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Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning

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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: closed (20 June 2021) | Viewed by 19530

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Special Issue Editors

Prof. Dr. Sergey Churakov

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Guest Editor

1. Laboratory for Waste Management, Paul Scherrer Institute, Forschungsstrasse 111, 5232 Villigen PSI, Switzerland
2. Institute of Geology, University of Bern, 3012 Bern, Switzerland
Interests: multiscale reactive transport simulations; transport and retention in porous media; mechanistic understanding of mineral reactivity; atomic-scale structure of mineral fluid interfaces

Dr. Fulvio Di Lorenzo

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Guest Editor

Institute of Geology, University of Bern, 3012 Bern, Switzerland
Interests: experimental mineralogy; water–rock interaction; solid solution–aqueous solution systems; ion partitioning; low-temperature geochemistry; geological carbon storage; crystal growth and dissolution

Special Issue Information

Dear Colleagues,

Mechanistic process based description of mineral surface reactivity is essential for the fundamental understanding of geochemical cycles, advanced geochemical engineering and technological applications. These complex phenomena need complementary experimental and modelling investigations. Recent advances in high resolution surface characterization techniques and multi scale reactive transport simulations provide a basis to link bulk mineral reactivity and atomistic scale processes at mineral fluid interfaces. This Special Issue aims to become a milestone for the reconciliation of experimental and atomistic approaches for mineral reactivity with specific emphasis on retention and element partitioning processes. For this purpose, we seek for high-quality contributions dealing with mineral reactivity characterization at nanoscale and the modelling. The possibility to match measured and predicted properties of the mineral surfaces (towards the sorption of organic and inorganic contaminants and the partitioning of elements) could provide a solid experimental basis for computational methods and improve reliability of upscaling required in applied research. Contributions aiming to describe the properties of mineral–mineral, mineral–fluid, and mineral–gas interfaces are welcome to improve the understanding of heterogeneous system and, consequently, to broaden the range of geochemical predictability. This Special Issue is not suited for the reporting of bulk data or limited qualitative observations without in-depth quantitative model based interpretation of the results.

Prof. Dr. Sergey Churakov
Dr. Fulvio Di Lorenzo
Guest Editors

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Keywords

mineral surface reactivity
contaminant retention
ion partitioning
sorption
atomic scale structure and reactivity of mineral fluid interfaces
ab-initio simulations
molecular dynamics simulations
surface characterization
in situ mineral reaction
environmental remediation
nuclear waste disposal
applied geochemistry

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Published Papers (6 papers)

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Research

15 pages, 4152 KiB

Open AccessArticle

The Effect of pH, Ionic Strength and the Presence of Pb^II on the Formation of Calcium Carbonate from Homogenous Alkaline Solutions at Room Temperature

by Fulvio Di Lorenzo, Kay Steiner and Sergey V. Churakov

Minerals 2021, 11(7), 783; https://doi.org/10.3390/min11070783 - 19 Jul 2021

Cited by 5 | Viewed by 3298

Abstract

Precipitation of calcium carbonates in aqueous systems is an important factor controlling various industrial, biological, and geological processes. In the first part of this study, the well-known titration approach introduced by Gebauer and coworkers in 2008 s used to obtain reliable experimental dataset for the deep understanding of CaCO₃ nucleation kinetics in supersaturated solutions over a broad range of pH and ionic strength conditions. In the second part, the effect of impurities, i.e., 1 mol% of Pb²⁺, was assessed in the same range of experimental conditions. Divalent lead has been shown to have an inhibitory effect in all ranges of the conditions tested except for pH 8 and low ionic strength (≤0.15 mol/L). Future investigations might take advantage of the methodology and the data provided in this work to investigate the effect of other system variables. The investigation of all the major variables and the assessment of eventual synergic effects could improve our ability to predict the formation of CaCO₃ in complex natural systems. Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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14 pages, 2817 KiB

