Stochastic analysis of the effect of heterogeneity and fractures on radionuclide transport in a low-permeability clay layer

Deep low-permeability clay layers are considered as safe environments for disposal of high-level radioactive waste. In Belgium, the Boom Clay is a candidate host rock for deep geological disposal. In this study, we analyze the effects of fractures and spatially variable hydraulic conductivity on radionuclide migration through the clay. Fracture geometry and properties are simulated with Monte Carlo simulation. The heterogeneity of hydraulic conductivity is simulated by direct sequential co-simulation using measurements of hydraulic conductivity and four types of secondary variables. The hydraulic conductivity and fracture simulations are used as input for a transport model. Radionuclide fluxes computed with this heterogeneous model are compared with fluxes obtained with a homogeneous model. The output fluxes of the heterogeneous model differ at most 8% from the homogeneous model. The main safety function of the Boom Clay is thus not affected by the fractures and the spatial variability of hydraulic conductivity.     

Stochastic analysis of the effect of spatial variability of diffusion parameters on radionuclide transport in a low permeability clay layer

Most studies that incorporate subsurface heterogeneity in groundwater flow and transport models only analyze and simulate the spatial variability of hydraulic conductivity. Heterogeneity of the other flow and transport parameters are usually neglected. This approach is often justified, but there are, however, cases in which disregarding the heterogeneity of the other flow and transport parameters can be questionable. In low permeability media, for instance, diffusion is often the dominant transport mechanism. It therefore seems logical to incorporate the spatial variability of the diffusion parameters in the transport model. This study therefore analyses and simulates the spatial variability of the effective diffusion coefficient and the diffusion accessible porosity with geostatistical techniques and incorporates their heterogeneity in the transport model of a low permeability formation. The formation studied was Boom clay (Belgium), a candidate host rock for the deep geological disposal of high-level radioactive waste. The calculated output radionuclide fluxes of this model are compared with the fluxes calculated with a homogeneous model and a model with a heterogeneous hydraulic conductivity distribution. This analysis shows that the heterogeneity of the diffusion parameters has a much larger effect on the calculated output radionuclide fluxes than the heterogeneity of hydraulic conductivity in the low permeability medium under study.     

Studying the migration behaviour of selenate in Boom Clay by electromigration

For the disposal of high-level waste (HLW) in a deep geological formation as Boom Clay, safety assessment studies have shown that long lived ⁷⁹Se is one of the more critical fission products. Therefore, the knowledge of its migration properties (diffusion, retention) through the geological barrier (Boom Clay) is of paramount importance. The migration behaviour of selenium strongly depends on its speciation. Under reducing conditions, selenide would be the dominant species and selenium migration would mainly be controlled by the low solubility of Se(−II)-bearing minerals. However Se species are often found in redox disequilibrium and more oxidized species might also coexist. Therefore, the study of selenate migration requires attention, as it might be the most mobile selenium species in the host rock. Electromigration experiments performed with a ⁷⁵Se-labeled selenate in Boom Clay indicate a high mobility for this species. The apparent diffusion coefficient (D_app) of selenate in Boom Clay is estimated from electromigration experiments performed under different electric fields. Using two independent approaches, the value of D_app for selenate is shown to fall in the range from 1.7×10⁻¹¹ to 6.2×10⁻¹¹ m² s⁻¹. Moreover, no reduction of selenate in Boom Clay was observed.     

