Special Issue "Mineral Surface Reactions at the Nanoscale"

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

Deadline for manuscript submissions: closed (30 June 2018).

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A printed edition of this Special Issue is available here.

Special Issue Editor

Dr. Christine V. Putnis
E-Mail Website
Guest Editor
Institut für Mineralogie, University of Münster, 48149 Münster, Germany
The Institute for Geoscience Research, Curtin University, 6845 Perth, Australia
Interests: mineral surface reactions; nano-imaging using in situ AFM experiments; defining the mineral–fluid interface; nanoparticles; pre-nucleation clusters; interface-coupled dissolution-precipiation mechanism; environmental remediation; element mobilisation

Special Issue Information

Dear Colleagues,

Reactions at mineral surfaces are central to all geochemical processes. Because water is ubiquitous on Earth—at least reaching down to the crust-mantle boundary—processes occurring at the mineral–aqueous fluid interface control the evolution of the minerals making up the rocks of the Earth. Indeed, we can go as far as to say that the Earth as we know it has been shaped by reactions at mineral surfaces. Life itself is totally dependent on these mineral surface reactions that release the elements necessary for living plants and animals to exist. Thus, mineral surfaces are essential for a large range of important Earth processes. Apart from maintaining life they also control processes such as weathering of rocks and hence soil formation, biomineralization, the fate of contaminants and possible remediation strategies, including element sequestration, and on a larger scale, metamorphism, ore deposit formation and global element cycling. In recent years it has been through the development of advanced analytical methods that mineral surface reactions have been imaged and analyzed at the nanoscale. This has enabled exciting new possibilities for clarifying the mechanisms that govern mineral–fluid reactions. Industrial processes, environmental remediation and nuclear waste disposal methods, medical research and the pharmaceutical industry are all benefitting from the recent advances in understanding mineral surface reactions at the nanoscale. This Special Issue aims to highlight the role and importance of mineral surfaces in many varying fields of research.

Dr. Christine V. Putnis
Guest Editor

Manuscript Submission Information

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Keywords

  • mineral surface
  • interface
  • nanoscale
  • nanoparticles
  • dissolution
  • crystal growth
  • replacement
  • coupled reactions
  • environment
  • contamination
  • remediation
  • sequestration
  • element cycling

Published Papers (13 papers)

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Editorial

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Open AccessEditorial
Editorial for Special Issue “Mineral Surface Reactions at the Nanoscale”
Minerals 2019, 9(3), 185; https://doi.org/10.3390/min9030185 - 17 Mar 2019
Abstract
Reactions at mineral surfaces are central to all geochemical processes. As minerals comprise the rocks of the Earth, the processes occurring at the mineral–aqueous fluid interface control the evolution of the rocks and, hence, the structure of the crust of the Earth during [...] Read more.
Reactions at mineral surfaces are central to all geochemical processes. As minerals comprise the rocks of the Earth, the processes occurring at the mineral–aqueous fluid interface control the evolution of the rocks and, hence, the structure of the crust of the Earth during such processes at metamorphism, metasomatism, and weathering. In recent years, focus has been concentrated on mineral surface reactions made possible through the development of advanced analytical techniques, such as atomic force microscopy (AFM), advanced electron microscopies (SEM and TEM), phase shift interferometry, confocal Raman spectroscopy, advanced synchrotron-based applications, complemented by molecular simulations, to confirm or predict the results of experimental studies. In particular, the development of analytical methods that allow direct observations of mineral–fluid reactions at the nanoscale have revealed new and significant aspects of the kinetics and mechanisms of reactions taking place in fundamental mineral–fluid systems. These experimental and computational studies have enabled new and exciting possibilities to elucidate the mechanisms that govern mineral–fluid reactions, as well as the kinetics of these processes, and, hence, to enhance our ability to predict potential mineral behavior. In this Special Issue “Mineral Surface Reactions at the Nanoscale”, we present 12 contributions that highlight the role and importance of mineral surfaces in varying fields of research. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available

