Long-term non-isothermal reactive transport model of compacted bentonite, concrete and corrosion products in a HLW repository in clay.

Radioactive waste disposal in deep geological repositories envisages engineered barriers such as carbon-steel canisters, compacted bentonite and concrete liners. The stability and performance of the bentonite barrier could be affected by the corrosion products at the canister-bentonite interface and the hyper-alkaline conditions caused by the degradation of concrete at the bentonite-concrete interface. Additionally, the host clay formation could also be affected by the hyper-alkaline plume at the concrete-clay interface. Here we present a non-isothermal multicomponent reactive transport model of the long-term (1Ma) interactions of the compacted bentonite with the corrosion products of a carbon-steel canister and the concrete liner of the engineered barrier of a high-level radioactive waste repository in clay. Model results show that magnetite is the main corrosion product. Its precipitation reduces significantly the porosity of the bentonite near the canister. The degradation of the concrete liner leads to the precipitation of secondary minerals and the reduction of the porosity of the bentonite and the clay formation at their interfaces with the concrete liner. The reduction of the porosity becomes especially relevant at t=104years. The zones affected by pore clogging at the canister-bentonite and concrete-clay interfaces at 1Ma are approximately equal to 1 and 3.3cm thick, respectively. The hyper-alkaline front (pH>8.5) spreads 2.5cm into the clay formation after 1Ma. Our simulation results share the key features of the models reported by others for engineered barrier systems at similar chemical conditions, including: 1) Pore clogging at the canister-bentonite and concrete-clay interfaces; 2) Narrow alteration zones; and 3) Limited smectite dissolution after 1Ma.

Identifiability of diffusion and sorption parameters from in situ diffusion experiments by using simultaneously tracer dilution and claystone data.

In situ diffusion experiments are performed in geological formations at underground research laboratories to overcome the limitations of laboratory diffusion experiments and investigate scale effects. Tracer concentrations are monitored at the injection interval during the experiment (dilution data) and measured from host rock samples around the injection interval at the end of the experiment (overcoring data). Diffusion and sorption parameters are derived from the inverse numerical modeling of the measured tracer data. The identifiability and the uncertainties of tritium and (22)Na(+) diffusion and sorption parameters are studied here by synthetic experiments having the same characteristics as the in situ diffusion and retention (DR) experiment performed on Opalinus Clay. Contrary to previous identifiability analyses of in situ diffusion experiments, which used either dilution or overcoring data at approximate locations, our analysis of the parameter identifiability relies simultaneously on dilution and overcoring data, accounts for the actual position of the overcoring samples in the claystone, uses realistic values of the standard deviation of the measurement errors, relies on model identification criteria to select the most appropriate hypothesis about the existence of a borehole disturbed zone and addresses the effect of errors in the location of the sampling profiles. The simultaneous use of dilution and overcoring data provides accurate parameter estimates in the presence of measurement errors, allows the identification of the right hypothesis about the borehole disturbed zone and diminishes other model uncertainties such as those caused by errors in the volume of the circulation system and the effective diffusion coefficient of the filter. The proper interpretation of the experiment requires the right hypothesis about the borehole disturbed zone. A wrong assumption leads to large estimation errors. The use of model identification criteria helps in the selection of the best model. Small errors in the depth of the overcoring samples lead to large parameter estimation errors. Therefore, attention should be paid to minimize the errors in positioning the depth of the samples. The results of the identifiability analysis do not depend on the particular realization of random numbers.

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis.

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO(2)(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO(3)(-) and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions.

Inverse modeling of multicomponent reactive transport through single and dual porosity media.

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.

Modelling geochemical and microbial consumption of dissolved oxygen after backfilling a high level radiactive waste repository.

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste (HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived from calibration of the REX in situ experiment carried out at the Aspö underground laboratory. The role of geochemical and microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.

Large-scale modeling of reactive solute transport in fracture zones of granitic bedrocks.

Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Aspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Aspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157-172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid-base, redox processes, dissolution-precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na+ and Ca2+. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of iron monosulphides contained in Baltic seafloor sediments. Based on these results, microbially mediated processes are postulated as the most likely hypothesis to explain the measured increase of dissolved bicarbonates and sulphates after tunnel construction.

An Experimental Study on the Ion-Exchange Behavior of the Smectite of Cabo de Gata (Almería, Spain): FEBEX Bentonite.

Binary cation-exchange processes (Na-K, Na-Mg, and Na-Ca) have been investigated at 25 degrees C in samples of bentonite from Cabo de Gata (Almería, SE Spain). Exchange isotherms and Vanselow selectivity coefficients indicate that the preference of this bentonite for K(+), Ca(2+), and Mg(2+) ions is greater than that for the Na(+) ion. The change in (i)(j)K(V) as a function of the equivalent fraction of cation M, E(M), is interpreted on the basis of the presence of different types of adsorption/exchange sites (tetrahedral, octahedral, and edge sites). For the Na/K exchange, (K)(Na)K(V) exhibits a steep decrease for E(K)<0.25-0.3. This is interpreted as due to preferential exchange at the tetrahedral sites. However, the opposite behavior is observed in the case of Ca and Mg, with a noticeable increase of (i)(Na)K(V) for E(Ca)(E(M(g)))>0.6-0.8. The compared selectivities of Ca and Mg for this smectite are nearly equal. As far as the exchanger is concerned, the Na-Ca and Na-Mg exchange is nearly ideal, in the raoultian sense. Thermodynamic exchange constants and the corresponding Gibbs free energies of reaction have been computed from (i)(j)K(V) coefficients. This allow us to quantify the exchanger's affinity sequence, which appears to be Na(+)