Hollow Cylinder Tests on Boom Clay: Modelling of Strain Localization in the Anisotropic Excavation Damaged Zone

Boom Clay is extensively studied as a potential candidate to host underground nuclear waste disposal in Belgium. To guarantee the safety of such a disposal, the mechanical behaviour of the clay during gallery excavation must be properly predicted. In that purpose, a hollow cylinder experiment on Boom Clay has been designed to reproduce, in a small-scale test, the Excavation Damaged Zone (EDZ) as experienced during the excavation of a disposal gallery in the underground. In this article, the focus is made on the hydro-mechanical constitutive interpretation of the displacement (experimentally obtained by medium resolution X-ray tomography scanning). The coupled hydro-mechanical response of Boom Clay in this experiment is addressed through finite element computations with a constitutive model including strain hardening/softening, elastic and plastic cross-anisotropy and a regularization method for the modelling of strain localization processes. The obtained results evidence the directional dependency of the mechanical response of the clay. The softening behaviour induces transient strain localization processes, addressed through a hydro-mechanical second grade model. The shape of the obtained damaged zone is clearly affected by the anisotropy of the materials, evidencing an eye-shaped EDZ. The modelling results agree with experiments not only qualitatively (in terms of the shape of the induced damaged zone), but also quantitatively (for the obtained displacement in three particular radial directions).     

Thermo-hydro-mechanical simulation of ATLAS in situ large scale test in Boom Clay

Following the need for understanding and quantifying the effect of temperature on the response of a candidate host formation for radioactive waste disposal, finite element modelling of an in situ thermal experiment has been carried out. Based on a thermo-hydro-mechanical (THM) finite element approach including a consistent thermo-plastic constitutive model, it has been possible to reproduce the THM response of a clay formation submitted to in situ thermal loading. The simulated large-scale experiment, called ATLAS was designed in the underground research facility (HADES-URF) in Mol, Belgium. After an extensive literature analysis on the thermal, hydraulic and mechanical characteristics of Boom Clay, laboratory tests were simulated to calibrate model parameters. The results of the finite element modelling of the ATLAS experiment were compared with in situ measurements and revealed the necessity to account for flow diffusion in all three directions through a 2D axisymmetric analysis. Finally, those results were interpreted in the light of elasto-thermoplasticity, which emphasizes the significant role of thermo-plastic processes in the global THM response of the clay formation.     

Diffusion-driven transport in clayrock formations

Clay mineral-rich sedimentary formations are currently under investigation to evaluate their potential use as host formations for installation of deep underground disposal facilities for radioactive waste (e.g. Boom Clay (BE), Opalinus Clay (CH), Callovo–Oxfordian argillite (FR)). The ultimate safety of the corresponding repository concepts depends largely on the capacity of the host formation to limit the flux towards the biosphere of radionuclides (RN) contained in the waste to acceptably low levels. Data for diffusion-driven transfer in these formations shows extreme differences in the measured or modelled behaviour for various radionuclides, e.g. between halogen RN (³⁶Cl, ¹²⁹I) and actinides (^238,235U, ²³⁷Np, ²³²Th, etc.), which result from major differences between RN of the effects on transport of two phenomena: diffusion and sorption. This paper describes recent research aimed at improving understanding of these two phenomena, focusing on the results of studies carried out during the EC Funmig IP on clayrocks from the above three formations and from the Boda formation (HU).     

Assessing the oxidising effect of NaNO3 and NaNO2 from disposed Eurobitum bituminised radioactive waste on the dissolved organic matter in Boom Clay

In Belgium, compatibility studies are performed in view of the final disposal of nitrate-containing bituminised intermediate-level radioactive waste in Boom Clay, which is considered as a potential host formation. Due to the presence of large amounts of nitrate in the waste, a slow release of nitrate (and to a smaller extent also nitrite) into the Boom Clay is expected. Nitrate and/or nitrite reduction by redox-active components of the host rock may cause a geochemical perturbation of the clay and subsequently might affect its barrier function against the migration of radionuclides. This paper therefore addresses the possible oxidation of one of the main redox-active components of the Boom Clay, i.e. dissolved organic matter, by nitrate and nitrite. For this, abiotic and microbially mediated nitrate and nitrite reduction was studied during long-term batch tests (2–2.5 years) in Boom Clay pore water, containing 155 ± 15 mg C/l present as humic and fulvic acids. Changes in the reducing capacity of the DOM due to oxidation were assessed successfully using two oxidants, namely ferricyanide and ferric citrate. The results of these experiments indicate that an abiotic reaction between DOM and nitrate does not occur or is characterised by very slow kinetics. On the other hand, a slow microbial nitrate reduction to nitrite was observed and the associated oxidation of DOM was confirmed by a decrease in the (partial) reducing capacity of DOM for ferric citrate. In contrast to nitrate, nitrite was shown to oxidise DOM both abiotically and mediated by microbes through (chemo)denitrification, although these reactions also seem to occur only at a rather slow rate. No significant change in the maximally obtainable reducing capacity of DOM (using ferricyanide) was detected during any of the observed reactions, suggesting that the impact of such a slow heterotrophic nitrate reduction is very limited.     

