Boom Clay Research Articles

Gas transport in Boom Clay: the role of the HADES URL in process understanding

Abstract Since the 1990s, SCK CEN, EIG EURIDICE and ONDRAF/NIRAS have been investigating the impact of gas generation on the Boom Clay and the engineered barriers. Several experiments have been performed to study gas transport in Boom Clay at laboratory scale and in the HADES URL. This paper gives an overview of these experiments. The transition from the laboratory to the in-situ scale is still a challenging task. It is our ambition to address these issues for Boom Clay, starting with the diffusive transport of dissolved gas. A large set of gas diffusion coefficients in Boom Clay from small-scale lab experiments (centimetre scale) is already available, and in order to validate these for use on a larger (metre) scale, an in-situ diffusion experiment with dissolved gas will be performed in the HADES URL, using the existing boreholes. In this new experiment, called NEMESIS, dissolved neon gas will be injected in one filter, and its diffusion will be monitored by three other filters. By re-using existing boreholes dating from the 1990s, the NEMESIS experiment will continue to provide new diffusion data for the next five years.

Coupled flow and transport modelling of a large-scale in situ migration experiment with 14 C-labelled natural organic matter colloids in Boom Clay

Abstract Twenty-five years ago, a unique long-term and large-scale in situ experiment with 14 C-labelled natural organic matter (NOM) was set up at the HADES underground research facility in Mol (Belgium) to study its migration behaviour. Natural organic matter plays an important role in the mobility of various safety-relevant radionuclides, which is critical in the context of Safety & Performance Assessment (SA/PA) calculations for a possible nuclear waste repository. The objective of this work is to enlarge the confidence in current NOM transport models by validating them with the in situ experiment, which is still continued to this day. Stepwise adding more complexity to the model resulted in a 10-parameter model with which excellent fits to the data are obtained. The model considers two different fractions that are transported by advection and diffusion and can be subject to both irreversible and reversible immobilization processes. The associated fitted parameter values compare well with values determined on small-scale migration experiments. This builds confidence in the NOM transport model, which in turn contributes to the confidence in the outcome of the radionuclide migration calculations performed in the context of SA/PA. These results again highlight the incredible value of such long-running experiments at underground research facilities like HADES.

The role of the HADES URL in better understanding of the Boom Clay pore water geochemistry

Abstract When assessing a rock formation for its suitability as a potential host rock for the disposal of radioactive waste, knowledge about its pore water chemical composition is essential. When the HADES underground research laboratory became operational in the early 1980s, it offered the possibility of extracting pore water from Boom Clay. At the time, however, there was almost no experience of sampling pore water from deep clay formations. The low hydraulic conductivity of clays makes it difficult to extract pore water and the sampling process itself can induce changes in the observed chemical characteristics due to oxidation and re-equilibration with the ambient air. In the past decades, significant progress has been made in the techniques and protocols to sample and monitor pore water. The use of nitrogen instead of compressed air to drill boreholes and installing piezometers limited the disturbances induced by oxidation of the clay. Furthermore, an advanced system was developed to simultaneously sample pore water and dissolved gases and measure some key geochemical parameters such as pH, pCO 2 and redox potential under in situ conditions. This has resulted in a more reliable characterization of the Boom Clay pore water and a better understanding of perturbing processes such as oxidation.

The construction of the HADES underground research laboratory and its role in the development of the Belgian concept of a deep geological repository

Abstract When the Belgian Nuclear Research Centre (SCK CEN) launched a research, development and demonstration programme on geological disposal in the 1970s, it was not certain if a deep geological repository could be constructed in poorly indurated clay. This was tested by constructing the HADES underground research laboratory (URL) in Boom Clay, 225 m below SCK CEN's site in Mol. The construction history of the URL reflects how the understanding of the Boom Clay increased and how the excavation techniques and design of the gallery lining improved. It demonstrated that shafts, galleries and crossings between galleries can be constructed using industrial techniques. It also allowed characterization of the hydromechanical response of the clay and the clay disturbances induced by the excavation. This increased understanding is also reflected in the evolution of the geological disposal concept considered in Belgium. The current disposal concept foresees the installation of seals in the shafts and galleries. The HADES URL also offered the opportunity to test possible seal designs and develop a better understanding of the behaviour of bentonite, a possible seal material, owing to its swelling capacity, under in situ conditions.

