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

  • J.-M. R. Génin (a1), S. J. Mills (a2), A. G. Christy (a3), O. Guérin (a4), A. J. Herbillon (a5), E. Kuzmann (a6), G. Ona-Nguema (a7), C. Ruby (a1) and C. Upadhyay (a8)...

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.

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Benali, O., Abdelmoula, M., Refait, Ph. and Génin, J.-M.R. (2001) Effect of orthophosphate on the oxidation products of Fe(II)-Fe(III) hydroxycarbonate: the transformation of green rust to ferrihydrite. Geochimica et Cosmochimica Acta, 65, 17151726.
Bernal, J.D., Dasgupta, D.R. and Mackay, A.L. (1959) The oxides and hydroxides of iron and their structural inter-relationships. Clay Minerals Bulletin, 4, 1530.
Bookin, A.S. and Drits, V.A. (1993) Polytype diversity of the hydrotalcite-like minerals. I. Possible polytypes and their diffraction features. Clays and Clay Minerals, 41, 551557.
Bookin, A.S., Cherkashin, V.I. and Drits, V.A. (1993a) Reinterpretation of the X-ray diffraction patterns of stichtite and reevesite. Clays and Clay Minerals, 41, 631634.
Bookin, A.S., Cherkashin, V.I. and Drits, V.A. (1993b) Polytype diversity of the hydrotalcite-like minerals. II. Determination of the polytypes of experimentally studied varieties. Clays and Clay Minerals, 41, 558564.
Brese, N.E. and O’Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192197.
Carlson, L. and Schwertmann, U. (1980) Natural occurrence of feroxyhite (d-FeOOH). Clays and Clay Minerals, 28, 272280.
Christensen, B.C., Balic-Zunic, T., Dideriksen, K. and Stipp, S.L.S. (2009) Identification of green rust in groundwater. Environmental Science & Technology, 43, 34363441.
Drissi, S.H., Refait, Ph., Abdelmoula, M. and Génin, J.-M.R. (1995) The preparation and thermodynamic properties of Fe(II)-Fe(III) hydroxycarbonate (green rust 1); Pourbaix diagram of iron in carbonatecontaining aqueous media. Corrosion Science, 37, 20252041.
Feitknecht, W. and Keller, G. (1950) Über die Dunkelgrünen Hydroxyverbindungen des Eisens. Zeitschrift für Anorganische und Allgemeine Chemie, 262, 6168.[in German].
Gancedo, J.R., Martínez, M.L. and Oton, J.M. (1976) Mössbauer spectroscopy study of corrosion products of iron with ammonium nitrate in aqueous solutions. Journal de Physique, 37, C6 297–C6 299.
Génin, J.-M.R. (2013) From fougèrite to mössbauerite through trébeurdenite; redox reactions in gleysols and role of bacteria. Mössbauer Effect Reference and Data Journal, Chinese Academy of Sciences, 36, 113160.
Génin, J.-M.R. and Ruby, C. (2004) Anion and cation distribution in Fe(II-III) hydroxysalts green rusts from XRD and Mössbauer analysis (carbonate, chloride, sulphate…); the “fougèrite” mineral. Solid State Science, 6, 705718.
Génin, J.-M.R. and Ruby, C. (2008a) Composition and anion ordering in some FeII-III hydroxysalt green rusts (carbonate, oxalate, methanoate); the fougèrite mineral. Solid State Science, 10, 244259.
Génin, J.-M.R. and Ruby, C. (2008b) Structure of some FeII-III hydroxysalt green rusts (carbonate, oxalate, methanoate) from Mö ssbauer spectrsocopy. Hyperfine Interactions, 185, 191196.