In situ and laboratory investigation of the alteration of Boom Clay (Oligocene) at the air–geological barrier interface within the Mol underground facility (Belgium): Consequences on kerogen and bitumen compositions

The Boom Clay formation (Oligocene) is studied as a reference host rock for methodological studies on deep geological disposal of radioactive waste. During excavation of galleries within the Clay formation (HADES underground research facility, Mol, Belgium), the physico-chemical conditions are significantly modified as an air–clay interface is created. In order to study the long-term impact of the air–clay contact on the organic matter contained in the Boom Clay, two types of samples were studied: (1) a reference series of clay samples having been in contact with the atmosphere of the HADES gallery for increasing times up to several years and (2) unaltered clay samples submitted to artificial oxidation in a ventilated oven at 80 °C. The evolution of geochemical data of the two series was compared using Rock-Eval pyrolysis, GC–MS and size exclusion chromatography. The organic matter of the unaltered clays sampled in the HADES galleries is dominated by type III kerogen (terrestrial) with some contribution of type II (marine) and is thermally immature. The evolution of geochemical parameters during air alteration for the two series are very similar. They show progressive oxidation of kerogen accompanied by the release of bitumen enriched in low molecular weight constituents. Molecular analysis evidences the presence of a complex mixture of aliphatic and aromatic O-bearing compounds, inherited from the degradation of kerogen as well as from the clay catalyzed oxidation of the bitumen. These results show that (1) air oxidation is a major process in the in situ alteration of the organic matter of Boom Clay within the HADES galleries, (2) laboratory oxidation experiments at 80 °C yield similar results as in situ air alteration of Boom Clay and (3) artificial air oxidation may be used to assess the long term exposure of the organic matter to air.     

Laboratory and In Situ Simulation Tests of the Excavation Damaged Zone Around Galleries in Opalinus Clay

In the context of nuclear waste disposal in clay formations, laboratory and in situ simulation experiments were performed to study at reduced scale the excavation damaged zone (EDZ) around tunnels in the indurated Opalinus Clay at Mont Terri, Switzerland. In the laboratory, thick-walled hollow cylindrical specimens were subjected to a mechanical unloading mimicking a gallery excavation. In samples cored parallel to bedding, cracks sub-parallel to the bedding planes open and lead to a buckling failure in two regions that extend from the borehole in the direction normal to bedding. The behaviour is clearly anisotropic. On the other hand, in experiments performed on specimens cored perpendicular to bedding, there is no indication of failure around the hole and the response of the hollow cylinder sample is mainly isotropic. The in situ experiment at Mont Terri which consisted in the overcoring of a resin-injected borehole that follows the bedding strike of the Opalinus Clay showed a striking similarity between the induced damaged zone and the fracture pattern observed in the hollow cylinder tests on samples cored parallel to bedding and such a bedding controlled “Excavation” Damaged Zone is as well consistent with the distinct fracture patterns observed at Mont Terri depending on the orientation of holes/galleries with respect to the bedding planes. Interestingly, the damaged zone observed in the hollow cylinder tests on samples cored parallel to bedding and in situ around URL galleries is found to develop in reverse directions in Boom Clay (Mol) and in Opalinus Clay (Mont Terri). This most probably results from different failure mechanisms, i.e. shear failure along conjugated planes in the plastic Boom Clay, but bedding plane splitting and buckling in the indurated Opalinus Clay.     

