Abstract
Particularly interesting chemical variability in the U4+ phosphate mineral vyacheslavite from Menzenschwand (Germany) has been discovered and investigated by means of electron-diffraction and micro-chemical methods. Suggested variability comprises the elevated contents of calcium and rare-earth elements (REEs or Ln). Based on the crystal structure refinement from 3D electron diffraction data, the structural formula of Ca-rich vyacheslavite studied is U0.895Ca0.105 PO4(OH)0.790(H2O)0.210. In general, such compositional variability involving Ca2+ can be expressed as U1–x CaxPO4(OH)1–2x(H2O)2x. Based on detailed electron-probe microanalysis, regions extremely enriched in Y and Ln have been discovered, characterized by the contents up to 11 wt% of Y2O3 and ~4.5 wt% of Ln2O3. In addition to the above-mentioned substitution mechanism, substitution involving Y and Ln can be expressed as U4+ + OH– → REE3+ + H2O. Although the structure refinement has not provided direct evidence of H2O in the studied nano-fragments of vyacheslavite, the presence of H2O and its substitution at OH– sites is a reasonable and necessary charge-balancing mechanism. One H atom site was located during structure refinements; however, an additional H-site is only partially occupied and thus was not revealed from the refinement despite the high-quality data. Substitutional trends observed here suggest possible miscibility or structural relationship between vyacheslavite, rhabdophane, and ningyoite that may depend strongly on OH/H2O content, considering that all crystallize under similar paragenetic conditions.
Funding statement: This study was funded by the Czech Science Foundation (GACR 20-11949S to G.S. and J.P.), and by OP VVV project (Geobarr CZ.02.1.01/0.0/0.0/16_026/ 0008459 to R.S.)
Acknowledgments
We express our thanks to Stephan Wolfsried (Waiblingen, Germany) and Carsten Slotta (Hausach, Germany) for their kind cooperation in providing us with the specimens used in this research project. The earlier version of the manuscript greatly benefited from the constructive reviews of an anonymous referee and Travis Olds.
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