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The behavior of nitrogen during magmatic degassing and the potential kinetic fractionation between N and other volatile species (H, C, O, noble gases) are poorly known due to the paucity of N diffusion data in silicate melts. To better constrain N mobility during magmatic processes, we investigated N diffusion in silicate melts under reducing conditions. We developed uniaxial diffusion experiments at 1 atm, 1425 °C, and under nominally anhydrous reducing conditions f O 2 $\left(f_{\mathrm{O}_{2}}\right.$ ≤ IW-5.1, where IW is oxygen fugacity, fO2, reported in log units relative to the iron-wüstite buffer), in which N was chemically dissolved in silicate melts as nitride (N3–). Although several experimental designs were tested (platinum, amorphous graphite, and compacted graphite crucibles), only N diffusion experiments at IW-8 in compacted graphite crucibles for simplified basaltic andesite melts were successful. Measured N difusivity (DN) is on the order of 5.3 ± 1.5 × 10–12 m2 s–1, two orders of magnitude lower than N chemical diffusion in soda-lime silicate melts (Frischat et al. 1978). This difference suggests that nitride difusivity increases with an increasing degree of melt depolymerization. The dependence of N3– diffusion on melt composition is greater than that of Ar. Furthermore, N3– diffusion in basaltic-andesitic melts is significantly slower than that of Ar in similarly polymerized andesitic-tholeiitic melts at magmatic temperatures (1400–1450 °C; Nowak et al. 2004). This implies that N/Ar ratios can be fractionated during reducing magmatic processes, such as during early Earth's magma ocean stages. [ABSTRACT FROM AUTHOR]

Mg-rich olivine is a ubiquitous phase in type I porphyritic chondrules in various classes of chondritic meteorites. The anhedral shape of olivine grains, their size distribution, as well as their poikilitic textures within low-Ca pyroxene suggest that olivines suffer dissolution during chondrule formation. Owing to a set of high-temperature experiments (1450-1540 °C) we determined the kinetics of resorption of forsterite in molten silicates, using for the first time X-ray microtomography. Results indicate that forsterite dissolution in chondrule-like melts is a very fast process with rates that range from ~5 μm min−1 to ~22 μm min−1. Forsterite dissolution strongly depends on the melt composition, with rates decreasing with increasing the magnesium and/or the silica content of the melt. An empirical model based on forsterite saturation and viscosity of the starting melt composition successfully reproduces the forsteritic olivine dissolution rates as a function of temperature and composition for both our experiments and those of the literature. Application of our results to chondrules could explain the textures of zoned type I chondrules during their formation by gas-melt interaction. We show that the olivine/liquid ratio on one hand and the silica entrance from the gas phase (SiOg) into the chondrule melt on the other hand, have counteracting effects on the Mg-rich olivine dissolution behavior. Silica entrance would favor dissolution by maintaining disequilibrium between olivine and melt. Hence, this would explain the preferential dissolution of olivine as well as the preferential abundances of pyroxene at the margins of chondrules. Incipient dissolution would also occur in the silica-poorer melt of chondrule core but should be followed by crystallization of new olivine (overgrowth and/or newly grown crystals). While explaining textures and grain size distributions of olivines, as well as the centripetal distribution of low-Ca pyroxene in porphyritic chondrules, this scenario could also be consistent with the diverse chemical, isotopic, and thermal conditions recorded by olivines in a given chondrule. [ABSTRACT FROM AUTHOR]

Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications of the silicate network itself as the glass transition temperature is approached: as the available free volume (available site for diffusive jumps) is modified, noble gas diffusion is no longer solely temperature-activated but also becomes sensitive to the kinetics of network rearrangements. The non-Arrhenian behavior of noble gas diffusion close to Tg is well described by a modified Vogel-Tammann-Fulcher (VTF) equation: D/a² = A1/a² * exp (-B1/R(T -- T2 - C/RT) where D is the diffusion coefficient, a the diffusion domain size (taken to be the size of the sample), A1 and C are respectively equivalent to the pre-exponential factor and to the activation energy (Ea in J mol-1) of the classical Arrhenius equation, B1 can be interpreted as a "pseudo-activation energy" that reflects the influence of the silicate network relaxation, T2 is the temperature where the diffusion regime switches from Arrhenian to non-Arrhenian, and R is the gas constant (=8.314 J K-1 mol-1). Finally, our step heating diffusion experiments suggest that at T close to Tg, noble gas isotopes may suffer kinetic fractionation at a degree larger than that predicted by Graham's law. In the case of 40Ar and 36Ar, the traditional assumption based on Graham's law is that the ratio D 40Ar/D 36Ar should be equal to 0.95 (the square root of the ratio of the mass of 36Ar over the mass of 40Ar). In our experiment with glass G1, D40Ar/D36Ar rapidly decreased with decreasing temperature, from near unity (0.98 ± 0.14) at T > 1040 K to 0.76 when close to Tg (T = 1003 K). Replicate experiments are needed to confirm the strong kinetic fractionation of heavy noble gases close to the transition temperature. [ABSTRACT FROM AUTHOR]