Hollow Cylinder Simulation Experiments of Galleries in Boom Clay Formation

In the context of nuclear waste disposal in clay formations, laboratory experiments were performed to study at reduced scale the excavation damaged zone (EDZ) induced by the construction of galleries in the Boom clay formation. For this purpose, thick-walled hollow cylindrical samples were subjected (after recovery of in situ stress conditions) to a decrease in the inner confining pressure aiming at mimicking a gallery excavation. X-ray computed tomography (XRCT) scans of the specimens were carried out through the testing cell before and after the mechanical unloading and allowed to quantify the displacements undergone by the clay as a result of the mechanical unloading. The deformation of the hollow cylinders and the inferred extent of the damaged zone around the central hole are found to depend on the orientation of the specimen with respect to the bedding planes and show a great similarity with in situ observations around galleries and boreholes at Mol URL in the Boom clay formation. In the experiments performed on samples cored parallel to the bedding, the damaged zone is not symmetrical with respect to the hole axis and extends more in the direction parallel to the bedding. It is the same for the radial convergence of the hole walls which is larger in the direction parallel to bedding than in the perpendicular one. In contrast, a test on a sample cored perpendicularly to the bedding did not show any ovalisation of the central hole after the mechanical unloading. These observations confirm the significance of the pre-existing planes of weakness (bedding planes) in Boom clay and the need for a correct consideration of the related mechanical anisotropy.     

The effect of high pH alkaline solutions on the mineral stability of the Boom Clay – Batch experiments at 60 °C

Boom Clay is currently viewed as a reference host formation for studies on deep geological disposal of radioactive waste in Belgium. The interactions between bulk rock Boom Clay and 0.1 M KOH, 0.1 M NaOH, 0.1 M Ca(OH)₂, young cement water and evolved cement water solutions, ranging in pH from 12.5 to 13.2, were examined as static batch experiments at 60 °C to simulate alkaline plume perturbations, which are expected to occur in the repository due to the presence of concrete. Both liquids and solids were investigated at specific times between 90 and 510 days in order to control the elemental budget and to search for potential mineralogical alterations. Also, the clay fraction was separated from the whole-rock Boom Clay at the end of each run and characterized for its mineralogical composition. Thereby, the importance of the mineral matrix to buffer the alkaline attack and the role of organic matter to protect clay minerals were also addressed. The results indicate that the degree of geochemical perturbation in Boom Clay is dependent on the initial pH of the applied solution together with the nature of the major cation in the reactant fluids. The higher the initial pH of the media, the stronger its interaction with Boom Clay. No major non-clay mineralogical alteration of the Boom Clay was detected, but dissolution of kaolinite, smectite and illite occurred within the studied experimental conditions. The dissolution of clays is accompanied by the decrease in the layer charge, followed by a decrease in the cation-exchange capacity. The highest TOC values coincide with the highest total elemental concentrations in the leachates, and correspondingly, the highest dissolution degree. However, no quantitative link could be established between the degree of organic matter decomposition and clay dissolution.     

Hydrogeology of a fractured shale (Opalinus Clay): Implications for deep geological disposal of radioactive wastes

As part of the Swiss programme for high-level radioactive-waste disposal, a Jurassic shale (Opalinus Clay) is being investigated as a potential host rock. Observations in clay pits and the results of a German research programme focusing on hazardous waste disposal have demonstrated that, at depths of 10–30 m, the permeability of the Opalinus Clay decreases by several orders of magnitude. Hydraulic tests in deeper boreholes (test intervals below 300 m) yielded hydraulic conductivities <10^–12 m/s, even though joints and faults were included in some of the test intervals. These measurements are consistent with hydrogeological data from Opalinus Clay sections in ten tunnels in the Folded Jura of northern Switzerland. Despite extensive faulting, only a few indications of minor water inflow were encountered in more than 6,600 m of tunnel. All inflows were in tunnel sections where the overburden is less than 200 m. The hydraulic data are consistent with clay pore-water hydrochemical and isotopic data. The extensive hydrogeological data base – part of which derives from particularly unfavourable geological environments – provides arguments that advective transport through faults and joints is not a critical issue for the suitability of Opalinus Clay as a host rock for deep geological waste disposal. Electronic Publication     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Determination of kinetic parameters and simulation of early CO2 production from the Boom Clay kerogen under low thermal stress