Génin, J.-M.R., Olowe, A.A., Refait, Ph. and Simon, L. (1996) On the stoichiometry and Pourbaix diagram of Fe(II)-Fe(III) hydroxy-sulphate or sulphate-containing green rust 2: an electrochemical and Mössbauer spectroscopy study. Corrosion Science, 38, 17511762.
Génin, J.-M.R., Bourrié, G., Trolard, F., Abdelmoula, M., Jaffrezic, A., Refait, Ph., Maitre, V., Humbert, B. and Herbillon, A. (1998a) Thermodynamic equilibria in aqueous suspensions of synthetic and natural Fe(II)-Fe(III) green rusts: occurrences of the mineral in hydromorphic soils. Environmental Science & Technology, 32, 10581068.
Génin, J.-M.R., Refait, Ph., Simon, L. and Drissi, S.H. (1998b) Preparation and Eh-pH diagrams of Fe(II)- Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate. Hyperfine Interactions, 111, 313318.
Génin, J.-M.R., Aïssa, R., Géhin, A. Abdelmoula, M., Benali, O., Ernstsen, V., Ona-Nguema, G., Upadhyay, C. and Ruby, C. (2005) Fougèrite and FeII-III hydroxycarbonate green rust: ordering, deprotonation and/or cation substitution; structure of hydrotalcite-like compounds and mythosic ferrosic hydroxide Fe(OH)(2+x) . Solid State Sciences, 7, 545572.
Génin, J.-M.R., Abdelmoula, M., Ruby, C. and Upadhyay, C. (2006a) Speciation of iron; characterisation and structure of green rusts and FeII-III hydroxycarbonate fougè rite. Comptes Rendus Geosciences, 338, 402419.
Génin, J.-M.R., Ruby, C., Géhin, A. and Refait, Ph. (2006b) Synthesis of green rusts by oxidation of Fe(OH)2, their products of oxidation and reduction of ferric oxyhydroxides; Eh-pH Pourbaix diagrams. Comptes Rendus Geosciences, 338, 433446.
Génin, J.-M.R., Ruby, C. and Upadhyay, C. (2006c) Structure and thermodynamics of ferrous, stoichiometric and ferric oxyhydroxycarbonate green rusts; redox flexibility and fougèrite mineral. Solid State Science, 8, 13301343.
Génin, J.-M.R., Guérin, O. Herbillon, A.J., Kuzman, E., Mills, S.J., Morin, G., Ona-Nguema, G., Ruby, C. and Upadhyay, C. (2012) Redox topotactic reactions in FeII-III (oxy)-hydroxycarbonate new minerals related to fougèrite in gleysols; “trébeurdenite” and “mö ssbauerite”. Hyperfine Interactions, 204, 7181.
Girard, A. and Chaudron, G. (1935) Sur la constitution de la rouille. Comptes Rendus de l’Academie des Sciences de Paris, 200, 127129.
Laugier, J. and Bochu, B. (2000) CHECKCELL: a software performing automatic cell/space group determination. Collaborative computational project number 14 (CCP14). Laboratoire des Materiaux et du Genie Physique de l’Ecole Superieure de Physique de Grenoble, France.
Legrand, L., Abdelmoula, M., Géhin, A. Chaussé, A. and Génin, J.-M.R. (2001) Electrochemical formation of a new Fe(II)-Fe(IIII) hydroxy-carbonate green rust: characterisation and morphology. Electrochimica Acta, 46, 18151822.
Mills, S.J., Whitfield, P.S., Wilson, S.A., Woodhouse, J.N., Dipple, G.M., Raudsepp, M. and Francis, C.A. (2011) The crystal structure of stichtite, re-examination of barbertonite, and the nature of polytytpism in MgCr hydrotalcites. American Mineralogist, 96, 179187.
Mills, S.J., Christy, A.G., Génin, J.-M.R., Kameda, T. and Colombo, F. (2012a) Nomenclature of the hydrotalcite supergroup: natural layered double hydroxides. Mineralogical Magazine, 76, 12891336.
