RESUMEN
The initial melts erupted by a Hawaiian volcano have a range of alkalic compositions but are rarely observed as they are covered by enormous volumes of shield stage tholeiites. A remarkable record of the early evolution of Hawaiian volcanoes, however, is preserved by a volcanic sandstone dredged from the submarine flank of Kilauea, which contains a suite of petrogenetically related pre-shield basanite to nephelinite glasses. Here we show that the systematic variation in the rare earth element (REE) patterns of these samples requires the fractional crystallisation of garnet. A fractionating assemblage of Ca-rich garnet (32%), omphacitic clinopyroxene (63%), and minor phlogopite can explain the variation in the major and trace element contents of the suite. The results suggest fractional crystallisation of eclogite from a primitive Hawaiian melt near the base of the lithosphere (>90 km) and that a deep magma chamber is the first stage in the development of a Hawaiian volcano.
RESUMEN
Raman spectra were obtained simultaneously from the liquid and vapor phases of pure water trapped at the critical density (322 kg·m-3) within synthetic inclusions in quartz. As these inclusions are heated up to the critical temperature (373.946 °C), the liquid phase decreases in density and the maximum of the Raman OH-stretching band increases in wavenumber. Conversely, as the vapor phase increases in density, the maximum of the Raman OH-stretching band decreases in wavenumber. The Raman bands of the liquid and vapor phases converge to a single band at the critical point of water, where the fluid exists as a single phase. A comparison of the band centroids for the vapor and liquid phases of water indicates respective increases and decreases in the amount of hydrogen bonding in these phases as a function of increasing and decreasing density. These effects were further quantified by peak-fitting the Raman OH-stretching peak with five Gaussian components. All the Gaussian components of the liquid phase decrease in amplitude with increasing temperature with the exception of the double donor-single acceptor (H2O)4 cluster, which increases in amplitude and becomes the most intense component at temperatures above 300 °C. The Raman spectra of the vapor phase are dominated by the free OH component at temperatures below 300 °C, but, above this temperature, the double donor-single acceptor (H2O)4 cluster is again the most intense band. The results indicate that a significant quantity of water clusters is present in both liquid and vapor water at high temperatures and that supercritical water can be considered as a mixture of small water clusters [(H2O)n, n = 1-4] dominated by the double donor-single acceptor (H2O)4 cluster.
RESUMEN
Understanding the links between chemical composition, nano-structure and the dynamic properties of silicate melts and glasses is fundamental to both Earth and Materials Sciences. Central to this is whether the distribution of mobile metallic ions is random or not. In silicate systems, such as window glass, it is well-established that the short-range structure is not random but metal ions cluster, forming percolation channels through a partly broken network of corner-sharing SiO4 tetrahedra. In alumino-silicate glasses and melts, extensively used in industry and representing most of the Earth magmas, metal ions compensate the electrical charge deficit of AlO4- tetrahedra, but until now clustering has not been confirmed. Here we report how major changes in melt viscosity, together with glass Raman and Nuclear Magnetic Resonance measurements and Molecular Dynamics simulations, demonstrate that metal ions nano-segregate into percolation channels, making this a universal phenomenon of oxide glasses and melts. Furthermore, we can explain how, in both single and mixed alkali compositions, metal ion clustering and percolation radically affect melt mobility, central to understanding industrial and geological processes.