occurred during burial diagenesis, involving chemical compaction. Later, during the return to the surface associated to the Cenozoic orogens, another phase of meteoric diagenesis affected the uppermost few metres below the outcropping portions of the formation, but without modifying significantly the previously acquired petrophysical properties. Consequently, an intra-formational boundary was progressively developed at around 75 m (from the top reference). This boundary separates (1) a lower half of the Calcaires du Barrois with dense and tight micrites, showing high Young's modulus values, and a moderate intensity of fractures, from (2) an upper half with microporous micrites showing low Young's modulus values, and almost devoid of fractures. A transitional zone of about 30 m thick, with intermediate properties, sitting above this boundary and below the only thin metre-scale macroporous grainstone level of the formation, accommodated most of the deformation linked to the Cenozoic Western European orogens and is intensively fractured. The current hydrogeological model considers a purely sedimentological boundary to delimit two sub-aquifers within the Calcaires du Barrois Formation. This will have to be reappraised since it is here demonstrated that the real boundary is located significantly higher in the formation and is inherited from a multi-stage diagenetic history. These findings will complement and influence planning for the Industrial Centre's project.

Iodide retention characteristics on oxidized Cu coupon in saline and alkaline environments: Perspectives on high-level radioactive waste disposal

Radioactive iodine, particularly 129I, is one of the most hazardous radioisotopes found in deep geological repositories for high-level radioactive waste (HLW). This study investigated the iodide retention capacity of Cu coupons, simulating Cu canisters, under potential repository conditions. In saline environments (0.1 M NaCl + 0.01 M MgSO4), iodide was immobilized through CuI(s) formation on the oxidized surface of Cu coupons. This process was facilitated by the favorable affinity between Cu+ oxidized from the Cu coupons and I−. The iodide retention capacity of Cu coupons exhibited notable sensitivity to the pH and chemical composition of the solutions. Cu+ remained stably complexed with Cl− under saline conditions, leading to the CuI(s) formation. However, in distilled water, iodide retention decreased over time due to the transformation of CuI to CuO through Cu oxidation. In an alkaline solution (0.1 M KOH), iodide retention was negligible. These results indicate that radioactive iodide ions, released in the event of canister failure, can be effectively immobilized, and their migration to the ecosystem can be impeded through CuI(s) formation on oxidized Cu canisters in saline conditions. Consequently, Cu canisters can serve as an effective barrier against radioactive iodide migration and as a long-term isolation medium for HLW, particularly under saline conditions.

Gas-entry pressure impact on the evaluation of hydrogen migration at different scales of a deep geological disposal of radioactive waste

Although the importance of gas-entry pressure in simulating two-phase liquid–gas flow in porous media has been studied at the column and borehole scales, its impact on the simulation of transient hydraulic-gas at different scales of a deep geological repository of radioactive waste (DGR) in low permeability clay rock during the post-closure phase has not yet been studied. The purpose of this work is to show that neglecting this phenomenon can lead to underestimation of the maximum gas pressure and water–gas fluxes simulated within the host rock and backfilled drift network. This could impact the performance of the engineered barrier system of a DGR. Simulations performed for a high-level waste disposal cell and for a simplified repository composed of hundreds of disposal cells situated in a clay host rock, show that gas preferentially migrates through the DGR components with low capillary entry pressures, such as the excavation damaged zone (Refers to the zone where fractures develop due to failure of the rock mass around galleries after tunneling) (EDZ), the engineered barriers materials (backfill, bentonite-plug…) and interfaces between the EDZ and these materials. Such a result could have significant consequences on the performance of a repository, due to the accumulation of gas in the drift network and high increase of gas pressure, which could lead to the host rock hydraulic fracturing.

Assessing Sensor Integrity for Nuclear Waste Monitoring Using Graph Neural Networks.