Characterization of Boom Clay anisotropic THM behaviour based on two heating tests at different scales in the HADES URL

Abstract To examine the impact of the heat generated by high-level radioactive waste on Boom Clay, two heater tests have been launched in the HADES underground research facility: the small-scale ATLAS Heater Test and the large-scale PRACLAY Heater Test. The major objective of these tests is to confirm and refine the thermo-hydro-mechanical (THM) constitutive models and associated parameter values obtained from a laboratory characterization programme. This paper presents the observations from the ATLAS and PRACLAY heater tests and the combined numerical modelling of these tests. To characterize the excavation damaged zone in the clay around these tests, a mechanical model with a strain-dependent elastic modulus is introduced for the Boom Clay. The consistency between the observations from laboratory tests and in-situ tests and the outcomes from the numerical models strengthen the confidence in our understanding of the THM behaviour of Boom Clay. They also enabled us to validate the mechanical model and produce a set of anisotropic THM property values for both intact and damaged Boom Clay.

CP1 and Tribicarb-3D: unique long-term and large-scale in situ migration tests in Boom Clay at the HADES Underground Research Laboratory

Abstract Assessing the long-term safety of a deep geological repository for the disposal of radioactive waste depends on an adequate understanding of the processes governing radionuclide transport. From the early days of the research on geological disposal in clay in Belgium, large-scale, long-term in situ migration experiments were started to test whether our knowledge acquired about small-scale samples can be scaled up in time and space. These experiments use multi-filter piezometers to introduce radiotracers in a ‘source filter’ and monitor their breakthrough in ‘monitoring filters’. The CP1 experiment started in 1988 and used HTO as a tracer, while the Tribicarb-3D started in 1995 and used a cocktail of HTO and H 14 CO 3 − . At the start of these experiments, blind predictions were made based on lab-derived parameters and a simple representation of the hydrological system. Several decades later, these blind predictions still describe the data remarkably well. These tests provide valuable data for upscaling and validating the transport models in Boom Clay and allow us to estimate transport parameters at a larger scale. They provide strong arguments that the radiological safety of a deep geological repository in a clay rock can be guaranteed.

An experimental methodology to assess the impact of desaturation on gas diffusion in clay based materials

The transport of gas in clay-based materials is dominated by diffusion. SCK CEN has studied and recorded an extensive data set of diffusion coefficients of gases in various saturated clays (Boom Clay, Opalinus Clay, Callovo-Oxfordian claystone and bentonites) used in Europe as host formations or in engineered barrier systems in the context of deep geological disposal of high and intermediate level nuclear wastes. However, partially saturated conditions may exist during the life cycle of a radioactive waste repository. The current study aims at establishing an experimental method to measure the diffusion coefficients of various gases in partially saturated clay-based materials by means of double through diffusion tests (cross diffusion of gases across the porous sample, driven by concentration gradients) and to assess the impact of desaturation on gas diffusivity. Historically, gas diffusion measurements have been performed under dissolved conditions with continuous water and dissolved gas flow around the clay sample. However, since the saturation degree of the sample has to be constant, a novel setup has been designed and optimized to operate under a pure gas phase under controlled relative humidity (RH). The experimental concept consists of cross diffusion of gas mixtures from two reservoirs at a fixed relative humidity on either side of the sample cell, namely, the upstream and downstream reservoirs. The RH is controlled using the same saturated salt solutions in both reservoirs. During the experiment, gases will diffuse from the upstream to the downstream reservoir. By measuring the change in gas composition in the downstream reservoir with a gas analyzer equipped with a mass spectrometer (which expresses the gas composition in terms of partial pressure), the gas flux and hence the diffusion coefficient is estimated by applying steady state Fick’s first law. The experimental methodology has been validated by performing an experiment on a sandy-clay sample of known petrophysical properties, at full saturation.