Research

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Open AccessCommunication
Identification of Surface Processes in Individual Minerals of a Complex Ore through the Analysis of Polished Sections Using Polarization Microscopy and X-ray Photoelectron Spectroscopy (XPS)
Minerals 2018, 8(10), 427; https://doi.org/10.3390/min8100427 - 28 Sep 2018
Cited by 1
Abstract
Understanding the changes of a mineral during ore processing is of capital importance for the development of strategies aimed at increasing the efficiency of metal extraction. This task is often difficult due to the variability of the ore in terms of composition, mineralogy [...] Read more.
Understanding the changes of a mineral during ore processing is of capital importance for the development of strategies aimed at increasing the efficiency of metal extraction. This task is often difficult due to the variability of the ore in terms of composition, mineralogy and texture. In particular, surface processes such as metal re-adsorption (preg-robbing) on specific minerals are difficult to evaluate, even though they may be of importance as the re-adsorbed material can be blocking the valuable mineral and negatively affect the extraction process. Here, we show a simple yet powerful approach, through which surface processes in individual minerals are identified by combining polarization microscopy (MP) and X-ray photoelectron spectroscopy (XPS). Taking as an example a silver-containing polymetallic sulfide ore from the Peruvian central Andes (pyrite-based with small amounts of galena), we track the changes in the sample during the course of cyanidation. While polarization microscopy is instrumental for identifying mineralogical species, XPS provides evidence of the re-adsorption of lead on a pyrite surface, possibly as lead oxide/hydroxide. The surface of pyrite does not show significant changes after the leaching process according to the microscopic results, although forms of oxidized iron are detected together with the re-adsorption of lead by XPS. Galena, embedded in pyrite, dissolves during cyanide leaching, as evidenced by PM and by the decrease of XPS signals at the positions associated with sulfide and sulfate. At the same time, the rise of a lead peak at a different position confirms that the re-adsorbed lead species cannot be sulfides or sulfates. Interestingly, lead is not detected on covellite surfaces during leaching, which shows that lead re-adsorption is a process that depends on the nature of the mineral. The methodology shown here is a tool of significant importance for understanding complex surface processes affecting various minerals during metal extraction. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Aqueous Fe(II)-Induced Phase Transformation of Ferrihydrite Coupled Adsorption/Immobilization of Rare Earth Elements
Minerals 2018, 8(8), 357; https://doi.org/10.3390/min8080357 - 18 Aug 2018
Cited by 3
Abstract
The phase transformation of iron minerals induced by aqueous Fe(II) (Fe(II)aq) is a critical geochemical reaction which greatly affects the geochemical behavior of soil elements. How the geochemical behavior of rare earth elements (REEs) is affected by the Fe(II)aq-induced [...] Read more.
The phase transformation of iron minerals induced by aqueous Fe(II) (Fe(II)aq) is a critical geochemical reaction which greatly affects the geochemical behavior of soil elements. How the geochemical behavior of rare earth elements (REEs) is affected by the Fe(II)aq-induced phase transformation of iron minerals, however, is still unknown. The present study investigated the adsorption and immobilization of REEs during the Fe(II)aq-induced phase transformation of ferrihydrite. The results show that the heavy REEs of Ho(III) were more efficiently adsorbed and stabilized compared with the light REEs of La(III) by ferrihydrite and its transformation products, which was due to the higher adsorptive affinity and smaller atomic radius of Ho(III). Both La(III) and Ho(III) inhibited the Fe atom exchange between Fe(II)aq and ferrihydrite, and sequentially, the Fe(II)aq-induced phase transformation rates of ferrihydrite, because of the competitive adsorption with Fe(II)aq on the surface of iron (hydr)oxides. Owing to the larger amounts of adsorbed and stabilized Ho(III), the inhibition of the Fe(II)aq-induced phase transformation of ferrihydrite affected by Ho(III) was higher than that by La(III). Our findings suggest an important role for the Fe(II)aq-induced phase transformation of iron (hydr)oxides in assessing the mobility and transfer behavior of REEs, as well as for their occurrence in earth surface environments. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Metal Sequestration through Coupled Dissolution–Precipitation at the Brucite–Water Interface
Minerals 2018, 8(8), 346; https://doi.org/10.3390/min8080346 - 10 Aug 2018
