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The (Mg,Fe²⁺) substitution in ferri-clinoholmquistite, Li₂(Mg,Fe²⁺)₃Fe³⁺₂O₂₂(OH)₂

¹ Dipartimento di Scienze della Terra, Università "G. D'Annunzio", I-66013 Chieti Scalo, Italy
² Dipartimento di Scienze Geologiche, Università Roma Tre, Largo S. Leonardo Murialdo 1, I-00146 Roma, Italy
³ Department Geological Sciences, University of Manitoba, Winnipeg, Manitoba 3RT 2N2, Canada
⁴ Dipartimento di Sanità Pubblica, Sezione di Fisica, INFM, Università di Parma, Via Volturno 39, I–43100 Parma, Italy
⁵ ISTO, UMR 6113, 1A, Rue de la Férollerie, F-45071, Orléans Cedex 2, France

^* Corresponding author, e-mail: g.iezzi{at}unich.it

Amphiboles have been synthesized by hydrothermal techniques at 500–600 °C, 1 Kbar P_(H2O) and low oxygen fugacity (close to NNO) at nominal compositions along the join ferri-clinoholmquistite [Li₂Mg₃Fe³⁺₂Si₈O₂₂(OH)2] - ferri-clinoferroholmquistite [Li₂Fe²⁺Fe³+₂Si₈O₂₂(OH)₂]. SEM-EDS and X-ray powder diffraction show that at 500 °C, amphibole is the dominant phase in the run assemblage, together with minor clinopyroxene + quartz, in the Fe-rich side of the join, up to 50 mol. % ferri-holmquistite component in the system. For higher Mg contents, an assemblage consisting of predominant clinopyroxene + quartz is obtained, and amphibole is only a minor phase. At 600 °C, the situation is reversed: amphibole is the predominant phase in the Mg-rich side of the join (60–100 mol. % ferri-holmquistite component in the system). X-ray powder-diffraction patterns can be indexed in space group C2/m and cell parameters show well-defined linear trends as a function of nominal amphibole composition. Mössbauer spectra show that Fe³⁺ is strongly ordered at the M2 site, whereas Fe²⁺ is disordered over the B and C sites. The infrared OH-stretching spectra of intermediate compositions show fine structure caused by ordering of Mg and Fe²⁺ over the M1 and M3 sites in the amphibole; this fine structure consists of four main bands assigned to the four local combinations of (Mg,Fe²⁺) at M(1,3). The relative intensities of these bands show that there is almost complete Mg-Fe²⁺ substitution at M(1,3) in ferri-clinoholmquistite and that there is no significant short-range ordering (cluster and/or anti-clustering) between these two cations at the M(1,3) sites. The IR spectra show, in addition, four minor components that are assigned to (Fe²⁺,Mg) at M(4), indicating that the amphibole composition departs from the nominal one following the vector ^M4Fe^{2+ M2}Mg ^M2Fe_–1^{3+ M4}Li_–1.

Key-words: ferri-clinoholmquistite, synthesis, cell-parameters, infrared and Mössbauer spectroscopy, short-range order.

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