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Special Issue "Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants"

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A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Crystallography and Physical Chemistry of Minerals & Nanominerals".

Deadline for manuscript submissions: 31 May 2023 | Viewed by 7534

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Special Issue Editors

Dr. Katharina Müller

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Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden, Germany
Interests: aqueous environmental geochemistry of contaminants; actinides; fission products; in situ time-resolved spectroscopy and microscopy; molecular reactions at mineral–water interfaces

Dr. Norbert Jordan

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Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden, Germany
Interests: actinides; fission products; rare earth elements; spectroscopy; microscopy; solid–water interfacial reactions; surface complexation modelling; complexation of actinides/rare earth elements in aqueous systems

Special Issue Information

Dear Colleagues,

The migration of (radioactive) contaminant ions in an aqueous environment is strongly affected by their molecular reactions at the solid−water interface, including physical adsorption, ion exchange, chemisorption, surface precipitation, sorption of colloidal phases, electron transfer (oxidation state changes), coordination changes (number and/or type of ligands around the sorbed species), as well as the modification of the surface structure of the substrate (dissolution/secondary phase formation). These molecular reactions are triggered by a variety of environmental conditions, such as concentrations, pH, ionic strength, and temperature.

In this Special Issue, we seek innovative contributions that provide new kinetic and molecular insights into interfacial reactions in the geosphere. We invite research papers involving the application of various spectroscopic, microscopic, and microcalorimetric techniques combined with theoretical approaches (e.g., quantum chemistry), surface complexation, and reactive transport modelling, with the aim to provide a more profound understanding of the structures, thermodynamics, and kinetics of interface phenomena. We also specifically welcome contributions dealing with developments or improvements of in situ and time-resolved experimental setups to resolve kinetic processes. Further emphasis is placed on the resolution of experimentally challenging conditions, such as trace concentrations, high pH values, moderate to high salinities, and elevated temperatures.

Dr. Katharina Müller
Dr. Norbert Jordan
Guest Editors

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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 2000 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

actinides
fission products
retention mechanisms
molecular reaction
radionuclides
spectroscopy
microscopy
calorimetry
quantum chemistry
kinetics
surface complexation modelling
reactive transport modelling
mineral–water interfaces
secondary phase formation
redox reactions
surface reactions
in situ techniques

Published Papers (8 papers)

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Research

Open AccessArticle

Mechanisms Governing ⁹⁰Sr Removal and Remobilisation in a VLLW Surface Disposal Concept

and

Minerals 2023, 13(3), 436; https://doi.org/10.3390/min13030436 - 18 Mar 2023

Viewed by 569

Abstract

Flow-through columns were used to assess potential long-term trends in ⁹⁰Sr biogeochemistry and transport in a Finnish near-surface very low-level waste (VLLW) repository concept. Experiments simulated the effects of water intrusion and flow through the repository barrier and backfill materials, examining impacts on ⁹⁰Sr migration. Artificial rainwater containing 2.0 mg/L stable Sr (as a proxy for ⁹⁰Sr) was pumped through column systems that had varying compositions from a matrix of rock flour (backfill material), bentonite (backfill/sealing material), and carbon steel (waste encapsulation material), for 295 days. Effluent geochemistry was monitored throughout. Sr retention behaviour in all column systems was broadly similar. Sr removal from influent rainwater was marked (~95% removed) at the beginning of the experiments, and this degree of removal was maintained for 20 days. Thereafter, Sr concentrations in the effluents began to rise, reaching ~2 mg/L by 295 days. Further, 56%–67% of added Sr was retained in the repository materials over the 295-day reaction period. Analysis of the effluents indicated that colloids did not form; as such, Sr output was likely to be aqueous Sr²⁺. Upon completion of the experiment, solid-associated Sr distribution and speciation in the columns were assessed through column sectioning and post-mortem analyses, which encompassed the following: total acid digests, sequential extractions, and XAS analysis. The total acid digests and sequential extractions showed that Sr was evenly distributed throughout the columns and that the majority (68%–87%) of solid-associated Sr was in the exchangeable fraction (MgCl₂). This suggested that a major part of the solid-phase Sr was weakly bound to the column materials via outer-sphere sorption. Interestingly, a smaller amount of Sr (7%–23%) could only be extracted by aqua regia, suggesting that a proportion of Sr may bind more strongly to the barrier materials. XAS analysis of select samples confirmed that the dominant Sr phase was sorbed to the rock flour and bentonite, but not corroded carbon steel. Columns were also subject to remobilisation experiments using artificial rain- and seawater without added Sr. While rainwater remobilised Sr slowly, high-ionic strength seawater remobilised Sr at much higher rates in the systems containing bentonite. Interestingly, Sr was well retained in the rock flour-only system following rain and seawater intrusion. Overall, the results indicate that the column materials provide reactive surfaces for Sr removal should it be released from waste packages; however, the backfill and barrier materials have limited retention capacity, and the dominant sorption interaction is relatively weak. The safety case for the shallow disposal of radioactive waste should consider the possibility of seawater intrusion and that the bentonite-bound Sr was significantly more susceptible to remobilisation following seawater, despite retaining slightly more Sr during sorption experiments. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