Cited by 3
Abstract
The increasing release of potentially toxic metals from industrial processes can lead to highly elevated concentrations of these metals in soil, and ground- and surface-waters. Today, metal pollution is one of the most serious environmental problems and thus, the development of effective remediation [...] Read more.
The increasing release of potentially toxic metals from industrial processes can lead to highly elevated concentrations of these metals in soil, and ground- and surface-waters. Today, metal pollution is one of the most serious environmental problems and thus, the development of effective remediation strategies is of paramount importance. In this context, it is critical to understand how dissolved metals interact with mineral surfaces in soil–water environments. Here, we assessed the processes that govern the interactions between six common metals (Zn, Cd, Co, Ni, Cu, and Pb) with natural brucite (Mg(OH)2) surfaces. Using atomic force microscopy and a flow-through cell, we followed the coupled process of brucite dissolution and subsequent nucleation and growth of various metal bearing precipitates at a nanometer scale. Scanning electron microscopy and Raman spectroscopy allowed for the identification of the precipitates as metal hydroxide phases. Our observations and thermodynamic calculations indicate that this coupled dissolution–precipitation process is governed by a fluid boundary layer at the brucite–water interface. Importantly, this layer differs in composition and pH from the bulk solution. These results contribute to an improved mechanistic understanding of sorption reactions at mineral surfaces that control the mobility and fate of toxic metals in the environment. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Water Structure, Dynamics and Ion Adsorption at the Aqueous {010} Brushite Surface
Minerals 2018, 8(8), 334; https://doi.org/10.3390/min8080334 - 03 Aug 2018
Cited by 2
Abstract
Understanding the growth processes of calcium phosphate minerals in aqueous environments has implications for both health and geology. Brushite, in particular, is a component of certain kidney stones and is used as a bone implant coating. Understanding the water–brushite interface at the molecular [...] Read more.
Understanding the growth processes of calcium phosphate minerals in aqueous environments has implications for both health and geology. Brushite, in particular, is a component of certain kidney stones and is used as a bone implant coating. Understanding the water–brushite interface at the molecular scale will help inform the control of its growth. Liquid-ordering and the rates of water exchange at the brushite–solution interface have been examined through the use of molecular dynamics simulation and the results compared to surface X-ray diffraction data. This comparison highlights discrepancies between the two sets of results, regardless of whether force field or first principles methods are used in the simulations, or the extent of water coverage. In order to probe other possible reasons for this difference, the free energies for the adsorption of several ions on brushite were computed. Given the exothermic nature found in some cases, it is possible that the discrepancy in the surface electron density may be caused by adsorption of excess ions. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite
Minerals 2018, 8(8), 315; https://doi.org/10.3390/min8080315 - 26 Jul 2018
Cited by 2
Abstract
We present results of bioaragonite to apatite conversion in bivalve, coral and cuttlebone skeletons, biological hard materials distinguished by specific microstructures, skeletal densities, original porosities and biopolymer contents. The most profound conversion occurs in the cuttlebone of the cephalopod Sepia officinalis, the [...] Read more.
We present results of bioaragonite to apatite conversion in bivalve, coral and cuttlebone skeletons, biological hard materials distinguished by specific microstructures, skeletal densities, original porosities and biopolymer contents. The most profound conversion occurs in the cuttlebone of the cephalopod Sepia officinalis, the least effect is observed for the nacreous shell portion of the bivalve Hyriopsis cumingii. The shell of the bivalve Arctica islandica consists of cross-lamellar aragonite, is dense at its innermost and porous at the seaward pointing shell layers. Increased porosity facilitates infiltration of the reaction fluid and renders large surface areas for the dissolution of aragonite and conversion to apatite. Skeletal microstructures of the coral Porites sp. and prismatic H. cumingii allow considerable conversion to apatite. Even though the surface area in Porites sp. is significantly larger in comparison to that of prismatic H. cumingii, the coral skeleton consists of clusters of dense, acicular aragonite. Conversion in the