A deep geological repository for radioactive waste, such as Andra's Cigéo project, requires long-term (persistent) monitoring. To achieve this goal, data from a network of sensors are acquired. This network is subject to deterioration over time due to environmental effects (radioactivity, mechanical deterioration of the cell, etc.), and it is paramount to assess each sensor's integrity and ensure data consistency to enable the precise monitoring of the facilities. Graph neural networks (GNNs) are suitable for detecting faulty sensors in complex networks because they accurately depict physical phenomena that occur in a system and take the sensor network's local structure into consideration in the predictions. In this work, we leveraged the availability of the experimental data acquired in Andra's Underground Research Laboratory (URL) to train a graph neural network for the assessment of data integrity. The experiment considered in this work emulated the thermal loading of a high-level waste (HLW) demonstrator cell (i.e., the heating of the containment cell by nuclear waste). Using real experiment data acquired in Andra's URL in a deep geological layer was one of the novelties of this work. The used model was a GNN that inputted the temperature field from the sensors (at the current and past steps) and returned the state of each individual sensor, i.e., faulty or not. The other novelty of this work lay in the application of the GraphSAGE model which was modified with elements of the Graph Net framework to detect faulty sensors, with up to half of the sensors in the network being faulty at once. This proportion of faulty sensors was explained by the use of distributed sensors (optic fiber) and the environmental effects on the cell. The GNNs trained on the experimental data were ultimately compared against other standard classification methods (thresholding, artificial neural networks, etc.), which demonstrated their effectiveness in the assessment of data integrity.

Towards Reliable Barrier Systems: A Constrained XGBoost Model Coupled with Gray Wolf Optimization for Maximum Swelling Pressure of Bentonite

Bentonite and bentonite mixtures are used as buffer material for deep geological radioactive waste repositories. The proper determination of bentonite maximum swelling pressure is important as it influences the long-term stability and sealing characteristics of the barrier system. We developed a constrained machine learning model based on extreme gradient boosting (XGBoost) algorithm tuned with grey wolf optimization (GWO) to determine the maximum swelling pressure of bentonite and bentonite mixtures. We integrated a penalty term into the XGBoost algorithm’s loss function to constrain the model during the training phase ensuring meaningful predictions. To this end, we compiled a dataset containing 305 experimental data of bentonite maximum swelling pressure and other relevant soil properties including montmorillonite content, liquid limit, plastic limit, plasticity index, initial water content, and soil dry density to develop the model. The performance of the hybrid GWO-XGBoost model was benchmarked against feed-forward and cascade-forward neural network models. The GWO-XGBoost model showed a better performance in estimating the experimental values comparing to the other models, thereby demonstrating its effectiveness and reliability in determining the maximum swelling pressure of bentonite and bentonite mixtures.

Scenario development for safety assessment in deep geologic disposal of high-level radioactive waste and spent nuclear fuel: A review.

Radiation and radioactive substances result in the production of radioactive wastes which require safe management and disposal to avoid risks to human health and the environment. To ensure permanent safe disposal, the performance of a deep geological repository for radioactive waste is assessed against internationally agreed risk-based standards. Assessing postclosure safety of the future system's evolution includes screening of features, events, and processes (FEPs) relevant to the situation, their subsequent development into scenarios, and finally the development and execution of safety assessment (SA) models. Global FEP catalogs describe important natural and man-made repository system features and identify events and processes that may affect these features into the future. By combining FEPs, many of which are uncertain, different possible future system evolution scenarios are derived. Repository licensing should consider both the reference or "base" evolution as well as alternative futures that may lead to radiation release, pollution, or exposures. Scenarios are used to derive and consider both base and alternative evolutions, often through production of scenario-specific SA models and the recombination of their results into an assessment of the risk of harm. While the FEP-based scenario development process outlined here has evolved somewhat since its development in the 1980s, the fundamental ideas remain unchanged. A spectrum of common approaches is given here (e.g., bottom-up vs. top-down scenario development, probabilistic vs. bounding handling of uncertainty), related to how individual numerical models for possible futures are converted into a determination as to whether the system is safe (i.e., how aleatoric uncertainty and scenarios are integrated through bounding or Monte Carlo approaches).

