The octahedral sheet of metamorphic 2M1-phengites: A combined EMPA and AXANES study

Two types of metamorphic phengites are known: one is linked to high pressure and is 3T; the other is 2M{sub 1}, and its composition is linked to rock-compositional constraints. This work investigates the octahedral sheet crystal-chemical differences between the two phengite types. Seven dioctahedral micas were studied: (1) one 3T phengite from an ultrahigh-pressure metagranitoid in the Dora Maira massif, Italy (P {approx} 4.3 GPa, T {approx} 730 C); (2) five 2M{sub 1} phengites from medium-P orthogneisses in the Eastern Alps metamorphic basement, Italy (P {le} 0.7 GPa, T {approx} 500-600 C); and (3) one 2M{sub 1} ferroan muscovite from pegmatite in Antarctica (P {le} 0.2 GPa, T {approx}500 C). All micas display significant extents of celadonite substitution. In particular, the 2M{sub 1}-phengite formulae (calculated on the basis of 11 O) have 0.68 < {sup IV}Al < 0.82 atoms per formula unit (apfu); octahedral atoms are dominated by Al (1.6-1.8 apfu), with minor and variable Fe (0.20-0.35 apfu) and Mg (0.05-0.17 apfu), and very minor Ti, Mn, and Cr. Total octahedral occupancies are slightly above 2.00 apfu, i.e., there seems to be partial occupancy of the third M site. For all micas, we recorded XAFS spectra on mosaics of carefullymore » separated flakes oriented flat on a plastic support that could be rotated so as to account for the polarization of the synchrotron radiation beam, and we processed them on the basis of the AXANES theory. Spectra show angle-dependent absorption variations for Al and Fe, which can be deconvoluted and fitted by dichroic effects. Pre-edges consistently show most Fe to be Fe{sup 3+} and little angle-dependent intensity variations. The 2M{sub 1}-ferroan muscovite from Antarctica displays the same AXANES behavior as 2M{sub 1}-phengites. By contrast, the ultrahigh-pressure 3T-phengite from Dora Maira (having {sup IV}Al = 0.42 apfu, and Al and Mg as the dominant octahedral constituents) has XAFS spectra that differ significantly. Not only is the {sup IV}Al feature strongly reduced, in agreement with the increased Si content, but also Fe XAFS spectra show one broad feature only, indicating that all Fe is Fe{sup 2+} in a fully disordered distribution with no angle-dependent variations. We conclude that this 3T-phengite is actually contaminated by exsolved Fe-bearing pyrope platelets, which cannot be resolved under SEM examination; by contrast, the 2M{sub 1}-phengites, unrelated to high-pressure, suggest Al/Fe{sup 3+} order over the M1 and (M2, M3) sites, as also does the 2M{sub 1} pegmatitic muscovite.« les

Pressure-induced coordination change of Ti in silicate glass: a XANES study

The effect of pressure on titanium coordination in glasses, with composition K2TiSi4O11, quenched isobarically from liquids equilibrated at high pressure (5, 10, 15, 20, 25, 30 kbar respectively) and T=1600° C has been investigated by X-ray absorption spectroscopy (XAS). The XANES spectra collected at the Ti K-edge clearly show a variation with pressure that is related to changes in the geometrical environment around the Ti atoms. By comparison with spectra of standard materials, the XANES spectra of the glasses suggest a relatively low average coordination number (near 5) in samples quenched at low pressure and a higher coordination number (near 6) in samples quenched from the highest pressure. The combination of XANES data with density and compressibility measurements supports the idea that a mixture of 6- and lower coordinated (4- and/ or 5-coordinated) Ti geometries are present in the 1 bar glass, and an increasing proportion of 6-coordinated Ti occurs in the glasses synthesized at progressively higher pressures

Minerals from the Carpathian Mountains and from Transylvania donated by Joseph II (1785) to the museum of the Collegio Nazareno, Rome, Italy

