Structural systematics of Ge substitution in primitive pyroxenes

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Marco E. Ciriotti
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Structural systematics of Ge substitution in primitive pyroxenes

Messaggio da Marco E. Ciriotti » sab 02 gen, 2016 19:06

Prossima pubblicazione.

▪ Welch, M.D. & Pawley, A.R. (2016): Structural systematics of Ge substitution in primitive pyroxenes. Physics and Chemistry of Minerals, 43, (in press).

Pyroxenes of general stoichiometry Mg(Ge x Si1−x )O3 were encountered in attempts to synthesise Ge-substituted talcs at 0.2 GPa, 650–700 °C. Orthopyroxenes (Pbca) of compositions x = 0.21, 0.30, and 0.34 were identified, and also a P21/c clinopyroxene of composition x = 0.63, and C2/c clinopyroxenes of compositions x = 0.91 and 1. End-member clinoenstatite MgSiO3-P21/c synthesised at 16 GPa, 1300 °C and transformed from C2/c was also included in the study. Crystal structure refinements using single-crystal XRD data showed that unit-cell parameters vary linearly with Si–Ge for the Pbca and P21/c pyroxenes, both of which have two symmetrically non-equivalent tetrahedral chains. Refinement of Si–Ge occupancies at tetrahedral sites showed that the two chains of all primitive pyroxenes have very different compositions, with XGe(TB) ≫ XGe(TA). This difference arises from the greater flexibility of the B-chain to rotate in response to tetrahedral expansion due to increasing Ge content. The TA-M2 shared polyhedral edge imposes significant constraints on the flexibility of the A-chain, which can accommodate much less Ge than the B-chain. Linear trends of cell parameters, site occupancies, and structural parameters for the primitive pyroxenes, when extrapolated to published data for MgGeO3–Pbca, extend across the entire Si–Ge join.
Marco E. Ciriotti

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