Pore‐Scale Modeling of Water and Ion Diffusion in Partially Saturated Clays

AbstractAn accurate mechanistic understanding of solute diffusion in partially saturated clays is critical for assessing the safety of deep geological repositories for radioactive waste. In this study, a pore‐scale numerical framework is developed to simulate water and ion diffusion in partially saturated clays. First, the two‐phase Shan‐Chen Lattice Boltzmann method is employed to establish the liquid‐gas distribution in a reconstructed three‐dimensional pore geometry of a clay. An equivalent solute method is also developed and validated to improve the numerical stability of the solution at the liquid/gas interface corresponding to steep variations of the concentration and diffusion coefficient of the water tracer. By using a mobility‐distance relationship from molecular simulations, Fick's law is numerically solved to simulate water diffusion in nanopores, while the coupled Poisson‐Boltzmann‐Nernst‐Planck equations are solved to simulate ion diffusion under the influence of the electrical double layer (EDL). Our model reveals that the decrease of relative effective diffusion coefficients during the desaturation is more pronounced for ions than for water, due to the additional transport pathway of water tracers in the gas phase. The obtained effective diffusion coefficients of tritiated water and ions agree well with reported data from compacted sedimentary rocks. By comparing the local electric potential and the distribution of ion concentrations in single pores, the simulation results suggest that the EDL in unsaturated clays has a more complex influence on ion distribution than under fully water‐saturated conditions. This study provides critical insights into the coupled transport processes of solutes in partially saturated clays.

Water-rock interactions of uranium deposits: A field investigation and laboratory batch experiment

Interactions between bedrock and groundwater in the far-field of a deep geological repository (DGR) for high-level radioactive waste significantly affect the transport of uranium, which is the major radionuclide in a DGR. Therefore, the present study evaluated the geochemical behavior of uranium by assessing the hydrogeochemical characteristics of groundwater, surface water, mine water, and quarry runoff water in the Okcheon metamorphic belt, which represents a natural analogue study site in Korea. A batch experiment was also conducted to further elucidate the interactions between the uranium-containing rock and groundwater in the study area. The results of the field investigation indicated that uranium in groundwater formed aqueous complexes in the form of calcium uranyl tricarbonate. The concentrations of uranium in groundwater were low, at less than 1 μg L−1, which seems to be attributable to the dissolutions of uraninite, coffinite, UO2(am), and U4O9(c) under the moderately reduced condition and subsequent control by co-precipitation with iron (hydr)oxides. The results of the batch experiment showed that uranium concentrations may be controlled by adsorption or surface complexation with iron oxides. The field study demonstrates the equilibrium state maintained in the current geochemical conditions at the study site, while the batch experiment provides implications regarding the reaction processes over time. Overall, this study showed that uranium forms complexes with carbonate and sulfate under the geochemical conditions of the study site, and that its mobility could be restricted through co-precipitation or adsorption/surface complexation. This study is expected to contribute to a comprehensive understanding of how the behavior of uranium is affected by the evolution of geochemical conditions around the DGR.

Free swelling behavior of MX80 bentonite under elevated temperatures up to 200 °C

This paper focuses on understanding trends in the swelling potential of MX80 bentonite under temperatures up to 200 °C using a high-pressure cell. The free swelling behavior of expansive clays under high temperature and high fluid pressure conditions that may be encountered in geological repositories for high-level radioactive waste is important as the swelling potential is closely linked with key transition points on the physical and chemical properties of these clays. Free swell tests performed at temperatures ranging from 22 to 200 °C under sufficient pressure to ensure that the pore water remains as a superheated liquid were performed to assess whether the swell index of bentonite follows similar non-monotonic trends with temperature as observed in the literature for the cation exchange capacity. The measured swell indices follow an increasing-decreasing trend with a transition close to 100 °C. The experimental results can be used to guide parameter selection in long-term simulations on the buffer behavior of the buffer material, which requires an understanding of temperature effects on the coupled thermal-hydraulic-mechanical properties governing these processes.