latter is sluggish at first as most apatite precipitates only onto its surface area. However, the process is accelerated when, in addition, fluids enter the hard tissue at centers of calcification. The prismatic shell portion of H. cumingii is readily transformed to apatite as we find here an increased porosity between prisms as well as within the membranes encasing the prisms. In conclusion, we observe distinct differences in bioaragonite to apatite conversion rates and kinetics depending on the feasibility of the reaction fluid to access aragonite crystallites. The latter is dependent on the content of biopolymers within the hard tissue, their feasibility to be decomposed, the extent of newly formed mineral surface area and the specific biogenic ultra- and microstructures. Full article
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Open AccessArticle
Temporal Evolution of Calcite Surface Dissolution Kinetics
Minerals 2018, 8(6), 256; https://doi.org/10.3390/min8060256 - 16 Jun 2018
Cited by 3
Abstract
This brief paper presents a rare dataset: a set of quantitative, topographic measurements of a dissolving calcite crystal over a relatively large and fixed field of view (~400 μm2) and long total reaction time (>6 h). Using [...] Read more.
This brief paper presents a rare dataset: a set of quantitative, topographic measurements of a dissolving calcite crystal over a relatively large and fixed field of view (~400 μm2) and long total reaction time (>6 h). Using a vertical scanning interferometer and patented fluid flow cell, surface height maps of a dissolving calcite crystal were produced by periodically and repetitively removing reactant fluid, rapidly acquiring a height dataset, and returning the sample to a wetted, reacting state. These reaction-measurement cycles were accomplished without changing the crystal surface position relative to the instrument’s optic axis, with an approximate frequency of one data acquisition per six minutes’ reaction (~10/h). In the standard fashion, computed differences in surface height over time yield a detailed velocity map of the retreating surface as a function of time. This dataset thus constitutes a near-continuous record of reaction, and can be used to both understand the relationship between changes in the overall dissolution rate of the surface and the morphology of the surface itself, particularly the relationship of (a) large, persistent features (e.g., etch pits related to screw dislocations; (b) small, short-lived features (e.g., so-called pancake pits probably related to point defects); (c) complex features that reflect organization on a large scale over a long period of time (i.e., coalescent “super” steps), to surface normal retreat and step wave formation. Although roughly similar in frequency of observation to an in situ atomic force microscopy (AFM) fluid cell, this vertical scanning interferometry (VSI) method reveals details of the interaction of surface features over a significantly larger scale, yielding insight into the role of various components in terms of their contribution to the cumulative dissolution rate as a function of space and time. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Metasomatic Replacement of Albite in Nature and Experiments
Minerals 2018, 8(5), 214; https://doi.org/10.3390/min8050214 - 17 May 2018
Cited by 2
Abstract
Replacement of albite by sodium-rich, secondary phases is a common phenomenon, observed in different geological settings and commonly attributed to alkaline metasomatism. We investigated growth of nepheline and sodalite on albite in time series experiments between two and 14 days. A total of [...] Read more.
Replacement of albite by sodium-rich, secondary phases is a common phenomenon, observed in different geological settings and commonly attributed to alkaline metasomatism. We investigated growth of nepheline and sodalite on albite in time series experiments between two and 14 days. A total of 42 hydrothermal experiments were performed in cold-seal hydrothermal vessels at a constant pressure of 4 kbar and 200–800 °C in the system SiO2–Al2O3–NaCl–H2O. To allow for fluid flow and material transport, a double-capsule technique was used; hereby, a perforated inner Pt capsule was filled with cleavage fragments of natural albite, whereas the shut outer Au capsule was filled with γ-Al2O3 and the NaCl–H2O solution. Complete overgrowth of albite by sodalite and nepheline occurred after just two days of experiments. At high salinity (≥17 wt % NaCl) sodalite is the stable reaction product over the whole temperature range whereas nepheline occurs at a lower relative bulk salinity than sodalite and is restricted to a high temperature of ≥700 °C. The transformation of albite starts along its grain margins, cracks or twin lamellae. Along the reaction front sodalite crystallizes as small euhedral and highly