Site occupancies in synthetic monoclinic amphiboles: Rietveld structure refinement and infrared spectroscopy of (nickel, magnesium, cobalt)-richterite.
Résumé
Amphiboles were synthesized at 750 8C, 1 kbar (H2O) on the binary joins (nickel, magnesium)-richterite and (magnesium, cobalt)-richterite. Structural variations and site occupancies were characterized by Rietveld structure refinement, with final RBragg indices in the range 4–9%, and by powder infrared spectroscopy in the principal OH-stretching region. Site-occupancy refinement of Ni-Mg and Mg-Co distributions give the partition coefficients over M1,3 and M2 where KM21 5 (M21/Mg)M1,3/(M21/Mg)M2, and M21 5 Ni21 or Co21, K 5 2.98 6 0.37 and K 5 1.34 6 0.31. Both Kd Ni Co values are greater than 1.0, d d whereas [6]r(Ni21 ) , [6]r(Mg) , [6]r(Co21 ); this indicates that cation size is not the primary factor affecting the ordering of Ni-Mg and Mg-Co over the octahedral sites. The infrared spectra of intermediate binary compositions show fine structure caused by ordering of Ni- Mg or Mg-Co over the M1,3 sites and by ordering of Na and M (vacancy) at the A site; thus intermediate compositions show an eight-band spectrum in the principal OHstretching region. Precise band intensities were derived by nonlinear least-squares fitting of Gaussian band shapes to the observed spectra. The relative observed intensities of the combinations of bands 3IA1 2IB1 IC and IB 1 2IC 1 3ID are in accord with the equations o o o o o o of Burns and Strens (1966), indicating that there is no significant variation in molar absorptivity with frequency (energy) for individual bands within a single sample (spectrum). Combined with the results of Skogby and Rossman (1991) on polarized single-crystal infrared spectra of amphiboles, this result suggests that different local configurations of M1,3 cations in amphiboles couple such that the transition probabilities of the associated OH groups are equal.
Domaines
Géochimie
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