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Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab...
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Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Environmental Mineralogy and Biogeochemistry".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 42920

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Dr. Ana María Fernández

E-Mail Website
Guest Editor
Centro de Investigaciones Energéticas Medioambientales y Tecnológicas, 28040 Madrid, Spain
Interests: pore water chemistry; clay mineral synthesis; clay formations; properties of clays and natural raw materials; applicability of bentonites in European HLRW repositories
Special Issues, Collections and Topics in MDPI journals
Dr. Stephan Kaufhold

E-Mail Website
Guest Editor
Bundesanstalt fur Geowissenschaften und Rohstoffe, 30655 Hannover, Germany
Interests: properties of clays and natural functional raw materials; applicability of bentonites in European HLRW repositories; adsorption mechanisms in soils and geotechnical barriers; development of new or modified mineralogical methods frequently based on a collection of reference materials
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Markus Olin

E-Mail Website
Guest Editor
Final Disposal of Spent Nuclear Fuel, VTT Technical Research Centre of Finland Ltd, Kivimiehentie 3, Espoo, P.O. Box 1000, FI-02044 VTT, Finland
Interests: chemistry and mechanics of bentonite clay; diffusion and sorption of radionuclides
Special Issues, Collections and Topics in MDPI journals
Dr. Lian-Ge Zheng

E-Mail Website
Guest Editor
Nuclear Energy and Waste Program Head, Energy Geoscience Division, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720, USA
Interests: numerical modeling of non-isothermal, multiphase flow and multi-component reactive transport in porous media; inverse methodologies of parameter estimation; coupled modeling of thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes in the subsurface
Dr. Paul Wersin

E-Mail Website1 Website2
Guest Editor
Institute of Geological Sciences, University of Bern, Baltzerstrasse 1+3, 3012 Bern, Switzerland
Interests: bentonites; geochemistry in the engineered barrier system (EBS) of high-level waste repositories; diffusion processes in the EBS; geochemistry and diffusion in argillaceous host rocks; steel corrosion and its impact on the bentonite barrier; transport of radionuclides in the EBS and host rock
Dr. James Wilson

E-Mail Website
Guest Editor
Wilson Scientific Ltd., Warrington WA3 6TR, UK
Interests: bentonite; iron–bentonite interactions; cement/concrete chemistry; cement–clay interactions; geochemical modelling; chemotoxic species
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

We are pleased to announce the launch of a new a Special Issue of the journal Minerals that shall present a set of themed articles on “Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water interactions from Lab and Large-Scale Tests”. The main focus will be on geochemical and mineralogical processes observed from heating/hydration experiments performed at different scales, which may alter the structure and properties of bentonites and/or clayrocks used as barriers in the context of deep geological disposal of nuclear fuels and radioactive waste.

Bentonites and clayrocks are an essential component of the multi-barrier system securing the long-term safety of the final disposal of nuclear waste. The efficiency of such engineered and natural clay barriers relies on their physical and chemical confinement properties. Therefore, the long-term preservation of these properties over large periods is an important issue. From a geochemical point of view, the clayey mineral’s function to isolate the canisters from water and retard the migration of radionuclides also means maintaining a suitable chemical and mineralogical environment for canister integrity, radionuclide retention, and mechanical stability over time, buffering possible alteration/deterioration processes of the nanoporous clay materials.

One scientific approach used to tackle the prediction of long-term clay barrier behavior is through the analysis of results from experiments conducted in laboratory, large-scale mock-up tests, and in situ experiments conducted in underground research laboratories (URL) at real scale and under realistic conditions. These tests provide the opportunity to understand and quantify the processes and to evaluate the behavior of the clay minerals.

Different experiments have been performed over time using bentonites and natural clayrocks. Around 40 years ago, a few commercial high-quality bentonites were acquired for their study as buffer and backfill materials in the construction of engineering barrier systems (EBS) for the isolation of high-level radioactive waste. Today, highly compacted bentonite blocks, high-density bentonite pellets or a mixture thereof are being used both in laboratory and large-scale in situ experiments (FEBEX, LOT, ABM, FE experiment, etc.).

In the case of clayrocks, these experiments are conducted in URLs. Twenty-six URLs were set up in 10 countries between 1965 and 2006. In Europe, three of them were constructed in clayrocks environments: HADES (Belgium, 1980- , Boom Clay plastic clayrock), Mont Terri (Switzerland, 1995- , Opalinus Clay consolidated clayrock), and Meuse/Haute-Marne or Bure URL (France, 2000- , Callovo-Oxfordian consolidated clayrock), where many geochemical/mineralogical studies are currently being performed.

An overview of the results found up to date may contribute to establish the know-how about the understanding of the thermo-/hydro-chemical processes affecting to the clay minerals, and their response to different perturbations (e.g., desaturation, corrosion, gases produced and consumed, interactions with other materials, and inorganic/organic species), which may produce physico-chemical changes affecting their mechanical (swelling, permeability, etc.) and sorption properties. This may contribute to validate applied technologies, to the design of future experiments for unresolved questions, and to validate modeling tools required for interpretation and prediction of the evolution of such processes.