Boom Clay pore-water geochemistry at the Mol site: Chemical equilibrium constraints on the concentrations of major elements

It is important to understand the mechanisms controlling the chemistry of the pore water in the Boom Clay, which has been studied as a reference host rock for the geological disposal of radioactive waste. The chemistry of the pore water and the related properties of the Boom Clay were investigated experimentally. This paper presents the results of equilibrium calculations and discusses the probable chemical constraints that control the concentrations of major elements in the pore water. The present-day Boom Clay pore water is a dilute NaHCO3 solution of 10–20 mM, and the concentration increases with the depth of the Boom Clay over a thickness of 65 m around the underground laboratory at approximately 200 m below sea level. The present-day NaHCO3 water is likely a result of freshwater infiltration, and the concentration profile observed must have been affected by waters from upper and lower aquifers. Among the minerals found in the Boom Clay, equilibrium calculations indicate that the pore water is in equilibrium with calcite, dolomite, siderite, pyrite, and quartz. Aluminium silicate minerals, kaolinite and chlorite, are also possibly in equilibrium, but their saturation states cannot be fully demonstrated mainly because of uncertainties associated with the pore-water concentration of aluminium. Cation exchange, an important property of clays, seems to be controlling only the pore-water concentration of potassium. Concentrations of other cation exchangeable elements, such as calcium and magnesium, are more likely regulated by the solubility of carbonate minerals. On clay surfaces, however, cation-exchange reactions are evidenced and control occupancies of all exchangeable cations. The cation-exchange pool on clay responds to the increase in NaHCO3 concentration with depth, and the surface occupancies vary according to the selectivity of exchangeable cations. Equilibrium calculations allow us to propose a Boom Clay reference model that is able to explain the observed pore-water chemistry. This model is compared to other models in the literature, such as those for the Opalinus Clay in Switzerland and Callovo-Oxfordian Clay in France, which have also been studied for the purpose of radioactive waste disposal. Future studies to improve our understanding of the Boom Clay pore-water geochemistry include i) accurate determination of the pore-water concentration of aluminium, which is crucial for studying the mineral saturation state of aluminium silicates; ii) improving understanding of the mineralogical composition of dolomite in the Boom Clay and its dissolution mechanisms; iii) reassessment of magnesium cation-exchange occupancy on clay surfaces; and iv) improving pore-water sampling and analysis techniques with respect to pH and pCO2 measurements to avoid perturbations to water samples so that the in situ conditions can be preserved to a maximum extent.

Characterizing groundwater heat transport in a complex lowland aquifer using paleo-temperature reconstruction, satellite data, temperature–depth profiles, and numerical models

Abstract. Heat is a naturally occurring, widespread groundwater tracer that can be used to identify flow patterns in groundwater systems. Temperature measurements, being relatively inexpensive and effortless to gather, represent a valuable source of information which can be exploited to reduce uncertainties on groundwater flow, and, for example, support performance assessment studies on waste disposal sites. In a lowland setting, however, hydraulic gradients are typically small, and whether temperature measurements can be used to inform us about catchment-scale groundwater flow remains an open question. For the Neogene Aquifer in Flanders, groundwater flow and solute transport models have been developed in the framework of safety and feasibility studies for the underlying Boom Clay formation as a potential host rock for geological disposal of radioactive waste. However, the simulated fluxes by these models are still subject to large uncertainties as they are typically constrained by hydraulic heads only. In the current study, we use a state-of-the-art 3D steady-state groundwater flow model, calibrated against hydraulic head measurements, to build a 3D transient heat transport model, for assessing the use of heat as an additional state variable, in a lowland setting and at the catchment scale. We therefore use temperature–depth (TD) profiles as additional state variable observations for inverse conditioning. Furthermore, a Holocene paleo-temperature time curve was constructed based on paleo-temperature reconstructions in Europe from several sources in combination with land surface temperature (LST) remotely sensed monthly data from 2001 to 2019 (retrieved from NASA's Moderate Resolution Imaging Spectroradiometer, MODIS). The aim of the research is to understand the mechanisms of heat transport and to characterize the temperature distribution and dynamics in the Neogene Aquifer. The simulation results clearly underline advection/convection and conduction as the major heat transport mechanisms, with a reduced role of advection/convection in zones where flux magnitudes are low, which suggests that temperature is also a useful indicator in a lowland setting. Furthermore, the performed scenarios highlight the important roles of (i) surface hydrological features and withdrawals driving local groundwater flow systems and (ii) the inclusion of subsurface features like faults in the conceptualization and development of hydrogeological investigations. These findings serve as a proxy of the influence of advective transport and barrier/conduit role of faults, particularly for the Rauw fault in this case, and suggest that solutes released from the Boom Clay might be affected in similar ways.

