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Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related...
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Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition

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: 30 May 2025 | Viewed by 6366

Special Issue Editor

Dr. Nikita V. Chukanov

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Guest Editor
Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Chernogolovka, 142432 Moscow, Russia
Interests: new mineral species; infrared spectroscopy of minerals; mineralogy of akaline rocks and related pegmatites and hydrothermal systems; organic mineralogy; crystal chemistry and properties of microporous minerals
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Special Issue Information

Dear Colleagues,

Many minerals and related crystalline compounds are characterized by the phenomenon of isomorphism, during which substitution of some components by others in certain positions of the crystal structure leads to the formation of series of solid solutions. This phenomenon is one of the factors determining mineral diversity. As a rule, in the taxonomy of minerals, assemblages of isostructural or structurally similar mineral species that form complete or incomplete series of solid solutions are considered to be mineral groups.

It is customary to distinguish isovalent, heterovalent, and blocky isomorphism. Elements with the same valence or ions of the same charge take part in isovalent isomorphism. Elements with different valences participate in heterovalent isomorphism, which requires charge compensation through the heterovalent substitution of atoms at another position of the crystal structure. Blocky isomorphism is realized by the most complex mechanisms involving large groups of atoms, and it is often accompanied by changes in local configurations and the coordination numbers of atoms.

Isomorphic admixtures in minerals (including trace elements) and chemical zoning of their crystals are important geochemical markers that reflect the conditions of mineral formation because fluid properties (temperature, pressure, chemical composition, pH, oxygen fugacity, etc.) affect the substitutions. On the other hand, isomorphic substitutions affect the properties of minerals, including those characteristics that make it possible to consider minerals as prototypes of materials with technologically important properties. These materials may be used in ion exchange, sorption, immobilization of heavy metals and radionuclides, as optical materials, ionic conductors, and so on.

This Special Issue will focus on recent advances in the study of isomorphism and compositional variability in minerals and related compounds.

Dr. Nikita V. Chukanov
Guest Editor

Manuscript Submission Information

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

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

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

Keywords

  • chemical composition
  • crystal chemistry
  • isomorphism
  • solid solution
  • doping
  • color centers
  • chemical defects
  • chemical zoning
  • trace elements
  • thermodynamics control of major and trace elements in substitutions and solid solutions
  • geochemical markers

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Related Special Issue

Published Papers (6 papers)

