Porewater chemistry of Opalinus Clay revisited: Findings from 25 years of data collection at the Mont Terri Rock Laboratory.

The characterisation of porewater chemistry in nanoporous clayrocks is a difficult task. Appropriate extraction methods that have been developed fairly recently and the Mont Terri Rock Laboratory (Switzerland) have played a pioneer role in this regard. During the last 25 years high-quality data from the Opalinus Clay have been acquired. Notably, since the early synthesis of Pearson et al. (2003) a considerable number of newer data from borehole waters and waters extracted from drillcores have been generated. In this study, borehole, squeezing, leaching and cation exchange data were critically evaluated in order to derive a consistent porewater chemistry database across the formation. The results underline that the porewater composition is not constant but exhibits a regular change towards the formation boundaries. This is explained by diffusive exchange between the Na–Cl type porewater and the two bounding freshwater aquifers. Furthermore, the porewater is constrained by cation exchange, carbonate mineral and celestite equilibria. Major solute data obtained from borehole waters and squeezed waters are broadly consistent, although the latter exhibit somewhat more scatter. Overall, the knowledge on porewaters at the Mont Terri Rock Laboratory has been significantly improved. In particular, this regards the spatial profiles of major elements besides Cl, and better constraints on exchanger composition and pH/pCO2 conditions

3D modelling of long-term sulfide corrosion of copper canisters in a spent nuclear fuel repository

Copper canisters are a central component in the safety of the Finnish spent fuel repository concept (KBS-3), where the main corrodent potentially affecting the canister integrity is sulfide. In this study, a 3D numerical model is developed to assess the evolution of sulfide fluxes and the spatially resolved canister corrosion depths for the Finnish spent nuclear fuel repository concept. The backfilled tunnel and the disposal hole are implemented using repository geometries, with sulfide being produced at their interface with the rock (excavation damaged zone) by sulfate reducing bacteria (SRB). Recent experimental findings regarding the microbial sulfate reduction process as well as the scavenging of sulfide via iron (oxy)hydroxides are incorporated in the reactive transport model. Long-term simulations are performed, predicting a heterogeneous corrosion of the canister with a max. corrosion depth of 1.3 mm at the bottom corner after one million years. The evolution of sulfide fluxes shows two main phases, depending on the source of sulfate: first sulfate is supplied by the dissolution of gypsum from the bentonite barriers, followed by a steady, low-level supply from the groundwater. Sensitivity cases demonstrate that both the organic carbon and Fe(III) oxide contents in the bentonite are critical to the corrosion evolution, by being the main electron donor for SRB activities and the major sulfide scavenger in the bentonite, respectively. The backfilled tunnel contributes little to the flux of corrosive sulfide to the canister due to the attenuation by Fe(III)-oxides/hydroxides but induces a notable flux of sulfate into the disposal hole

Eighteen years of steel–bentonite interaction in the FEBEX in situ test at the Grimsel Test Site in Switzerland

Corrosion of steel canisters containing buried high-level radioactive waste is a relevant issue for the long-term integrity of repositories. The purpose of the present study was to evaluate this issue by examining two differently corroded blocks originating from a full-scale in situ test of the FEBEX bentonite site in Switzerland. The FEBEX experiment was designed initially as a feasibility test of an engineered clay barrier system and was recently dismantled after 18 years of activity. Samples were studied by ‘spatially resolved’ and ‘bulk’ experimental methods, including Scanning Electron Microscopy, Elemental Energy Dispersive Spectroscopy (SEM-EDX), μ- Raman spectroscopy, X-ray Fluorescence (XRF), X-ray Diffraction (XRD), and 57Fe Mössbauer spectrometry, with a focus on Fe-bearing phases. In one of the blocks, corrosion of the steel liner led to diffusion of Fe into the bentonite, resulting in the formation of large (width > 140 mm) red, orange, and blue colored halos. Goethite was identified as the main corrosion product in the red and orange zones while no excess Fe2+ (compared to the unaffected bentonite) was observed there. Excess Fe2+ was found to have diffused further into the clay (in the blue zones) but its speciation could not be unambiguously clarified. The results indicate the occurrence of newly formed octahedral Fe2+ either as Fe2+ sorbed on the clay or as structural Fe2+ inside the clay (following electron transfer from sorbed Fe2+). No other indications of clay transformation or newly formed clay phases were found. The overall pattern indicates that diffusion of Fe was initiated when oxidizing conditions were still prevailing inside the bentonite block, resulting in the accumulation of Fe3+ close to the interface (up to three times the original Fe content), and continued when reducing conditions were reached, allowing deeper diffusion of Fe2+ into the clay (inducing an increase of 10– 12% of the Fe content)

Exploring diffusion and sorption processes at the Mont Terri rock laboratory (Switzerland): lessons learned from 20 years of field research

Transport and retardation parameters of radionuclides, which are needed to perform a safety analysis for a deep geological repository for radioactive waste in a compacted claystone such as Opalinus Clay, must be based on a detailed understanding of the mobility of nuclides at different spatial scales (laboratory, field, geological unit). Thanks to steadily improving experimental designs, similar tracer compositions in different experiments and complementary small laboratory-scale diffusion tests, a unique and large database could be compiled. This paper presents the main findings of 20 years of diffusion and retention experiments at the Mont Terri rock laboratory and their impact on safety analysis

Unravelling the corrosion processes at steel/bentonite nterfaces in in situ tests

Microscopic and spectroscopic analyses were conducted on steel/bentonite interface samples removed from four in situ experiments that were carried out in three underground research laboratories at different temperatures and under different hydraulic and geochemical conditions. The results provide valuable information about the corrosion processes occurring in high-level radioactive waste repositories. Systematic patterns can be deduced from the results, irrespective of carbon steel grade, type of bentonite and its degree of compaction, geochemical environment or experimental setup. Thus, a clear dependence of the corrosion rates on temperature and exposure period, as well as on the availability of H2O and O2 provided by the surrounding bentonite buffer, is observed. Furthermore, Fe(II) ions released by corrosion interact with the structural Fe in the clay. Recent developments highlight the usefulness of reactive transport modelling in understanding the coupled corrosion and Fe–clay interaction processes