Open AccessArticle

Competing Sorption of Se(IV) and Se(VI) on Schwertmannite

by Bouchra Marouane, Ning Chen, Martin Obst and Stefan Peiffer

Minerals 2021, 11(7), 764; https://doi.org/10.3390/min11070764 - 15 Jul 2021

Cited by 5 | Viewed by 2733

Abstract

Schwertmannite (SHM) is a naturally occurring mineral that has been shown to effectively scavenge oxyanions from contaminated water. In this study, Fourier-transform infrared spectroscopy and X-ray absorption spectroscopy techniques in combination with wet-chemical techniques were used to study the competitive sorption of Se(IV) and Se(VI) at pH 3. The experiments were conducted with three types of schwertmannite obtained from oxidative synthesis, biogenic synthesis and high-pressure compaction at different initial Se concentrations and mixing ratios for 48 h and 56 days, respectively. A threshold value for the uptake mechanisms was identified, which reflects the amount of easily exchangeable sulphate (~0.5 mmol/g). At adsorbate concentrations below this threshold, an inner-sphere corner-sharing bidentate binuclear complex forms upon exchange with sulphate. At higher concentrations, both oxyanions become bound to SHM through co-occurrence of mainly inner-sphere and partly outer-sphere corner-sharing bidentate binuclear complexes with Fe(III) containing surface sites. Single species experiments clearly indicate a higher affinity of SHM for Se(IV). However, in mixed species experiments, competitive sorption occurs with equal or even preferential uptake of Se(VI) at concentrations much lower than the threshold value, presumably due to geometrical similarity between selenate and sulphate, and increasing preference for Se(IV) at high Se concentrations. Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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18 pages, 7186 KiB

Open AccessFeature PaperArticle

Pb²⁺ Uptake by Magnesite: The Competition between Thermodynamic Driving Force and Reaction Kinetics

by Fulvio Di Lorenzo, Tobias Arnold and Sergey V. Churakov

Minerals 2021, 11(4), 415; https://doi.org/10.3390/min11040415 - 14 Apr 2021

Cited by 2 | Viewed by 3654

Abstract

The thermodynamic properties of carbonate minerals suggest a possibility for the use of the abundant materials (e.g., magnesite) for removing harmful divalent heavy metals (e.g., Pb²⁺). Despite the favourable thermodynamic condition for such transformation, batch experiments performed in this work indicate that the kinetic of the magnesite dissolution at room temperature is very slow. Another set of co-precipitation experiments from homogenous solution in the Mg-Pb^II-CO₂-H₂O system reveal that the solids formed can be grouped into two categories depending on the Pb/Mg ratio. The atomic ratio Pb/Mg is about 1 and 10 in the Mg-rich and Pb-rich phases, respectively. Both phases show a significant enrichment in Pb if compared with the initial stoichiometry of the aqueous solutions (Pb/Mg initial = 1 × 10^{− 2}–1 × 10⁻⁴). Finally, the growth of {10.4} magnesite surfaces in the absence and in the presence of Pb²⁺ was studied by in situ atomic force microscopy (AFM) measurements. In the presence of the foreign ion, a ten-fold increase in the spreading rate of the obtuse steps was observed. Further, the effect of solution ageing was also tested. We observed the nucleation of a secondary phase that quickly grows on the {10.4} surfaces of magnesite. The preferential incorporation of Pb²⁺ into the solid phase observed during precipitation and the catalytic effect of Pb²⁺ on magnesite growth are promising results for the development of environmental remediation processes. These processes, different from the transformation of magnesite into cerussite, are not limited by the slow dissolution rate of magnesite. Precipitation and growth require an external carbon source, thus they could be combined with carbon sequestration techniques. Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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24 pages, 6617 KiB

Open AccessArticle

First Steps towards Understanding the Non-Linear Impact of Mg on Calcite Solubility: A Molecular Dynamics Study

by Janou A. Koskamp, Sergio E. Ruiz Hernandez, Nora H. De Leeuw and Mariette Wolthers

Minerals 2021, 11(4), 407; https://doi.org/10.3390/min11040407 - 13 Apr 2021

Cited by 5 | Viewed by 2866

Abstract

Magnesium (Mg²⁺) is one of the most common impurities in calcite and is known to have a non-linear impact on the solubility of magnesian calcites. Using molecular dynamics (MD), we observed that Mg²⁺ impacts overall surface energies, local free energy profiles, interfacial water density, structure and dynamics and, at higher concentrations, it also causes crystal surface deformation. Low Mg concentrations did not alter the overall crystal structure, but stabilised Ca²⁺ locally and tended to increase the etch pit nucleation energy. As a result, Ca-extraction energies over a wide range of 39 kJ/mol were observed. Calcite surfaces with an island were less stable compared to flat surfaces, and the incorporation of Mg²⁺ destabilised the island surface further, increasing the surface energy and the calcium extraction energies. In general, Ca²⁺ is less stable in islands of high Mg²⁺ concentrations. The local variation in free energies depends on the amount and distance to nearest Mg in addition to local disruption of interfacial water and the flexibility of surface carbonate ions to rotate. The result is a complex interplay of these characteristics that cause variability in local dissolution energies. Taken together, these results illustrate molecular scale processes behind the non-linear impact of Mg²⁺ concentration on the solubility of magnesium-bearing calcites. Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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17 pages, 6726 KiB

