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Ardennite, tiragalloite and medaite: structural control of (As5+,V5+,Si4+)O4 tetrahedra in silicates

Published online by Cambridge University Press:  05 July 2018

M. Nagashima  and
T. Armbruster
M. Nagashima*
Affiliation:
Mineralogical Crystallography, Institute of Geological Sciences, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland
T. Armbruster
Affiliation:
Mineralogical Crystallography, Institute of Geological Sciences, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland
*
*E-mail: piemontite@gmail.com
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Abstract

Several silicate-minerals, such as ardennite – Mn2+4MgAl5[Si5(As5+,V5+)O22](OH)6, Z = 2, tiragalloite – Mn2+4[Si3As5+O12(OH)], Z = 4 and medaite – Mn2+6[Si5(V5+,As5+)O18(OH)], Z = 4 possess (V5+,As5+,P5+)O4 tetrahedra. Using electron-microprobe analysis (EMPA) and single-crystal X-ray diffraction methods, the crystal chemistry of ardennite from Salam-Château, Belgium and the Vernetto mine, Italy, tiragalloite from the Gambatesa mine, Italy, and medaite from the Molinello mine, Italy and the Fianel mine, Switzerland, were studied. Structure refinements converged to R1 values of 2.10–5.67%. According to chemical analysis, the Σ(As+V+P) content increases with decreasing Si content. Thus, Si replaces pentavalent cations in tetrahedral coordination. The (As5+,V5+,P5+,Si4+)O4 tetrahedra are categorized by their connections to SiO4 tetrahedra. The (As5+,V5+,P5+,Si4+)O4 tetrahedron of ardennite is isolated, and those of tiragalloite and medaite terminate a tetrahedral chain. The <T–O> of the isolated (As5+,V5+,P5+,Si4+)O4 tetrahedron shows a positive correlation with the mean ionic radius. For (As5+,V5+,P5+,Si4+)O4 tetrahedra with one T–O–T link, <T–O> and mean ionic radius are also correlated. In addition, the longest bridging T–O bond occurs between (As,V,P,Si)O4 and the adjacent SiO4 tetrahedron. The bridging O atom is over-bonded to satisfy the charge requirement of Σ(As+V+Si).

Keywords

ardennitetiragalloitemedaitecrystal structureAsVpentavalent cationstetrahedral site
Type
Research Article
Information
Mineralogical Magazine , Volume 74 , Issue 1 , February 2010 , pp. 55 - 71
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

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Supplementary Table S7

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Supplementary Table S8

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