Modelling the thermo-mechanical behaviour of a rock joint

The CNSC, the Canadian regulator for the nuclear industry, participated in DECOVALEX-2023 Task G that focuses on the thermo (T) - hydro (H)- mechanical (M) behaviour of rock joints. Joints are omnipresent in rock masses and are planes of weakness in the host rock. When deep geological repositories (DGRs) for radioactive waste are being considered in areas where rock joints are present, the joints could be preferential pathways for radionuclide migration. Therefore, their THM behaviour must be better understood to assess the safety of the DGR. Under different possible internal and external perturbations, a joint can move by shear and dilation. If the joint crosses the emplacement area of a waste container, the heat generated from the waste can itself induce shearing of the joint. Excessive shear movement can in turn lead to failure of the container, resulting in earlier release of radionuclides. Furthermore, dilation that might accompany shear, results in an increase in the joint aperture creating a faster flow path for radionuclide transport. Mathematical models are important tools that need to be developed and employed, in order to assess joint shear and dilation under different loading conditions, such as the heat generated from the emplaced waste. The authors have developed such a mathematical model based on a macroscopic formulation within the framework of elasto-plasticity. It is verified against analytical solutions and validated against shear under constant normal load tests and thermal shearing tests of joints in granite.

Experimental study of hydraulic properties of the granite fracture under heating-cooling cycles

The fracture within the surrounding rock will suffer heating-cooling process for the high-level radioactive waste (HLW) geological repository after the disposal of the HLW, and the conductivity variation of fracture to the heating-cooling process is crucial for the long-term safety of the HLW repository. To study the response of hydraulic properties to temperature of granite fracture, the hydraulic conductivity measurement of granite fracture was carried out during heating-cooling cycles (25 °C-120 °C-25 °C) with different confining pressures (3 MPa, 5 MPa and 8 MPa). In addition, the variation of morphology, pore structure and mineral distribution of fractured granite were analyzed using nuclear magnetic resonance and digital image processing technology. Results show that the hydraulic aperture continuously decreased with increasing temperature, then slightly recovered with the decrease of temperature during the first heating-cooling process. For the second heating-cooling process, the evolution of the hydraulic aperture with temperature is similar to the first heating-cooling cycle, while the variation magnitude was decreased significantly. The confining pressure affect the recovery ability of hydraulic aperture during the cooling process, the hydraulic aperture recover decreased with the increasing confining pressure. Combined effects of the confining pressure and thermal effect control the plastic deformation and fracture aperture of granite fracture. A formula considering the influence of temperature and confining pressure was developed to characterize the hydraulic aperture of granite fracture. In addition, variations in morphyology and mineral distribution were analyzed of granite fracture before and after the test. Result shows that the roughness of fracture surfaces decreased, and biotite and feldspar increased while quartz decreased after tests. Findings from the study could provide important reference for the HLW geological disposal engineering.

Swiss deep drilling campaign 2019–2022: Geological overview and rock properties with focus on porosity and pore-space architecture

A recently completed deep drilling campaign, comprising 9 deep boreholes penetrating the Mesozoic sedimentary sequence of northern Switzerland, yielded >6 km of drillcore. One of the main objectives was to characterise the low-permeability sequence with the lower Jurassic Opalinus Clay in its centre, motivated by the site selection for a deep geological repository for radioactive waste. In this context, the chemical and isotopic composition of the porewater, as well as the mineralogical and petrophysical properties of the rocks, were among the main study targets. In this paper, the main objective was the characterisation of the lithologically diverse Jurassic rock sequence with focus on mineralogy, porosity and pore-space architecture. Given the large amount of data, a well constrained relationship between clay content (relating to fine-grained sheet-silicate minerals) and porosity could be established. Porosity increases with clay content along a concave curve, but in detail minor formation-specific differences of the positions relative to the best-fit curve were identified. These are attributed to the highly variable deposition rates that resulted in different times available for early diagenesis to alter the rock fabric by mineral dissolution and cementation, thereby affecting the compaction behaviour. Pore-size distributions were obtained from N2 ad-/desorption isotherms. A distinct peak at a radius of 3 nm can be clearly correlated with clay minerals, whereas limestones are dominated by pore sizes in the range of 40–100 nm, and marls show intermediate distributions. A conceptual framework is proposed distinguishing a nanometric porosity that is proportional to the clay content and a contribution of larger pores that are related to the geometric incompatibility between platy clay minerals and isometric calcite or quartz. The contribution of these larger pore is thought to explain the curvature of the clay content-porosity relationship and the more limited compaction of the clay in pressure shadows adjacent to the larger grains. A number of outliers towards high porosity at a given clay content were identified in oolites (most strongly in Fe-rich oolites), sandstones and a unit containing coral-reef material. All these units have in common the presence of competent calcite or quartz grains at the time of deposition, leading to grain-supported fabrics and therefore to a more limited compaction in the interstitial pore space.

