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Influence of C–O–H Volatiles on Ni, Co, and P Partition between Silicate Melt and Liquid Metal Fe Alloy at 4 GPa, 1550°C

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Abstract—

A set of experiments was carried out in the system NaAlSi3O8–FeO–NiO–CoO–SiC–NaH2PO4 at 1550°C, 4 GPa, and oxygen fugacity (fO2) 0.5–2.9 log. units below the iron–wüstite (IW) buffer to estimate how C–O–H components can affect Ni, Co, and P partition between silicate melt and a liquid metallic phase at redox conditions under which the metallic phase is segregated into melting products of the early reduced mantles of the Earth and other planetary bodies. It has been established that the Ni, Co, and P partition coefficients D(М)met/sil between silicate melts saturated with carbon and containing dissolved C–O–H volatiles (mainly in the form of OH groups, H2 and CH4) at relatively oxidized conditions (fO2 > IW – 1.5) correspond to D(М)met/sil values expected of metal–silicate melt equilibrium in volatile-free systems at analogous P, T, fO2, and nbo/t parameters. Under more reduced conditions (fO2 ≤ IW – 2), the presence of C–O–H volatiles leads to a decrease in D(М)met/sil for Ni and P compared to that in “dry” melts. This difference increases with decreasing fO2 and reaches ~0.5 and more than one order of magnitude for Ni and P, respectively, at fO2 = IW – 2.9. The effect of volatiles on D(Co)met/sil is much weaker, and hence, a decrease in fO2 leads to that D(Ni)met/sil and D(Co)met/sil converge. The Raman spectra of the experimental glasses and their SIMS analyses for hydrogen show that water content (OH + H2O) in the melts decreases with decreasing fO2, whereas the contents of CH4 and complexes with C–H bonds significantly increases. The likely reasons for the decrease in D(М)met/sil under strongly reduced conditions may be changes in the structure of the silicate melts and the origin of complex compounds of siderophile elements with volatiles in these melts.

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Notes

  1. According to experimental data, throughout the whole fO2 range (from IW to IW – 3), the valence of cobalt is 2+ (1300–2200°C, 0.001–5 GPa), and that of phosphorus is 5+ (1190–1600°C, 0.001 GPa) (see Siebert et al., 2011, Suppl. E, for a review of the experimental data.)

  2. The M–Fe exchange partition coefficient) between metal alloy and silicate melt can be expressed in a general form through the partition coefficients D(Mi)met/sil and D(Fe)met/sil as Kd(M–Fe)met/sil = (D#(Mi)met/sil/D#(Fe)met/sil)n/2 = (D(Mi)met/sil/D(Fe)met/sil)n/2β(n/2 – 1), where β is a recalculation coefficient (see Eq. (6)). For bivalent Ni and Co, this expression has a simpler form Kd(M–Fe) = D(Mi)met/sil/D(Fe)met/sil.

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ACKNOWLEDGMENTS

The authors thank B.N. Ryzhenko and O.I. Yakovlev for discussion of the manuscript and for valuable comments.

Funding

This study was carried out under government-financed project 0137-2019-0017 for the Vernadsky Institute and was supported by the Russian Foundation for Basic Research, project no. 17-05-00713, and by Program I.16 of the Presidium of the Russian Academy of Sciences.

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  1. Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKhI), Russian Academy of Sciences, 119991, Moscow, Russia

    O. A. Lukanin, T. I. Tsekhonya, V. V. Koltashev & N. N. Kononkova

  2. Fiber Optics Research Center, Russian Academy of Sciences, 119333, Moscow, Russia

    V. V. Koltashev

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  1. O. A. Lukanin
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Correspondence to O. A. Lukanin, T. I. Tsekhonya or V. V. Koltashev.

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Translated by E. Kurdyukov

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Lukanin, O.A., Tsekhonya, T.I., Koltashev, V.V. et al. Influence of C–O–H Volatiles on Ni, Co, and P Partition between Silicate Melt and Liquid Metal Fe Alloy at 4 GPa, 1550°C. Geochem. Int. 58, 670–686 (2020). https://doi.org/10.1134/S0016702920060063

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