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See detailCrystal chemistry of natural and synthetic fillowite-type phosphates
Hatert, Frédéric ULg; Keller, Paul; Grew, Ed et al

Conference (2008)

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See detailThe crystal structure of sursassite from the Lienne valley, Stavelot Massif, Belgium
Hatert, Frédéric ULg; Fransolet, André-Mathieu ULg; Wouters, Johan et al

in European Journal of Mineralogy (2008), 20

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See detailThe stability of primary alluaudites in granitic pegmatites: an experimental investigation of the Na-2(Mn2-2x Fe1+2x )(PO4)(3) system
Hatert, Frédéric ULg; Fransolet, André-Mathieu ULg; Maresch, Walter W.

in Contributions to Mineralogy & Petrology (2006), 152(4), 399-419

In order to assess the geothermometric potential of the Na-2(Mn2-2x Fe1+2x )(PO4)(3) system (x = 0-1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal ... [more ▼]

In order to assess the geothermometric potential of the Na-2(Mn2-2x Fe1+2x )(PO4)(3) system (x = 0-1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800 degrees C, at 1 kbar, under an oxygen fugacity (f(O-2)) controlled by the Ni-NiO (NNO), Fe2O3-Fe3O4 (HM), Cu2O-CuO (CT), and Fe-Fe3O4 (MI) buffers. When f(O-2) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500 degrees C, whereas the association alluaudite + maricite appears between 500 and 700 degrees C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because maricite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na2MnFe2+Fe3+(PO4)(3), has been positioned in the f(O-2)-T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate. [less ▲]

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See detailPreliminary data on the stability of fillowite-type phosphates : an experimental investigation of the Na[Mn,Fe(II)]4(PO4)3 system
Rondeux, Mélanie ULg; Hatert, Frédéric ULg; Fransolet, André-Mathieu ULg

in Berichte der Deutschen Mineralogischen Gesellschaft : Beihefte zum European Journal of Mineralogy (2006), 18

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See detailThe stability of iron-rich alluaudites in granitic pegmatites : an experimental investigation of the Na-Fe(II)-Fe(III) (+PO4) system
Hatert, Frédéric ULg; Fransolet, André-Mathieu ULg

in Berichte der Deutschen Mineralogischen Gesellschaft : Beihefte zum European Journal of Mineralogy (2006), 18

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See detailHydrothermal synthesis and crystal structure of Na(Na,Mn)(7)Mn-22(PO4)(18)0.5H(2)O, a new compound of fillowite structure type
Keller, Paul; Hatert, Frédéric ULg; Lissner, Falk et al

in European Journal of Mineralogy (2006), 18(6), 765-774

The chemical compound Na(Na,Mn)(7)Mn-22(PO4)(18)center dot 0.5H(2)O was synthesized with a Tuttle pressure vessel at 800 degrees C and 1 kbar during experimental investigations on the conditions of ... [more ▼]

The chemical compound Na(Na,Mn)(7)Mn-22(PO4)(18)center dot 0.5H(2)O was synthesized with a Tuttle pressure vessel at 800 degrees C and 1 kbar during experimental investigations on the conditions of fillowite formation. The crystal structure of a single-crystal, space group R (No. 148), a = 15.2741(9), c = 43.334(3) angstrom, Z = 6, was determined from X-ray intensity data and refined up to R-1 = 0.0728 and R-l{FO > 4 sigma(FO)} = 0.0546. The crystal structure of Na(Na,Mn)(7)Mn-22(PO4)(18)center dot 0.5H(2)O is similar to the structure of fillowite, Na6Ca3(Mn,Fe)(21)(PO4)(18.), but a significant difference between the synthetic H2O containing compound and fillowite is the replacement of (Na12)O-8(-) by Mn(H2O)(2)O-5(-) polyhedra, which form characteristic six-member rings. The coordination polyhedra around Na12 and Mn12 are so different that simple isomorphous substitution of Na12 by Mn12 is very unlikely, but whole six-member rings either of (Na12)O-8(-) or (Mn12)(H2O)(2)O-5 polyhedra seem to be distributed statistically over the crystal structure. No indication for ordering, e.g. sheet by sheet, has been observed. Na(Na,Mn)(7)Mn-22(PO4)(18)center dot 0.5H(2)O is the first fillowite-like compound for which water is located in the structure from single-crystal study. This result is proved by infrared spectral data and indicates that water can play an essential role in the fillowite structure-type. Structural features of the synthetic compounds Na(Na,Mn)(7)Mn-22(PO4)(18)center dot 0.5H(2)O, Na4Ca4Mg21(PO4)(18) and fillowite are compared. [less ▲]

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See detailA structural, infrared, and Mossbauer spectral study of rosemaryite, NaMnFe3+Al(PO4)(3)
Hatert, Frédéric ULg; Hermann, R. P.; Fransolet, André-Mathieu ULg et al

in European Journal of Mineralogy (2006), 18(6, NOV-DEC), 775-785

Rosemaryite, ideally NaMnFe(3+)AI(PO4)(3), has been collected in the Buranga pegmatite, Rwanda. A single-crystal structure refinement was performed to R-1 = 4.01 %, in the P2(1)/n space group, with a = 12 ... [more ▼]

