Search

Abstract: Recent developments documenting high temperature isotope fractionations of a variety of elements (Li, Mg, Si, Ca, Fe, Ni) by a variety of processes (evaporation, chemical diffusion and thermal diffusion) are reviewed along with some recent applications of these fractionations to Earth and meteoritic problems. [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: A first order characteristic of the relative abundance of the elements in solar system materials ranging in size from inclusions in primitive meteorites to planetary sized objects such as the Earth and the Moon is that they are very much like that of the Sun for the more refractory elements but systematically depleted to varying degrees in the more volatile elements. This is taken as evidence that evaporation and and/or condensation were important processes in determining the distinctive chemical properties of solar system materials. In some instances there is also isotopic evidence suggesting evaporation in that certain materials are found enriched in the heavy isotopes of their more volatile elements. Here model calculations are used to explore how the relative rates of various key processes determine the relationship between elemental and isotopic fractionation during partial evaporation and partial condensation. The natural measure of time for the systems considered here is the evaporation or condensation timescale defined as the time it would take under the prevailing conditions for evaporation or condensation to completely transfer the element of interest between the two phases of the system. The other timescales considered involve the rate of change of temperature, the rate at which gas is removed from further interaction with the condensed phase, and the rates of diffusion in the condensed and gas phases. The results show that a key determinant of whether or not elemental fractionations have associated isotopic effects is the ratio of the partial pressure of a volatile element (Pi) to its saturation vapor pressure (Pi,sat) over the condensed phase. Systems in which the rate of temperature change or of gas removal are slow compared to the evaporation or condensation timescale will be in the limit Pi ∼ Pi,sat and thus will have little or no isotopic fractionation because at the high temperatures considered here there is negligible equilibrium fractionation of isotopes. If on the other hand the temperature changes are relatively fast, then Pi ≠ Pi,sat and there will be both elemental and isotopic fractionation during partial evaporation or partial condensation. Rapid removal of evolved gas results in Pi ≪ Pi,sat which will produce isotopically heavy evaporation residues. Diffusion-limited regimes, where transports within a phase are not sufficiently fast to maintain chemical and or isotopic homogeneity, will typically produce less isotopic fractionation than had the phases remained well mixed. The model results are used to suggest a likely explanation for the heavy silicon and magnesium isotopic composition of Type B CAIs (as due to rapid partial melting and subsequent cooling at rates of a few °C per hour), for the uniformity of the potassium isotopic composition of chondrules despite large differences in potassium depletions (as due to volatilization of potassium by reheating in regions of large but variable chondrules per unit volume), and that the remarkable uniformity of the potassium isotopic composition of solar system materials is not a measure of the relative importance of evaporation and condensation but rather due to the solar nebula having evolved sufficiently slowly that materials did not significantly depart from chemical equilibrium. [Copyright &y& Elsevier]

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]