Assessment of the evolution of the redox conditions in a low and intermediate level nuclear waste repository (SFR1, Sweden)

The evaluation of the redox conditions in an intermediate and low level radioactive waste repository such as SFR1 (Sweden) is of high relevance in the assessment of its future performance. The SFR1 repository contains heterogeneous types of wastes, of different activity levels and with very different materials, both in the waste itself and as immobilisation matrices and packaging. The level of complexity also applies to the different reactivity of the materials, so that an assessment of the uncertainties in the study of how the redox conditions would evolve must consider different processes, materials and parameters. This paper provides an assessment of the evolution of the redox conditions in the SFR1. The approach followed is based on the evaluation of the evolution of the redox conditions and the reducing capacity in 15 individual waste package types, selected as being representative of most of the different waste package types present or planned to be deposited in the SFR1. The model considers different geochemical processes of redox relevance in the system. The assessment of the redox evolution of the different vaults of the repository is obtained by combining the results of the modelled individual waste package types. According to the model results, corrosion of the steel-based material present in the repository keeps the system under reducing conditions for long time periods. The simulations have considered both the presence and the absence of microbial activity. In the initial step after the repository closure, the microbial mediated oxidation of organic matter rapidly causes the depletion of oxygen in the system. The system is afterwards kept under reducing conditions, and hydrogen is generated due to the anoxic corrosion of steel. The times for exhaustion of the steel contained in the vaults vary from 5 ky to more than 60 ky in the different vaults, depending on the amount and the surface area of steel. After the complete corrosion of steel, the system still keeps a high reducing capacity, due to the magnetite formed as steel corrosion product. The redox potential in the vaults is calculated to evolve from oxidising at very short times, due the initial oxygen content, to very reducing at times shorter than 5 years after repository closure. The redox potential imposed by the anoxic corrosion of steel and hydrogen production is on the order of -0.75 V at pH 12.5. In case of assuming that the system responds to the Fe(III)/Magnetite system, and considering the uncertainty in the pH due to the degradation of the concrete barriers, the redox potential would be in the range -0.7 to -0.01V. A Monte-Carlo probabilistic analysis on the rate of corrosion of steel shows that the reducing capacity of the system provided by magnetite is not exhausted at the end of the assessment period, even assuming the highest corrosion rates for steel. Simulations assuming presence of oxic water due to glacial melting, intruding the system 60 ky after repository closure, indicate that magnetite is progressively oxidised, forming Fe(III) oxides. The time at which magnetite is completely oxidised varies depending on the amount of steel initially present in the waste package. The behaviour of Np, Pu, Tc and Se under the conditions foreseen for this repository is discussed

Retention and diffusion of radioactive and toxic species on cementitious systems: Main outcome of the CEBAMA project

Cement-based materials are key components in radioactive waste repository barrier systems. To improve the available knowledge base, the European CEBAMA (Cement-based materials) project aimed to provide insight on general processes and phenomena that can be easily transferred to different applications. A bottom up approach was used to study radionuclide retention by cementitious materials, encompassing both individual cement mineral phases and hardened cement pastes. Solubility experiments were conducted with Be, Mo and Se under high pH conditions to provide realistic solubility limits and radionuclide speciation schemes as a prerequisite for meaningful adsorption studies. A number of retention mechanisms were addressed including adsorption, solid solution formation and precipitation of radionuclides within new solid phases formed during cement hydration and evolution. Sorption/desorption experiments were carried out on several anionic radionuclides and/or toxic elements which have received less attention to date, namely: Be, Mo, Tc, I, Se, Cl, Ra and 14C. Solid solution formation between radionuclides in a range of oxidation states (Se, I and Mo) with the main aqueous components (OH−, SO4 −2, Cl−) of cementitious systems on AFm phases were also investigated

Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon

The carbon–carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (−0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials

Andra thermodynamic database for performance assessment: ThermoChimie

International audienceThermodynamic data are an essential input for relevance of geochemical modeling and more particularly to assess the behavior of radionuclides and other pollutants in the performance assessment of a radioactive waste repository. ThermoChimie (http://www.thermochimie-tdb.com/), the thermodynamic database developed by Andra, meets the requirements of completeness, accuracy and consistency for numerous radionuclides and chemotoxic elements and various major components of a geological repository: solid phases constitutive of the host-rock, bentonites, concretes, and corresponding secondary minerals with respect to their long term evolution. ThermoChimie developments are also dedicated to evaluating specific conditions of the near field of radioactive waste, in particular regarding temperature increase and release of organic ligands or soluble salts. ThermoChimie database is extracted into compatible formats with different geochemical codes, allowing an overall consistency between different models using it in support. (c) 2014 Elsevier Ltd. All rights reserved

URANIUM BEHAVIOR IN CALLOVO-OXFORDIAN CLAY ROCK FORMATION; FROM LABORATORY-DERIVED MODELS TO IN-SITU KD VALUES

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