Water can form different chemical bonds with the ionic entities composing silicate melts. Because of that, its influence on the physico-chemical properties of magmas can vary with silicate composition and water content, temperature, and pressure. To further our understanding of how silicate chemical composition governs proton distribution in magmas, the environment of protons in hydrous alkali (Li, Na, K) silicate glasses was varied as a function of the type of alkali metal and total water content. From H-1 MAS NMR spectroscopy, H+ are distributed among five different structural environments in alkali silicate glasses. One of these environments is in the form of H2O molecules (H2Omol). The four others are the proton environments associated with Si-OH bonding, and perhaps also with M-OH bonding (with M = Li, Na, or K). Those environments differ in their O-O distance and extent of hydrogen bonding. H2Omol, species are located in an environment with an O-O distance of similar to 290 pm. OH- groups are in environments with O-O distances from 240 to 305 pm. The ionic radius of the alkalis, and hence their ionic field strength, determines the fraction of water dissolved as H2Omol and OH- groups, as well as the distribution of protons in the various OH- environments. The mean volume of the H+ oxygen coordination sphere was calculated using the H-1(+) NMR signal intensity and the mean O-O distance around H+. Increasing ionic radius of the alkali metal in silicate glasses results in a decrease of this mean volume. The partial molar volume of water in the corresponding melts determined through other technics seems to vary in a comparable way. Therefore, the chemical composition of silicate melts may control the partial molar volume of dissolved water because of its influence on the structural environment of protons. This probably also plays a role in determining water solubility.

Carbon speciation in and partitioning among silicate-saturated C-O-H fluids and (C-0-H)-saturated melts have been determined similar to 1.7 GPa and 900 degrees C under reducing and oxidizing conditions. The measurements were conducted in situ while the samples were at the conditions of interest. The solution equilibria were (1) 204(4) + Q(n) = 2CH(3)(-) + H2O + Q(n+1) and (2) 2CO(3)(2-) + H2O + 2Q(n+1) = HCO3- + 2Q(n), under reducing and oxidizing conditions, and where the superscript, n, in the Q(n)species denotes number of bridging oxygen in the silicate species (Q-species). The abundance ratios, CH3/CH4 and HCO3-/CO32-, increase with temperature. The enthalpy change associated with the species transformation differs for fluids and melts and also for oxidized and reduced carbon [Reducing: Delta H-(1)(fluid) = 16 +/- 5 kJ/mol, Delta H-(1)(melt) = 50 +/- 5 kJ/mol; oxidizing Delta H-(2)(fluid) = 81 +/- 14 kJ/mol]. For the exchange equilibrium of CH4 and CH3 species between fluid and melt, the temperature-dependent equilibrium constant (XCH4/XCH3)(fluid)/(XCH4/XCH3)(melt), yields Delta H = 34 +/- 3 kJ/mol.

Previous studies of hydrous glasses and melts with infrared spectroscopy have led to the conclusion that the IR combination peaks near 4500 and 5200 cm(-1) reflect the existence of OH- (hydroxyl) groups and H2Omol water molecules in those materials. Here, we show that the glass chemical composition can impact profoundly the intensities and frequencies of the fundamental O-H stretching signal and, therefore, potentially those of the 4500 and 5200 cm(-1) combination peaks. In alkali silicate glasses, compositional effects can give rise to peaks assigned to fundamental O-H stretching at frequencies as low as 2300 cm(-1). This expanded range of Raman intensity assigned to O-H stretch is increasingly important as the ionic radius of the alkali metal increases. As a result, the combination of the fundamental O-H stretch in OH- groups with the Si-O-H stretch located near 910 cm(-1) gives rise to a complex combination signal that can extend to frequencies much lower than 4200 cm(-1). This combination signal then becomes unresolvable from the high-frequency limb of the band assigned to fundamental O-H stretch vibration in the infrared spectra. It follows that, when O-H stretch signals from OH- groups extend to below 3000 cm(-1) the 4500 cm(-1) peak does not represent the total OH- signal. Under such circumstances, this infrared peak may not be a good proxy for determining the concentration of OH- hydroxyl groups for glassy silicate materials.