Thus, our Special Issue will cover a broad range of relevant topics of interest. Insights related to the following aspects will be included in this Special Issue:

  1. Mineral alteration: dissolution and redistribution of primary mineral phases and precipitation/neoformation of secondary minerals;
  2. Physico-chemical properties modification (cation exchange capacity, cation exchange population, surface complexation, crystallochemical structure, layer charge and swelling ability);
  3. Microstructure changes affecting sorption processes (porosity, water adsorption, ion exchange, radionuclide sorption, etc.);
  4. Clayrock- or Bentonite-groundwater interactions;
  5. Changes in pore water chemistry;
  6. Corrosion and metal/interface processes;
  7. Smectite and other clay mineral structural stability;
  8. Redox Chemistry and redox state evolution, affecting the structural stability and speciation of dissolved ions and radionuclides;
  9. Influence of gases produced and consumed under oxidized and reducing conditions and/or a desaturation phase on geochemistry/mineralogy;
  10. Organics and their influence on geochemistry/mineralogy;
  11. Microbial-mediated mineral alteration and geochemical evolution;
  12. Geochemical modeling, reactive transport and computational quantum mechanical modeling.

Dr. Ana María Fernández
Dr. Stephan Kaufhold
Prof. Dr. Markus Olin
Dr. Lian-Ge Zheng
Dr. Paul Wersin
Dr. James Wilson
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • bentonite
  • clayrocks
  • clay–water interaction
  • temperature influence
  • mineral alteration
  • geochemistry
  • clay properties
  • microstructure
  • CEC
  • pore water
  • gas
  • redox
  • organics
  • microbes
  • waste disposal
  • geochemical modeling

Published Papers (18 papers)

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Editorial

Jump to: Research

4 pages, 221 KiB  
Editorial
Editorial for Special Issue “Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests”
by Ana María Fernández, Stephan Kaufhold, Markus Olin, Lian-Ge Zheng, Paul Wersin and James Wilson
Minerals 2022, 12(5), 569; https://0-doi-org.brum.beds.ac.uk/10.3390/min12050569 - 30 Apr 2022
Cited by 2 | Viewed by 1260
Abstract
This Special Issue “Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests” covers a broad range of relevant and interesting topics related to deep geological disposal of nuclear fuels and radioactive waste [...] Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)

