Experiments quantifying elemental and isotopic fractionations during evaporation of CAI-like melts in low-pressure hydrogen and in vacuum : Constraints on thermal processing of CAI in the protoplanetary disk

This work was supported by NASA grant NNX17AE84G (to R.M.). Magnesium isotopic measurements were supported by NSF grant EAR-17407706 (to F.-Z. T.). P.S. and the Si isotope measurements made at the St Andrews Isotope Group (STAiG) at the University of St Andrews were supported by NERC grant NE/R002134/1 a Carnegie Trust Research Incentive Grant. Evaporation experiments at Hokkaido University were supported by the Ministry of Education, Sports, Science, and Technology KAKENHI Grant (to S.T.).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 H2 magnesium and silicon evaporate ∼2.8 times faster than at 2×10−5 bar H2 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-PH2) and sample size. The independence of chemical and isotopic evaporation trajectories on PH2 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 PH2. The experimental data suggest that it would take less than 25 minutes 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 PH2∼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 hour 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.PostprintPeer reviewe

Conditions in the protoplanetary disk as seen by the type B CAIs

Type B coarse-grained calcium-aluminum-rich inclusions (CAIs) are the oldest known materials to have formed in the solar system and are a unique source of information regarding conditions and processes in the protoplanetary disk around the young sun. Recent experimental results on the crystallization and evaporation of type B-like silicate melts allow us to place the following constraints on the conditions in the protoplanetary disk during the formation of type B CAIs. 1) Once type B CAIs precursors have been condensed from a solar composition gas, they were reheated at 1250-1450 degrees C, as is indicated by their igneous texture. 2) The melilite mantles characteristic of type B1 CAIs could be formed by crystallization of magnesium- and silicon-depleted melt in the outer part of the partially molten droplets. Such depletion can arise when evaporation is fast compared to chemical diffusion in the melt. This requires the pressure of the surrounding solar composition gas to be at least 10^(-4) bars during the initial crystallization of melilite mantle. Type B2 CAIs with uniform distribution of melilite are expected to form at pressures less than 10^(-5) bars. 3) Evaporation calculations are used to place bounds on the thermal history of the type B CAIs. Observed compositional zoning in melilite suggests that the temperatures in the protoplanetary disk where the type B CAIs resided after crystallization could not have exceeded ~1000 degrees C for more than a few tens of thousands of years. A recent calculation of the physical conditions associated with nebular shocks produced transient temperatures and gas pressures very much like what we find is required to melt reasonable CAI precursors and evaporate these sufficiently quickly to make a type B1 CAI.The Meteoritics & Planetary Science archives are made available by the Meteoritical Society and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

Laboratory Experiments Bearing on the Origin and Evolution of Olivine-rich Chondrules

Evaporation rates of K2O, Na2O, and FeO from chondrule-like liquids and the associated potassium isotopic fractionation of the evaporation residues were measured to help understand the processes and conditions that affected the chemical and isotopic compositions of olivine-rich Type IA and Type IIA chondrules from Semarkona. Both types of chondrules show evidence of having been significantly or totally molten. However, these chondrules do not have large or systematic potassium isotopic fractionation of the sort found in the laboratory evaporation experiments. The experimental results reported here provide new data regarding the evaporation kinetics of sodium and potassium from a chondrule-like melt and the potassium isotopic fractionation of evaporation residues run under various conditions ranging from high vacuum to pressures of one bar of H2+CO2, or H2, or helium. The lack of systematic isotopic fractionation of potassium in the Type IIA and Type IA chondrules compared with what is found in the vacuum and one-bar evaporation residues is interpreted as indicating that they evolved in a partially closed system where the residence time of the surrounding gas was sufficiently long for it to have become saturated in the evaporating species and for isotopic equilibration between the gas and the melt. A diffusion couple experiment juxtaposing chondrule-like melts with different potassium concentrations showed that the diffusivity of potassium is sufficiently fast at liquidus temperatures (DK>2-10-4cm2/s at 1650-C) that diffusion-limited evaporation cannot explain why, despite their having been molten, the Type IIA and Type IA chondrules show no systematic potassium isotopic fractionation

Kinetic Isotopic Fractionation During Diffusion of Ionic Species in Water

Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine D{sub Li}/D{sub K}, D{sub 7{sub Li}}/D{sub 6{sub Li}}, D{sub 25{sub Mg}}/D{sub 24{sub Mg}}, D{sub 26{sub Mg}}/D{sub 25{sub Mg}}, and D{sub 37{sub Cl}}/D{sub 35{sub Cl}}. The measured ratio of the diffusion coefficients for Li and K in water (D{sub Li}/D{sub K} = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D{sub 7{sub Li}}/D{sub 6{sub Li}} = 0.99772 {+-} 0.00026). This difference in the diffusion coefficient of {sup 7}Li compared to {sup 6}Li is significantly less than reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D{sub 25{sub Mg}}/D{sub 24{sub Mg}} = 1.00003 {+-} 0.00006). Cl isotopes were fractionated during diffusion in water (D{sub 37{sub Cl}}/D{sub 35{sub Cl}} = 0.99857 {+-} 0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water, being a polar liquid, surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in reducing isotopic fractionation associated with diffusion

Reassessing the thermal history of martian meteorite Shergotty and Apollo mare basalt 15555 using kinetic isotope fractionation of zoned minerals

International audienceElemental abundance and isotopic fractionation profiles across zoned minerals from a martian meteorite (Shergotty) and from a lunar olivine-normative mare basalt (Apollo 15555) were used to place constraints on the thermal evolution of their host rocks. The isotopic measurements were used to determine the extent to which diffusion was responsible for, or modified, the zoning. The key concept is that mineral zoning that is the result of diffusion, or that was significantly affected by diffusion, will have an associated diagnostic isotopic fractionation that can quantify the extent of mass transfer by diffusion. Once the extent of diffusion was determined, the mineral zoning was used to constrain the thermal history. An isotopic and chemical profile measured across a large zoned pigeonite grain from Shergotty showed no significant isotopic fractionation of either magnesium or lithium, which is evidence that the chemical zoning was dominantly the result of crystallization from an evolving melt and that the crystallization must have taken place at a sufficiently fast rate that there was not time for any significant mass transfer by diffusion. Model calculations for the evolution of the fast-diffusing lithium showed that this would have required a cooling at a rate of about ∼150 °C/h or more. Measurable isotopic fractionation across a zoned olivine grain from lunar mare basalt 15555 indicated that the chemical zoning was mainly due to crystallization that was modified by a small but quantifiable amount of diffusion. The results of a diffusion calculation that was able to account for the amplitude and spatial scale of the isotopic fractionation across the olivine grain yielded an estimate of 0.2 °C/h for the cooling rate of 15555. The results of an earlier study of zoned augite and olivine grains from martian nakhlite meteorite NWA 817 were reviewed for comparison with the results from Shergotty. The isotopic fractionations near the edges of grains from NWA 817 showed that, in contrast to Shergotty, the lithium zoning in augite and of magnesium in olivine was due entirely to diffusion. The isotopic fractionation data across zoned minerals from the martian meteorites and from the lunar basalt were key for documenting and quantifying the extent of mass transfer by diffusion, which was a crucial step for validating the use of diffusion modeling to estimate their cooling rates