Formation of Sulfate Minerals in Natural and Industrial Environments

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 (14 May 2021) | Viewed by 36864

Special Issue Editors


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Guest Editor
Federal Institute for Materials Research and Testing (BAM), 12205 Berlin, Germany
Interests: nucleation and growth of minerals; scattering and diffraction methods

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Guest Editor
Université Grenoble Alpes, Université Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, F-38000 Grenoble, France
Interests: nucleation and growth of minerals; in-situ observation; additive-controlled mineralization

Special Issue Information

Dear Colleagues,

It is our pleasure to announce a Special Issue of Minerals entitled “Formation and Properties of Sulfate Minerals in Natural and Industrial Environments”. Sulfate ions are ubiquitous in the environment, and as a result sulfate-containing minerals constitute one of the largest and most important groups of minerals. They play a key role in the global sulfur cycle and serve as indicators of past environmental conditions on Earth and beyond. A variety of products relying on the crystallization of sulfate minerals have been employed since antiquity, and today they are an essential part of a wide array of industrial and cultural applications, including grout, mortar, and cement production, dye synthesis, glass production and metallurgical processes, decorative products, and all sorts of wastewater treatments. Furthermore, the formation of sulfate minerals is a common nuisance in many engineering environments (e.g., water desalination and oil production environments) as sulfates form a encrustation (scale) that is difficult to remove, which decreases efficiency and increases operation costs.

For this Special Issue, we invite submissions from a broad scope of subjects related to the formation and properties of sulfate minerals. Potential topics include, but are not limited to the following themes:

  • nucleation and growth of sulfate-containing minerals;
  • kinetic and thermodynamic aspects of the formation and transformation of sulfate-containing minerals;
  • sulfate-containing minerals in cement and other novel binders;
  • sulfate-containing minerals on Earth and beyond;
  • the processing of sulfate-containing minerals from cultural heritage and archaeological perspectives;
  • sulfate scale formation and inhibition mechanisms.

Dr. Tomasz M. Stawski
Dr. Alexander E.S. Van Driessche
Guest Editors

Manuscript Submission Information

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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 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

  • sulfate
  • calcium
  • barium
  • strontium
  • aluminium
  • crystallization
  • nucleation
  • hydration
  • precipitation
  • cement
  • mortar
  • scale

Published Papers (10 papers)

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Editorial

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3 pages, 181 KiB  
Editorial
Editorial for Special Issue “Formation of Sulfate Minerals in Natural and Industrial Environments”
by Tomasz M. Stawski and Alexander E. S. Van Driessche
Minerals 2022, 12(3), 299; https://doi.org/10.3390/min12030299 - 26 Feb 2022
Viewed by 1536
Abstract
Sulfate is abundant in the environment and, as a result, sulfate-containing minerals constitute a large and important focus of research [...] Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)