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Research

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14 pages, 2299 KiB  
Article
Berthierine-2H1 from Lovozero Alkaline Massif, Kola Peninsula, Russia: First Structure Model for Berthierine and Complexity-Stability Relations
by Sergey V. Krivovichev, Victor N. Yakovenchuk, Olga F. Goychuk, Yakov A. Pakhomovskii and Vladimir G. Krivovichev
Minerals 2025, 15(1), 13; https://doi.org/10.3390/min15010013 - 26 Dec 2024
Viewed by 899
Abstract
Berthierine was found in a natrolite vein intersecting volcanogenic-sedimentary rocks on the slope of Mt. Quamdespakh in the upper reaches of the Suolwai River, Lovozero alkaline massif, Kola peninsula, Russian Arctic. The mineral occurs as well-formed translucent pyramidal crystals up to 250 μm [...] Read more.
Berthierine was found in a natrolite vein intersecting volcanogenic-sedimentary rocks on the slope of Mt. Quamdespakh in the upper reaches of the Suolwai River, Lovozero alkaline massif, Kola peninsula, Russian Arctic. The mineral occurs as well-formed translucent pyramidal crystals up to 250 μm in size. The chemical composition determined by electron microprobe analysis corresponds to the empirical formula VI(Fe2+1.99Al0.94Mg0.03Mn0.04)Σ3.00[IV(Si1.15Al0.85)Σ2.00O5] [(OH)3.92O0.08]Σ4.00; the idealized formula is VI(Fe2+2Al)[IV(SiAl)O5](OH)4. The crystal-structure determination (the first detailed crystal-structure characterization of berthierine) shows that the Lovozero mineral is hexagonal, P63cm (a = 5.3903(4), c = 14.0146(10) Å, V = 352.64(6) Å3, R1 = 0.053 for 338 unique observed reflections), and corresponds to the 2H1 polytype of serpentine-group minerals with 1:1 tetrahedral-octahedral layers. The unit cell contains two M3[T2O5](OH)4 layers (M = Fe2+,Al; T = Si,Al) stacked along the c axis. The calculations of information-based structural and topological complexity parameters indicate that berthierine is structurally and topologically simpler than its chlorite-group polymorph chamosite. Since berthierine usually crystallizes metastably in the stability field of chamosite, the complexity analysis is agreement with the Goldsmith rule that states that, in Ostwald sequences of crystallization, metastable phases are simpler and more disordered than their stable counterparts. This observation can be applied to a general case of the metastable formation of serpentine-group minerals prior to the crystallization of chlorites. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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12 pages, 4421 KiB  
Article
The Crystal Chemistry and Structure of V-Bearing Silicocarnotite from Andradite–Gehlenite–Pseudowollastonite Paralava of the Hatrurim Complex, Israel
by Evgeny V. Galuskin, Irina O. Galuskina, Maria Książek, Joachim Kusz, Yevgeny Vapnik and Grzegorz Zieliński
Minerals 2024, 14(12), 1301; https://doi.org/10.3390/min14121301 - 23 Dec 2024
Viewed by 649
Abstract
Silicocarnotite, Ca5[(PO4)(SiO4)](PO4), was first described from slag over 140 years ago. In 2013, it was officially recognised as a mineral after being discovered in the larnite–gehlenite hornfels of the pyrometamorphic Hatrurim Complex. This paper describes [...] Read more.
Silicocarnotite, Ca5[(PO4)(SiO4)](PO4), was first described from slag over 140 years ago. In 2013, it was officially recognised as a mineral after being discovered in the larnite–gehlenite hornfels of the pyrometamorphic Hatrurim Complex. This paper describes the composition and structure of V-bearing silicocarnotite, crystals of which were found in a thin paralava vein cutting through the gehlenite hornfels. A network of thin paralava veins a few centimetres thick is widespread in the gehlenite hornfels of the Hatrurim Basin, Negev Desert, Israel. These veins, typically coarse crystalline rock and traditionally referred to as paralava, have a symmetrical structure and do not contain glass. Silicocarnotite in the paralava, whose primary rock-forming minerals are gehlenite, flamite, Ti-bearing andradite, rankinite and pseudowollastonite, was a relatively late-stage high-temperature mineral, crystallising at temperatures above 1100 °C. It formed from the reaction of a Si-rich residual melt with pre-existing fluorapatite. A single-crystal structural study of silicocarnotite (Pnma, a = 6.72970(12) Å, b = 15.5109(3) Å, c = 10.1147(2) Å) suggests that the phenomenon of Ca1 position splitting observed in this mineral is most likely related to the partial ordering of Si and P in the T2O4 tetrahedrons. Raman studies of silicocarnotite with varying vanadium content have shown that phases with V2O5 content of 3–5 wt.% exhibit additional bands at approximately 864 cm−1, corresponding to vibrations of ν1(VO4)3−. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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19 pages, 7882 KiB  
