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Sb-rich rutile in the manganese concentrations at St. Marcel-Praborna, Aosta Valley, Italy: petrology and crystal-chemistry

Published online by Cambridge University Press:  05 July 2018

David C. Smith  and
Elena-Adriana Perseil
David C. Smith
Affiliation:
Laboratoire de Minéralogie, Muséum National d'Histoire Naturelle, 61 Rue Buffon, 75005 Paris, France
Elena-Adriana Perseil
Affiliation:
Laboratoire de Minéralogie, Muséum National d'Histoire Naturelle, 61 Rue Buffon, 75005 Paris, France CNRS, Unité de Recherche Associée n° 736, 61 Rue Buffon, 75005 Paris, France
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Abstract

The petrographical, crystal-chemical and petrogenetical aspects of rutile rich in antimony (up to 33.75 wt.% Sb2O5; equal to 0.2 Sb5+ per O = 2) from St. Marcel-Praborna in the Aosta Valley, Italy, were re-examined. These compositions occur in two different petrographical environments (within the rock matrix or as microinclusions within Sb-rich titanite) in the manganese concentrations at this locality. The new data confirm our earlier hypothesis that two distinct petrogenetical/crystal-chemical processes both occurred: 1. Sb-metasomatism of pre-existing Sb-free rutile inclusions; and 2. creation of neoblastic Sb-rich rutile by the expulsion of Ti from pre-existing Sb-free titanite being metasomatized by Sb to form Sb-rich titanite. In the literature, Sb in minerals is variably considered as being trivalent and/or pentavalent. This work demonstrates that within rutile it is entirely Sb5+, substituting for Ti4+ by the following heterovalent cation exchange mechanism which is also the dominant one in the host Sb-rich titanite: 2 viR4+ = viR3+ + viR5+, where viR3+ = (Al,Cr,Mn,Fe)3+. A near-perfect correlation of ΣR5+vs. ΣR3+ (r > 0.98) is perturbed only by the presence of trace amounts of Ca2+, Sr2+ and Ba2+. Traces of Mn4+, Si4+ and/or (OH)− might also be present. These alkaline earth cations are the largest cations ever recorded in the rutile structure and are seemingly too large to occupy normal octahedral sites. The cation exchange mechanism involved might be that found in the ‘trirutile’ mineral group: 3 viR4+ = viR2+ + 2 viR5+. Alternatively these large divalent cations may be situated in the lozenge-shaped tunnels of the rutile structure, by analogy with other large cations occupying the wider subrectangular tunnels in the analogous cryptomelane/hollandite/priderite, romanéchite and todorokite mineral groups. This leads to a possible new cation exchange mechanism for the rutile structure: 2 viR4+ + tunelvacant = 2 viR3+ + tunnelR2+.

Keywords

antimonyrutiletitaniteroméitecrystal-chemistrypetrologySt. Marcel-PrabornaItaly
Type
Research Article
Information
Mineralogical Magazine , Volume 61 , Issue 408 , October 1997 , pp. 655 - 669
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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