The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al₂O₃-FeO-Fe₂O₃-MgO-Na₂O-SiO₂-H₂O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f_O2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f_O2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.     

Porewater chemistry in compacted bentonite: Application to the engineered buffer barrier at the Olkiluoto site

Compacted bentonite is used as sealing and buffer material in engineered barrier systems (EBS) of high-level radioactive waste repositories. The chemical characteristics of this clay and its porewater affect the migration of radionuclides eventually released from the waste. They also determine the integrity and long-term performance of the clay barriers. Key features are the structural negative charge and the large proportion of structural (interlayer) water of the main mineral montmorillonite, which leads to exclusion of anions and a surplus of cations in a large part of the porosity space. The objective of this contribution was to assess the impact of different porosity model concepts on porewater chemistry in compacted bentonite in the context of the planned Finnish spent nuclear fuel repository at Olkiluoto. First, a structural model based on well-established crystallographic and electrostatic considerations was set up to estimate the fractions of the different porosity types. In view of the uncertainty related to the chemical properties of the interlayer water, two very different model concepts (anion-free interlayer, Donnan space), together with a well-established thermodynamic model for bentonite, were applied to derive the porewater composition of the bentonite buffer at Olkiluoto. The simulations indicate very similar results in the “free” water composition for the two models and thus support the validity of the reference porewater concept commonly used in performance assessment of waste repositories. Differences between the models are evident in the composition of the water affected by the surface charge (i.e. diffuse double layer and interlayer). These reflect the conceptual uncertainty in current multi-porosity diffusion models.     

Physico/chemical stability of smectite clays

There is convincing evidence from field data that smectite clay undergoes conversion primarily to illite and chlorite if it is fully water-saturated and heated. The conversion may take place through mixed-layer formation with increasing illite/smectite ratio at higher temperatures and pressures. This process requires dehydration of the interlamellar space, for which either an external pressure or drying are needed. An alternative mechanism that takes place without dehydration, is dissolution of smectite and neoformation of illite. Both processes imply reorganization of the smectite crystal lattice for which the activation energy is fairly high, meaning that the conversion is negligible at temperatures lower than about 60°C. At elevated temperatures the conversion rate is controlled by the access to potassium for either mechanism.

An ongoing detailed investigation of this subject has led to a tentative model for the smectite-to-illite conversion in natural sediments and in canister-embedding clay in high-level radioactive waste (HLW) repositories.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Environmental geochemistry of the derelict Webbs Consols mine,New South Wales,Australia

Small-scale mining and mineral processing at the Webbs Consols polymetallic PbZnAg deposit in northern New South Wales, Australia has caused a significant environmental impact on streams, soils and vegetation. Unconfined waste rock dumps and tailings dams are the source of the problems. The partly oxidised sulphidic mine wastes contain abundant sulphides (arsenopyrite, sphalerite, galena) and oxidation products (scorodite, anglesite, smectite, Fe-oxyhydroxides), and possess extreme As and Pb (wt% levels) and elevated Ag, Cd, Cu, Sb and Zn values. Contemporary sulphide oxidation, hardpan formation, crystallisation of mineral efflorescences and acid mine drainage generation occur within the waste repositories. Acid seepages (pH 1.9–6.0) from waste dumps, tailings dams and mine workings display extreme As, Pb and Zn and elevated Cd, Cu and Sb contents. Drainage from the area is by the strongly contaminated Webbs Consols Creek and although this stream joins and is diluted by the much larger Severn River, contamination of water and stream sediments in the latter is evident for 1–5 km, and 12 km respectively, downstream of the mine site. The pronounced contamination of local and regional soils and sediments, despite the relatively small scale of the former operation, is due to the high metal tenor of abandoned waste material and the scarcity of neutralising minerals. Any rehabilitation plan of the site should include the relocation of waste materials to higher ground and capping, with only partial neutralisation of the waste to pH 4–5 in order to limit potential dissolution of scorodite and mobilisation of As into seepages and stream waters.     