Evaluation of a Long-Term Thermal Load on the Sealing Characteristics of Potential Sediments for a Deep Radioactive Waste Disposal

An in situ and a batch heating experiment were applied on the fine-grained sediments of the Opalinus Clay from Mont Terri (Switzerland) and the Boom Clay of Mol (Belgium), both being currently studied as potential host formations for deep nuclear waste disposal. The purpose was here to test the impact of a 100 °C temperature rise that is expected to be produced by nuclear waste in deep repositories. The experiment on the Opalinus Clay mimicked real conditions with 8-months operating heating devices stored in core drillings into the rock. The comparison of the major, trace, rare-earth elemental contents and of the whole-rock K-Ar data before and after heating shows only a few variations beyond analytical uncertainty. However, the necessary drillings for collecting control samples after the experiment added an unexpected uncertainty to the analyses due to the natural heterogeneity of the rock formation, even if very limited. To overcome this aspect, Boom Clay ground material was subjected to a batch experiment in sealed containers during several years. The drawback being here the fact that controls were limited with, however, similar reproducible results that also suggest limited elemental transfers from rock size into that of the <2 μm material, unless the whole rocks lost more elements than the fine fractions. The analyses generated by the two experiments point to identical conclusions: a visible degassing and dewatering of the minerals that did not induce a visible alteration/degradation of the host-rock safety characteristics after the short-term temperature increase.

PH and microbial community determine the denitrifying activity in the presence of nitrate-containing radioactive waste.

An important fraction of the currently stored volume of long-lived intermediate-level radioactive waste in Belgium contains large amounts of NaNO3 homogeneously dispersed in a hard bituminous matrix. Geological disposal of this waste form in a water-saturated sedimentary formation such as Boom Clay will result in the leaching of high concentrations of NaNO3, which could cause a geochemical perturbation of the surrounding clay, possibly affecting some of the favorable characteristics of the host formation. In addition, hyper-alkaline conditions are expected for thousands of years, imposed by the cementitious materials used as backfill material. Microbial nitrate reduction is a well-known process and can result in the accumulation of nitrite or nitrogenous gases. This could lead to the oxidation of redox-active Boom Clay components, which could (locally) decrease the reducing capacity of the clay formation. Here, we compared nitrate reduction processes between two microbial communities at different pH related to a geological repository environment and in the presence of a nitrate-containing waste simulate during 1 year in batch experiments. We showed that the microbial community from in Boom Clay borehole water was able to carry out nitrate reduction in the presence of acetate at pH 10.5, although the maximum rate of 1.3 ± 0.2 mM NO3 -/day was much lower compared to that observed at pH 9 (2.9 mM NO3 -/day). However, microbial activity at pH 10.5 was likely limited by a phosphate shortage. This study further confirmed that the Harpur Hill sediment harbors a microbial community adapted to high pH conditions. It reduced twice as much nitrate at pH 10.5 compared to pH 9 and the maximum nitrate reduction rate was higher at pH 10.5 compared to that at pH 9, i.e., 3.4 ± 0.8 mM NO3 -/day versus 2.2 ± 0.4 mM NO3 -/day. Both communities were able to form biofilms on non-radioactive Eurobitum. However, for both microbial communities, pH 12.5 seems to be a limiting condition for microbial activity as no nitrate reduction nor biofilm was observed. Nevertheless, pH alone is not sufficient to eliminate microbial presence, but it can induce a significant shift in the microbial community composition and reduce its nitrate reducing activity. Furthermore, at the interface between the cementitious disposal gallery and the clay host rock, the pH will not be sufficiently high to inhibit microbial nitrate reduction.