Article
The Crystal Chemistry of Boussingaultite, (NH4)2Mg(SO4)2·6H2O, and Its Derivatives in a Wide Temperature Range
by Elena S. Zhitova, Rezeda M. Sheveleva, Andrey A. Zolotarev, Roman Yu. Shendrik, Elizaveta A. Pankrushina, Konstantin A. Turovsky, Margarita S. Avdontceva, Maria G. Krzhizhanovskaya, Natalia S. Vlasenko, Anatoly A. Zolotarev, Mikhail A. Rassomakhin and Sergey V. Krivovichev
Minerals 2024, 14(10), 1052; https://doi.org/10.3390/min14101052 - 20 Oct 2024
Viewed by 1323
Abstract
The crystal structure, thermal behavior, and vibrational spectra of the anthropogenic analogue of boussingaultite, (NH4)2Mg(SO4)2·6H2O, and its dehydrated counterpart efremovite, (NH4)2Mg2(SO4)3, were studied [...] Read more.
The crystal structure, thermal behavior, and vibrational spectra of the anthropogenic analogue of boussingaultite, (NH4)2Mg(SO4)2·6H2O, and its dehydrated counterpart efremovite, (NH4)2Mg2(SO4)3, were studied in detail. The sample from the Chelyabinsk burning coal dumps has the composition of (NH4)1.92(Mg1.02Mn0.01Fe0.01)∑1.04(SO4)2·6H2O and crystallizes in the space group P21/a, with a = 9.3183(4), b = 12.6070(4), c = 6.2054(3) Å, β = 107.115(5)°, V = 696.70(5) Å3 (at 20 °C), Z = 2. The thermal evolution steps are as follows: boussingaultite (NH4)2Mg(SO4)2·6H2O (25–90 °C) → X-ray amorphous phase (100–150 °C) → efremovite (NH4)2Mg2(SO4)3 (160–340 °C) → MgSO4 Cmcm + Pbnm (340–580 °C) → MgSO4 Pbnm (580–700 °C). Thermal expansion is anisotropic, with the coefficients (×106 °C−1) α11 = 52(2), α22 = 68(2), α33 = –89(3), and αv = 31(3) at T = –123 °C; and α11 = 53(2), α22 = 67(2), α33 = 15(1), and αv = 136(3) at T = 60 °C. The maximal thermal expansion is along the b-axis and is due to straightening of corrugated pseudolayers (within the ab plane) of Mg(H2O)6 octahedra and SO4 tetrahedra with NH4 groups in the interlayer space. Vibrational spectroscopy outlines the general trend of dehydration and deammonization as the difference in the temperature intervals of these transformation steps allows separation of O–H and N–H vibrations in the process of dehydration by infrared and Raman spectroscopy. The intermediate partially dehydrated modification of boussingaultite was detected by in situ Raman spectroscopy at 110 °C that may correspond to ammonium leonite. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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18 pages, 3399 KiB  
Article
A New Mineral Calcioveatchite, SrCaB11O16(OH)5·H2O, and the Veatchite–Calcioveatchite Isomorphous Series
by Igor V. Pekov, Natalia V. Zubkova, Vladimir N. Apollonov, Vasiliy O. Yapaskupt, Sergey N. Britvin and Dmitry Yu. Pushcharovsky
Minerals 2024, 14(9), 901; https://doi.org/10.3390/min14090901 - 2 Sep 2024
Cited by 1 | Viewed by 862
Abstract
The new mineral calcioveatchite, ideally SrCaB11O16(OH)5·H2O, is a Ca-Sr-ordered analogue of veatchite. It was found at the Nepskoe potassium salt deposit, Irkutsk Oblast, Siberia, Russia in halite-sylvite and sylvite-carnallite rocks, with boracite, hilgardite, kurgantaite, hydroboracite, [...] Read more.
The new mineral calcioveatchite, ideally SrCaB11O16(OH)5·H2O, is a Ca-Sr-ordered analogue of veatchite. It was found at the Nepskoe potassium salt deposit, Irkutsk Oblast, Siberia, Russia in halite-sylvite and sylvite-carnallite rocks, with boracite, hilgardite, kurgantaite, hydroboracite, volkovskite, veatchite, anhydrite, magnesite, and quartz. Calcioveatchite forms prismatic or tabular crystals up to 1 × 1.5 × 3 mm3 and crystal clusters up to 3 mm across. It is transparent and colourless with vitreous lustre. Calcioveatchite is brittle, cleavage is perfect on {010}, the Mohs’ hardness is ca 2, Dmeas is 2.58(1), and Dcalc is 2.567 g cm−3. Calcioveatchite is optically biaxial (+), α = 1.543(2), β = 1.550(5), γ = 1.626(2), 2Vmeas = 30(10)°, and 2Vcalc = 35°. The average chemical composition (wt.