porous grains forming polycrystalline aggregates. Coarse sodalite dominates in the outermost domains of the reaction zones, suggesting recrystallization. Sodalite may contain fluid inclusions with trapped NaCl-rich brine, demonstrating that the interconnected microporosity provides excellent pathways for fluid-assisted material transport. Highly porous nepheline forms large, euhedral crystals with rectangular outline. Sodalite and nepheline in natural rock samples display only minor porosity but fluid and secondary mineral inclusions, pointing to coarsening of a previously present microporosity. The reaction interface between sodalite and albite in natural rock samples is marked by open channels in transmission electron microscopy. In many of the experiments, a zone of Si–H-rich, amorphous material is developed at the reaction front, which occurs at a temperature of up to of 750 °C as nanometer to 350 µm wide reaction zone around albite. This change in composition corresponds with the abrupt termination of the crystalline feldspar structure. The presence of sodalite as micro- to nanometer-sized, euhedral crystals within the amorphous zone demonstrates, that both the sodalite reaction rim and the amorphous material allow for fluid-assisted material transport between the crystalline albite (release of Si, Al) and the bulk fluid (H2O, Na, Cl). This texture, moreover, suggests that the amorphous phase represents a metastable interstage reaction product, which is progressively replaced by sodalite and nepheline. Remarkably, product sodalite, nepheline, and the amorphous material largely inherit the trace element budget of the respective ancestor albite, indicating that at least part of the trace elements remained fixed during the reaction process. The observed reaction textures in both natural and experimental samples indicate an interfacial dissolution–reprecipitation mechanism. Results of our study bear important implications with respect to mineral replacement in the presence of a fluid phase, especially regarding the interpretation of trace element patterns of the product phases. Full article
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Open AccessArticle
The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration
Minerals 2018, 8(5), 209; https://doi.org/10.3390/min8050209 - 11 May 2018
Cited by 5
Abstract
One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its [...] Read more.
One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO3) carbonation (silicate dissolution → carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessArticle
Interfacial Precipitation of Phosphate on Hematite and Goethite
Minerals 2018, 8(5), 207; https://doi.org/10.3390/min8050207 - 10 May 2018
Cited by 2
Abstract
Adsorption and subsequent precipitation of dissolved phosphates on iron oxides, such as hematite and goethite, is of considerable importance in predicting the bioavailability of phosphates. We used in situ atomic force microscopy (AFM) to image the kinetic processes of phosphate-bearing solutions interacting with [...] Read more.
Adsorption and subsequent precipitation of dissolved phosphates on iron oxides, such as hematite and goethite, is of considerable importance in predicting the bioavailability of phosphates. We used in situ atomic force microscopy (AFM) to image the kinetic processes of phosphate-bearing solutions interacting with hematite or goethite surfaces. The nucleation of nanoparticles (1.0–4.0 nm in height) of iron phosphate (Fe(III)-P) phases, possibly an amorphous phase at the initial stages, was observed during the dissolution of both hematite and goethite at the earliest crystallization stages. This was followed by a subsequent aggregation stage where larger particles and layered precipitates are formed under different pH values, ionic strengths, and organic additives. Kinetic analysis of the surface nucleation of Fe-P phases in 50 mM NH4H2PO4 at pH 4.5 showed the nucleation rate was greater on goethite than hematite. Enhanced goethite and hematite dissolution in the presence of 10 mM AlCl3 resulted in a rapid increase in Fe-P nucleation rates. A low concentration of citrate promoted the nucleation, whereas nucleation was inhibited at higher concentrations of citrate. By modeling using PHREEQC, calculated saturation indices (SI) showed that the three Fe(III)-P phases of cacoxenite, tinticite, and strengite may be supersaturated in the reacted solutions. Cacoxenite is predicted to be more thermodynamically favorable in all the phosphate solutions if equilibrium is reached with respect to hematite or goethite, although possibly only amorphous precipitates were observed at the earliest stages. These direct observations at the nanoscale may improve our understanding of phosphate immobilization in iron oxide-rich acid soils. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Review