A multi-scale insight into gas transport in a deep Cenozoic clay

The migration of gases is crucial to ensure the long-term feasibility of argillaceous formations for the deep disposal of radioactive waste. This paper presents an experimental investigation with a multi-scale perspective on the response to gas transport of initially saturated Boom Clay (Belgium). Gas injection tests have been performed under oedometer conditions at different controlled-volume rates, constant total vertical stress and different sample orientations (flow orthogonal or parallel to bedding planes). The results confirm soil expansion and consequent degradation during injection that has a significant impact on the aperture of localised gas pathways (fissures) and increases intrinsic permeability during the gas pressure dissipation stage. The analyses with complementary techniques (mercury intrusion porosimetry, field-emission scanning electron microscopy and X-ray micro-tomography) confirm the opening of fissures with different apertures and separations at the microstructural scale. Large-aperture fissures develop along the weaker bedding planes. These techniques allow the volume of fissures to be quantified, which does not significantly depend on gas flow direction, as also measured in the isotropic response of the gas effective permeability. A scalar damage variable derived from the fissured fraction has been used to assess the gas-entry pressure reduction and the intrinsic permeability increase after the gas tests in both directions.

Sn(IV) Sorption onto Illite and Boom Clay: Effect of Carbonate and Dissolved Organic Matter

126Sn is a long-lived fission product and it is important to assess its sorption onto the host rocks surrounding a possible nuclear waste repository. Boom Clay (BC) is under investigation in Belgium as a potential host rock. To better understand Sn(IV) sorption onto the clay minerals constituting BC, sorption of Sn(IV) was here investigated on Illite du Puy (IdP), from pH 3 to 12. Sorption isotherms at pH ~8.4 were acquired in the presence and absence of carbonate, and in the presence and absence of BC dissolved organic matter (DOM). Sn(IV) strongly sorbed on IdP over the full range of the pHs and concentrations investigated. In the presence of carbonates, Sn(IV) sorption was slightly decreased, highlighting the Sn(IV)–carbonate complexation. DOM reduced the Sn(IV) sorption, confirming the strong complexation of Sn(IV) with DOM. The results were modelled with the 2-site protolysis non-electrostatic surface complexation model. The surface complexation constants and aqueous complexation constants with carbonate and DOM were optimized to describe the experimental data. The applicability of the component additivity approach (CAA) was also tested to describe the experimental Sn(IV) sorption isotherm acquired on BC in BC pore water. The CAA did not allow accurate prediction of Sn(IV) sorption on BC, highlighting the high sensitivity of the model to the Sn(IV)-DOM complexation.

Using helium-4, tritium, carbon-14 and other hydrogeochemical evidence to evaluate the groundwater age distribution: The case of the Neogene aquifer, Belgium

Apparent groundwater age dating has been proven useful and robust in understanding water origin and mixing processes, particularly when multiple tracers are considered. However, even though now extensively used, the age tracers have not been widely applied in the general practice of flow and transport model calibration. A multi tracer-study was carried out in the Neogene aquifer in Flanders to quantify the apparent age and construct a joint interpretation for the delineation of different groundwater flow systems. This understanding is critical as part of the safety and feasibility studies for the underlying Boom Clay Formation that has been considered as a potential host rock for the geological disposal of radioactive waste. In this study, we combine evidence from tritium/helium-3 (3H/3He), helium-4 (4He) and radiocarbon (14C) dating as well as stable isotopic (δ18O, δ2H) and hydrochemical signatures in combination with particle tracking-based age distributions from the 3D groundwater flow model. The results of the study indicate that mixing of groundwater with young and old fractions occurs predominantly in the central part of the aquifer which is made evident by the coexistence of 3H (pre and post-bomb pulse Era), 14C and 4He in several groundwater samples. The mixing between water of different origin is also supported by the sampled stable isotopic and hydrochemical composition of groundwater. Particle tracking residence time results show an acceptable agreement with apparent ages derived from age tracers for young (≤100 years) and old (>1000 years) groundwater. Groundwater with ages between 100 and 1000 years is likely a mixture of water with young/old fractions and shows the strongest discrepancies between advective model ages and age tracer based apparent ages. On the basis of our findings, we distinguish between three groundwater flow systems in the Neogene aquifer: i) a shallow/local flow system, with groundwater originating from modern meteoric water; ii) a deep/semi-regional flow system, characterized by old groundwater where the presence of 4Herad is significant; iii) a mixed zone of groundwater flow where the recently infiltrated meteoric water mixes with discharging old groundwater. These results have helped us to refine previously proposed conceptual models for the study area and will in the end reduce uncertainties relevant to the potential future geological disposal of radioactive waste.

