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Abstract: Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100–200°C from one end to the other. The chemical diffusion experiments showed fractionations of 26Mg/24Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to with β =0.05. The thermal diffusion experiments showed that a temperature difference of about 100°C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1wt% in the colder end while SiO2 was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150°C produced an 8‰ enrichment of 26Mg/24Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6×10−2‰/°C/amu. [Copyright &y& Elsevier]

Abstract: Vacuum evaporation experiments with Type B CAI-like starting compositions were carried out at temperatures of 1600, 1700, 1800, and 1900°C to determine the evaporation kinetics and evaporation coefficients of silicon and magnesium as a function of temperature as well as the kinetic isotope fractionation factor for magnesium. The vacuum evaporation kinetics of silicon and magnesium are well characterized by a relation of the form J = J oe−E/RT with J o =4.17×107 molcm−2 s−1, E =576±36kJmol−1 for magnesium, J o =3.81×106 molcm−2 s−1, E =551±63kJmol−1 for silicon. These rates only apply to evaporation into vacuum whereas the actual Type B CAIs were almost certainly surrounded by a finite pressure of a hydrogen-dominated gas. A more general formulation for the evaporation kinetics of silicon and magnesium from a Type B CAI-like liquid that applies equally to vacuum and conditions of finite hydrogen pressure involves combining our determinations of the evaporation coefficients for these elements as a function of temperature (γ = γ 0e−E/RT with γ 0 =25.3, E =92±37kJmol−1 for γ Si; γ 0 =143, E =121±53kJmol−1 for γ Mg) with a thermodynamic model for the saturation vapor pressures of Mg and SiO over the condensed phase. High-precision determinations of the magnesium isotopic composition of the evaporation residues from samples of different size and different evaporation temperature were made using a multicollector inductively coupled plasma mass spectrometer. The kinetic isotopic fractionation factors derived from this data set show that there is a distinct temperature effect, such that the isotopic fractionation for a given amount of magnesium evaporated is smaller at lower temperature. We did not find any significant change in the isotope fractionation factor related to sample size, which we interpret to mean that recondensation and finite chemical diffusion in the melt did not affect the isotopic fractionations. Extrapolating the magnesium kinetic isotope fractionations factors from the temperature range of our experiments to temperatures corresponding to partially molten Type B CAI compositions (1250–1400°C) results in a value of α Mg ≈0.991, which is significantly different from the commonly used value of . [Copyright &y& Elsevier]

Abstract: Type B CAIs are subdivided into B1s, with well-developed melilite mantles, and B2s, with randomly distributed melilite. Despite intensive study, the origin of the characteristic melilite mantle of the B1s remains unclear. Recently, we proposed that formation of the melilite mantle is caused by depletion of the droplet surface in volatile magnesium and silicon due to higher evaporation rates of volatile species compared to their slow diffusion rates in the melt, thus making possible crystallization of melilite at the edge of the CAI first, followed by its crystallization in the central parts at lower temperatures. Here, we present the results of an experimental study that aimed to reproduce the texture observed in natural Type B CAIs. First, we experimentally determined crystallization temperatures of melilite for three melt compositions, which, combined with literature data, allowed us to find a simple relationship between the melt composition, crystallization temperature, and composition of first crystallizing melilite. Second, we conducted a series of evaporation and cooling experiments exposing CAI-like melts to gas mixtures with different oxygen fugacities . Cooling of the molten droplets in gases with resulted in crystallization of randomly distributed melilite, while under more reducing conditions, melilite mantles have been formed. Chemical profiles through samples quenched right before melilite started to crystallize showed no chemical gradients in samples exposed to relatively oxidizing gases , while the near-surface parts of the samples exposed to very reducing gases were depleted in volatile MgO and SiO2, and enriched in refractory Al2O3. Using these experimental results and the fact that the evaporation rate of magnesium and silicon from CAI-like melts is proportional to , we estimate that Type B1 CAIs could be formed by evaporation of a partially molten precursor in a gas of solar composition with . Type B2 CAIs could form by slower evaporation of the same precursors in the same gas with . [Copyright &y& Elsevier]