Uranium(VI) Sorption onto Hardened Cement Paste under High Saline and Alkaline Conditions

Nathalie Macé

Jacques Page

and

Pascal E. Reiller

Minerals 2023, 13(3), 325; https://doi.org/10.3390/min13030325 - 25 Feb 2023

Viewed by 380

Abstract

Evaluation of the mobility behaviour of radionuclides under highly saline and alkaline conditions is a major concern for the performance assessment of radioactive waste disposal. The aim of this study was to determine the effect of up to 2.8 mol/kg_solution content of NaNO₃, on the solubility and the retention of U(VI) at 22 °C onto a hardened cement paste (HCP) prepared from ordinary Portland cement (CEM I). To avoid the interference of the high salt concentration and ionic strength, and because of the expected low solubility of uranium under such alkaline conditions, time-resolved laser fluorescence spectroscopy (TRLFS) was selected to accurately measure U(VI) concentration in solution using the standard addition method in 85% H₃PO₄. This allows both limiting the dilution and matrix effects and determining the resulting [U(VI)] in solution with acceptable precision for the distribution factor (R_d) in both sorption and desorption experiments. The operational solubility limit measured at high ionic strength lowered by a factor of three compared to the reference cementitious condition, and its R_d values decreased by a factor ca. four. The sorption of U(VI) appears to be reversible under these conditions. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

On the Sorption Mode of U(IV) at Calcium Silicate Hydrate: A Comparison of Adsorption, Absorption in the Interlayer, and Incorporation by Means of Density Functional Calculations

Ion Chiorescu

Alena Kremleva

and

Sven Krüger

Minerals 2022, 12(12), 1541; https://doi.org/10.3390/min12121541 - 30 Nov 2022

Cited by 1 | Viewed by 618

Abstract

Calcium silicate hydrate (C-S-H) is the main product of cement hydration and has also been shown to be the main sorbing phase of actinide ions interacting with cement. U(IV) has been chosen as an exemplary actinide ion to study actinide sorption at C-S-H as U is the main element in highly active radioactive waste and because reducing conditions are foreseen in a deep geological repository for such waste. U(IV) surface adsorption, absorption in the interlayer, and incorporation into the calcium oxide layer of C-S-H has been modeled quantum mechanically, applying a density functional approach. For each sorption mode various sites have been considered and a combined dynamic equilibration and optimization approach has been applied to generate a set of representative stable sorption complexes. At the surface and in the interlayer similar U(IV) hydroxo complexes stabilized by Ca²⁺ ions have been determined as sorbates. Surface adsorption tends to be preferred over absorption in the interlayer for the same type of sites. Incorporation of U(IV) in the CaO layer yields the most favorable sorption site. This result is supported by good qualitative agreement of structures with EXAFS results for other actinides in the oxidation state IV, leading to a new interpretation of the experimental results. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

A Combined Extended X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Study of Americium vs. Yttrium Adsorption on Corundum (α–Al₂O₃)

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Minerals 2022, 12(11), 1380; https://doi.org/10.3390/min12111380 - 29 Oct 2022