Experimental study of water-extractable sulphate in Opalinus Clay and implications for deriving porewater concentrations

In northern Switzerland, the Opalinus Clay, a Jurassic claystone formation, is foreseen as host rock for a deep geological repository for radioactive waste. Characterizing its porewater is of particular importance for assessing the mobility of radionuclides and the stability of the engineered barriers. Although the porewater composition of the Opalinus Clay is fairly well known, there is still controversy on the sources of sulphate obtained by different porewater characterization methods. A striking observation is that sulphate concentrations from aqueous extraction and recalculated to in-situ conditions are consistently much higher than sulphate concentrations measured in borehole waters, squeezed waters and advectively displaced waters (“excess sulphate”). Accordingly, the main objective of this study is to better investigate the processes affecting dissolved sulphate concentrations during aqueous extraction and, thus, to reduce uncertainties in predicting the concentrations of this compound in the Opalinus Clay porewater. To this end, a series of extraction experiments were conducted using variable solid/liquid ratios, extraction times and extract solutions. In order to suppress sulphide-mineral oxidation, all the experiments were performed in a glovebox under oxygen-free conditions (atmosphere and solutions). Measurements of the sulphur and oxygen isotope composition of the dissolved sulphate in aqueous extracts are aimed to further constrain the source of the “excess sulphate”. Finally, the plausibility of the SO4 data from extraction experiments in terms of their representativeness for in-situ conditions was evaluated by simple geochemical modelling. The modelling shows that SO4 concentrations from aqueous extracts recalculated to in-situ conditions imply dissolved and exchangeable cation concentrations which are not consistent with measured data, thus, attesting non-conservative behaviour for sulphate during aqueous extraction. However, the various extraction experiments showed that pyrite oxidation was successfully suppressed during the experiments and neither contributions from e.g. organic material, congruent calcite dissolution and/or sulphate mineral dissolution provide enough SO4 to explain the “excess sulphate”. Ultimately, the various extraction experiments failed to definitely identify the source of the “excess sulphate” in aqueous extracts. However, the good agreement found between the δ18O and δ34S values of dissolved SO4 in aqueous extracts and those of borehole waters suggest that the “excess sulphate” might be weakly bound to mineral surfaces.

Assessment of canister degradation for the encapsulation of spent nuclear fuel: Key research issues encountered in recent regulatory reviews and government decision making in Sweden

Abstract. Regulatory review of a licence application for construction and operation of a geological repository for radioactive waste should not only be based on information provided by the applicant but also on viewpoints brought up by stakeholders and decision makers. In the Swedish Radiation Safety Authority's (SSM) licensing review of a spent fuel repository at the Forsmark site, the main concerns brought up in court hearings, from national consultations and by the Swedish government were focused around the long-term protective capacity of the copper canisters with cast iron inserts. The most debated canister degradation mechanisms were anoxic corrosion of copper (in oxygen gas free water), localised sulphide corrosion (pitting corrosion and stress corrosion cracking), the influence of gamma radiation, and strain hardening of the canister cast iron insert. The main question addressed by SSM is not whether such effects can be ruled out altogether, but rather their potential extent and influence on canister integrity during a sufficiently long period in the repository environment. Constraints are mainly based on rock properties and associated hydrological and geochemical factors known from site investigation and knowledge about the protective capability of the buffer barrier. The key factors are in general well characterised and cover for instance sulphide availability, groundwater flow, mass transfer rates and expected mechanical loading on canisters in the repository environment. The canister corrosion/degradation mechanisms reviewed in this paper are judged by SSM to have a small or limited importance for demonstration of regulatory compliance, taking into account the characteristics of the site, the function of the buffer, and the margins provided by the significant thickness and mechanical strength of the proposed canister.