Mills, S.J., Kampf, A.R., Housley, R.M., Favreau, G., Pasero, M., Biagioni, C., Merlino, S., Berbain, C. and Orlandi, P. (2012b) Omsite, (Ni,Cu)2Fe3+ (OH)6[Sb(OH)6], a new member of the cualstibite group from Oms, France. Mineralogical Magazine, 76, 13471354.
Olowe, A.A. and Génin, J.-M.R. (1991) Mechanism of oxidation of ferrous hydroxide in sulfated aqueous media: importance of the initial ratio of the reactants. Corrosion Science, 32, 965984.
Ona-Nguema, G., Abdelmoula, M., Jorand, F., Benali, O., Géhin, A. Block, J.C. and Génin, J.-M.R. (2002) Iron (II,III) hydroxycarbonate green rust formation and stabilization from lepidocrocite bioreduction. Environmental Science & Technology, 36, 1620.
Pourbaix, M. (1975) Leçons en corrosion électrochimique. CEBELCOR, Brussels, 377 pp.
Refait, Ph. and Génin, J.-M.R. (1993) The oxidation of ferrous hydroxide in chloride-containing aqueous media and Pourbaix diagrams of green rust one. Corrosion Science, 34, 797819.
Refait, Ph. and Génin, J.-M.R. (1994) The transformation of chloride-containing green rust one into sulphated green rust two by oxidation in mixed Cl–áand SO42– aqueous media. Corrosion Science, 36, 5565.
Richardson, I.G. (2013) Clarification of possible ordered distributions of trivalent cations in layered double hydroxides and an explanation for the observed variation in the lower solid-solution limit. Acta Crystallographica, B69, 629633.
Ruby, C., Upadhyay, C., Géhin, A. Ona-Nguema, G. and Génin, J.-M.R. (2006) In situ redox flexibility of FeII-III oxyhydroxycarbonate green rust and fougèrite. Environmental Science & Technology, 40, 46964702.
Ruby, C., Abdelmoula, M., Naille, S., Renard, A., Khare, V., Ona-Nguema, G., Morin, G. and Génin, J.-M.R. (2010) Oxidation modes and thermodynamics of FeII-III oxyhydroxycarbonate green rust: dissolution-precipitation versus in situ deprotonation. Geochimica et Cosmochimica Acta, 74, 953966.
Rusch, B., Génin, J.-M.R., Ruby, C., Abdelmoula, M. and Bonville, P. (2008a) Ferrimagnetic properties in FeII-FeIII (oxy)hydroxycarbonate green rusts. Solid State Sciences, 10, 4049.
Rusch, B., Génin, J.-M.R., Ruby, C., Abdelmoula, M. and Bonville, P. (2008b) Mö ssbauer study of magnetism in FeII-FeIII (oxy)hydroxycarbonate green rusts; ferrimagnetism of FeII-FeIII hydroxycarbonate. Hyperfine Interactions, 187, 712.
Simon, L., François, M. Refait, Ph., Renaudin, G., Lelaurain, M. and Génin, J.-M.R. (2003) Structure of the Fe(II-III) layered double hydroxylsulphate green rust two from Rietveld analysis. Solid State Sciences, 5, 327334.
Taylor, R.M. (1980) Formation and properties of Fe(II)- Fe(III) hydroxy-carbonate and its possible significance in soil formation. Clay Minerals, 15, 369382.
Trolard, F., Bourrié, G., Abdelmoula, M., Refait, Ph. and Feder, F. (2007) Fougèrite, a new mineral of the pyroaurite-iowaite group: description and crystal structure. Clays and Clay Minerals, 55, 323334.
Vysostskii, G.N. (1905) Gley. Eurasian Soil Science (Pochvovedenie), 4, 291327.

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

  • J.-M. R. Génin (a1), S. J. Mills (a2), A. G. Christy (a3), O. Guérin (a4), A. J. Herbillon (a5), E. Kuzmann (a6), G. Ona-Nguema (a7), C. Ruby (a1) and C. Upadhyay (a8)...

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