Description: We present a new hydrothermal moissanite cell for in situ experiments at pressures up to 1000 bar and temperature to 850 °C. The original moissanite cell presented by Schiavi et al. (2010) was redesigned to allow precise control of fluid pressure. The new device consists of a cylindrical sample chamber drilled into a bulk piece of NIMONIC 105 super alloy, which is connected through a capillary to an external pressure control system. Sealing is provided by two gold gasket rings between the moissanite windows and the sample chamber. The new technique allows the direct observation of various phenomena, such as bubble nucleation, bubble growth, crystal growth, and crystal dissolution in silicate melts, at accurately controlled rates of heating, cooling, and compression or decompression. Several pilot experiments on bubble nucleation and growth at temperature of 715 °C and under variable pressure regimes (pressure oscillations between 500 and 1000 bar and decompression from 800 to 200 bar at variable decompression rates) were conducted using a haplogranitic glass as starting material. Bubble nucleation occurs in a short single event upon heating of the melt above the glass transition temperature and upon decompression, but only during the first 100 bar of decompression. New bubbles nucleate only at a distance from existing bubbles larger than the mean diffusive path of water in the melt. Bubbles expand and shrink instantaneously in response to any pressure change. The bubble-bubble contact induced during pressure cycling and decompression does not favor bubble coalescence, which is never observed at contact times shorter than 60 s. However, repeated pressure changes favor the diffusive coarsening of larger bubbles at the expense of the smaller ones (Ostwald ripening). Experiments with the haplogranite show that, under the most favorable conditions of volatile supersaturation (as imposed by the experiment), highly viscous melts are likely to maintain the packing of bubbles for longer time before fragmentation. In-situ observations with the new hydrothermal moissanite cell allow to carefully assess the conditions of bubble nucleation, eliminating the uncertainty given by the post mortem observation of samples run using conventional experimental techniques.

Description: We have studied the speciation of carbon monoxide in both Fe-bearing and Fe-free basaltic glasses using Raman, FTIR, and Mössbauer spectroscopy. We show that a band at 2110 cm –1 in the Raman spectrum and another band at 2210 cm –1 in the FTIR spectrum occur both in the Fe-bearing and Fe-free samples, implying that they cannot be due to any Fe-bearing species. This observation is consistent with 57 Fe Mössbauer spectra, which do not show any evidence for Fe species with zero isomer shift, as expected for carbonyls. Thermodynamic calculations show that iron carbonyl in basaltic melts under crustal and upper mantle conditions may only be a trace species. Rather than being due to distinct chemical species, the range of vibrational frequencies observed for carbon monoxide in silicate glasses appears to be due to rather subtle interactions of the CO molecule with the matrix. Similar effects are known from the extensive literature on carbon monoxide adsorption on oxides and other surfaces. In the melt at high temperature, there is likely little interaction of the CO molecule with the silicate matrix and solubility may be largely controlled by pressure, temperature, and the overall polymerization or ionic porosity of the melt.

Description: Melt inclusion data from primitive arc basalts from Mexico and Kamchatka show clear positive correlations of "fluid mobile element"/H 2 O ratios with the Cl/H 2 O ratio, suggesting that the trace element content of subduction zone fluids is strongly enhanced by complexing with chloride. This effect is observed for large-ion lithophile (LILE) elements, (e.g., Rb and Sr), but also for the light rare earth elements (REE, e.g., La and Ce) as well as for U. The correlations of these elements with Cl/H 2 O cannot be explained by the addition of sediment melts or slab melts to the mantle source, since Cl has no effect on the solubility or partitioning of these elements in silicate melt systems. On the other hand, the observed relationship of trace element abundance with Cl is consistent with a large body of experimental data showing greatly enhanced partitioning into aqueous fluid upon addition of chloride. Accordingly, it appears that a dilute, Cl-bearing aqueous fluid is the main carrier of LILE, light REE, and U from the slab to the source of melting in arcs. Moreover, elevated Ce/H 2 O ratios clearly correlate with fluid salinity and therefore are not suitable as a "slab geothermometer." From a synopsis of experimental and melt inclusion data, it is suggested that the importance of sediment or slab melting in the generation of arc magmas is likely overestimated, while the effects of trace element scavenging from the mantle wedge may be underestimated. Moreover, establishing reliable data sets for the fluid/mineral partition coefficients of trace elements as a function of pressure, temperature, and salinity requires additional efforts, since most of the commonly used experimental strategies have severe drawbacks and potential pitfalls.