Swelling characteristics of compacted lateritic soil–bentonite mixtures subjected to municipal waste leachate contamination

Compacted soil–bentonite mixtures are finding wide application as buffer material for waste repositories for their favorable self-sealing qualities. The swelling properties of such materials which serve as a measure of their self-sealing capabilities and, thus, the efficiency of the repository in sealing off their contents from the environment are closely related to the chemistry of the leachate that emanate from the wastes. For this reason, the swelling parameters (namely swelling potential and pressure) of compacted lateritic soil–bentonite mixtures under consideration for use as barrier in municipal waste landfill were evaluated. Series of swelling potential and pressure tests were performed using variable content (0–10 %) of bentonite at predetermined optimum moisture content. Soil mixtures were compacted with British Standard Heavy compactive effort and saturated with processed tap water as well as three leachate solutions of varying ionic strength that were generated in active open dump landfills. Experimental results showed that swelling potential based on the free swell together with the maximum swell pressures of compacted soil mixtures measured at equilibrium increased approximately linearly with increase in the amount of bentonite when inundated with processed tap water and the three leachate solutions. On the other hand, these swelling parameters decreased as the ionic strength of the leachate solutions measured by their electrical conductivity increased for the various soil mixtures. These results provide an insight into the swelling behavior and the possible degradation in the efficiency of the proposed lateritic soil–bentonite mixtures in relation to their use as buffer material in waste landfills.     

Use of solution-mined caverns in salt for oil and gas storage and toxic waste disposal in Germany

The need for storage caverns for oil and gas, and repositories for toxic chemical waste is increasing world-wide. Rock salt formations are particularly suitable for the construction of cavities for such purposes. Owing to its favourable geomechanical properties, rock salt remains stable over long periods of time without support, and it can be shown that the geological barrier of the host rock remains intact for a remarkably long time.

Safety analysis must be made for each proposed site based on site-specific data. The methods of doing this are well known and related technical recommendations exist in Germany. These recommendations apply to the planning, construction, operation and post-operational management of salt caverns used for the underground disposal of hazardous wastes. In particular, geotechnical site-specific safety verification, as required by the government's technical regulations on wastes (TA-Abfall) under the section “Underground Disposal”, is required. This safety verification must cover the entire system comprising the waste, the cavern and the surrounding rocks. For this purpose geomechanical models have to be developed. The steps which must be taken when carrying out geological engineering site explorations and when determining geotechnical parameters are discussed. In addition, recommendations are made for the design and construction of underground repositories.

For liquid-filled caverns, long-term sealing from the biosphere is of particular interest. In this instance it must be shown that the natural increase in pressure in the closed cavity due to long-term convergence does not exceed the fracture pressure. A special filled test (scale 1:1) has been performed to study this.     

Hydromechanical modelling of the SEALEX experiments

Numerical modelling of coupled physical processes in bentonite–sand mixtures under the geological conditions is significant for designing and constructing sealing systems in deep underground repositories for highly radioactive nuclear waste. Within the framework of DECOVALEX 2015, Task A, this work presents the model validation of OpenGeoSys by numerical modelling of coupled hydromechanical (HM) processes in bentonite–sand mixtures. Parameters used in the HM model were determined by modelling the laboratory tests of the sealing experiment (SEALEX). Afterwards these parameters were applied for the modelling of a small-scale mock-up test considering the influence of technological gap and incidental fail of the seal in the sealing system. In order to investigate the availability of employing these HM parameters and numerical models directly to field predictions, the modelling results and measured data of an in situ SEALEX experiment were analysed comparatively. The modelling results reproduced well the main features in HM behaviour of the compacted bentonite–sand mixture, which denotes that the adopted HM models and parameters are adequate for describing the HM processes in the sealing system. It is necessary to take the elastoplastic behaviour and evolution of the permeability of bentonite–sand mixtures into account when using the adopted models to reproduce the HM processes of a sealing system.     

Lab-scale performance of selected expandable clays under HLW repository conditions

Smectite clay has been proposed for embedding canisters with highly radioactive waste in deep repositories because of its isolating capacity. Montmorillonite-rich bentonite is a premier buffer candidate for many national organizations that are responsible for disposal of such waste. Experience from the use of drilling mud at large depths indicates that other smectite clay minerals are more stable chemically and saponite is one of them. The physical properties of smectitic mixed-layer minerals like Friedland clay are known to be less sensitive to high salt contents and such clay may also be a buffer candidate. Montmorillonite-rich MX-80 clay, Greek saponite with a minor amount of palygorskite, and Friedland clay were investigated in hydrothermal tests with dense samples confined in oedometers with 95 °C temperature at one end, which was made of copper, and 35 °C at the other, for 8 weeks. A 1 % CaCl₂ solution was circulated through a filter at the cold end. At the end of the tests, the samples were sliced into three parts, which were tested with respect to expandability, hydraulic conductivity, and chemical composition. The tests showed that while the saponite was hardly changed at all and did not take up any copper, MX-80 underwent substantial changes in physical performance and adsorbed significant amounts of copper. The Friedland clay sample was intermediate in both respects.     