Experiments exposing Type B calcium-, aluminum-rich inclusion (CAI)-like melts at high temperatures to high vacuum or reducing hydrogen-rich gas mixtures were used to determine the rates and consequences of elemental and isotopic fractionation by evaporation. Silicon and magnesium were found to evaporate much faster than calcium and aluminum, and the resulting residual liquid trajectories in composition space are reproduced via a thermodynamic model for the saturation vapor pressure of the evaporating species. Isotopic fractionations associated with evaporation were measured for magnesium. The resulting relationship between fraction of magnesium lost and enrichment of the residue in the heavy isotopes of magnesium follows a Rayleigh fractionation curve with a fractionation factor that is close to, but not exactly, the theoretically expected value. The rate of evaporation is found to be a strong function of temperature, oxygen fugacity, and melt composition, which can be understood and modeled in terms of the dependence of the saturation vapor pressures on these variables. The relationship between evaporation rate, which we measure, and calculated saturation vapor involves empirical evaporation coefficients that we find to be significantly less than one (∼0.1). Analytical and numerical models are used to characterize how diffusion in both the melt and in the surrounding gas affects evaporation rates and the degree of chemical and isotopic fractionation. The experimental data and theoretical considerations are combined to give a parameterization of the rates and consequences of evaporation of Type B CAI-like liquids, which is then used to translate the measured isotopic fractionation of Type B CAIs into constraints on their thermal history. Cooling rates of the order of 10°C per hour are indicated. [Copyright &y& Elsevier]

Arising from F. Huang, P. et al. 464, 396-400 (2010); Huang et al. replyIt was recently shown that relatively large (compared to analytical precision) steady state thermal isotope fractionations are produced in silicate melts whenever temperature differences are maintained for a sufficiently long time. Huang et al. reported new data on thermal isotopic fractionation of magnesium, calcium, and iron in silicate liquids, and claimed (1) that thermal isotopic fractionations in silicate liquids are independent of composition and temperature, and (2) that their 'results lead to a simple and robust framework for characterizing isotope fractionations by thermal diffusion in natural and synthetic systems'. Here I consider whether the data and arguments presented by Huang et al. support their claims. In summary, I caution against assuming (on the basis of the data presented by Huang et al.) that the thermal isotopic fractionations are independent of temperature and composition, or that a framework of the type claimed has been found. [ABSTRACT FROM AUTHOR]

It is widely believed that the precursors of coarse-grained CAIs in chondrites are solar nebula condensates that were later reheated and melted to a high degree. Such melting under low-pressure conditions is expected to result in evaporation of moderately volatile magnesium and silicon and their mass-dependent isotopic fractionation. The evaporation of silicate melts has been extensively studied in vacuum laboratory experiments and a large experimental database on chemical and isotopic fractionations now exists. Nevertheless, it remains unclear if vacuum evaporation of CAI-like melts adequately describes the evaporation in the hydrogen-rich gas of the solar nebula. Here we report the results of a detailed experimental study on evaporation of a such melt at 1600 °C in both vacuum and low-pressure hydrogen gas, using 1.5- and 2.5-mm diameter samples. The experiments show that although at 2 × 10−4 bar H 2 magnesium and silicon evaporate ∼2.8 times faster than at 2 × 10−5 bar H 2 and ∼45 times faster than in vacuum, their relative evaporation rates and isotopic fractionation factors remain the same. This means that the chemical and isotopic evolutions of all evaporation residues plot along a single evaporation trajectory regardless of experimental conditions (vacuum or low-P H2) and sample size. The independence of chemical and isotopic evaporation trajectories on P H2 of the surrounding gas imply that the existing extensive experimental database on vacuum evaporation of CAI-like materials can be safely used to model the evaporation under solar nebula conditions, taking into account the dependence of evaporation kinetics on P H2. The experimental data suggest that it would take less than 25 min at 1600 °C to evaporate 15–50% of magnesium and 5–20% of silicon from a 2.5-mm diameter sample in a solar nebula with P H2 ∼2 × 10−4 bar and to enrich the residual melt in heavy magnesium and silicon isotopes up to δ25Mg ∼5–10‰ and δ29Si ∼2–4‰. The expected chemical and isotopic features are compatible to those typically observed in coarse-grained Type A and B CAIs. Evaporation for ∼1 h will produce δ25Mg ∼30–35‰ and δ29Si ∼10–15‰, close to the values in highly fractionated Type F and FUN CAIs. These very short timescales suggest melting and evaporation of CAI precursors in very short dynamic heating events. The experimental results reported here provide a stringent test of proposed astrophysical models for the origin and evolution of CAIs. [ABSTRACT FROM AUTHOR]

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [ α 2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium ( α 25,24 for 25 Mg/ 24 Mg), silicon ( α 29,28 for 29 Si/ 28 Si) and oxygen ( α 18,16 for 18 O/ 16 O) from the forsterite-rich melt at 1900 °C. The values of α 25,24 = 0.98383 ± 0.00033 and α 29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α 18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α 25,24 and α 29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1. [ABSTRACT FROM AUTHOR]