Surface-mediated redox activity in the Pyrite – Nitrate/nitrite – Hydrogen system under conditions relevant for the geological disposal of bituminized waste in Boom Clay

The reactivity of a system with pyrite powder, nitrate or nitrite, and hydrogen in a 15 mM sodium bicarbonate solution was assessed over the course of 2 years in the frame of compatibility studies of nitrate-containing bituminized radioactive waste with the host rock for final disposal. A series of batch tests was performed with pyrite suspensions in bicarbonate solution to which nitrate or nitrite was added before filling the headspace of the recipient with a constant, and non-renewed, volume of 100% pure hydrogen gas (initial PH2 1.5 bara). Under anoxic conditions and at room temperature, hydrogen reacted readily with nitrate and nitrite in the presence of pyrite powder. Ammonia was formed while hydrogen was consumed. Based on the XPS analyses of the pyrite surface and the absence of dissolved pyrite oxidation products, the pyrite surface was not oxidized. Moreover, no reaction between hydrogen and nitrate or nitrite was observed in the absence of pyrite. This reaction was thus clearly mediated by the Boom Clay pyrite surface. The reducing atmosphere kept the pyrite surface intact and protected it from precipitation of carbonates from the medium, thus effectively preventing pyrite surface deactivation, previously observed under anoxic conditions in the absence of H2. Overall, only 5% of the 0.1 M of nitrate that was added to the tests, was reduced over the course of 2 years, without complete consumption of H2. Nitrite was added in a lower concentration of 0.05 M, but was more reactive: about 50% of nitrite was reduced, producing stoichiometric amounts of ammonia, and nearly depleting the H2 in the gas phase. The possible consequences of these processes for the final repository performance are also discussed.

Using Reduced Basis Approximation for Efficient Surrogate-Based Inverse Identification of Thermo-Hydro-Mechanical Parameters from an In Situ Heating Test

In this paper, a reduced-order model built from the reduced basis (RB) method is used as a surrogate for an inverse identification problem related to coupled thermo-hydro-mechanical (THM) processes. The RB space—spanned by solutions of the governing THM equations—is constructed using a greedy adaptive procedure guided by an a posteriori error estimator that selects the optimal snapshot points in a given parametric space. The RB model is assessed in terms of accuracy and computational cost reduction for the three-dimensional transient coupled problem described by the ATLAS III small-scale in situ heating test. The substantial system size reduction and the associated significant computational gain result in a surrogate model suitable for parameter identification procedures in the Boom Clay material. The effectiveness of the proposed strategy is demonstrated by performing inverse analysis based on direct-search and genetic algorithm (GA) optimization supported by real sensor measurement data where 800 times faster computational speed-up was achieved.