Research

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17 pages, 1078 KiB  
Article
Long-Term Evolution of Uranium Mobility within Sulfated Mill Tailings in Arid Regions: A Reactive Transport Study
by Nicolas Seigneur, Laurent De Windt, Adrien Déjeant, Vincent Lagneau and Michaël Descostes
Minerals 2021, 11(11), 1201; https://doi.org/10.3390/min11111201 - 28 Oct 2021
Cited by 12 | Viewed by 1947
Abstract
Management of mill tailings is an important part of mining operations that aims at preventing environmental dispersion of contaminants of concern. To this end, geochemical models and reactive transport modeling provide a quantitative assessment of the mobility of the main contaminants. In arid [...] Read more.
Management of mill tailings is an important part of mining operations that aims at preventing environmental dispersion of contaminants of concern. To this end, geochemical models and reactive transport modeling provide a quantitative assessment of the mobility of the main contaminants. In arid regions with limited rainfall and intense evaporation, solutes transport may significantly differ from the usual gravity-driven vertical flow. In the uranium tailings of the Cominak mine (Niger), these evaporative processes resulted in the crystallization of gypsum, and to a lesser extent jarosite, and in the formation of surface levels of sulfated gypcrete, locally enriched in uranium. We present a fully coupled reactive transport modeling approach using HYTEC, encompassing evaporation, to quantitatively reproduce the complex sequence of observed coupled hydrogeochemical processes. The sulfated gypcrete formation, porosity evolution and solid uranium content were successfully reproduced at the surface and paleosurfaces of the tailing deposit. Simulations confirm that high solubility uranyl-sulfate phase may form at the atmospheric boundary where evaporation takes place, which would then be transformed into uranyl-phosphate phases after being watered or buried under fresh tailings. As these phases usually exhibit a lower solubility, this transition is beneficial for mine operators and tailings management. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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22 pages, 2137 KiB  
Article
Barite Scaling Potential Modelled for Fractured-Porous Geothermal Reservoirs
by Morgan Tranter, Marco De Lucia and Michael Kühn
Minerals 2021, 11(11), 1198; https://doi.org/10.3390/min11111198 - 28 Oct 2021
Cited by 6 | Viewed by 1533
Abstract
Barite scalings are a common cause of permanent formation damage to deep geothermal reservoirs. Well injectivity can be impaired because the ooling of saline fluids reduces the solubility of barite, and the continuous re-injection of supersaturated fluids forces barite to precipitate in the [...] Read more.
Barite scalings are a common cause of permanent formation damage to deep geothermal reservoirs. Well injectivity can be impaired because the ooling of saline fluids reduces the solubility of barite, and the continuous re-injection of supersaturated fluids forces barite to precipitate in the host rock. Stimulated reservoirs in the Upper Rhine Graben often have multiple relevant flow paths in the porous matrix and fracture zones, sometimes spanning multiple stratigraphical units to achieve the economically necessary injectivity. While the influence of barite scaling on injectivity has been investigated for purely porous media, the role of fractures within reservoirs consisting of both fractured and porous sections is still not well understood. Here, we present hydro-chemical simulations of a dual-layer geothermal reservoir to study the long-term impact of barite scale formation on well injectivity. Our results show that, compared to purely porous reservoirs, fractured porous reservoirs have a significantly reduced scaling risk by up to 50%, depending on the flow rate ratio of fractures. Injectivity loss is doubled, however, if the amount of active fractures is increased by one order of magnitude, while the mean fracture aperture is decreased, provided the fractured aquifer dictates the injection rate. We conclude that fractured, and especially hydraulically stimulated, reservoirs are generally less affected by barite scaling and that large, but few, fractures are favourable. We present a scaling score for fractured-porous reservoirs, which is composed of easily derivable quantities such as the radial equilibrium length and precipitation potential. This score is suggested for use approximating the scaling potential and its impact on injectivity of a fractured-porous reservoir for geothermal exploitation. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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15 pages, 2131 KiB  
Article
A Review of the Commercial Uses of Sulphate Minerals from the Titanium Dioxide Pigment Industry: The Case of Huelva (Spain)
by Manuel Jesús Gázquez, Manuel Contreras, Silvia María Pérez-Moreno, Jose Luis Guerrero, Melquiades Casas-Ruiz and Juan Pedro Bolívar
Minerals 2021, 11(6), 575; https://doi.org/10.3390/min11060575 - 28 May 2021
