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Crystal chemistry of a Mg-vesuvianite and implications of phase equilibria in the system CaO-MgO-Al2O3-SiO2-H2O-CO21
Authors:J W VALLEY  D R PEACOR  J R BOWMAN  E J ESSENE  M J ALLARD
Abstract:Abstract Chemical analysis (including H2, F2, FeO, Fe2O3) of a Mg-vesuvianite from Georgetown, Calif., USA, yields a formula, Ca18.92Mg1.88Fe3+0.40Al10.97Si17.81- O69.0.1(OH)8.84F0.14, in good agreement on a cation basis with the analysis reported by Pabst (1936). X-ray and electron diffraction reveal sharp reflections violating the space group P4/nnc as consistent with domains having space groups P4/n and P4nc. Refinement of the average crystal structure in space group P4/nnc is consistent with occupancy of the A site with Al, of the half-occupied B site by 0.8 Mg and 0.2 Fe, of the half-occupied C site by Ca, of the Ca (1,2,3) sites by Ca, and the OH and O(10) sites by OH and O. We infer an idealized formula for Mg-vesuvianite to be Ca19Mg(MgAl7)Al4Si18O69(OH)9, which is related to Fe3+-vesuvianite by the substitutions Mg + OH = Fe3++ O in the B and O(10) sites and Fe3+= Al in the AlFe site. Thermodynamic calculations using this formula for Mg-vesuvianite are consistent with the phase equilibria of Hochella, Liou, Keskinen & Kim (1982) but inconsistent with those of Olesch (1978). Further work is needed in determining the composition and entropy of synthetic vs natural vesuvianite before quantitative phase equilibria can be dependably generated. A qualitative analysis of reactions in the system CaO-MgO-Al2O3-SiO2-H2O-CO2 shows that assemblages with Mg-vesuvianite are stable to high T in the absence of quartz and require water-rich conditions (XH2O > 0.8). In the presence of wollastonite, Mg-vesuvianite requires very water-rich conditions (XH2O > 0.97).
Keywords:Key-words: petrogenetic grid  vesuvianite
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