The main purpose of the present study is to evaluate the nature and amount of gaseous compounds that would be generated from the Boom Clay kerogen due to the foreseen thermal stress associated with the geological disposal of high activity nuclear waste. To this end, pyrolysis experiments were carried out on this low maturity, O-rich kerogen with focus on mild conditions, including Rock–Eval and closed pyrolyses using a wide range of temperature/time conditions. The residual kerogen recovered after the closed pyrolyses was re-examined by Rock–Eval and elemental analyses and the components of the gas fractions were identified and quantified by gas chromatography. These experiments showed substantial production of CO₂ (corresponding to ca. 1/5 of the total O content of the kerogen) under mild thermal stress. The kinetic parameters (frequency factor and distribution of activation energy) of this early production of CO₂ were determined and used to simulate the possible consequences for the deep disposal of highly radioactive waste. Extrapolation to thermal stresses, corresponding to 80 and 100 °C over 1 ka, indicated that this production of CO₂ might influence the geochemistry and perhaps therefore the effectiveness of the geological barrier. For example, unless diffusion out of the heated zone counterbalances the effect of CO₂ generation, significant acidification and large changes in bicarbonate concentration may take place, in the interstitial water of the clay, at a time scale of only tens to a few hundred years.     

Coupled thermo-hydro-bio-geochemical reactive transport model of CERBERUS heating and radiation experiment in Boom clay

Final disposal of high-level radioactive waste in deep repositories in clay formations is being considered by several countries. Repository safety assessment requires the use of 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 CERBERUS experiment carried out at the HADES facility excavated in the Boom clay formation at Mol (Belgium). This long-term experiment is aimed at evaluating the effect of heating and radiation in Boom clay. The test was performed in a cased well drilled at 223 m depth and lasted from 1989 to 1994. A ⁶⁰Co source of 400 TBq and two heaters were emplaced inside the well. Dose rate, temperature, porewater pressure and pH/Eh were measured in situ during the experiment and gas and porewater samples were taken for chemical analyses. Here a coupled thermo-hydro-geochemical (THC) model of the CERBERUS experiment is presented which accounts simultaneously for heating, radiation, solute diffusion and a suite of geochemical reactions including: aqueous complexation, acid–base, redox, mineral dissolution/precipitation, cation exchange and gas dissolution/ex-solution. Computed results indicate that heating and radiation causes a slight oxidation, a decrease in pH, slight changes in porewater chemistry and pyrite dissolution near the well. THC model results follow the general evolution of chemical data, but cannot fit SO₄ data. Model discrepancies are partly overcome when microbially-mediated Fe and SO₄ reduction are taken into account in a coupled thermo-hydro-bio-geochemical (THBC) model. This THBC model captures the trends of geochemical data, improves the fit to dissolved SO₄ and predicts pyrite precipitation, a process observed near the CERBERUS well. The ability of the THBC numerical model to reproduce the overall trends of geochemical data of the CERBERUS experiment provides confidence in such a model as a suitable tool for the long-term prediction of geochemistry in the near field of a HLW repository in clay. However, the small number of available chemical data throughout the experiment and the lack of DOC and microbial data allow only a partial validation of the THBC model.     