Rosemaryite, ideally NaMnFe(3+)AI(PO4)(3), has been collected in the Buranga pegmatite, Rwanda. A single-crystal structure refinement was performed to R-1 = 4.01 %, in the P2(1)/n space group, with a = 12.001(2), b = 12.396(1), c = 6.329(1) angstrom, beta 114.48(1)degrees, Vol. = 856.9(2) angstrom(3), Z = 4. The crystal structure and cation distributions are similar to those of ferrorosemaryite, NaFe2+Fe3+Al(PO4)(3), and qingheiite, Na2MnMgAl(PO4)(3), but aluminium predominantly occurs in the M(2a) site, not in the M(2b) site as observed in ferrowyllieite, Na2Fe22+Al(PO4)(3). The topologies of the X(1a) and X(1b) crystallographic sites are identical to those found in ferrorosemaryite, and correspond to a distorted octahedron and to a distorted cube, respectively. The [7+1]-coordinated X(2) site is a very distorted gable disphenoid, similar to the A(2)' site of the alluaudite structure. Mossbauer spectra have been obtained from 4.2 to 295 K, and fitted with a model including two Fe3+ and two Fe2+ doublets. The Fe2+ component corresponding to 2/3 of the Fe2+ spectral area and having a smaller quadrupole splitting of 2.63 mm/s at 15 K, is assigned to the Fe2+ on the M(2a) site, and the Fe2+ component with the larger quadrupole splitting of 3.17 mm/s at 15 K, is assigned to the Fe2+ on the M(1) site. Fe3+ is located only at the M(2a) and M(2b) sites, and the Fe3+ component corresponding to 3/4 of the Fe3+ and exhibiting the larger quadrupole spitting of 0.77 mm/s at 15 K, is most likely associated with Fe3+ on the M(2b) site. The infrared spectrum of rosemaryite shows absorption bands at 3450 and 1624 cm(-1), bands that arise from the vibrational modes of H2O and confirm the presence of water in the channels of the wyllieite structure. A comparison of both the Mossbauer spectra and structural data of rosemaryite with those of other phosphates of the alluaudite and wyllieite groups, is also presented. [less ▲]

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See detailCrystal chemistry of the hydrothermally synthesized Na-2(Mn1-xFex2+)(2)Fe3+(PO4)(3) alluaudite-type solid solution
Hatert, Frédéric ULg; Rebbouh, Leila; Hermann, Raphaël P. et al

in American Mineralogist (2005), 90(4), 653-662

Several compounds of the Na-2(Mn1-xFex2x)(2)Fe3+(PO4)(3) solid solition have been hydrothermally synthesized at 400 degrees C and 1 kbar; pure alluaudite-like compounds have been obtained for x = 0.00, 0 ... [more ▼]

Several compounds of the Na-2(Mn1-xFex2x)(2)Fe3+(PO4)(3) solid solition have been hydrothermally synthesized at 400 degrees C and 1 kbar; pure alluaudite-like compounds have been obtained for x = 0.00, 0.25, 0.50, 0.75, and 1.00. Rietveld refinements of the powder X-ray diffraction patterns indicate the presence of Na+ at the Al and A2' sites, Mn2+ and Fe2+ at the M1 site, and Mn2+, Fe2+, and Fe3+ at the M2 site. The presence of small amounts of Na+ at the M1 site and Mn2+ at the Al site indicates a partially disordered distribution of these cations. An excellent linear correlation has been established between the M1-M2 distance and the energy of the infrared band attributed to the M2+-O vibrations. The Mossbauer spectra, measured between 85 and 295 K, were analyzed in terms of a model which includes the next-nearest neighbor interactions at the M2 and M1 crystallographic sites. Fe2+ and Fe3+ isomer shifts are typical of the alluaudite structure and exhibit the expected second-order Doppler shift. The derived iron vibrating masses and Mossbauer lattice temperatures are within the range of values expected for iron cations in all octahedral environment. The Fe2+ and Fe3+ quadrupole splittings are typical of the alluaudite structure, and the temperature dependence of the Fe2+ quadrupole splitting was fit with the Ingalls model, which yielded a ground state orbital splitting of ca. 460 to 735 cm(-1) for the Fe2+ sites. The isomer shifts and quadrupole splittings of Fe2+ at the M1 site are larger than those of Fe2+ at M2, indicating that the M1 site is both larger and more distorted than the M2 site. [less ▲]

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See detailFerrorosemaryite, NaFe2+Fe3+Al(PO4)3, a new phosphate mineral from the Rubindi pegmatite, Rwanda.
Hatert, Frédéric ULg; Lefèvre, Pierre; Fransolet, André-Mathieu ULg et al

in European Journal of Mineralogy (2005), 17

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