Glasses for immobilization of low- and intermediate-level radioactive waste

Reprocessing of spent nuclear fuel (SNF) for recovery of fissionable elements is a precondition of long-term development of nuclear energetics. Solution of this problem is hindered by the production of a great amount of liquid waste; 99% of its volume is low- and intermediate-level radioactive waste (LILW). The volume of high-level radioactive waste (HLW), which is characterized by high heat release, does not exceed a fraction of a percent. Solubility of glasses at an elevated temperature makes them unfit for immobilization of HLW, the insulation of which is ensured only by mineral-like matrices. At the same time, glasses are a perfect matrix for LILW, which are distinguished by low heat release. The solubility of borosilicate glass at a low temperature is so low that even a glass with relatively low resistance enables them to retain safety of under-ground LILW depositories without additional engineering barriers. The optimal technology of liquid confinement is their concentration and immobilization in borosilicate glasses, which are disposed in shallow-seated geological repositories. The vitrification of 1 m³ liquid LILW with a salt concentration of ～300 kg/m³ leaves behind only 0.2 m³ waste, that is, 4–6 times less than by bitumen impregnation and 10 times less than by cementation. Environmental and economic advantages of LILW vitrification result from (1) low solubility of the vitrified LILW in natural water; (2) significant reduction of LILW volume; (3) possibility to dispose the vitrified waste without additional engineering barriers under shallow conditions and in diverse geological media; (4) the strength of glass makes its transportation and storage possible; and finally (5) reliable longterm safety of repositories. When the composition of the glass matrix for LILW is being chosen, attention should be paid to the factors that ensure high technological and economic efficiency of vitrification. The study of vitrified LILW from the Kursk nuclear power plant with high-power channel reactors (HPCR; equivalent Russian acronym, RBMK) and the Kalinin nuclear power plant with pressurized water reactors (PWR; equivalent Russian acronym VVER) after their 14-yr storage in the shallow-seated repository at the MosNPO Radon testing ground has confirmed the safety of repositories ensured by confinement properties of borosilicate matrix. The most efficient vitrification technology is based on cold crucible induction melting. If the content of a chemical element in waste exceeds its solubility in glass, a crystalline phase is formed in the course of vitrification, so that the glass ceramics become a matrix for such waste. Vitrified waste with high Fe; Na and Al; Na, Fe, and Al; Na and B is characterized. The composition of frit and its proportion to waste depends on waste composition. This procedure requires careful laboratory testing.     

Effect of salt concentration on desiccation cracking behavior of GMZ bentonite

Bentonite has been proposed for use as an engineering barrier and buffer in nuclear waste repositories and has been used frequently in municipal waste landfills. The cracking behavior and deformation properties of this material can be influenced by the chemistry of pore water. In the present work, the influence of salt concentration on the desiccation cracking behavior of GMZ bentonite was investigated with laboratory experiments. Image processing techniques and SEM tests were performed on the specimens which had undergone the desiccation testing in order to analyze the cracking mechanisms. Results show that the water evaporation process can be identified by a steady rate stage, a falling rate stage and a residual stage. The water evaporation rate is strongly affected by the salt concentration of the pore water; higher salt concentrations result in lower evaporation rates; the final water content is strongly impacted by a high initial salinity; otherwise the water contents are very similar for the residual stage. During desiccating, most of cracks appeared at the steady evaporation stage. The cracking morphology and patterns were greatly affected by the salt concentration of the pore water; and larger crack lengths and lower crack densities were obtained as the initial salinity was increased.     

Temperature effects on the hydraulic behaviour of an unsaturated clay

The influence of temperature on the hydraulic properties of unsaturated clays is of major concern in the design of engineered barriers in underground repositories for high-level radioactive waste disposal. This paper presents an experimental study centred on the investigation of the influence of temperature on soil hydraulic properties related to water retention and permeability. Laboratory tests were conducted on artificially prepared unsaturated fabrics obtained from a natural kaolinitic-illitic clay. Special attention is given to the testing procedures involving controlled suction and temperature oedometer cells and the application of the vapour equilibrium technique at high temperatures. Retention curves at different temperatures show that total suction tends to reduce with increasing temperatures at constant water content. Temperature influence on water permeability is more relevant at low matric suctions corresponding to bulk water preponderance (inter-aggregate zone). Below a degree of saturation of 75% no clear effect is detected. Experimental data show that temperature dependence on permeability at constant degree of saturation and constant void ratio is smaller than what could be expected from the thermal change in water viscosity. This behaviour suggests that phenomena such as porosity redistribution and thermo-chemical interactions, which alter clay fabric and pore fluid, can be relevant.     

Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity

We propose a thermodynamic approach to model the stepwise dehydration with increasing temperature or decreasing H₂O activity of K, Na, Ca and Mg-smectite. The approach relies on the relative stability of the different solid-solutions that describe the hydration of di- or trioctahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge smectite to mica, through high-charge smectite and illite. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimising. Our results account for the progressive evolution of smectite to interlayered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/smectite compared to mica + kaolinite or pyrophyllite assemblages. The results suggest that the enthalpic contribution of interlayer water is a function of the ionic potential of the interlayer cation and the number of interlayer water molecules. This evolution makes possible to estimate the standard-state thermodynamic parameters and hydration-temperature behaviour of smectite of virtually all possible compositions. For the four-interlayer cations considered in the study, our model reproduces the 3 → 2 → 1 water-layer transitions that accompany a reduction of water activity or an increase of temperature at ambient pressure. The range of water content and interlayer distance calculated for the 3w, 2w and 1w states are also in fair agreement with the experimental values at ambient pressure.     

Thermal and physical properties of reconsolidated crushed rock salt as a function of porosity and temperature

Crushed salt can be used as backfill to bury and conduct heat away from radioactive waste in salt repositories. As the crushed salt compacts during reconsolidation, its thermal, mechanical and hydrologic properties will change in a manner related to the porosity. Measurements of crushed salt thermal properties are conducted to evaluate such relationships. A simple mixture theory model is presented to predict thermal conductivity of consolidating salt in repository conditions. Experimental work was completed to evaluate the model by measuring thermal conductivity, thermal diffusivity and specific heat of crushed salt as a function of porosity and temperature. Sample porosity ranged from 0 to 46 %, and measurements were made at ambient pressure, from room temperature to 300 °C. These are the temperature conditions expected in a radioactive waste storage facility. Crushed salt thermal conductivity decreases with increasing porosity and temperature. Thermal diffusivity showed little porosity dependence but decreased with increasing temperature. Specific heat also shows little porosity dependence but increases with increasing temperature. Fracture porosity in deformed bedded salt cores appears to reduce thermal conductivity more dramatically than inter- and intra-granular porosity in consolidated salt. A long-term effort to dry crushed salt at high temperatures resulted in a 0.48 weight-percent loss of water that had resided at grain boundaries and in intra-granular fluid inclusions. While this loss does not significantly affect thermal properties, the release of this water volume could impact the mechanical response of the reconsolidating salt and host rock.     

高喷灌浆技术在污水管道围封中的应用

高喷灌浆技术用于土木、水利防渗加固工程，取得了丰富的成功经验和显著的经济效益。其用途和适用范围是其它任何技术无法比拟的，用于这方面的防渗加固工程实例并不少见，但用于电厂污水管道围封加固工程是该技术的最新应用成果，工程取得了成功。介绍的是高喷灌浆技术用于电厂污水管道围封加固中成功的实例。     

水悬浮体系中蒙脱石和凹凸棒石的互相作用及其意义

由于晶体结构的制约，蒙脱石和凹凸棒石具有不同的形态和物理化学性质，在水悬浮体系中必定存在蒙脱石和凹凸棒石的互相作用，但这种互相作用的形式和科学意义未曾被人认知。通过蒙脱石和凹凸棒石分散、悬浮液混合、固液分离处理，经XRD、TEM、SSA分析证实，水悬浮体系蒙脱石和凹凸棒石存在胶体互相作用，并且以面-面形式结合。研究结果的理论和实际意义表现在以下三个方面：①为合理解释凹凸棒石蒙脱石混合粘土吸附现象和物理化学性质提供新的视角；②凹凸棒石可以作为蒙脱石粘土的改性剂，在蒙脱石粘土中添加少量的凹凸棒石即可达到提高比表面积的效果，可以利用蒙脱石和凹凸棒石的互相作用来制备类似柱撑粘土的纳米孔结构材料；③凹凸棒石粘土样品湿法处理时，水悬浮体系中不同矿物胶体颗粒互相作用会影响X射线粉末衍射分析结果，对此现象在粘土矿物定量研究中应引起重视。     