Cited by 10 | Viewed by 3319
Abstract
This study was focused on the historical evolution of the waste management policy carried out by the Spanish industry devoted to titanium dioxide pigments manufacturing for minimising its environmental impact. This challenge was achieved by modifying the original chemical process and converting the [...] Read more.
This study was focused on the historical evolution of the waste management policy carried out by the Spanish industry devoted to titanium dioxide pigments manufacturing for minimising its environmental impact. This challenge was achieved by modifying the original chemical process and converting the originally dissolved sulphate and sulphuric acid present in the final streams of the factory into sulphate minerals (melanterite FeSO4·7H2O, szomolnokite FeSO4·H2O, and gypsum CaSO4·2H2O). These by-products were physicochemically, mineralogically and radiologically characterised in order to gain basic information for its subsequent commercial use. Some of the uses summarised in this study for both ferrous sulphates are as a supplier of iron to prevent chlorosis, animal food, manufacture of cement (to reduce Cr VI), primary flocculants for ferrous sulphates, magnetite nanoparticle and nano-Fe2O3 formation, production of magnetite concentrate, remediation of polluted soils with metals, and treatment of wastewaters. Red gypsum was analysed as a substitute for natural gypsum in the manufacture of cement, construction materials, inhibitor in soil erosion, and the immobilisation of heavy metals in agricultural soils and carbonation processes. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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15 pages, 8332 KiB  
Article
High Temperature Sulfate Minerals Forming on the Burning Coal Dumps from Upper Silesia, Poland
by Jan Parafiniuk and Rafał Siuda
Minerals 2021, 11(2), 228; https://doi.org/10.3390/min11020228 - 23 Feb 2021
Cited by 5 | Viewed by 2344
Abstract
The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-heaps. Three burning heaps located in the Upper Silesian coal basin in Czerwionka-Leszczyny, Radlin and Rydułtowy near Rybnik were selected for the research. The occurrence of godovikovite, millosevichite, [...] Read more.
The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-heaps. Three burning heaps located in the Upper Silesian coal basin in Czerwionka-Leszczyny, Radlin and Rydułtowy near Rybnik were selected for the research. The occurrence of godovikovite, millosevichite, steklite and an unnamed MgSO4, sometimes accompanied by subordinate admixtures of mikasaite, sabieite, efremovite, langbeinite and aphthitalite has been recorded from these locations. Occasionally they form monomineral aggregates, but usually occur as mixtures practically impossible to separate. The minerals form microcrystalline masses with a characteristic vesicular structure resembling a solidified foam or pumice. The sulfates crystallize from hot fire gases, similar to high temperature volcanic exhalations. The gases transport volatile components from the center of the fire but their chemical compositions are not yet known. Their cooling in the near-surface part of the heap results in condensation from the vapors as viscous liquid mass, from which the investigated minerals then crystallize. Their crystallization temperatures can be estimated from direct measurements of the temperatures of sulfate accumulation in the burning dumps and studies of their thermal decomposition. Millosevichite and steklite crystallize in the temperature range of 510–650 °C, MgSO4 forms at 510–600 °C and godovikovite in the slightly lower range of 280–450 (546) °C. These values are higher than those previously reported. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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13 pages, 2496 KiB  
Article
Environmental Evaluation of Gypsum Plasterboard Recycling
by Karin Weimann, Christian Adam, Matthias Buchert and Juergen Sutter
Minerals 2021, 11(2), 101; https://doi.org/10.3390/min11020101 - 21 Jan 2021
Cited by 22 | Viewed by 5308
Abstract
Gypsum is widely used in the construction sector, and its worldwide consumption has been increasing for several decades. Depending on the lifetime of the used gypsum products, an increase of gypsum in construction and demolition waste follows. Especially against the background of a [...] Read more.