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Open AccessReview
Mineral Transformations in Gold–(Silver) Tellurides in the Presence of Fluids: Nature and Experiment
Minerals 2019, 9(3), 167; https://doi.org/10.3390/min9030167 - 09 Mar 2019
Cited by 2
Abstract
Gold–(silver) telluride minerals constitute a major part of the gold endowment at a number of important deposits across the globe. A brief overview of the chemistry and structure of the main gold and silver telluride minerals is presented, focusing on the relationships between [...] Read more.
Gold–(silver) telluride minerals constitute a major part of the gold endowment at a number of important deposits across the globe. A brief overview of the chemistry and structure of the main gold and silver telluride minerals is presented, focusing on the relationships between calaverite, krennerite, and sylvanite, which have overlapping compositions. These three minerals are replaced by gold–silver alloys when subjected to the actions of hydrothermal fluids under mild hydrothermal conditions (≤220 °C). An overview of the product textures, reaction mechanisms, and kinetics of the oxidative leaching of tellurium from gold–(silver) tellurides is presented. For calaverite and krennerite, the replacement reactions are relatively simple interface-coupled dissolution-reprecipitation reactions. In these reactions, the telluride minerals dissolve at the reaction interface and gold immediately precipitates and grows as gold filaments; the tellurium is oxidized to Te(IV) and is lost to the bulk solution. The replacement of sylvanite is more complex and involves two competing pathways leading to either a gold spongy alloy or a mixture of calaverite, hessite, and petzite. This work highlights the substantial progress that has been made in recent years towards understanding the mineralization processes of natural gold–(silver) telluride minerals and mustard gold under hydrothermal conditions. The results of these studies have potential implications for the industrial treatment of gold-bearing telluride minerals. Full article
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale) Printed Edition available
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Open AccessReview
Tracing Mineral Reactions Using Confocal Raman Spectroscopy
Minerals 2018, 8(4), 158; https://doi.org/10.3390/min8040158 - 13 Apr 2018
Cited by 3
Abstract
Raman spectroscopy is a powerful tool used to identify mineral phases, study aqueous solutions and gas inclusions as well as providing crystallinity, crystallographic orientation and chemistry of mineral phases. When united with isotopic tracers, the information gained from Raman spectroscopy can be expanded [...] Read more.
Raman spectroscopy is a powerful tool used to identify mineral phases, study aqueous solutions and gas inclusions as well as providing crystallinity, crystallographic orientation and chemistry of mineral phases. When united with isotopic tracers, the information gained from Raman spectroscopy can be expanded and includes kinetic information on isotope substitution and replacement mechanisms. This review will examine the research to date that utilizes Raman spectroscopy and isotopic tracers. Beginning with the Raman effect and its use in mineralogy, the review will show how the kinetics of isotope exchange between an oxyanion and isotopically enriched water can be determined in situ. Moreover, we show how isotope tracers can help to unravel the mechanisms of mineral replacement that occur at the nanoscale and how they lead to the formation of pseudomorphs. Finally, the use of isotopic tracers as an in situ clock for mineral replacement processes will be discussed as well as where this area of research can potentially be applied in the future. Full article
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Other

Open AccessCommentary
How Can Additives Control the Early Stages of Mineralisation?
Minerals 2018, 8(5), 179; https://doi.org/10.3390/min8050179 - 26 Apr 2018
Cited by 7
Abstract
The interactions between additives and mineral precursors and intermediates are at the heart of additive-controlled crystallisation, which is of high importance for various fields. In this commentary, we reflect on potential modes of additive control according to classical nucleation theory on one hand, [...] Read more.
The interactions between additives and mineral precursors and intermediates are at the heart of additive-controlled crystallisation, which is of high importance for various fields. In this commentary, we reflect on potential modes of additive control according to classical nucleation theory on one hand, and from the viewpoint of the so-called pre-nucleation cluster pathway on the other. This includes a brief review of the corresponding literature. While the roles of additives are discussed generally, i.e., without specific chemical or structural details, corresponding properties are outlined where possible. Altogether, our discussion illustrates that “non-classical” nucleation pathways promise an improved understanding of additive-controlled scenarios, which could be utilised in targeted applications in various fields, ranging from scale inhibition to materials chemistry. Full article
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