Research

Jump to: Editorial

37 pages, 22170 KiB  
Article
Characterization of Bentonites from the In Situ ABM5 Heater Experiment at Äspö Hard Rock Laboratory, Sweden
by Ana María Fernández, José F. Marco, Paula Nieto, Fco. Javier León, Luz María Robredo, María Ángeles Clavero, Ana Isabel Cardona, Sergio Fernández, Daniel Svensson and Patrik Sellin
Minerals 2022, 12(4), 471; https://0-doi-org.brum.beds.ac.uk/10.3390/min12040471 - 12 Apr 2022
Cited by 7 | Viewed by 3032
Abstract
The Alternative Buffer Material ABM5 experiment is an in situ medium-scale experiment performed at Äspö Hard Rock Laboratory (HRL) conducted by SKB in Sweden with the aim of analysing the long-term stability of bentonites used as an engineering barrier for a high-level radioactive [...] Read more.
The Alternative Buffer Material ABM5 experiment is an in situ medium-scale experiment performed at Äspö Hard Rock Laboratory (HRL) conducted by SKB in Sweden with the aim of analysing the long-term stability of bentonites used as an engineering barrier for a high-level radioactive waste repository (HLWR). In this work, four different ring-shaped Ca- and Na-bentonite blocks, which were piled around a carbon steel cylindrical heater, subjected to a maximum temperature of 250 °C and hydrated with saline Na-Ca-Cl Äspö groundwater (0.91 ionic strength), were characterized after dismantling. This work allowed us to identify the main geochemical processes involved, as well as the modifications in the physico-chemical properties and pore water composition after 4.4 years of treatment. No significant modifications in mineralogy were observed in samples close to the heater contact, except an increase in Fe content due to C-steel corrosion, carbonate dissolution/precipitation (mainly calcite and siderite) and Mg increase. No magnetite and a low amount of Fe(II) inside the clay mineral structure were detected. No modifications were observed in the smectite structure, except a slight increase in total and tetrahedral charge. A decrease in external surface area and cation exchange capacity (CEC) was found in all samples, with lower values being detected at the heater contact. As a consequence of the diffusion of the infiltrating groundwater, a modification of the composition at clay mineral exchange sites occurred. Ca-bentonites increased their Na content at exchange sites, whereas Na-bentonite increased their Ca content. Exchangeable Mg content decreased in all bentonites, except in MX-80 located at the bottom part of the package. A salinity gradient is observed through the bentonite blocks from the granite to the heater contact due to anions are controlled by diffusion and anion exclusion. The pore water chemistry of bentonites evolved as a function of the diffusion transport of the groundwater, the chemical equilibrium of cations at exchange sites and mineral dissolution/precipitation processes. These reactions are in turn dependent on temperature and water vapor fluxes. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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20 pages, 9887 KiB  
Article
Reactive Transport Modelling of the Long-Term Interaction between Carbon Steel and MX-80 Bentonite at 25 °C
by M. Carme Chaparro, Nicolas Finck, Volker Metz and Horst Geckeis
Minerals 2021, 11(11), 1272; https://0-doi-org.brum.beds.ac.uk/10.3390/min11111272 - 16 Nov 2021
Cited by 12 | Viewed by 2027
Abstract
The geological disposal in deep bedrock repositories is the preferred option for the management of high-level radioactive waste (HLW). In some of these concepts, carbon steel is considered as a potential canister material and bentonites are planned as backfill material to protect metallic [...] Read more.
The geological disposal in deep bedrock repositories is the preferred option for the management of high-level radioactive waste (HLW). In some of these concepts, carbon steel is considered as a potential canister material and bentonites are planned as backfill material to protect metallic waste containers. Therefore, a 1D radial reactive transport model has been developed in order to better understand the processes occurring during the long-term iron-bentonite interaction. The numerical model accounts for diffusion, aqueous complexation reactions, mineral dissolution/precipitation and cation exchange at a constant temperature of 25 °C under anoxic conditions. Our results suggest that Fe is sorbed at the montmorillonite surface via cation exchange in the short-term, and it is consumed by formation of the secondary phases in the long-term. The numerical model predicts precipitation of nontronite, magnetite and greenalite as corrosion products. Calcite precipitates due to cation exchange in the short-term and due to montmorillonite dissolution in the long-term. Results further reveal a significant increase in pH in the long-term, while dissolution/precipitation reactions result in limited variations of the porosity. A sensitivity analysis has also been performed to test the effect of selected parameters, such as corrosion rate, diffusion coefficient and composition of the bentonite porewater, on the corrosion processes. Overall, outcomes suggest that the predicted main corrosion products in the long-term are Fe-silicate minerals, such phases thus should deserve further attention as a chemical barrier in the diffusion of radionuclides to the repository far field. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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16 pages, 3960 KiB  
Article
In Situ Measurements of the Hydration Behavior of Compacted Milos (SD80) Bentonite by Wet-Cell X-ray Diffraction in an Opalinus Clay Pore Water and a Diluted Cap Rock Brine
by Tobias Manzel, Carolin Podlech, Georg Grathoff, Stephan Kaufhold and Laurence N. Warr
Minerals 2021, 11(10), 1082; https://0-doi-org.brum.beds.ac.uk/10.3390/min11101082 - 30 Sep 2021
Cited by 2 | Viewed by 1719
Abstract
Compacted bentonite is currently being considered as a suitable backfill material for sealing underground repositories for radioactive waste as part of a multi-barrier concept. Although showing favorable properties for this purpose (swelling capability, low permeability, and high adsorption capacity), the best choice of [...] Read more.