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Abstract

Adsorption reactions on mineral surfaces are influenced by the overall concentration of the adsorbing metal cation. Different site types (strong vs. weak ones) are often included to describe the complexation reactions in the various concentration regimes. More specifically, strong sites are presumed to retain metal ions at low sorbate concentrations, while weak sites contribute to metal ion retention when the sorbate concentration increases. The involvement of different sites in the sorption reaction may, thereby, also be influenced by competing cations, which increase the overall metal ion concentration in the system. To date, very little is known about the complex structures and metal ion speciation in these hypothetical strong- and weak-site regimes, especially in competing scenarios. In the present study, we have investigated the uptake of the actinide americium on corundum (α–Al₂O₃) in the absence and presence of yttrium as competing metal by combining extended X-ray absorption fine structure spectroscopy (EXAFS) with density functional theory (DFT) calculations. Isotherm studies using the radioactive ¹⁵²Eu tracer were used to identify the sorption regimes where strong sites and weak sites contribute to the sorption reaction. The overall americium concentration, as well as the presence of yttrium could be seen to influence both the amount of americium uptake by corundum, but also the speciation at the surface. More specifically, increasing the Am³⁺ or Y³⁺ concentrations from the strong site to the weak site concentration regimes in the mineral suspensions resulted in a decrease in the overall Am–O coordination number from nine to eight, with a subsequent shortening of the average Am–O bond length. DFT calculations suggest a reduction of the surface coordination with increasing metal–ion loading, postulating the formation of tetradentate and tridentate Am³⁺ complexes at low and high surface coverages, respectively. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

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

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Minerals 2022, 12(9), 1078; https://doi.org/10.3390/min12091078 - 26 Aug 2022

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Abstract

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. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessFeature PaperArticle

Ion and Particle Size Effects on the Surface Reactivity of Anatase Nanoparticle–Aqueous Electrolyte Interfaces: Experimental, Density Functional Theory, and Surface Complexation Modeling Studies

Moira K. Ridley

Michael L. Machesky

and

James D. Kubicki

Minerals 2022, 12(7), 907; https://doi.org/10.3390/min12070907 - 20 Jul 2022

Viewed by 863

Abstract

At the nanoscale, particle size affects the surface reactivity of anatase–water interfaces. Here, we investigate the effect of electrolyte media and particle size on the primary charging behavior of anatase nanoparticles. Macroscopic experiments, potentiometric titrations, were used to quantitatively evaluate surface charge of a suite of monodisperse nanometer sized (4, 20, and 40 nm) anatase samples in five aqueous electrolyte solutions. The electrolyte media included alkaline chloride solutions (LiCl, NaCl, KCl, and RCl) and Na-Trifluoromethanesulfonate (NaTr). Titrations were completed at 25 °C, as a function of pH (3–11) and ionic strength (from 0.005 to 0.3 m). At the molecular scale, density functional theory (DFT) simulations were used to evaluate the most stable cation surface species on the predominant (101) anatase surface. In all electrolyte media, primary charging increased with increasing particle size. At high ionic strength, the development of negative surface charge followed reverse lyotropic behavior: charge density increased in the order RbCl < KCl < NaCl < LiCl. Positive surface charge was greater in NaCl than in NaTr media. From the DFT simulations, all cations formed inner-sphere surface species, but the most stable coordination geometry varied. The specific inner-sphere adsorption geometries are dependent on the ionic radius. The experimental data were described using surface complexation modeling (SCM), constrained by the DFT results. The SCM used the charge distribution (CD) and multisite (MUSIC) models, with a two-layer (inner- and outer-Helmholtz planes) description of the electric double layer. Subtle charging differences between the smallest and larger anatase particles were the same in each electrolyte media. These results further our understanding of solid–aqueous solution interface reactivity of nanoparticles. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

Surface Coverage- and Excitation Laser Wavelength-Dependent Luminescence Properties of U(VI) Species Adsorbed on Amorphous SiO₂

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Minerals 2022, 12(2), 230; https://doi.org/10.3390/min12020230 - 10 Feb 2022