Determination of the anisotropic thermal conductivity of the Boom Clay based on a combined numerical interpretation of two in situ heater tests at different scales

Determination of the anisotropic thermal conductivity of the Boom Clay based on a combined numerical interpretation of two in situ heater tests at different scales

Processing of seismic diffractions from carbonate nodules in clay formations

The problem of localizing small (relative to wavelength) scatterers by diffractions to enhance their use in identifying small-scale details in a seismic image is extremely important in shallow exploration to identify interesting features such as fractures, caves, and faults. The conventional approach based on seismic reflection is limited in resolution by the Rayleigh criterion. In certain acquisition geometries, such as crosswell surveys aimed at obtaining high-resolution signals, the availability of suitable data sets for effective migration depends on the spatial extent of the available source and receiver data intervals. With the aim of overcoming the resolution limits of seismic reflection, we study the detectability, response, and location of meter- and possibly submeter-dimension carbonate concretions (septaria) in the Boom Clay Formation (potential host rocks for radioactive waste disposal) by diffraction analysis of high-frequency signals. We investigate diffraction wavefields by signal separation, focusing, and high-resolution coherency analysis using the multiple signal classification method and semblance. The investigation is performed for two different surveys in Belgium, a shallow and high-resolution reverse vertical seismic profile (RVSP) and a near-offset crosswell application at Kruibeke and ON-MOL-2 sites, respectively. The data analysis is supported by synthetic wavefield modeling. The multioffset RVSP provides the appropriate geometry to observe and investigate the septaria diffractions from depth and the surface. The crosswell approach, calibrated using synthetic data in the analysis of wavefield patterns in 2D, indicates promising imaging results with field data of a selected diffraction zone in the interwell area.

Pyrite oxidation by nitrate and nitrite in sodium bicarbonate solution under anoxic and abiotic conditions

Pyrite reactivity with nitrate and nitrite was assessed in long-term batch tests to assess its possible oxidation in anoxic conditions at pH 8.5, at room temperature and atmospheric pressure. This was done in the frame of compatibility studies of nitrate-containing radioactive waste with a pyrite-containing clay host rock for geological disposal. Abiotic pyrite suspensions were prepared under inert atmosphere in 15 mM bicarbonate medium, as this simulates the inorganic carbon and pH conditions in the pore water of Boom Clay, which is a potential host rock for geological disposal in Belgium. Two forms of pyrite powder were used, formed via different genetic pathways and exhibiting a different morphology, namely pyrite obtained by crushing a large crystal cluster and pyrite extracted from Boom Clay by flotation. The reactivity of these two pyrite forms with nitrate and nitrite is reported and compared. Overall, after 2–2.5 years under abiotic conditions and inert atmosphere, no significant reaction between crushed pyrite and nitrate was detected, while a very limited reaction was observed between Boom Clay pyrite and nitrate. Between pyrite and nitrite, which is known to be more reactive than nitrate, a slow reaction took place for both forms of pyrite, with no significantly higher reactivity with the Boom Blay pyrite. The variability between the replicates of Boom Clay pyrite were also larger than for crushed pyrite. Overall, nitrate and nitrite induced a very limited, if any, oxidation reaction of the pyrite powders. These observations are important in assessing the safety of geological disposal of nitrate-containing radioactive waste.

A general analytical expression for pore size distribution based on probability theory

The pore structure of soils and rocks plays a crucial role in geotechnical, geo-environmental and geological engineering, as it dominates the hydro-mechanical behaviour, gas- and liquid-permeability as well as material transport property of soils and rocks. A large amount of pore size distribution (PSD) data of porous materials have been experimentally determined in the past decades and are currently available in the literature. However, a general expression to parameterize these PSD curves is still missing. In this study, a general multimodal PSD model is developed based on the probability theory, which is a strong tool to quantify the complex soil microstructure precisely. The parameters in the model possess a clear physical meaning. The model is validated by reproducing the PSD curves of two clays and a sand-clay mixture having a complex pore structure. The parameterized PSD curves demonstrate a strong consistency with the measurements. In addition, the model is applied to predict the PSD evolution under hydro-mechanical processes (e.g., compaction, saturation- swelling-process), the water content – soil suction – dry density relationship of Boom clay after compaction and the time-dependent PSD evolution of MX80 Bentonite. Beside soils, the proposed general multimodal PSD relationship can describe the pore structure of any other porous and granular material, as all the underlying physics is the same for all of them. The proposed model can be incorporated into the existing effective stress parameter formulation, permeability models and constitutive models of unsaturated multimodal soils.