Compacted bentonite is currently being considered as a suitable backfill material for sealing underground repositories for radioactive waste as part of a multi-barrier concept. Although showing favorable properties for this purpose (swelling capability, low permeability, and high adsorption capacity), the best choice of material remains unclear. The goal of this study was to examine and compare the hydration behavior of a Milos (Greek) Ca-bentonite sample (SD80) in two types of simulated ground water: (i) Opalinus clay pore water, and (ii) a diluted saline cap rock brine using a confined volume, flow-through reaction cell adapted for in situ monitoring by X-ray diffraction. Based on wet-cell X-ray diffractometry (XRD) and calculations with the software CALCMIX of the smectite d(001) reflection, it was possible to quantify the abundance of water layers (WL) in the interlayer spaces and the amount of non-interlayer water uptake during hydration using the two types of solutions. This was done by varying WL distributions to fit the CALCMIX-simulated XRD model to the observed data. Hydrating SD80 bentonite with Opalinus clay pore water resulted in the formation of a dominant mixture of 3- and 4-WLs. The preservation of ca. 10% 1-WLs and the apparent disappearance of 2-WLs in this hydrated sample are attributed to small quantities of interlayer K (ca. 8% of exchangeable cations). The SD80 bentonite of equivalent packing density that was hydrated in diluted cap rock brine also contained ca. 15% 1-WLs, associated with a slightly higher concentration of interlayer K. However, this sample showed notable suppression of WL thickness with 2- and 3-WLs dominating in the steady-state condition. This effect is to be expected for the higher salt content of the brine but the observed generation of CO2 gas in this experiment, derived from enhanced dissolution of calcite, may have contributed to the suppression of WL thickness. Based on a comparison with all published wet-cell bentonite hydration experiments, the ratio of packing density to the total layer charge of smectite is suggested as a useful proxy for predicting the relative amounts of interlayer and non-interlayer water incorporated during hydration. Such information is important for assessing the subsequent rates of chemical transport through the bentonite barrier. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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17 pages, 4126 KiB  
Article
A MiniSandwich Experiment with Blended Ca-Bentonite and Pearson Water—Hydration, Swelling, Solute Transport and Cation Exchange
by Katja Emmerich, Eleanor Bakker, Franz Königer, Christopher Rölke, Till Popp, Sarah Häußer, Ralf Diedel and Rainer Schuhmann
Minerals 2021, 11(10), 1061; https://0-doi-org.brum.beds.ac.uk/10.3390/min11101061 - 28 Sep 2021
Cited by 2 | Viewed by 1557
Abstract
Shaft seals are geotechnical barriers in nuclear waste deposits and underground mines. The Sandwich sealing system consists of alternating sealing segments (DS) of bentonite and equipotential segments (ES). MiniSandwich experiments were performed with blended Ca-bentonite (90 mm diameter and 125 mm height) to [...] Read more.
Shaft seals are geotechnical barriers in nuclear waste deposits and underground mines. The Sandwich sealing system consists of alternating sealing segments (DS) of bentonite and equipotential segments (ES). MiniSandwich experiments were performed with blended Ca-bentonite (90 mm diameter and 125 mm height) to study hydration, swelling, solute transport and cation exchange during hydration with A3 Pearson water, which resembles pore water of Opalinus Clay Formation at sandy facies. Two experiments were run in parallel with DS installed either in one-layer hydrate state (1W) or in air-dry two-layer hydrate (2W) state. Breakthrough at 0.3 MPa injection pressure occurred after 20 days and the fluid inlet was closed after 543 days, where 4289 mL and 2984 mL, respectively, passed both cells. Final hydraulic permeability was 2.0–2.7 × 10−17 m2. Cells were kept for another 142 days before dismantling. Swelling of DS resulted in slight compaction of ES. No changes in the mineralogy of the DS and ES material despite precipitated halite and sulfates occurred. Overall cation exchange capacity of the DS does not change, maintaining an overall value of 72 ± 2 cmol(+)/kg. Exchangeable Na+ strongly increased while exchangeable Ca2+ decreased. Exchangeable Mg2+ and K+ remained nearly constant. Sodium concentration in the outflow indicated two different exchange processes while the concentration of calcium and magnesium decreased potentially. Concentration of sulfate increased in the outflow, until it reached a constant value and chloride concentration decreased to a minimum before it slightly increased to a constant value. The available data set will be used to adapt numerical models for a mechanism-based description of the observed physical and geochemical processes. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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23 pages, 5098 KiB  
Article
Evolution of the Reaction and Alteration of Mudstone with Ordinary Portland Cement Leachates: Sequential Flow Experiments and Reactive-Transport Modelling
by Keith Bateman, Shota Murayama, Yuji Hanamachi, James Wilson, Takamasa Seta, Yuki Amano, Mitsuru Kubota, Yuji Ohuchi and Yukio Tachi
Minerals 2021, 11(9), 1026; https://0-doi-org.brum.beds.ac.uk/10.3390/min11091026 - 21 Sep 2021
Cited by 2 | Viewed by 1784
Abstract
The construction of a repository for geological disposal of radioactive waste will include the use of cement-based materials. Following closure, groundwater will saturate the repository and the extensive use of cement will result in the development of a highly alkaline porewater, pH > [...] Read more.
The construction of a repository for geological disposal of radioactive waste will include the use of cement-based materials. Following closure, groundwater will saturate the repository and the extensive use of cement will result in the development of a highly alkaline porewater, pH > 12.5; this fluid will migrate into and react with the host rock. The chemistry of the fluid will evolve over time, initially high [Na] and [K], evolving to a Ca-rich fluid, and finally returning to the groundwater composition. This evolving chemistry will affect the long-term performance of the repository, altering the physical and chemical properties, including radionuclide behaviour. Understanding these changes forms the basis for predicting the long-term evolution of the repository. This study focused on the determination of the nature and extent of the chemical reaction, as well as the formation and persistence of secondary mineral phases within a mudstone, comparing data from sequential flow experiments with the results of reactive transport modelling. The reaction of the mudstone with the cement leachates resulted in small changes in pH with the precipitation of calcium aluminium silicate hydrate (C-(A-)S-H) phases of varying compositions. As the system evolves, secondary C-(A-)S-H phases re-dissolve and are replaced by secondary carbonates. This general sequence was successfully simulated using reactive transport modelling. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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18 pages, 2850 KiB  
Article
Thermally Induced Bentonite Alterations in the SKB ABM5 Hot Bentonite Experiment
by Ritwick Sudheer Kumar, Carolin Podlech, Georg Grathoff, Laurence N. Warr and Daniel Svensson