Geochemical characterization and modelling of the Toarcian/Domerian porewater at the Tournemire underground research laboratory

For safety evaluation of hazardous waste repositories in clay-rocks, a thorough assessment of porewater chemistry and water–rock interactions is required. However, this objective is a challenging task due to the low hydraulic conductivity and water content of such rocks, which subsequently renders porewater sampling difficult (without inducing perturbations). For this reason, an indirect approach was developed to determine porewater composition of clay-rocks, by a geochemical model of water–rock interaction using some properties of the rock and the solution. The goal of this paper is to obtain the porewater composition of the Toarcian/Domerian argillaceous formation at Tournemire (South of France), for which a reliable model is still lacking. The following work presents a comprehensive characterization of the geochemical system of the Tournemire clay-rock, including mineralogy, petrology, mobile anions, cation exchange properties, accessible porosity and CO₂ partial pressure. Perturbation corrections from fracture water sampling were also computed. These water were found in sealed fractures (Beaucaire et al., 2008) and their radiocarbon apparent age is estimated at 20 ka. Their age together with their equilibrium situation allow considering these fracture waters as representative of the formation porewater. The model developed to calculate the Tournemire porewater composition is essentially based on cation exchange by a multi-site approach, but equilibrium with some mineral phases (calcite, quartz and pyrite) is also considered. Different exchange sites of different affinities towards cations are used, which proportions are given by the mineralogy. Exchange on illite is performed with a three-sites model, while one site is considered for smectite phases. Multi-site model results are compared with corrected fracture water data and two other models: a model only based on mineral equilibrium and a model using cation exchange on one global site. The best results were obtained with the models that take into account cation exchange and particularly with the multi-site model. The interest in considering a model with exchange sites of different affinities is particularly obvious for a satisfactory representation of the K⁺ content in solution. A dependence of K⁺ content to the amount of high affinity sites was observed, leading to an improvement of its simulation when uncertainty on mineralogical data is considered. Once validated, the multi-site model was applied at different levels of the Tournemire argillaceous formation to obtain a profile of the porewater composition.     

Chemical and isotopic characterization of water–rock interactions in shales induced by the intrusion of a basaltic dike: A natural analogue for radioactive waste disposal

Disposal of nuclear waste in deep geological formations is expected to induce thermal fluxes for hundreds of years with maximum temperature reaching about 100–150 °C in the nearfield argillaceous environment. The long-term behavior of clays subjected to such thermal gradients needs to be perfectly understood in safety assessment considerations. In this respect, a Toarcian argillaceous unit thermally disturbed by the intrusion of a 1.1-m wide basaltic dike at the Perthus pass (Herault, France), was studied in detail as a natural analogue. The thermal imprint induced by the dike was evaluated by a mineralogical, chemical and K–Ar study of the <2 μm clay fraction of shale samples collected at increasing distance from the basalt. The data suggest that the mineral composition of the shales was not significantly disturbed when the temperature was below 100–150 °C. Closer to the dike at 150–300 °C, changes such as progressive dissolution of chlorite and kaolinite, increased content of the mixed layers illite–smectite with more illite layers, complete decalcification and subsequent increased content of quartz, were found.At the eastern contact with the dike, the mineral and chemical compositions of both the shales and the basalt suggest water–rock interactions subsequent to the intrusion with precipitation of palagonite and renewed but discrete deposition of carbonate. A pencil cleavage developed in the shales during the dike emplacement probably favored water circulation along the contact. Strontium isotopic data suggest that the fluids of probable meteoric origin, reacted with Bathonian and Bajocian limestones before entering the underlying Toarcian shales.By analogy with deep geological radioactive waste repositories, the results report discrete mineralogical variations of the clays when subjected to temperatures of 100–150 °C that are expected in deep storage conditions. Beyond 150 °C, significant mineralogical changes may alter the physical and chemical properties of the shales, especially of the clay fraction. Also, the development of structural discontinuities in the so-called thermally disturbed zone might be of importance as these discontinuities might become zones for preferential fluid circulation. Finally, the study emphasizes the use of Rb–Sr and K–Ar isotopic systems as tracers of local circulating fluids related to low-grade thermal imprints.