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The heteropolymolybdate family: structural relations, nomenclature scheme and new species

Published online by Cambridge University Press:  05 July 2018

A. R. Kampf ,
S. J. Mills ,
M. S. Rumsey ,
M. Dini ,
W. D. Birch ,
J. Spratt ,
J. J. Pluth ,
I. M. Steele ,
R. A. Jenkins  and
W. W. Pinch
A. R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA
S. J. Mills
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne, Victoria 3001, Australia
M. S. Rumsey
Affiliation:
Earth Sciences Department, Natural History Museum, Cromwell Road, London SW7 5BD, UK
M. Dini
Affiliation:
Pasaje San Agustin 4045, La Serena, Chile
W. D. Birch
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne, Victoria 3001, Australia
J. Spratt
Affiliation:
Earth Sciences Department, Natural History Museum, Cromwell Road, London SW7 5BD, UK
J. J. Pluth
Affiliation:
Department of the Geophysical Sciences, The University of Chicago, 5734 S. Ellis Avenue, Chicago, Illinois 60637, USA
I. M. Steele
Affiliation:
Department of the Geophysical Sciences, The University of Chicago, 5734 S. Ellis Avenue, Chicago, Illinois 60637, USA
R. A. Jenkins
Affiliation:
4521 N. Via Madre, Tucson, Arizona 85749, USA
W. W. Pinch
Affiliation:
19 Stonebridge Lane, Pittsford, New York 14534, USA
*
*E-mail: [email protected]
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Abstract

Type specimens of the molybdoarsenates betpakdalite, natrobetpakdalite and obradovicite and the molybdophosphates mendozavilite, paramendozavilite and melkovite, and similar material from other sources, have been examined in an effort to elucidate the relations among these phases, which we designate as the heteropolymolybdate family of minerals. Using electron microprobe analysis, X-ray powder diffraction and single-crystal X-ray diffraction with crystal structure determination where possible, it was found that natrobetpakdalite, mendozavilite and melkovite are isostructural with betpakdalite and that obradovicite has a closely related structure.

The betpakdalite and obradovicite structure types are based on frameworks containing four-member clusters of edge-sharing MoO6 octahedra that link by sharing corners with other clusters, with Fe3+O6 octahedra and with PO4 or AsO4 tetrahedra (T). The structures differ in the linkages through the Fe3+O6 octahedra, which produce different but closely related framework configurations. The structures contain two types of non-framework cation sites, which are designated A and B. In general, there are two or more A sites partially occupied by disordered, generally larger cations that are coordinated to O atoms in the framework and to H2O molecules. The B site is occupied by a smaller cation that is octahedrally coordinated to H2O molecules. The general formula for minerals with either the betpakdalite or the obradovicite structure is: [A2(H2O)nB(H2O)6][Mo8T2Fe3+3O30+7(OH)7–x], where x is the total charge of the cations in the A and B sites (+3 to +7) and n is variable, ideally 17 for arsenates and 15 for phosphates. The ideal total number of A cations is defined as 2 in the general formula, but varies from 1 to 3.8 in analysed samples. Dominant cations at the A site include K, Na and Ca and at the B site Na, Ca, Mg, Cu and Fe. The combinations that have been identified in this study define six new heteropolymolybdate species.

A suffix-based nomenclature scheme is established for minerals of the betpakdalite, mendozavilite and obradovicite groups, with the following root names based on the structure types and the T-site cations: betpakdalite (T = As), mendozavilite (T = P) and obradovicite (T = As). Two suffixes of the form -AB, corresponding to the dominant cations in the two different types of non-framework cation sites complete the species name. The historical name melkovite is retained rather than introducing mendozavilite-CaCa.

Our investigation of the paramendozavilite type specimen revealed no paramendozavilite, but an apparently closely related new mineral; however, another sample of paramendozavilite analysed had K > Na.

Keywords

heteropolymolybdate familycrystal structurenew mineralbetpakdalitemelkovitemendozaviliteobradoviciteparamendozavilite
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 5 , October 2012 , pp. 1175 - 1207
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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Betpakdalite-CaMg.CIF

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Betpakdalite-CaMg structure factors

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Betpakdalite-NaNa.CIF

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Mendozavilite-NaCu.CIF

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Obradovicite-NaCu.CIF

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Obradovicite-NaNa.CIF

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Obradovicite-NaNa-structure-factors.doc

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Powder XRD tables

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