Minerals 2021, 11(9), 1017; https://0-doi-org.brum.beds.ac.uk/10.3390/min11091017 - 18 Sep 2021
Cited by 9 | Viewed by 2720
Abstract
Pilot sites are currently used to test the performance of bentonite barriers for sealing high-level radioactive waste repositories, but the degree of mineral stability under enhanced thermal conditions remains a topic of debate. This study focuses on the SKB ABM5 experiment, which ran [...] Read more.
Pilot sites are currently used to test the performance of bentonite barriers for sealing high-level radioactive waste repositories, but the degree of mineral stability under enhanced thermal conditions remains a topic of debate. This study focuses on the SKB ABM5 experiment, which ran for 5 years (2012 to 2017) and locally reached a maximum temperature of 250 °C. Five bentonites were investigated using XRD with Rietveld refinement, SEM-EDX and by measuring pH, CEC and EC. Samples extracted from bentonite blocks at 0.1, 1, 4 and 7 cm away from the heating pipe showed various stages of alteration related to the horizontal thermal gradient. Bentonites close to the contact with lower CEC values showed smectite alterations in the form of tetrahedral substitution of Si4+ by Al3+ and some octahedral metal substitutions, probably related to ferric/ferrous iron derived from corrosion of the heater during oxidative boiling, with pyrite dissolution and acidity occurring in some bentonite layers. This alteration was furthermore associated with higher amounts of hematite and minor calcite dissolution. However, as none of the bentonites showed any smectite loss and only displayed stronger alterations at the heater–bentonite contact, the sealants are considered to have remained largely intact. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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20 pages, 26059 KiB  
Article
Geochemical, Geotechnical, and Microbiological Changes in Mg/Ca Bentonite after Thermal Loading at 150 °C
by Vlastislav Kašpar, Šárka Šachlová, Eva Hofmanová, Bára Komárková, Václava Havlová, Claudia Aparicio, Kateřina Černá, Deepa Bartak and Veronika Hlaváčková
Minerals 2021, 11(9), 965; https://0-doi-org.brum.beds.ac.uk/10.3390/min11090965 - 03 Sep 2021
Cited by 8 | Viewed by 2232
Abstract
Bentonite buffers at temperatures beyond 100 °C could reduce the amount of high-level radioactive waste in a deep geological repository. However, it is necessary to demonstrate that the buffer surrounding the canisters withstands such elevated temperatures, while maintaining its safety functions (regarding long-term [...] Read more.
Bentonite buffers at temperatures beyond 100 °C could reduce the amount of high-level radioactive waste in a deep geological repository. However, it is necessary to demonstrate that the buffer surrounding the canisters withstands such elevated temperatures, while maintaining its safety functions (regarding long-term performance). For this reason, an experiment with thermal loading of bentonite powder at 150 °C was arranged. The paper presents changes that the Czech Mg/Ca bentonite underwent during heating for one year. These changes were examined by X-ray diffraction (XRD), thermal analysis with evolved gas analysis (TA-EGA), aqueous leachates, Cs sorption, cation exchange capacity (CEC), specific surface area (SSA), free swelling, saturated hydraulic conductivity, water retention curves (WRC), quantitative polymerase chain reaction (qPCR), and next-generation sequencing (NGS). It was concluded that montmorillonite was partially altered, in terms of the magnitude of the surface charge density of montmorillonite particles, based on the measurement interpretations of CEC, SSA, and Cs sorption. Montmorillonite alteration towards low- or non-swelling clay structures corresponded well to significantly lower swelling ability and water uptake ability, and higher saturated hydraulic conductivity of thermally loaded samples. Microbial survivability decreased with the thermal loading time, but it was not completely diminished, even in samples heated for one year. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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28 pages, 3404 KiB  
Article
Bentonite Alteration in Batch Reactor Experiments with and without Organic Supplements: Implications for the Disposal of Radioactive Waste
by Carolin Podlech, Nicole Matschiavelli, Markus Peltz, Sindy Kluge, Thuro Arnold, Andrea Cherkouk, Artur Meleshyn, Georg Grathoff and Laurence N. Warr
Minerals 2021, 11(9), 932; https://0-doi-org.brum.beds.ac.uk/10.3390/min11090932 - 27 Aug 2021
Cited by 7 | Viewed by 2177
Abstract
Bentonite is currently proposed as a potential backfill material for sealing high-level radioactive waste in underground repositories due to its low hydraulic conductivity, self-sealing ability and high adsorption capability. However, saline pore waters, high temperatures and the influence of microbes may cause mineralogical [...] Read more.
Bentonite is currently proposed as a potential backfill material for sealing high-level radioactive waste in underground repositories due to its low hydraulic conductivity, self-sealing ability and high adsorption capability. However, saline pore waters, high temperatures and the influence of microbes may cause mineralogical changes and affect the long-term performance of the bentonite barrier system. In this study, long-term static batch experiments were carried out at 25 °C and 90 °C for one and two years using two different industrial bentonites (SD80 from Greece, B36 from Slovakia) and two types of aqueous solutions, which simulated (a) Opalinus clay pore water with a salinity of 19 g·L−1, and (b) diluted cap rock solution with a salinity of 155 g·L−1. The bentonites were prepared with and without organic substrates to study the microbial community and their potential influence on bentonite mineralogy. Smectite alteration was dominated by metal ion substitutions, changes in layer charge and delamination during water–clay interaction. The degree of smectite alteration and changes in the microbial diversity depended largely on the respective bentonite and the experimental conditions. Thus, the low charged SD80 with 17% tetrahedral charge showed nearly no structural change in either of the aqueous solutions, whereas B36 as a medium charged smectite with 56% tetrahedral charge became more beidellitic with increasing temperature when reacted in the diluted cap rock solution. Based on these experiments, the alteration of the smectite is mainly attributed to the nature of the bentonite, pore water chemistry and temperature. A significant microbial influence on the here analyzed parameters was not observed within the two years of experimentation. However, as the detected genera are known to potentially influence geochemical processes, microbial-driven alteration occurring over longer time periods cannot be ruled out if organic nutrients are available at appropriate concentrations. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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25 pages, 7667 KiB  