Abstract The mineralogical museum of the Collegio Nazareno of the Piarists Order in Rome was founded by Gian Vincenzo Petrini c. 1760. It hosted minerals and rocks the Popes had received as gifts and given to Piarists to support their teaching, as well as minerals collected from Roman and Neapolitan volcanoes. On March 24, 1769, the museum was visited by Emperor Joseph II, officially there as an incognito tourist but, in fact, to organize the election of a Pope who would abolish the Jesuit Order. On June 14, 1785 the Emperor, by now King of Hungary as well, presented eight crates of minerals from mining areas in Transylvania and Upper Hungary, i.e. Slovakia. This collection had been organized by “Baron of Born”, who also wrote down descriptions of all the specimens (mostly ores), as referred to in Petrini (1791–92). The museum of the Collegio Nazareno has survived and the royal gift is partially preserved, curated by the Gruppo Mineralogico Romano (GMR), a private association of amateurs founded in 1982. The museum now exhibits a rare collection of minerals from 18th century central Europe, organized according to systematics that just preceeded the major scientific changes brought about in mineralogy by the crystallographic approach

X-ray absorption study of Ti-bearing silicate glasses

Ti K-edge XANES spectra have been collected on a series of Ti-bearing silicate glasses with metasilicate and tetrasilicate compositions. The intensity of the preedge feature in these spectra has been found to change with glass composition and varies from 29 to 58% (normalized intensity) suggesting a variation in structural environent around the absorbing atom. The pre-edge peak intensity increases for the alkali titanium tetrasilicate glasses from 35% to 58% in the order Li < Na < K < Rb, Cs whereas for the metasilicate compositions there is a maximum for the K-bearing glass. The pre-edge peak intensity remains constant for the alkaline earth titanium metasilicate glasses, Ca and Sr (34%) but increases slightly for Ba (41%). As the intensity of this feature is inversely correlated with coordination number, a comparison of the pre-edge intensity data for the investigated glasses with those of materials of known coordination number leads us to establish a regression equation and to infer that the average coordination number of Ti in these glasses ranges from 4.8 to 5.8. Large alkali cations appear to stabilize a relatively low average coordination number for Ti in silicate melts. The Ti structural environment results appear also to vary as a function of SiO2 content within the K2O-TiO2-SiO2 system. A number of physical properties of the melts from which these glasses were quenched and of other Ti-bearing silicate melts, have been determined in recent years. Clear evidence of a variable coordination number of Ti, consistent with the interpretation of the present XANES data is available from density measurements. These and other property determinations are compared with the present spectroscopic observations in an attempt to relate structure and properties in these melts which contain a major component with variable coordination number

Interlayer potassium and its neighboring atoms in micas : Crystal-chemical modeling and XANES spectroscopy

A detailed description of the interlayer site in trioctahedral true micas is presented based on a statistical appraisal of crystal-chemical, structural, and spectroscopic data determined on two sets of trioctahedral micas extensively studied by both X-ray diffraction refinement on single crystals (SC-XRD) and X-ray absorption fine spectroscopy (XAFS) at the potassium K -edge. Spectroscopy was carried out on both random powders and oriented cleavage flakes, the latter setting taking advantage of the polarized character of synchrotron radiation. Such an approach (AXANES) is shown to be complementary to crystal-chemical investigation based on SC-XRD refinement. However, the results are not definitive as they focus on few samples having extreme features only (e.g., end-members, unusual compositions, and samples with extreme and well-identified substitution mechanisms). The experimental absorption K -edge (XANES) for potassium was decomposed by calculation and extrapolated into a full in-plane absorption component (σ||) and a full out-of-plane absorption component (σ⊥). These two patterns reflect different structural features: σ|| represents the arrangement of the atoms located in the mica interlayer space and facing tetrahedral sheets; σ⊥ is associated with multiple-scattering interactions entering deep into the mica structure, thus also reflecting interactions with the heavy atoms (essentially Fe) located in the octahedral sheet. The out-of-plane patterns also provide insights into the electronic properties of the octahedral cations, such as their oxidation states (e.g., Fe2+ and Fe3+) and their ordering (e.g., trans - vs. cis -setting). It is also possible to distinguish between F- and OH-rich micas due to peculiar absorption features originating from the F vs. OH occupancy of the O4 octahedral site. Thus, combining crystal-chemical, structural, and spectroscopic information is shown to be a practical method that allows, on one hand, assignment of the observed spectroscopic features to precise structural pathways followed by the photoelectron within the mica structure and, on the other hand, clarification of the amount of electronic interactions and forces acting onto the individual atoms at the various structural sites

Fifty years since the first European synchrotron-radiation-derived XAFS spectrum (Frascati, 1963)

The first absorption spectra recorded in Europe using synchrotron radiation as the X-ray source were theK-edge of Al and theLIII-edge of Cu taken at Frascati electron synchrotron in May 1963 by the French–Italian group comprised of Y. Cauchois, C. Bonnelle and G. Missoni