Degassing of water during the ascent of hydrous magma in a volcanic edifice produces dramatic changes in the magma density and viscosity. This can profoundly affect the dynamics of volcanic eruptions. The water exsolution history, in turn, is driven by the water solubility and solution mechanisms in the silicate melt. Previous studies pointed to dissolved water in silicate glasses and melts existing as molecules (H2Omol species) and hydroxyl groups, OH. These latter OH groups commonly are considered bonded to Si4+ but may form other bonds, such as with alkali or alkaline-earth cations, for instance. Those forms of bonding influence the structure of hydrous melts in different ways and, therefore, their properties. As a result, exsolution of water from magmas may have different eruptive consequences depending on the initial bonding mechanisms of the dissolved water. However, despite their importance, the solution mechanisms of water in silicate melts are not clear. In particular, how chemical composition of melts affects water solubility and solution mechanism is not well understood. In the present experimental study, components of such information are reported via determination of how water interacts with the cationic network of alkali (Li, Na, and K) silicate quenched melts. Results from Si-29 single-pulse magic-angle spinning nuclear magnetic resonance (Si-29 SP MAS NMR), infrared, and Raman spectroscopies show that decreasing the ionic radius of alkali metal cation in silicate melts results in decreasing fraction of water dissolved as OH groups. The nature of OH bonding also changes as the alkali ionic radius changes. Therefore, as the speciation and bonding of water controls the degree of polymerization of melts, water will have different effects on the transport properties of silicate melts depending on their chemical composition. This conclusion, in turn, may affect volcanic phenomena related to the viscous relaxation of hydrous magmas, such as for instance the fragmentation process that occurs during explosive eruptions.

The hydrogen isotopic composition of melt inclusions trapped in phenocrysts during their crystallization and growth in a magma may contribute to a better understanding of the water cycle between the atmosphere, the hydrosphere and the lithosphere. Such understanding relies on the knowledge of the hydrogen isotopic fractionation factors between aqueous fluids, silicate melts, and minerals at temperature and pressure conditions relevant to the Earth's interior. Significant D/H fractionation between silicate melts and aqueous fluids was reported at hundreds of MPa and degrees C by using in situ measurements in hydrothermal diamond anvil cell (HDAC) experiments (Mysen, 2013a, 2013b, Am. Mineral. 98, 376-386 and 1754-1764). However, the available dataset is focused on fluids and melts with D/H ratios close to unity. The relevance of such data for natural processes that involve per mil variations of delta D-values may not always be clear. To address such concerns, the effect of the bulk D/H ratio on hydrogen isotope partitioning between water-saturated silicate melts and coexisting silicate-saturated aqueous fluids has been determined in the Na2O-Al2O3-SiO2-H2O-D2O system. To this end, in situ Raman spectroscopic measurements were performed on fluids and melts with bulk D/H ratios from 0.05 to 2.67 by using an externally-heated diamond anvil cell in the 300-800 degrees C and 200-1500 MPa temperature and pressure range, respectively.

The solubility and solution behavior of F and Cl in peralkaline aluminosilicate compositions in the systems Na2O-Al2O3-SiO2 and K2O-Al2O2O3-SiO2 have been determined for glasses quenched from melts equilibrated at 1400 and 1600 degrees C in the 1.0-2.5 GPa pressure range. With Al/(Al+Si) increasing from 0 to 0.33 in sodium aluminosilicate melts, F solubility (saturation concentration) increases from 3.3 to 7.4 mol%, whereas Cl solubility decreases from 5.7 to 2.5 mol%. There is no difference in F solubility in sodium or potassium aluminosilicate melts. However, the Cl solubility in potassic aluminosilicate melts is 40-60% lower than in sodic melts with the same AU(Al+Si) and Na or K mole fraction.

The interplay between the chemical composition and the molecular structure of silicate melts was central to the evolution of the Earth's crust, mantle and core. This interplay also affects geochemical records such as the partitioning of isotopes between minerals, melts and fluids in the Earth's interior. For instance, large H-2/H-1 fractionations between silicate melts and aqueous fluids have been observed at high temperature and pressure. Such behaviour may be promoted by the occurrence of H-2/H-1 intramolecular fractionation within the molecular structure of silicate melts. New Raman spectroscopy and H-1 and H-2 Nuclear Magnetic Resonance (NMR) spectroscopy data reveal the source of such H-2/H-1 intramolecular isotopic fractionation, showing that H-1 and H-2 fractionate between the silicate tetrahedral units. Such a process might affect other isotopic systems (e.g., N, C, or S) where the isotopes interact with the melt silicate network.