Article
Interaction of Corroding Iron with Eight Bentonites in the Alternative Buffer Materials Field Experiment (ABM2)
by Paul Wersin, Jebril Hadi, Andreas Jenni, Daniel Svensson, Jean-Marc Grenèche, Patrik Sellin and Olivier X. Leupin
Minerals 2021, 11(8), 907; https://0-doi-org.brum.beds.ac.uk/10.3390/min11080907 - 22 Aug 2021
Cited by 11 | Viewed by 2441
Abstract
Bentonite, a common smectite-rich buffer material, is in direct contact with corroding steel in many high-level radioactive waste repository designs. The interaction of iron with the smectite-rich clay may affect its swelling and sealing properties by processes such as alteration, redox reactions and [...] Read more.
Bentonite, a common smectite-rich buffer material, is in direct contact with corroding steel in many high-level radioactive waste repository designs. The interaction of iron with the smectite-rich clay may affect its swelling and sealing properties by processes such as alteration, redox reactions and cementation. The chemical interactions were investigated by analysing the Fe/clay interfaces of eight bentonite blocks which had been exposed to temperatures up to 130 °C for five years in the ABM2 borehole at the Äspö Hard Rock Laboratory managed by the Swedish Nuclear Fuel and Waste Management Co (SKB). Eleven interface samples were characterised by high spatial resolution methods, including scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and μ-Raman spectroscopy as well as by “bulk” methods X-ray diffraction, X-ray fluorescence and 57Fe Mössbauer spectrometry. Corrosion induced an iron front of 5–20 mm into the bentonite, except for the high-Fe bentonite where no Fe increase was detected. This Fe front consisted mainly of ferric (oxyhydr)oxides in addition to the structural Fe in the smectite fraction which had been partially reduced by the interaction process. Fe(II) was also found to extend further into the clay, but its nature could not be identified. The consistent behaviour is explained by the redox evolution, which shifts from oxidising to reducing conditions during the experiment. No indication of smectite alteration was found. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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20 pages, 3943 KiB  
Article
Mineralogical, Geochemical and Geotechnical Study of BCV 2017 Bentonite—The Initial State and the State following Thermal Treatment at 200 °C
by František Laufek, Irena Hanusová, Jiří Svoboda, Radek Vašíček, Jan Najser, Magdaléna Koubová, Michal Čurda, František Pticen, Lenka Vaculíková, Haiquan Sun and David Mašín
Minerals 2021, 11(8), 871; https://0-doi-org.brum.beds.ac.uk/10.3390/min11080871 - 12 Aug 2021
Cited by 8 | Viewed by 2682
Abstract
Bentonites are considered to be the most suitable materials for the multibarrier system of high-level radioactive waste repositories. Since BCV bentonite has been proved to be an ideal representative of Czech Ca-Mg bentonites in this respect, it has been included in the Czech [...] Read more.
Bentonites are considered to be the most suitable materials for the multibarrier system of high-level radioactive waste repositories. Since BCV bentonite has been proved to be an ideal representative of Czech Ca-Mg bentonites in this respect, it has been included in the Czech Radioactive Waste Repository Authority (SÚRAO) buffer and backfill R&D programme. Detailed knowledge of processes in the material induced by thermal loading provides invaluable assistance regarding the evolution of the material under repository conditions. Samples of both original BCV 2017 bentonite and the same material thermally treated at 200 °C were characterised by means of chemical analysis, powder X-ray diffraction, infrared spectroscopy, thermal analysis, cation exchange capacity, specific surface area (BET) measurements, the determination of the swell index, the liquid limit, the swelling pressure and water retention curves. The smectite in BCV 2017 bentonite comprises Ca-Mg montmorillonite with a significant degree of Fe3+ substitution in the octahedral sheet. Two main transformation processes were observed following heating at 200 °C over 27 months, the first of which comprised the dehydration of the montmorillonite and the subsequent reduction of the 001 basal distance from 14.5 Å (the original BCV 2017) to 9.8 Å, thus indicating the absence of water molecules in the interlayer space. The second concerned the dehydration and partial dehydroxylation of goethite. With the exception of the dehydration of the interlayer space, the PXRD and FTIR study revealed the crystallochemical stability of the montmorillonite in BCV 2017 bentonite under the selected experimental conditions. The geotechnical tests indicated no major changes in the mechanical properties of the thermally treated BCV 2017 bentonite, as demonstrated by the similar swelling pressure values. However, the variation in the swell index and the gradual increase in the liquid limit with the wetting time indicated a lower hydration rate. The retention curves consistently showed the lower retention capacity of the thermally treated samples, thus indicating the incomplete re-hydration of the thermally treated BCV 2017 exposed to air humidity and the difference in its behaviour compared to the material exposed to liquid water. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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33 pages, 5572 KiB  
Article
Ex and In Situ Reactivity and Sorption of Selenium in Opalinus Clay in the Presence of a Selenium Reducing Microbial Community
by Nele Bleyen, Joe S. Small, Kristel Mijnendonckx, Katrien Hendrix, Achim Albrecht, Pierre De Cannière, Maryna Surkova, Charles Wittebroodt and Elie Valcke
Minerals 2021, 11(7), 757; https://0-doi-org.brum.beds.ac.uk/10.3390/min11070757 - 13 Jul 2021
Cited by 6 | Viewed by 2394
Abstract
79Se is a critical radionuclide concerning the safety of deep geological disposal of certain radioactive wastes in clay-rich formations. To study the fate of selenium oxyanions in clayey rocks in the presence of a selenium reducing microbial community, in situ tests were [...] Read more.