泥岩隧道施工过程中渗流场与应力场全耦合损伤模型研究

在连续损伤力学理论基础上,将塑性损伤演化及渗流相互耦合的概念引入Mohr-Coulomb 破坏准则,用于分析在孔隙压力和塑性损伤演化共同作用下岩石损伤演化机制,建立了相应的有限元损伤数值分析模型,并应用于比利时核废料库开挖过程中泥岩隧道附近围岩发生损伤演化、渗流场和应力场耦合过程分析中,得到了开挖引起的围岩损伤特性、孔隙压力以及渗透性的变化规律,为进一步研究隧道流变过程水力耦合特性合理的数值计算模型建立方法提供基础。     

黏土岩温度-渗流-应力耦合特性试验与本构模型研究进展

高放废物处置库、垃圾填埋场等工程中常常涉及到温度场（T）、渗流场（H）和应力场（M）的耦合作用的问题。从试验和理论模型两个角度综述国内外黏土岩温度-渗流-应力耦合特性的研究进展,主要包括其传热特性、温度影响下的渗流特性、变形、强度、蠕变特性。在此基础上,重点分析了黏土岩水-热迁移模型以及热-力耦合本构模型的适应性。基于上述认识,通过试验研究了比利时Boom clay在温度作用下的强度、渗透性、蠕变性等特征。结果表明：随着温度升高,Boom clay的强度有所降低,渗透性显著增强,蠕变速率明显加快。提出了适用于Boom clay的THM耦合弹塑性损伤模型,计算结果验证了模型能合理反映温度的影响。最后,探讨了黏土岩THM耦合机理研究的不足和今后的研究方向。     

Simulation of thermal stress influence on the Boom Clay kerogen (Oligocene,Belgium) in relation to long-term storage of high activity nuclear waste: I. Study of generated soluble compounds

Closed pyrolyses were performed on the Boom Clay kerogen to simulate the weak thermal stress applied during the in situ CERBERUS heating experiment (80 °C for 5 a). Two stronger thermal stresses, encompassing the range generally considered for the long-term disposal of high-activity nuclear waste (80 °C for 1 ka and 120 °C for 3 ka), were also simulated. Quantitative and qualitative studies were carried out on the products thus generated with a focus on the C₁₂₊ fraction, especially on its polar components. It thus appeared that the soluble C₁₂₊ fractions generated during these simulation experiments comprise a wide variety of polar O- and/or N-containing compounds, including carboxylic acids and phenols. The nature and/or the relative abundance of these polar compounds exhibit strong variations, with the extent of the thermal stress, reflecting the primary cracking of different types of structures with different thermal stability and the occurrence of secondary degradation reactions. These observations support the idea that the compounds, generated upon exposure of the Boom Clay kerogen to a low to moderate thermal stress, may affect the effectiveness of the geological barrier upon long-term storage of high-activity nuclear waste.     

Migration studies of radionuclides in boom clay

Sorption results obtained with Boom clay for Am, Pu, Eu, Tc and Np under near in-situ conditions are presented, and the significance ofK_d values in Boom clay is discussed. Clay humic acids are shown to be a controlling factor in the sorption of Am, Eu, Np.

Results with Tc and Pu are different and need further examination. Experiments to determine the mobility of light molecular weight organic material in compacted Boom clay is discussed.     

Regional fluid characterisation and modelling of water–rock equilibria in the Boom clay Formation and in the Rupelian aquifer at Mol,Belgium

Interstitial water from the Boom clay Formation around the HADES (high activity disposal experimental site, an underground research facility belonging to the Nuclear research centre, SCK·CEN, at Mol-Dessel, Belgium.) underground research facility at Mol, Belgium, and waters sampled at different locations in the Rupelian aquifer, underlying the clay formation, have been studied. The Boom clay is a Tertiary mudrock containing about 55 % clay and the Rupelian aquifer is located in a silty layer. Special care was taken to adapt or improve measurement, sampling, conservation and analysis methods to get a reliable regional and local database, for the purpose of testing a general model describing the regulation and acquisition of the composition of these fluids. The isotopic and chemical composition of the waters allows them to be assigned to a common origin, namely mixing between a marine endmember and the clay interstitial water, followed by reequilibration with the host rock through dissolution–precipitation reactions involving identified secondary minerals. Oxidation–reduction state and trace element behavior are also discussed and the limits of the model are outlined.