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Title: Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Abstract

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, inmore » this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ41K and δ87Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.« less

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1];  [1];  [4];  [4];  [5];  [3];  [1]
  1. Univ. of Chicago, IL (United States)
  2. Univ. of Chicago, IL (United States); Carnegie Inst. of Science, Washington, DC (United States)
  3. Univ. of California, Los Angeles, CA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Carnegie Inst. of Science, Washington, DC (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Aeronautics and Space Administration (NASA)
OSTI Identifier:
1833818
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Volume: 5; Journal Issue: 4; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Vesta; Evaporation; K; Rb; diffusion; isotope; Elements; Potassium; Fractionation; Vacuum

Citation Formats

Zhang, Zhe J., Nie, Nicole Xike, Mendybaev, Ruslan A., Liu, Ming-Chang, Hu, Justin Jingya, Hopp, Timo, Alp, Esen E., Lavina, Barbara, Bullock, Emma S., McKeegan, Kevin D., and Dauphas, Nicolas. Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments. United States: N. p., 2021. Web. doi:10.1021/acsearthspacechem.0c00263.
Zhang, Zhe J., Nie, Nicole Xike, Mendybaev, Ruslan A., Liu, Ming-Chang, Hu, Justin Jingya, Hopp, Timo, Alp, Esen E., Lavina, Barbara, Bullock, Emma S., McKeegan, Kevin D., & Dauphas, Nicolas. Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments. United States. https://doi.org/10.1021/acsearthspacechem.0c00263
Zhang, Zhe J., Nie, Nicole Xike, Mendybaev, Ruslan A., Liu, Ming-Chang, Hu, Justin Jingya, Hopp, Timo, Alp, Esen E., Lavina, Barbara, Bullock, Emma S., McKeegan, Kevin D., and Dauphas, Nicolas. 2021. "Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments". United States. https://doi.org/10.1021/acsearthspacechem.0c00263. https://www.osti.gov/servlets/purl/1833818.
@article{osti_1833818,
title = {Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments},
author = {Zhang, Zhe J. and Nie, Nicole Xike and Mendybaev, Ruslan A. and Liu, Ming-Chang and Hu, Justin Jingya and Hopp, Timo and Alp, Esen E. and Lavina, Barbara and Bullock, Emma S. and McKeegan, Kevin D. and Dauphas, Nicolas},
abstractNote = {Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ41K and δ87Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.},
doi = {10.1021/acsearthspacechem.0c00263},
url = {https://www.osti.gov/biblio/1833818}, journal = {ACS Earth and Space Chemistry},
issn = {2472-3452},
number = 4,
volume = 5,
place = {United States},
year = {Thu Mar 11 00:00:00 EST 2021},
month = {Thu Mar 11 00:00:00 EST 2021}
}

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