Gypsum is widely used in the construction sector, and its worldwide consumption has been increasing for several decades. Depending on the lifetime of the used gypsum products, an increase of gypsum in construction and demolition waste follows. Especially against the background of a circular economy, the recycling of waste gypsum is of growing importance. However, the use of recycled gypsum only makes sense if it is environmentally friendly. Therefore, an evaluation of the environmental impacts of industrial-scale processing for the recycling of post-consumer gypsum waste was conducted. The evaluation was performed with an established life cycle assessment software. Original data provided by the industry and complementary data from a database for life cycle assessments were used for the calculations. Two scenarios for recycled gypsum with different transportation distances were calculated. These results were compared with the results of the environmental evaluation of gypsum derived from coal-fired power plants (FGD gypsum) and natural gypsum. The results showed that the utilization of recycled gypsum can be environmentally advantageous compared to the use of natural gypsum or FGD gypsum, especially in the impact categories of land transformation and resource consumption (abiotic depletion potential). For most environmental impact categories, the specific transportation distances have a strong influence. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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13 pages, 3810 KiB  
Article
Initial Stages of Gypsum Nucleation: The Role of “Nano/Microdust”
by Maxim Oshchepkov, Konstantin Popov, Anna Kovalenko, Anatoly Redchuk, Julia Dikareva and Irina Pochitalkina
Minerals 2020, 10(12), 1083; https://doi.org/10.3390/min10121083 - 02 Dec 2020
Cited by 20 | Viewed by 2512
Abstract
The primary nucleation mechanism of the gypsum in a bulk aqueous medium was identified as a heterogeneous one for 0.05 and 0.03 mol·L−1 CaSO4·2H2O solutions and 25 °C. By means of a particle counter and dynamic light scattering [...] Read more.
The primary nucleation mechanism of the gypsum in a bulk aqueous medium was identified as a heterogeneous one for 0.05 and 0.03 mol·L−1 CaSO4·2H2O solutions and 25 °C. By means of a particle counter and dynamic light scattering (DLS) technique, solid nano/microimpurities were found, and controlled in stock brines for gypsum supersaturated solutions preparation. It is demonstrated that the common procedure of reagent grade 0.10 mol·L‒1 CaCl2 and Na2SO4 aqueous solutions filtration via 200 nm membranes is capable to reduce the foreign solid microimpurities content (size > 100 nm) from 106 to 103 units in 1 mL, but fails to affect the more numerous nanofraction (size < 100 nm). Thus, the gypsum nucleation takes place in presence of a significant amount of “nano/microcodust” templates, and has a heterogenous character. The induction time, measured by conductivity for the similar supersaturation levels, reveals a well detectable dependence on nano/microdust concentent: an increasing background particle concentration substantially decreases the induction period at a constant saturation state and temperature, and thus increases the nucleation rate. Therefore, the gypsum nucleation reaction starts tentatively through the fast heterogeneous formation of well-defined, primary nuclei via [Ca2+], [SO42‒], and [CaSO4]o species sorption on the surface of “nano/microdust” particles. Thus, the “nano/microdust”, naturally occurring in any high purity chemical, plays a key role in sparingly soluble salts nucleation in the bulk aqueous medium. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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28 pages, 2808 KiB  
Article
Recrystallization and Uptake of 226Ra into Ba-Rich (Ba,Sr)SO4 Solid Solutions
by Felix Brandt, Martina Klinkenberg, Jenna Poonoosamy and Dirk Bosbach
Minerals 2020, 10(9), 812; https://doi.org/10.3390/min10090812 - 15 Sep 2020
Cited by 7 | Viewed by 2185
Abstract
226Ra is an important contributor to naturally occurring radioactive materials (NORM) and also considered in safety cases related to the disposal of spent nuclear fuel in a deep geological repository. Recrystallization and solid solution formation with sulfates is regarded as an important [...] Read more.
226Ra is an important contributor to naturally occurring radioactive materials (NORM) and also considered in safety cases related to the disposal of spent nuclear fuel in a deep geological repository. Recrystallization and solid solution formation with sulfates is regarded as an important retention mechanism for 226Ra. In natural systems sulfates often occur as (Ba,Sr)SO4. Therefore, we have chosen this solid solution at the Ba-rich end for investigations of the 226Ra uptake. The resulting 226Ra-solubility in aqueous solution was assessed in comparison with a thermodynamic model of the solid solution-aqueous solution system (Ba,Sr,Ra)SO4 + H2O. The temperature and composition of the initial (Ba,Sr)SO4 solid solution were varied. Measurements of the solution composition were combined with microscopic observations of the solid and thermodynamic modeling. A complex recrystallization behavior of the solid was observed, including the dissolution of significant amounts of the solid and formation of metastable phases. The re-equilibration of Ba-rich (Ba,Sr)SO4 to (Ba,Sr,Ra)SO4 leads to a major reconstruction of the solid. Already trace amounts of Sr in the solid solution can have a significant impact on the 226Ra solubility, depending on the temperature. The experimental findings confirm the thermodynamic model, although not all solids reached equilibrium with respect to all cations. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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Review

