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

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).