High structural complexity of potassium uranyl borates derived from high-temperature/high-pressure reactions.

Three new potassium uranyl borates, K12[(UO2)19(UO4)(B2O5)2(BO3)6(BO2OH)O10] ·nH2O (TPKBUO-1), K4[(UO2)5(BO3)2O4]·H2O (TPKBUO-2), and K15[(UO2)18(BO3)7O15] (TPKBUO-3), were synthesized under high-temperature/high-pressure conditions. In all three compounds, the U/B ratio exceeds 1. Boron exhibits BO3 coordination only, which is different from other uranyl borates prepared at room temperature or under mild hydrothermal conditions. A rare uranium(VI) tetraoxide core UO4O2, which is coordinated by two BO3 groups, is observed in the structure of TPKBUO-1. Both structures of TPKBUO-1 and TPKBUO-3 contain three different coordination environments of uranium, namely, UO4O2, UO2O4, and UO2O5 and UO2O4, UO2O5, and UO2O6 bipyramids in TPKBUO-1 and TPKBUO-3, respectively.

Rich coordination of Nd3+ in Mg2Nd13(BO3)8(SiO4)4(OH)3, derived from high-pressure/high-temperature conditions.

A neodymium borosilicate, Mg(2)Nd(13)(BO(3))(8)(SiO(4))(4)(OH)(3) (MgNdBSi-1), was obtained from a high-temperature (1400 °C), solid-state reaction under high-pressure conditions (4.5 GPa). MgNdBSi-1 contains six different types of Nd(3+) coordination environments with three different ligands: BO(3), SiO(4), and OH groups. Mg(2+) cations are only bond to BO(3) groups and form porous two-dimensional layers based on 12-membered ring fragments. Surprisingly, the OH groups are retained at high temperature and reside at the center of Mg-BO(3) rings.

High Temperature Evaporation and Isotopic Fractionation of K and Cu.

The chemical and isotopic signatures of moderately volatile elements are useful for understanding processes of volatile depletion in planetary formation and differentiation. However, the fractionation factors between gas and melt phases during evaporation that are required to model these planetary volatile depletion processes are still sparse. In this study, twenty heating experiments were conducted in 1 atm gas-mixing furnaces to constrain the behavior of K, Cu, and Zn evaporation and isotopic fractionation from basaltic melts at high temperatures. The temperatures range from 1300 °C to 1400 °C, and durations are from 2 to 8 days. Oxygen fugacities (fO2) range from one log unit below to ten log units above that of the iron-wüstite buffer (IW-1 to IW+10, corresponding to logfO2 of -10.7 to -0.68 at 1400 °C). The conditions were selected to achieve an evaporation-dominated regime (where timescales of diffusion << evaporation for trace elements) in order to avoid diffusion-limited evaporation. Our results show during evaporation Zn behaved as the most volatile, followed by Cu and then K, regardless of temperature and oxygen fugacity. Partitioning of Zn into spinel layers within experimental capsules, however, has been observed, which has substantial effects on the Zn isotope fractionation factor. Therefore, Zn results are presented but further discussion is excluded. Element loss depends on both temperature and oxygen fugacity, where higher temperatures and lower oxygen fugacities promote evaporation. However, with varying temperature and oxygen fugacity, the kinetic isotopic fractionation factors, α (where, R R 0 = f α - 1 ), for K and Cu remain constant, thus these factors can be applied to a wider range of conditions than those in this study. The experimentally determined fractionation factors for K, and Cu during evaporation from basaltic melts are 0.9944, and 0.9961, respectively. The fractionation factors for these elements with varying volatilities are all significantly larger than the "apparent observed fractionation factors," which approach one and are inferred from lunar basalts relative to the Bulk Silicate Earth. This observation suggests near-equilibrium conditions during volatile-element loss from the Moon as the "apparent observed fractionation factors" of lunar basalts are similar for all three elements.

Fractionation of the platinum-group elements during mantle melting.

Experiments in sulfide-silicate systems demonstrate that two sulfide phases are stable in the asthenospheric upper mantle: a crystalline osmium-iridium-ruthenium-enriched monosulfide and a rhodium-platinum-palladium-enriched sulfide melt. During silicate melt segregation, monosulfide stays in the solid residue, dominating the noble metal spectrum of residual mantle. The sulfide melt is entrained as immiscible droplets in the segregating silicate melt, defining the noble metal inventory of the basaltic component.