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The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature T g, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near T g. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different. [ABSTRACT FROM AUTHOR]

Long-lived active lava lakes are comparatively rare and are typically associated with low-viscosity basaltic magmas. Erebus volcano, Antarctica, is unique today in hosting a phonolitic lava lake. Phonolitic magmas can erupt explosively, as in the 79 CE Plinian eruption of Vesuvius volcano, Italy, and it is therefore important to understand their physical properties. The phonolite at Erebus has slightly higher silica content than that at Vesuvius yet its present activity is predominantly non-explosive. As a contribution to understanding such contrasting eruptive behaviour, we focus on the rheological differences between these comparable magmas. In particular, we evaluate the viscosity of the Erebus phonolite magma by integrating new experimental data within a theoretical and empirical framework. The resulting model enables estimation of the Erebus melt viscosity as a function of temperature, crystal and water concentrations, with an uncertainty of, at most, ± 0.45 log (Pa s). Using reported ranges for these parameters, we predict that the magma viscosity in the upper region of the plumbing system of Erebus ranges between 10 5 and 10 7 Pa s . This is substantially higher than has been hitherto considered with significant implications for modelling the dynamics of the lava lake, conduit and magma reservoir system. Our analysis highlights the generic challenges encountered in calculation of magma viscosity and presents an approach that can be applied to other cases. [ABSTRACT FROM AUTHOR]

Abstract: Dissociation of water into protons and hydroxyl ions is a fundamental feature of aqueous solutions. Although it exerts a profound influence on properties of magmas, this autoprotolysis reaction has been hitherto neglected for water dissolved in silicate melts. As made here with an acid–base model, in fact one has to deal with molecular water (H2Omol) and two kinds of hydroxyl groups, bonded or not to network-forming cations (OH and OH−, respectively) in hydrous silicate melts. By mixing cations and anions on distinct sublattices and quantifying the disproportionation of water dissolved in silicate melts into its ionic products, H+ and OH−, we reconcile spectroscopic determinations of water speciation, and highlight the main compositional features involving chemical exchanges between H2Omol, T OH and M OH groups (T and M being a former and a modifier, respectively). In particular, water addition to depolymerized systems, such as basalts, determine a relative predominance of OH− with respect to silicic systems, such that the increase of water concentration tends to immediately limit depolymerization rather than enhance it. This opens new perspectives to the understanding of the chemical control of hydrous magmas and their physical properties, as well as the attainment of saturation in hydrous minerals such as amphiboles or micas, particularly in depolymerized melts. [Copyright &y& Elsevier]