79Se is a critical radionuclide concerning the safety of deep geological disposal of certain radioactive wastes in clay-rich formations. To study the fate of selenium oxyanions in clayey rocks in the presence of a selenium reducing microbial community, in situ tests were performed in the Opalinus Clay at the Mont Terri Rock Laboratory (Switzerland). Furthermore, biotic and abiotic batch tests were performed to assess Se(VI) and Se(IV) reactivity in the presence of Opalinus Clay and/or stainless steel, in order to support the interpretation of the in situ tests. Geochemical modeling was applied to simulate Se(VI) reduction, Se(IV) sorption and solubility, and diffusion processes. This study shows that microbial activity is required to transform Se(VI) into more reduced and sorbing Se species in the Opalinus Clay, while in abiotic conditions, Se(VI) remains unreactive. On the other hand, Se(IV) can be reduced by microorganisms but can also sorb in the presence of clay without microorganisms. In situ microbial reduction of Se oxyanions can occur with electron donors provided by the clay itself. If microorganisms would be active in the clay surrounding a disposal facility, microbial reduction of leached Se could thus contribute to the overall retention of Se in clayey host rocks. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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15 pages, 27527 KiB  
Article
Swelling Pressure and Permeability of Compacted Bentonite from 10th Khutor Deposit (Russia)
by Artur Yu. Meleshyn, Sergey V. Zakusin and Victoria V. Krupskaya
Minerals 2021, 11(7), 742; https://0-doi-org.brum.beds.ac.uk/10.3390/min11070742 - 07 Jul 2021
Cited by 10 | Viewed by 3115
Abstract
Bentonites from the 10th Khutor deposit (Republic of Khakassia, Russia) are considered a potential buffer material for isolation of radioactive waste in the crystalline rocks of Yeniseyskiy site (Krasnoyarskiy region). This study presents the results of a series of permeameter experiments with bentonite [...] Read more.
Bentonites from the 10th Khutor deposit (Republic of Khakassia, Russia) are considered a potential buffer material for isolation of radioactive waste in the crystalline rocks of Yeniseyskiy site (Krasnoyarskiy region). This study presents the results of a series of permeameter experiments with bentonite compacted to dry densities of 1.4, 1.6, and 1.8 g/cm3, saturated and permeated by the artificial groundwater from Yeniseyskiy Site. Permeation was conducted at hydraulic gradients of 180–80,000 m/m to simulate potential hydraulic conditions in the early post-closure phase of a deep geological repository (DGR). The respective swelling pressures of 0.8 ± 0.3, 2.2 ± 0.6, and 6.3 ± 0.3 MPa and permeabilities of (27 ± 15) × 10−20, (3.4 ± 0.8) × 10−20, and (0.96 ± 0.26) × 10−20 m2 were observed for the hydraulic gradient of 2000 m/m, which is recommended for the determination of undisturbed swelling pressures and permeabilities in permeameter experiments. Upon incremental increases in the hydraulic gradient, swelling pressures at all densities and permeability at the density of 1.8 g/cm3 remained unchanged, whereas permeabilities at 1.4 and 1.6 g/cm3 decreased overall by a factor of approximately 5 and 1.7, respectively. Seepage-induced consolidation and/or reorganisation of bentonite microstructure are considered possible reasons for these decreases. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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18 pages, 57104 KiB  
Article
Mineralogical Analysis of Bentonite from the ABM5 Heater Experiment at Äspö Hard Rock Laboratory, Sweden
by Stephan Kaufhold, Reiner Dohrmann, Kristian Ufer, Daniel Svensson and Patrik Sellin
Minerals 2021, 11(7), 669; https://0-doi-org.brum.beds.ac.uk/10.3390/min11070669 - 23 Jun 2021
Cited by 7 | Viewed by 2257
Abstract
The present study reports on the analysis of all blocks of the ABM5 test, which is a medium scale bentonite buffer deposition test. In contrast to similar tests, the ABM5 was conducted at higher temperature (up to 250 °C). The aim of the [...] Read more.
The present study reports on the analysis of all blocks of the ABM5 test, which is a medium scale bentonite buffer deposition test. In contrast to similar tests, the ABM5 was conducted at higher temperature (up to 250 °C). The aim of the study was to characterize the chemical and mineralogical reactions and to identify the effect of the extraordinarily high temperature. Reactions observed were similar to those observed in previous and/or similar tests covering cation exchange, anion inflow, dissolution and precipitation of C- and S-phases, Fe corrosion, and Mg increase at the heater. Neither the type nor the extent of the different reactions could be related to the significantly higher temperature. However, due to the absence of lubricant used between heater and bentonite, it could be proved that the calcite previously present was dissolved and precipitated as siderite at the contact, pointing towards the importance of the presence of carbonate when considering different Fe corrosion products. Moreover, for the first time, a decrease of the Mg content at the heater was observed, which was probably because a Mg-rich clay was used. The reasons for Mg increase or decrease are still not completely understood. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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17 pages, 3487 KiB  
Article
Reactive Transport Simulation of Low-pH Cement Interacting with Opalinus Clay Using a Dual Porosity Electrostatic Model
by Andreas Jenni and Urs Mäder
Minerals 2021, 11(7), 664; https://0-doi-org.brum.beds.ac.uk/10.3390/min11070664 - 22 Jun 2021
Cited by 4 | Viewed by 1792
Abstract
Strong chemical gradients between clay and concrete porewater lead to diffusive transport across the interface and subsequent mineral reactions in both materials. These reactions may influence clay properties such as swelling behaviour, permeability or radionuclide retention, which are relevant for the safety of [...] Read more.
Strong chemical gradients between clay and concrete porewater lead to diffusive transport across the interface and subsequent mineral reactions in both materials. These reactions may influence clay properties such as swelling behaviour, permeability or radionuclide retention, which are relevant for the safety of a radioactive waste repository. Different cement types lead to different interactions with Opalinus Clay (OPA), which must be understood to choose the most suitable material. The consideration of anion-depleted porosity due to electrostatic repulsion in clay modelling substantially influences overall diffusive transport and pore clogging at interfaces. The identical dual porosity model approach previously used to predict interaction between Portland cement and OPA is now applied to low-alkali cement—OPA interaction. The predictions are compared with corresponding samples from the cement-clay interaction (CI) experiment in the Mont Terri underground rock laboratory (Switzerland). Predicted decalcification of the cement at the interface (depletion of C–S–H and absence of ettringite within 1 mm from the interface), the Mg enrichment in clay and cement close to the interface (neoformation of up to 17 vol% Mg hydroxides in concrete, and up to 6 vol% in OPA within 0.6 mm at the interface), and the slightly increased S content in the cement 3–4 mm away from the interface qualitatively match the sample characterisation. Simulations of Portland cement—OPA interaction indicate a weaker chemical disturbance over a larger distance compared with low-pH cement—OPA. In the latter case, local changes in porosity are stronger and lead to predicted pore clogging. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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19 pages, 6659 KiB  
