Synthesis and Characterization of (Ca,Sr)[C2O4]∙nH2O Solid Solutions: Variations of Phase Composition, Crystal Morphologies and in Ionic Substitutions

Rusakov, Aleksei V.; Kuz’mina, M. A.; Izatulina, Alina R.; Frank-Kamenetskaya, O. V.

doi:10.3390/cryst9120654

Cited by 6 publications

(5 citation statements)

References 29 publications

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“…The development of a third prism can be explained by the selective adsorption of citrate complexes, leading to the inhibition of the growth of this facet. A similar mechanism was previously revealed in Ca-Sr oxalates (analogues of weddellites) crystallizing from citrate-containing solutions [ 23 ]. Larger individual crystals of Mn-free glushinskite can be obtained with an excess of oxalate ions in the absence of citric acid.…”

Section: Discussionsupporting

confidence: 67%

Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology

Korneev

Izatulina

Kuz’mina

et al. 2022

IJMS

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To clarify the crystal chemical features of natural and synthetic oxalates Me2+(C2O4)∙2H2O (Me2+ = Fe, Mn, Mg, Zn), including minerals of the humboldtine group, solid solutions of lindbergite Mn(C2O4)∙2H2O–glushinskite Mg(C2O4)∙2H2O were precipitated under various conditions, close to those characteristic of mineralization in biofilms: at the stoichiometric ratios ((Mn + Mg)/C2O4 = 1) and non-stochiometric ratios ((Mn + Mg)/C2O4 < 1), in the presence and absence of citrate ions. Investigation of precipitates was carried out by powder X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Thermodynamic modelling was performed in order to evaluate the lindbergite–glushinskite equilibrium. It was shown that glushinskite belongs to the orthorhombic β-modification (sp. Gr. Fddd), while lindbergite has a monoclinic α-modification (sp. gr. C2/c). Mg ions incorporate lindbergite in much higher quantities than Mn ions incorporate glushinskite; moreover, Mn glushinskites are characterized by violations of long-range order in their crystal structure. Lindbergite–glushinskite transition occurs abruptly and can be classified as a first-order isodimorphic transition. The Me2+/C2O4 ratio and the presence of citric acid in the solution affect the isomorphic capacity of lindbergite and glushinskite, the width of the transition and the equilibrium Mg/Mn ratio. The transition is accompanied by continuous morphological changes in crystals and crystal intergrowths. Given the obtained results, it is necessary to take into account in biotechnologies aimed at the bioremediation/bioleaching of metals from media containing mixtures of cations (Mg, Mn, Fe, Zn).

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Section: Discussionsupporting

confidence: 67%

Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology

Korneev

Izatulina

Kuz’mina

et al. 2022

IJMS

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“…Replacement of calcium ions in whewellite and weddellite by divalent cations (Sr 2+ and Mg 2+ ) from the solution is also possible. The patterns of strontium incorporation into whewellite and weddellite was studied by us earlier [ 24 ]. An uneven distribution of isomorphic impurities near the surface of a growing face can cause local internal stress, which distorts the surface structure and inhibit the growth rate of the face [ 26 ].…”

Section: Discussionmentioning

confidence: 99%

“… Tetragonal prism faces in the faceting of weddellite crystals synthesized with citrate ions and some environmental ions: ( a ) with potassium cations (Synthesis 13), ( b ) with magnesium and sulfate ions (Synthesis 23), ( c ) with carbonate ions (Synthesis 20) and ( d ) with strontium cations [ 24 ]. …”

Section: Figurementioning

confidence: 99%

Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis

2021

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The present study is focused on the effect of biofilm medium chemistry on oxalate crystallization and contributes to the study of the patterns of microbial biomineralization and the development of nature-like technologies, using the metabolism of microscopic fungi. Calcium oxalates (weddellite and whewellite in different ratios) were synthesized by chemical precipitation in a weakly acidic environment (pH = 4–6), as is typical for the stationary phase of micromycetes growth, with a ratio of Ca2+/C2O42− = 4.0–5.5, at room temperature. Additives, which are common for biofilms on the surface of stone in an urban environment (citric, malic, succinic and fumaric acids; and K+, Mg2+, Fe3+, Sr2+, SO42+, PO43+ and CO32+ ions), were added to the solutions. The resulting precipitates were studied via X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS). It was revealed that organic acids, excreted by micromicetes, and some environmental ions, as well as their combinations, significantly affect the weddellite/whewellite ratio and the morphology of their phases (including the appearance of tetragonal prism faces of weddellite). The strongest unique effect leading to intensive crystallization of weddellite was only caused by the presence of citric acid additive in the medium. Minor changes in the composition of the additive components can lead to significant changes in the weddellite/whewellite ratio. The effect of the combination of additives on this ratio does not obey the law of additivity. The content of weddellite in the systems containing a representative set of both organic acids and environmental ions is ~20 wt%, which is in good agreement with natural systems.

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“…http://www.minsocam.org/ Kamenetskaya et al 2019;Zelenskaya et al 2020), most oxalate crystals synthesized by us were characterized by multiple splitting and the formation of spherulite-like (shard-like according to Ferrier et al 2019) and other aggregates (Figs. 1,3), which were absent for manganese and calcium oxalates found in biofilms on the surface of rocks (Wilson and Jones 1984;Frank-Kamenetskaya et al 2019). Besides, the size of synthesized crystals was significantly larger than that of natural samples.…”

Section: Regularities Of Fungal Oxalate Formationmentioning

confidence: 95%

Oxalate formation byAspergillus nigeron minerals of manganese ores

Frank‐Kamenetskaya

Zelenskaya

Izatulina

et al. 2022

American Mineralogist

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Microscopic fungi (micromycetes) play an important role in rock alteration often leading to formation of insoluble biogenic oxalates on rock/mineral surfaces. Oxalate crystallization under the influence of fungus Aspergillus niger (one of the most active stone destructors) was studied in vitro on two Mn,Ca-bearing minerals of manganese ores: todorokite (Na0.36,Ca0.09,K0.06,Sr0.03,Ba0.02)0.56(Mn5.53,Mg0.47)O12•3-4H2O and kutnohorite (Ca0.77,Mn0.23)(Mn0.74,Fe0.14,Mg0.11)(CO3)2. The underlying minerals and the products of their alteration were investigated using powder and single crystal X-ray diffraction, optical microscopy, SEM and EDX methods. It was shown that a more intense leaching of Ca-ions (compared to Mn-ions) from todorokite and kutnohorite leads to an earlier crystallization of calcium oxalates (predominantly whewellite) compared to manganese oxalates (lindbergite, falottaite). Crystallization of manganese oxalates on the surface of kutnohorite occurs in more acidic (compared to todorokite) medium through the formation of mycogenic Mn,Ca-bearing oxides, which are close in composition and structure to This is the peer-reviewed, final accepted version for American Mineralogist, published by the Mineralogical Society of America. The published version is subject to change. Cite as Authors (Year) Title. American Mineralogist, in press.

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Synthesis and Characterization of (Ca,Sr)[C2O4]∙nH2O Solid Solutions: Variations of Phase Composition, Crystal Morphologies and in Ionic Substitutions

Cited by 6 publications

References 29 publications

Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology

Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology

Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis

Oxalate formation byAspergillus nigeron minerals of manganese ores

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