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Crystal chemistry of kimzeyite from Anguillara, Mts. Sabatini, Italy

¹ Dipartimento Geomineralogico, Università di Bari, via E. Orabona 4, I-70125, Bari, Italy
² Dipartimento di Scienze Geologiche, Università di Romatre, via Ostiense 169, I-00154, Roma, Italy
³ Laboratoire de Minéralogie, Muséum National d'Histoire Naturelle, 61 rue de Buffon, F-75005, Paris, France

^* e-mail: scordari{at}lgxserver.uniba.it

A single garnet crystal of kimzeyite from Anguillara Sabazia, Sabatini Volcanic District (Rome), has been studied by electron probe microanalysis (EPMA), single crystal X-ray diffraction (XRD) and Raman spectroscopy (RS). X-ray intensities for the structure refinement were collected by means of both a conventional four circle diffractometer (CD) and an area detector (AD) diffractometer. Salient crystallographic data from AD measurements are: a = 12.397(4) Å, V = 1905.24 ų, µ= 25 cm^–1, crystal dimension 40 µm, D_x=3.83 g cm^–3. The chemical analyses allowed to ascertain that Ca, Ba, Fe, Al, Mg, REE, Zr, Si and Ti are present in the structure. The transition element distribution is: Fe³⁺(Y) << Fe³⁺(Z), and Ti as Ti⁴⁺ occurs only at Y. No hydrogen atoms were detected. The problem of the correct distribution of Ba and REE (essentially Eu and Gd) is dealt with, but not fully solved in the present study. Because of the very small amount of sample available and of the strong dilution of Ba and REE (0.03 and 0.02 atoms per formula unit respectively) the correct distribution of these atoms over the X and Y sites is problematical. The radius ratio rule and electrostatic requirements suggest Ba at X and REE at Y. From these principles, the following site distribution can be deduced: Ca²⁺ and Ba²⁺ at X; Mg²+, REE³⁺, Zr⁴⁺, Ti⁴⁺, Fe³⁺ at Y; Si⁴⁺, Al³⁺, Fe³⁺ at Z. On the other hand, structural details and the best fit between EPMA and XRD site populations indicate REE at X and Ba at Y. Bond strength theory arguments support this hypothesis.

The main substitution mechanisms can be summed up as follows: 1) Ti⁴⁺(Y) + Fe³⁺(Z) Si⁴⁺(Z) + M³⁺(Y) [schorlomite substitution]; 2) Zr⁴⁺(Y) + M³⁺(Z) Si⁴⁺(Z) + M³⁺(Y) [kimzeyite substitution]; 3) Mg²⁺(Y) + Zr⁴⁺(Y) 2M³⁺(Y) [morimotoite-like substitution], where M³⁺ = (Al, Fe). In addition, following the bond strength theory indications, another mechanism which possibly involves the X and Y sites is also taken into account: 4) REE³⁺(X) + Ba²⁺(Y) Ca²⁺(X) + M³⁺(Y).

Key-words: kimzeyite, Zr-garnet, EPMA, Raman spectroscopy, structure refinement.

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