Article
Reaction and Alteration of Mudstone with Ordinary Portland Cement and Low Alkali Cement Pore Fluids
by Keith Bateman, Yuki Amano, Mitsuru Kubota, Yuji Ohuchi and Yukio Tachi
Minerals 2021, 11(6), 588; https://0-doi-org.brum.beds.ac.uk/10.3390/min11060588 - 31 May 2021
Cited by 5 | Viewed by 2008
Abstract
The construction of a repository for the geological disposal of radioactive waste will utilize cement-based materials. Following closure, resaturation will result in the development of a highly alkaline porewater. The alkaline fluid will migrate and react with host rock, producing a chemically disturbed [...] Read more.
The construction of a repository for the geological disposal of radioactive waste will utilize cement-based materials. Following closure, resaturation will result in the development of a highly alkaline porewater. The alkaline fluid will migrate and react with host rock, producing a chemically disturbed zone (CDZ) around the repository. To understand how these conditions may evolve, a series of batch and flow experiments were conducted with Horonobe mudstone and fluids representative of the alkaline leachates expected from a cementitious repository. Both ordinary Portland cement (OPC) and low alkali cement (LAC) leachates were examined. The impact of the LAC leachates was more limited than the OPC leachates, with experiments using the LAC leachate showing the least reaction and lowest long-term pH of the different leachate types. The reaction was dominated by primary mineral dissolution, and in the case of OPC leachates, precipitation of secondary calcium-silicate-hydrate (C-S-H) phases. Flow experiments revealed that precipitation of the secondary phases was restricted to close to the initial contact zone of the fluids and mudstone. The experimental results demonstrate that a combination of both batch and flow-through experiments can provide the insights required for the understanding of the key geochemical interactions and the impact of transport. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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17 pages, 9473 KiB  
Article
Alteration of Bentonite Reacted with Cementitious Materials for 5 and 10 years in the Mont Terri Rock Laboratory (CI Experiment)
by Shingo Yokoyama, Misato Shimbashi, Daisuke Minato, Yasutaka Watanabe, Andreas Jenni and Urs Mäder
Minerals 2021, 11(3), 251; https://0-doi-org.brum.beds.ac.uk/10.3390/min11030251 - 28 Feb 2021
Cited by 11 | Viewed by 2381
Abstract
The cement–clay interaction (CI) experiment was carried out at the Mont Terri rock laboratory to complement the current knowledge on the influence that cementitious materials have on Opalinus Clay (OPA) and bentonite (MX). Drill cores including the interface of OPA, concrete (LAC = [...] Read more.
The cement–clay interaction (CI) experiment was carried out at the Mont Terri rock laboratory to complement the current knowledge on the influence that cementitious materials have on Opalinus Clay (OPA) and bentonite (MX). Drill cores including the interface of OPA, concrete (LAC = low-alkali binder, and OPC = ordinary Portland cement), and MX, which interacted for 4.9 and 10 years, were successfully retrieved after drilling, and detailed analyses were performed to evaluate potential mineralogical changes. The saturated compacted bentonites in core samples were divided into ten slices, profiling bentonite in the direction towards the interface, to evaluate the extent and spatial variation of the mineralogical alteration of bentonite. Regarding the mineral compositions of bentonite, cristobalite was dissolved within a range of 10 mm from the interface in both LAC-MX and OPC-MX, while calcite precipitated near the interface for OPC-MX. In LAC-MX and OPC-MX, secondary products containing Mg (e.g., M-S-H) also precipitated within 20 mm of the interface. These alterations of bentonite developed during the first 4.9 years, with very limited progress observed for the subsequent 5 years. Detectable changes in the mineralogical nature of montmorillonite (i.e., the formation of illite or beidellite, increase in layer charge) did not occur during the 10 years of interaction. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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25 pages, 15242 KiB  
Article
Gel Formation at the Front of Expanding Calcium Bentonites
by Katherine A. Daniels, Jon F. Harrington, Antoni E. Milodowski, Simon J. Kemp, Ian Mounteney and Patrik Sellin
Minerals 2021, 11(2), 215; https://0-doi-org.brum.beds.ac.uk/10.3390/min11020215 - 20 Feb 2021
Cited by 6 | Viewed by 2392
Abstract
The removal of potentially harmful radioactive waste from the anthroposphere will require disposal in geological repositories, the designs of which often favour the inclusion of a clay backfill or engineered barrier around the waste. Bentonite is often proposed as this engineered barrier and [...] Read more.
The removal of potentially harmful radioactive waste from the anthroposphere will require disposal in geological repositories, the designs of which often favour the inclusion of a clay backfill or engineered barrier around the waste. Bentonite is often proposed as this engineered barrier and understanding its long-term performance and behaviour is vital in establishing the safety case for its usage. There are many different compositions of bentonite that exist and much research has focussed on the properties and behaviour of both sodium (Na) and calcium (Ca) bentonites. This study focusses on the results of a swelling test on Bulgarian Ca bentonite that showed an unusual gel formation at the expanding front, unobserved in previous tests of this type using the sodium bentonite MX80. The Bulgarian Ca bentonite was able to swell to completely fill an internal void space over the duration of the test, with a thin gel layer present on one end of the sample. The properties of the gel, along with the rest of the bulk sample, have been investigated using ESEM, EXDA and XRD analyses and the formation mechanism has been attributed to the migration of nanoparticulate smectite through a more silica-rich matrix of the bentonite substrate. The migration of smectite clay out of the bulk of the sample has important implications for bentonite erosion where this engineered barrier interacts with flowing groundwater in repository host rocks. Full article
(This article belongs to the Special Issue Clay Mineral Transformations after Bentonite/Clayrocks and Heater/Water Interactions from Lab and Large-Scale Tests)
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