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20 pages, 5602 KiB  
Review
Evolution of the Astonishing Naica Giant Crystals in Chihuahua, Mexico
by Iván Jalil Antón Carreño-Márquez, Isaí Castillo-Sandoval, Bernardo Enrique Pérez-Cázares, Luis Edmundo Fuentes-Cobas, Hilda Esperanza Esparza-Ponce, Esperanza Menéndez-Méndez, María Elena Fuentes-Montero and María Elena Montero-Cabrera
Minerals 2021, 11(3), 292; https://doi.org/10.3390/min11030292 - 11 Mar 2021
Cited by 2 | Viewed by 5506
Abstract
Calcium sulfate (CaSO4) is one of the most common evaporites found in the earth’s crust. It can be found as four main variations: gypsum (CaSO4∙2H2O), bassanite (CaSO4∙0.5H2O), soluble anhydrite, and insoluble anhydrite (CaSO [...] Read more.
Calcium sulfate (CaSO4) is one of the most common evaporites found in the earth’s crust. It can be found as four main variations: gypsum (CaSO4∙2H2O), bassanite (CaSO4∙0.5H2O), soluble anhydrite, and insoluble anhydrite (CaSO4), being the key difference the hydration state of the sulfate mineral. Naica giant crystals’ growth starts from a supersaturated solution in a delicate thermodynamic balance close to equilibrium, where gypsum can form nanocrystals able to grow up to 11–12 m long. The growth rates are reported to be as slow as (1.4 ± 0.2) × 10−5 nm/s, taking thousands of years to form crystals with a unique smoothness and diaphaneity, which may or may not include solid or liquid inclusions. Conservation efforts can be traced back to other gypsum structures found prior to Naica’s. Furthermore, in the last two decades, several authors have explored the unique requirements in which these crystals grow, the characterization of their environment and microclimatic conditions, and the prediction of deterioration scenarios. We present a state-of-the-art review on the mentioned topics. Beyond the findings on the origin, in this work we present the current state and the foreseeable future of these astounding crystals. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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36 pages, 12165 KiB  
Review
Gypsum Precipitation under Saline Conditions: Thermodynamics, Kinetics, Morphology, and Size Distribution
by Amit G. Reiss, Ittai Gavrieli, Yoav O. Rosenberg, Itay J. Reznik, Andreas Luttge, Simon Emmanuel and Jiwchar Ganor
Minerals 2021, 11(2), 141; https://doi.org/10.3390/min11020141 - 30 Jan 2021
Cited by 34 | Viewed by 8762
Abstract
Gypsum (CaSO4·2H2O) is the most common sulfate mineral on Earth and is also found on Mars. It is an evaporitic mineral that predominantly precipitates from brines. In addition to its precipitation in natural environments, gypsum also forms an undesired [...] Read more.
Gypsum (CaSO4·2H2O) is the most common sulfate mineral on Earth and is also found on Mars. It is an evaporitic mineral that predominantly precipitates from brines. In addition to its precipitation in natural environments, gypsum also forms an undesired scale in many industrial processes that utilize or produce brines. Thus, better insights into gypsum formation can contribute to the understanding of natural processes, as well as improving industrial practices. Subsequently, the thermodynamics, nucleation and crystal growth mechanisms and kinetics, and how these factors shape the morphology of gypsum have been widely studied. Over the last decade, the precipitation of gypsum under saline and hypersaline conditions has been the focus of several studies. However, to date, most of the thermodynamic data are derived from experiments with artificial solutions that have limited background electrolytes and have Ca2+/SO42− ratios that are similar to the 1:1 ratio in the mineral. Moreover, direct observations of the nucleation and growth processes of gypsum are still derived from experimental settings that can be described as having low ionic strength. Thus, the mechanisms of gypsum precipitation under conditions from which the mineral precipitates in many natural environments and industrial processes are still less well known. The present review focuses on the precipitation of gypsum from a range of aspects. Special attention is given to brines. The effects of ionic strength, brine composition, and temperature on the thermodynamic settings are broadly discussed. The mechanisms and rates of gypsum nucleation and growth, and the effect the thermodynamic properties of the brine have on these processes is demonstrated by recent microscopic and macroscopic observations. The morphology and size distribution of gypsum crystals precipitation is examined in the light of the precipitation processes that shape these properties. Finally, the present review highlights discrepancies between microscopic and macroscopic observations, and studies carried out under low and high ionic strengths. The special challenges posed by experiments with brines are also discussed. Thus, while this review covers contemporary literature, it also outlines further research that is required in order to improve our understanding of gypsum precipitation in natural environments and industrial settings. Full article
(This article belongs to the Special Issue Formation of Sulfate Minerals in Natural and Industrial Environments)
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