Open AccessArticle

The Competitive Adsorption of Chromate and Sulfate on Ni-Substituted Magnetite Surfaces: An ATR-FTIR Study

by Xiaoju Lin, Gaoling Wei, Xiaoliang Liang, Jing Liu, Lingya Ma and Jianxi Zhu

Minerals 2021, 11(1), 88; https://doi.org/10.3390/min11010088 - 18 Jan 2021

Cited by 6 | Viewed by 3270

Abstract

With similar chemical properties and geometrical configurations, sulfate and chromate display interesting competitive adsorption on mineral surfaces. Although such issues have been investigated on several Fe (hydr)oxide surfaces, e.g., ferrihydrite, goethite and hematite, the competitive adsorption on magnetite surfaces and the constraint mechanism have seldom been studied. This impedes the understanding of the transfer and fate of chromate and sulfate on magnetite surfaces, as magnetite is not only a useful adsorbent but also an efficient reductant to decrease the mobility and toxicity of chromium. In the present study, the geometries of the competitive adsorption of chromate and sulfate on Ni-substituted magnetite surfaces over a pH range of 4–9 were investigated using in situ attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis. In individual adsorption, nonprotonated monodentate mononuclear (NMM) complexes dominated chromate adsorption, accompanied by a few bidentate binuclear (BB) complexes. For sulfate, NMM complexes and outer-sphere (OS) species predominated under acidic and neutral–alkaline conditions, respectively. The above variation in adsorption configuration resulted in the different adsorption competitiveness between chromate and sulfate at different pH values. Specifically, the NMM complexes of chromate were substituted by NMM sulfate complexes under acidic conditions and vice versa. However, under neutral and alkaline conditions, the OS species of sulfate scarcely affected the adsorption of chromate. The adsorption affinity of chromate and sulfate on Ni-substituted magnetite increased in the following order: OS complex (sulfate) < NMM complexes (chromate) < NMM complexes (sulfate). Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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21 pages, 8075 KiB

Open AccessArticle

Removal of Pb from Water: The Effectiveness of Gypsum and Calcite Mixtures

by Ana Roza Llera, Amalia Jimenez and Lurdes Fernández-Díaz

Minerals 2021, 11(1), 66; https://doi.org/10.3390/min11010066 - 11 Jan 2021

Cited by 7 | Viewed by 2818

Abstract

Anthropogenic lead pollution is an environmental problem that threatens the quality of soils and waters and endangers living organisms in numerous surface and subsurface habitats. Lead coprecipitation on mineral surfaces through dissolution-recrystallization processes has long-term effects on lead bioavailability. Gypsum and calcite are among the most abundant and reactive rock forming minerals present in numerous geological settings. In this work, we studied the interaction of slightly acidic (pH_i = 5.5) Pb-bearing aqueous solutions ([Pb]_i = 1 and 10 mM) with crystals of gypsum and/or calcite under atmospheric conditions. This interaction resulted in a reduction of the concentration of lead in the liquid phase due to the precipitation of newly formed Pb-bearing solid phases. The extent of this Pb removal mainly depended on the nature of the primary mineral phase involved in the interaction. Thus, when gypsum was the only solid phase initially present in the system, the Pb-bearing liquid-gypsum interaction resulted in Pb removals in the 98–99.8% range, regardless of [Pb]_i. In contrast, when the interaction took place with calcite, Pb removal strongly depended on [Pb]_i. It reached 99% when [Pb]_i = 1 mM, while it was much more modest (~13%) when [Pb]_i = 10 mM. Interestingly, Pb-removal was maximized for both [Pb]_i (99.9% for solutions with [Pb]_i = 10 mM and 99.7% for solutions with [Pb]_i = 1 mM) when Pb-polluted solutions simultaneously interacted with gypsum and calcite crystals. Despite the large Pb removals found in most of the cases studied, the final Pb concentration ([Pb]_f) in the liquid phase was always well above the maximum permitted in drinking water (0.01 ppm), with the minimum ([Pb]_f = 0.7 ppm) being obtained for solutions with [Pb]_i = 1 mM after their interaction with mixtures of gypsum and calcite crystals. This result suggests that integrating the use of mixtures of gypsum-calcite crystals might help to develop more efficient strategies for in-situ decontaminating Pb-polluted waters through mineral coprecipitation processes. Full article

(This article belongs to the Special Issue Mineral Surface Reactivity with Application to Contaminant Retention and Element Partitioning)

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