¹Ziyan Han,^1,2,3Hejiu Hui,^1,2Haizhen Wei,^1,2Weiqiang Li
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.05.007]
¹State Key Laboratory of Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210023, China
¹CAS Center for Excellence in Comparative Planetology, Hefei 230026, China
³CAS Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
Copyright Elsevier

The Moon is depleted in volatile elements and compounds, and lunar samples exhibit a wide range of Cl isotopic compositions, which is believed to result from the volatilization of metal chlorides (e.g., NaCl, KCl, and FeCl2). However, the Cl isotopic fractionation behavior during volatilization is not well constrained, particularly for metal chlorides. Furthermore, the effect of metal chloride evaporation on metal isotopes is poorly known. In the present study, we performed NaCl and KCl sublimation experiments to study Cl and K isotopic fractionations at temperatures ranging from 923 K to 1061 K and at pressures of 7×10–5 bar to 1 bar in an N2 atmosphere. The isotope fractionation factors of 37/35Cl(αgas–solid) from NaCl sublimation experiments are 0.9985±0.0002, 0.9958±0.0004, and 0.99807±0.00004 at 1, 10–2, and 7×10–5 bar, respectively. Those of 41/39K(αgas–solid) and 37/35Cl(αgas–solid) from KCl sublimation experiments are 0.99884±0.00004 and 0.9988±0.0003 at 1 bar, 0.9977±0.0002 and 0.9972±0.0003 at 10–2 bar, and 0.9989±0.0002 and 0.9989±0.0001 at 7×10–5 bar, respectively. Chlorine and K isotopes fractionate more at 10–2 bar than at 7×10–5 bar and 1 bar. The saturation index in all the sublimation experiments was >95%, which resulted in near-equilibrium isotopic fractionation at the sublimation interface. Therefore, the isotopic fractionation was controlled by mass transfer processes in the gas and solid phases. The isotopic fractionation at 10–2 bar was controlled by the chemical diffusion of sublimated gas in an N2 atmosphere with almost no convection effect, (i.e., Pe number close to zero), whereas the isotopic fractionation at 1 bar was suppressed by atmospheric convection with a turbulence factor of 0.4±0.1 (i.e., Pe number >1). The extremely high sublimation rate and the very slow diffusion in the sublimating solid at 7×10–5 bar suppressed isotopic fractionations. Based on our experimental results, calculations using Cl/K and Na/K in lunar materials reveal that degassing of KCl contributed very little (<0.2‰) to the K isotopic fractionation (>0.58‰) during lunar magma ocean degassing. The Cl isotopic fractionation factor from lunar samples is similar to our results at 10–2 bar. This similarity of Cl isotope fractionation indicates that there may have been a transient atmosphere above the lunar magma ocean.