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This work presents the results of a microthermometric and EPMA-SIMS study of melt inclusions in phenocrysts of rocks of the shoshonitic eruptive complex of Vulcano (Aeolian Islands, Italy). Different primitive magmas related to two different evolutionary series, an older one (50-25 ka) and a younger one (15 ka to 1890 A.D.), were identified as melt inclusions in olivine Fo 88-91 crystals. Both are characterized by high Ca/Al ratio and present very similar Rb/Sr, B/Be and patterns of trace elements, with Nb and Ti anomalies typical of a subduction zone. The two basalts present the same temperature of crystallization (1180B20 7C) and similar volatile abundances. The H 2 O, S and Cl contents are relatively high, whereas magmatic CO 2 concentrations are very low, probably due to CO 2 loss before low-pressure crystallization and entrapment of melt inclusions. The mineral chemistry of the basaltic assemblages and the high Ca/Al ratio of melt inclusions indicate an origin from a depleted, metasomatized clinopyroxene-rich peridotitic mantle. The younger primitive melt is characterized with respect to the older one by higher K 2 O and incompatible element abundances, by lower Zr/Nb and La/Nb, and by higher Ba/Rb and LREE enrichment. A different degree of partial melting of the same source can explain the chemical differences between the two magmas. However, some anomalies in Sr, Rb and K contents suggest either a slightly different source for the two magmas or differing extents of crustal contamination. Low-pressure degassing and cooling of the basaltic magmas produce shoshonitic liquids. The melt inclusions indicate evolutionary paths via fractional crystallization, leading to trachytic compositions during the older activity and to rhyolitic compositions during the recent one. The bulk-rock compositions record a more complex history than do the melt inclusions, due to the syneruptive mixing processes commonly affecting the magmas erupted at Vulcano. The composition and temperature data on melt inclusions suggest that in the older period of activity several shallow magmatic reservoirs existed; in the younger one a relatively homogeneous feeding system is active. The shallow magmatic reservoir feeding the recent eruptive activity probably has a vertical configuration, with basaltic magma in the deeper zones and differentiated magmas in shallower, low-volume, dike-like reservoirs.

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International audienceThe development of an accurate analytical procedure for determination of dissolved water in complex alumino-silicate glasses via micro-Raman analysis requires the assessment of the spectra topology dependence on glass composition. We report here a detailed study of the respective influence of bulk composition, iron oxidation state and total water content on the absolute and relative intensities of the main Raman bands related to glass network vibrations (LF: not, vert, similar490 cm−1; HF: not, vert, similar960 cm−1) and total water stretching (H2OT: not, vert, similar3550 cm−1) in natural glasses. The evolution of spectra topology was examined in (i) 33 anhydrous glasses produced by the re-melting of natural rock samples, which span a very large range of polymerisation degree (NBO/T from 0.00 to 1.16), (ii) 2 sets of synthetic anhydrous basaltic glasses with variable iron oxidation state (Fe3+/FeT from 0.05 to 0.87), and (iii) 6 sets of natural hydrous glasses (CH2OT from 0.4 to 7.0 wt%) with NBO/T varying from 0.01 to 0.76. In the explored domain of water concentration, external calibration procedure based on the H2OT band height is matrix-independent but its accuracy relies on precise control of the focusing depth and beam energy on the sample. Matrix-dependence strongly affects the internal calibrations based on H2OT height scaled to that of LF or HF bands but its effect decreases from acid (low NBO/T, SM) to basic (high NBO/T, SM) glasses. Structural parameters such as NBO/T (non-bridging oxygen per tetrahedron) and SM (sum of structural modifiers) describe the matrix-dependence better than simple compositional parameters (e.g. SiO2, Na2O + K2O). Iron oxidation state has only a minor influence on band topology in basalts and is thus not expected to significantly affect the Raman determinations of water in mafic (e.g. low SiO2, iron-rich) glasses. Modelling the evolution of the relative band height with polymerisation degree allows us to propose a general equation to predict the dissolved water content in natural glasses: View the MathML source where CH2OT is the total water content (in wt%) dissolved in glass; TOTN represents the computed ILF/IHF variation as a function of the calculated NBO/T and SM parameters; IH2ON is the H2O band height scaled to ratio of the reference bands; k is the linearity spectrometer response on the H2OT band in function of water content. The water concentrations of the reference glasses are reproduced using this equation with a standard deviation of 0.06 wt%. The adopted parameterisation provides a useful tool towards the characterisation of composition dependence of micro-Raman procedures for silicate glasses. We show, based on the widest range of glass compositions so far investigated, that accurate evaluation of dissolved water content is achieved by micro-Raman spectroscopy