Viewed by 863

Abstract

Time-resolved luminescence spectroscopy is usefully used to identify U(VI) surface species adsorbed on SiO₂. However, the cause of the inconsistent luminescence lifetimes and spectral shapes reported previously remains undetermined. In this study, the U(VI) surface coverage (Γ) and excitation laser wavelength (λ_ex) were examined as the predominant factors governing the luminescence properties of U(VI) surface species. At neutral pH, the luminescence lifetimes of U(VI) surface species increased with decreasing Γ. In the low-Γ region, where a relatively large number of adjacent surface sites are involved in the formation of multidentate surface complexes, the displacement of more number of coordinated water molecules in the equatorial plane of U(VI) results in a longer lifetime. The pH-dependent luminescence lifetimes of U(VI) surface species at the same U(VI) to SiO₂ concentration ratio in the pH range of 4.5–7.5 also explain the effect of the surface binding sites on the luminescence lifetime. The time-resolved luminescence properties of the U(VI) surface species were also investigated at different excitation wavelengths. Continued irradiation of the SiO₂ surface with a UV laser beam at λ_ex = 266 nm considerably reduced the luminescence intensities of the U(VI) surface species. The higher the laser pulse energy, the greater the decrease in luminescence intensity. Laser-induced thermal desorption (LITD) of U(VI) surface species is suggested to be the origin of the decrease in luminescence intensity. LITD effects were not observed at λ_ex = 355 and 422 nm, even at high laser pulse energies. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Open AccessArticle

Adsorption of Strontium onto Synthetic Iron(III) Oxide up to High Ionic Strength Systems

David García

Johannes Lützenkirchen

and

Minerals 2021, 11(10), 1093; https://doi.org/10.3390/min11101093 - 05 Oct 2021

Cited by 4 | Viewed by 1352

Abstract

In this work, the adsorption behavior of Sr onto a synthetic iron(III) oxide (hematite with traces of goethite) has been studied. This solid, which might be considered a representative of Fe³⁺ solid phases (iron corrosion products), was characterized by X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS), and its specific surface area was determined. Both XRD and XPS data are consistent with a mixed solid containing more than 90% hematite and 10% goethite. The solid was further characterized by fast acid-base titrations at different NaCl concentrations (from 0.1 to 5 M). Subsequently, for each background NaCl concentration used for the acid-base titrations, Sr-uptake experiments were carried out involving two different levels of Sr concentration (1 × 10⁻⁵ and 5 × 10⁻⁵ M, respectively) at constant solid concentration (7.3 g/L) as a function of −log([H⁺]/M). A Surface Complexation Model (SCM) was fitted to the experimental data, following a coupled Pitzer/surface complexation approach. The Pitzer model was applied to aqueous species. A Basic Stern Model was used for interfacial electrostatics of the system, which includes ion-specific effects via ion-specific pair-formation constants, whereas the Pitzer-approach involves ion-interaction parameters that enter the model through activity coefficients for aqueous species. A simple 1-pK model was applied (generic surface species, denoted as >XOH^−1/2). Parameter fitting was carried out using the general parameter estimation software UCODE, coupled to a modified version of FITEQL2. The combined approach describes the full set of data reasonably well and involves two Sr-surface complexes, one of them including chloride. Monodentate and bidentate models were tested and were found to perform equally well. The SCM is particularly able to account for the incomplete uptake of Sr at higher salt levels, supporting the idea that adsorption models conventionally used in salt concentrations below 1 M are applicable to high salt concentrations if the correct activity corrections for the aqueous species are applied. This generates a self-consistent model framework involving a practical approach for semi-mechanistic SCMs. The model framework of coupling conventional electrostatic double layer models for the surface with a Pitzer approach for the bulk solution earlier tested with strongly adsorbing solutes is here shown to be successful for more weakly adsorbing solutes. Full article

(This article belongs to the Special Issue Mineral-Water Interfaces and Interfacial Reactions with (Radioactive) Contaminants)

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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Andrey G. Kalinichev and co-authors
Katja Schmeide and co-authors
Natalia Mayordomo and co-authors

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