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Mössbauerite, Fe6 3+O4(OH)8[CO3]·3H2O, the fully oxidized ‘green rust’ mineral from Mont Saint-Michel Bay, France

Published online by Cambridge University Press:  05 July 2018

J.-M. R. Génin ,
S. J. Mills ,
A. G. Christy ,
O. Guérin ,
A. J. Herbillon ,
E. Kuzmann ,
G. Ona-Nguema ,
C. Ruby  and
C. Upadhyay
J.-M. R. Génin*
Affiliation:
Institut Jean Barriol FR2843 Université de Lorraine-CNRS, ESSTIN, 2 rue Jean Lamour, F-54500, Vandœuvre-Lès-Nancy, France
S. J. Mills*
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
A. G. Christy
Affiliation:
Centre for Advanced Microscopy, Sullivans Creek Road, Australian National University, Canberra 0200, ACT, Australia
O. Guérin
Affiliation:
Laboratoire de Géomorphologie, École Pratique des Hautes Études, 15 boulevard de la mer, F-35800 Dinard, France
A. J. Herbillon
Affiliation:
Unité des Sciences du Sol, Université Catholique de Louvain, B-1348 Louvain-la-Neuve, Belgium
E. Kuzmann
Affiliation:
Department of Chemistry, Eötvös Lorand University, Pazmany Peter setany, H1117, Budapest, Hungary
G. Ona-Nguema
Affiliation:
Institut Minéralogie et de Physique, Milieux Condensés, Université Pierre et Marie Curie, F75252 Paris, France
C. Ruby
Affiliation:
Institut Jean Barriol FR2843 Université de Lorraine-CNRS, ESSTIN, 2 rue Jean Lamour, F-54500, Vandœuvre-Lès-Nancy, France
C. Upadhyay
Affiliation:
School of Materials Science & Technology, IT-Banaras Hindu University, 221005 Varanasi, India
*
E-mails: [email protected]; [email protected]
E-mails: [email protected]; [email protected]
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Abstract

The new mineral mössbauerite (IMA2012−049), Fe6 3+O4(OH)8[CO3]·3H2O, is a member of the fougèrite group of the hydrotalcite supergroup. Thus, it has a layered double hydroxide-type structure, in which brucite-like layers [Fe6 3+O4(OH)8]2+ are intercalated with CO3 2− anions and water molecules. Mössbauerite is the fully oxidized analogue of fougèrite and trébeurdenite, related to them chemically by the exchange of (Fe3+O2−) with (Fe2+OH−). Mössbauerite, intimately intergrown with trébeurdenite, was discovered in intertidal gleys from Mont Saint-Michel Bay, France, along with quartz, feldspars and clay minerals. Mössbauerite is formed by the oxidation of the other members of the fougèrite group. Like them, it occurs as μm-scale platelets in gleys with restricted access to atmospheric O and decomposes rapidly when exposed to air. Identification and characterization of these minerals has relied on an electrochemical study of synthetic analogues and Mössbauer spectroscopy, which inspired the name of the new mineral.

Unlike fougèrite and trébeurdenite, which are blue-green, pure synthetic mössbauerite is orange in colour. Detailed optical and other physical properties could not be determined because of the small platelet size and instability. The hardness is probably 2−3, by analogy with other members of the supergroup and the density, calculated from unit-cell parameters, is 2.950 g/cm3. Synchrotron X-ray data indicate that the natural material is a nanoscale intergrowth of 2T and 3T polytypes; the latter probably has the 3T7 stacking sequence. The corresponding maximum possible space group symmetries are P m1 and P3m1. Unit-cell parameters for the 3T cell are a = 3.032(7) Å, c = 22.258(4) = 367.420 Å and Z = ½.

Mössbauer spectroscopy at 78 K indicates that two distinct Fe3+ environments exist in a 2:1 ratio. These are interpreted to be ordered within each layer, but without the development of a threedimensional superlattice. Mössbauerite undergoes gradual magnetic ordering at 70−80 K to a ferromagnetic state, below which it splits into three sextets S 1m, S 2m and S 3m, as measured at 15 K, and shows the same intensity ratio ½:⅙:⅓ as the three doublets for fougèrite D 1f, D 2f, D 3f in the paramagnetic state at 78 K. This suggests that there is also short-range coupling of interlayer carbonate anions with respect to the octahedral layers and that the 2D long-range order of carbonates in interlayers remains unchanged.

Keywords

gleysolslayered double hydroxideshydrotalcite supergroupfougèritetrébeurdeniteMössbaueritepolytypesMössbauer spectroscopy
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 2 , April 2014 , pp. 447 - 465
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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