%, electron microprobe, H2O calculated by stoichiometry) is: CaO 7.05, SrO 20.70, B2O3 61.96, H2O 10.22, and total 99.93. The empirical formula, calculated based on 22 O apfu = O16(OH)5(H2O) pfu, is Sr1.23Ca0.78B10.99O16(OH)5·H2O. Calcioveatchite is monoclinic, space group P21, a = 6.7030(3), b = 20.6438(9), c = 6.6056(3) Å, β = 119.153(7)°, V = 798.26(8) Å3, and Z = 2. Polytype: 1M. The strongest reflections of the powder XRD pattern [d,Å(I,%)(hkl)] are: 10.35(100)(020), 5.633(12)(110), 5.092(10)(120), 3.447(14)(060), 3.362(13)(101, 051), 3.309(38)(–102), 2.862(10)(012), and 2.585(19)(080). The crystal structure was solved based on single-crystal XRD data, R1 = 0.0420. Calcioveatchite (calcioveatchite-1M) is an isostructural analogue of veatchite-1M with the 11-fold cation polyhedron occupied mainly by Sr [Sr0.902(8)Ca0.098(8)] whereas the 10-fold polyhedron is Ca dominant [Ca0.686(7)Sr0.314(7)]. The chemical composition of veatchite from five localities in Russia (Nepskoe), Kazakhstan (Shoktybay and Chelkar in the North Caspian Region), and the USA (Tick Canyon and Billie Mine in California) was studied, and it is shown to exist in nature as a continuous, almost complete isomorphous series which extends from Ca-free veatchite, Sr2B11O16(OH)5·H2O, to calcioveatchite with the composition Sr1.14Ca0.87B10.99O16(OH)5·H2O. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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12 pages, 2099 KiB  
Article
Vladimirivanovite Revised: General Crystal Chemistry and Isomorphous Substitutions of Extra-Framework Species
by Nadezhda B. Bolotina, Nikita V. Chukanov, Anatoly N. Sapozhnikov, Natalia V. Zubkova, Igor V. Pekov, Dmitry A. Varlamov, Marina F. Vigasina, Maria O. Bulakh, Vasiliy O. Yapaskurt and Dmitry A. Ksenofontov
Minerals 2024, 14(9), 883; https://doi.org/10.3390/min14090883 - 29 Aug 2024
Viewed by 733
Abstract
New data on the crystal structure, chemical composition, and nature of extra-framework components of the orthorhombic sodalite-group mineral vladimirivanovite were obtained using chemical and single-crystal X-ray diffraction data as well as infrared and Raman spectroscopy. The crystal structure of vladimirivanovite is based on [...] Read more.
New data on the crystal structure, chemical composition, and nature of extra-framework components of the orthorhombic sodalite-group mineral vladimirivanovite were obtained using chemical and single-crystal X-ray diffraction data as well as infrared and Raman spectroscopy. The crystal structure of vladimirivanovite is based on the sodalite-type aluminosilicate framework with ordered Al and Si atoms. Sodalite-like cages are mainly occupied by Na+ and Ca2+ cations and (SO4)2− anions. It was shown that vladimirivanovite is characterized by significant variations in the content of extra-framework polysulfide groups (S3•−, S4), as well as other neutral molecules (H2O and CO2), the presence of which in the structure is the main cause of structural modulations and the orientation disordering of sulfate anions. Three samples with different S3•−:S4 ratios were studied. All of them are orthorhombic (space group Pnaa) with the unit-cell parameters a ≈ 9.1, b ≈ 12.9, and c ≈ 38.6 Å; Z = 6. The general crystal-chemical formula of vladimirivanovite is (Na+6.0–6.4Ca2+1.5–1.7)(Al6Si6O24)(SO42−,S3•−,S4)1.7–1.9(CO2)0–0.1·nH2O (n = 1–3), where the S4 molecule occurs in different conformation states. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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21 pages, 8559 KiB  
Review
Structural Principles of Ion-Conducting Mineral-like Crystals with Tetrahedral, Octahedral, and Mixed Frameworks
by Dmitry Pushcharovsky and Alexey Ivanov-Schitz
Minerals 2024, 14(8), 770; https://doi.org/10.3390/min14080770 - 29 Jul 2024
Cited by 3 | Viewed by 1203
Abstract
Materials with high ion mobility are widely used in many fields of modern science and technology. Over the last 40 years, they have thoroughly changed our world. The paper characterizes the structural features of minerals and their synthetic analogs possessing this property. Special [...] Read more.
Materials with high ion mobility are widely used in many fields of modern science and technology. Over the last 40 years, they have thoroughly changed our world. The paper characterizes the structural features of minerals and their synthetic analogs possessing this property. Special attention is paid to the ionic conductors with tetrahedral (zincite- and wurtzite-like), octahedral (ilmenite-like), and mixed (NASICON-like) frameworks. It is emphasized that the main conditions for fast ionic transport are related to the size and positions occupied by a mobile ion, their activation energy, the presence and diameter of conduction channels running inside the structure, isomorphic impurities, and other structural peculiarities. The results of the studies of solid electrolytes are dispersed in different editions, and the overview of new ideas related to their crystal structures was the focus of this paper. Full article
(This article belongs to the Special Issue Isomorphism, Chemical Variability, and Solid Solutions of Minerals and Related Compounds, 2nd Edition)
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