The behavior of volatiles in silicate-COH melts and fluids and hydrogen isotope fractionation between melt and fluid were determined experimentally to advance our understanding of the role of volatiles in magmatic processes. Experiments were conducted in situ while the samples were at the desired temperature and pressure to 825 degrees C and similar to 1.6 GPa and with variable redox conditions. Under oxidizing conditions, melt and fluid comprised CO2, CO3, HCO3, OH, H2O, and silicate components, whereas under reducing conditions, the species were CH4, H-2, H2O, and silicate components. Temperature-dependent hydrogen isotope exchange among structural entities within coexisting fluids and melts yields Delta H values near 14 and 24 kJ/mol and -5 and -1 kJ/mol under oxidizing and reducing conditions, respectively. This temperature (and probably pressure)-dependent D/H fractionation is because of interaction between D and H and silicate and C-bearing species in silicate-saturated fluids and in COH fluid-saturated melts. The temperature-and pressure-dependent D/H fractionation factors suggest that partial melts in the presence of COH volatiles in the upper mantle can have delta D values 100% or more lighter relative to coexisting silicate-saturated fluid. This effect is greater under oxidizing than under reducing conditions. It is suggested that delta D variations of upper mantle mid-ocean ridge basalt (MORB) sources, inferred from the delta D of MORB magmatic rocks, can be explained by variations in redox conditions during melting. Lower delta D values of the MORB magma reflect more reducing conditions in the mantle source.

The behavior of melts and fluids is at the core of understanding formation and evolution of the Earth. To advance our understanding of their role, high-pressure/-temperature experiments were employed to determine melt and fluid structure together with carbon isotope partitioning within and between (CH4 + H2O + H-2)-saturated aluminosilicate melts and (CH4 + H2O + H-2)-fluids. The samples were characterized with vibrational spectroscopy while at temperatures and pressures from 475 degrees to 850 degrees C and 92 to 1158 MPa, respectively.

Throughout the Earth's history, mass transport involved fluids. In order to address the circumstances under which Zr4+ may have been transported in this manner, its solubility behavior in aqueous fluid with and without NaOH and SiO2 in equilibrium with crystalline ZrO2 was determined from 550 to 950 degrees C and 60 to 1200 MPa. The measurements were carried out in situ while the samples were at the temperatures and pressures of interest. In ZrO2-H2O and ZrO2-SiO2-H2O fluids, the Zr4+ concentration ranges from <= 10 to similar to 70 ppm with increasing temperature and pressure. Addition of SiO2 to the ZrO2-H2O system does not affect these values appreciably. In these two environments, Zr4+ forms simple oxide complexes in the H2O fluid with Delta H similar to 40 kJ/mol for the solution equilibrium, ZrO2(solid) = ZrO2(fluid). The Zr4+ concentration in aqueous fluid increases about an order of magnitude upon addition of 1 M NaOH, which reflects the formation of zirconate complexes. The principal solution mechanism is ZrO2 + 4NaOH = Na4ZrO4 + 2H(2)O with Delta H similar to 200 kJ/mol. Addition of both SiO2 and NaOH to ZrO2-H2O enhances the Zr4+ by an additional factor of about 5 with the formation of partially protonated alkali zircon silicate complexes in the fluid. The principal solution mechanism is 2ZrO(2) + 2NaOH + 2SiO(2) = Na2Zr2Si2O9+ H2O with Delta H similar to 40 kJ/mol. These results, in combination with other published experimental data, imply that fluid released during high-temperature/high-pressure dehydration of hydrous mineral assemblages in the Earth's interior under some circumstances may carry significant concentrations of Zr and probably other high field strength elements (HFSEs). This suggestion is consistent with the occurrence of Zr-rich veins in high-grade metamorphic eclogite and granulite terranes. Moreover, aqueous fluids transported from dehydrating oceanic crust into overlying mantle source rocks of partial melting also may carry high-abundance HFSE of fluids released from dehydrating slabs and transported to the source rock of partial melting in the overlying mantle wedge. These processes may have been operational in the Earth's history within which subduction resembling that observed today was operational.