Acta Geochimica最新文献

Due to their high density, the ilmenite-bearing cumulates (IBC) (with or without KREEP) formed during the late-stage lunar magma ocean solidification are thought to sink into the underlying lunar mantle and trigger lunar mantle overturn. Geophysical evidence implied that IBC may descend deep inside the Moon and remain as a partially molten layer at the core-mantle boundary (CMB). However, partial melting may have occurred on the mixed mantle cumulates during the sinking of IBC/KREEP and the silicate melt may be positively buoyant, thus preventing the IBC/KREEP layer from sinking to the CMB. Here, we perform thermodynamic simulation on the stability of lunar mantle cumulates at different depths mixed with different amounts of IBC/KREEP from an updated LMO model. The modeling results suggest that the sinking of IBC/KREEP will cause at least 5 wt% partial melting in the shallow (~ 120 km) and a much larger degree of partial melting in the deep lunar mantle (~ 420 km). Due to the density contrast with the surrounding mantle, IBC/KREEP-bearing melts could potentially decouple under certain conditions. The modified lunar mantle by sinking of IBC/KREEP can better explain the formation of different kinds of lunar basaltic magma than the primary lunar mantle formed through differentiation of lunar magma ocean. Sinking of IBC/KREEP back into the lunar mantle may introduce plagioclase, clinopyroxene, garnet, and incompatible radioactive elements into the deep lunar mantle, which will further affect the thermal and chemical evolution of the lunar interior.

Isotope effects are pivotal in understanding silicate melt evaporation and planetary accretion processes. Based on the Hertz–Knudsen equation, the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions. Here, we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt. We propose a new model designed for silicate melt evaporation under vacuum. Our model considers multiple steps including mass transfer, chemical reaction, and nucleation. Our derivations reveal a kinetic isotopic fractionation factor (KIFF or α) α_{our model} = [m(¹species)/m(²species)]^0.5, where m(species) is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes, respectively. This model can effectively reproduce most reported KIFFs of laboratory experiments for various elements, i.e., Mg, Si, K, Rb, Fe, Ca, and Ti. And, the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the effects of low P_H2 pressure, composition, and temperature. In addition, we find that chemical reactions, diffusion, and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(− lnf) versus ln(t). Notably, our model allows for the theoretical calculations of parameters like activation energy (E_a), providing a novel approach to studying compositional and environmental effects on evaporation processes, and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.

Theoretical studies of the diffusional isotope effect in solids are still stuck in the 1960s and 1970s. With the development of high spatial resolution mass spectrometers, isotopic data of mineral grains are rapidly accumulated. To dig up information from these data, molecular-level theoretical models are urgently needed. Based on the microscopic definition of the diffusion coefficient (D), a new theoretical framework for calculating the diffusional isotope effect (DIE_(v)) (in terms of D^*/D) for vacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism. The newly derived equation shows that the DIE_(v) can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained. The calculated DIE_(v) values of ¹⁹⁹Au/¹⁹⁵Au and ⁶⁰Co/⁵⁷Co during diffusion in Cu and Au metals are all within 1% of errors compared to the experimental data, which shows that this theoretical model is reasonable and precise.

Perchlorate and chlorate are present in various extraterrestrial celestial bodies throughout the solar system, such as Mars, the moon, and asteroids. To date, the origin mechanisms of perchlorate and chlorate on the Martian surface have been well-established; however, relatively little attention has been cast to airless bodies. Here, we experimentally investigated the potential oxidation mechanisms of chloride to chlorate and perchlorate, such as ultraviolet irradiation under H₂O- and O₂-free conditions and mechanical pulverization processes. Individual minerals, olivine, pyroxene, ilmenite, magnetite, TiO₂ and anhydrous ferric sulfate, and lunar regolith simulants (low Ti, CLRS-1; high-Ti, CLRS-2) and their metallic iron (Fe⁰) bearing counterparts were examined. We found that pulverization of dry matrix material-halite mixtures, even in the presence of O₂, does not necessarily lead to perchlorate and chlorate formation without involving water. Under photocatalytic and H₂O- and O₂-free conditions, olivine and pyroxene can produce oxychlorine (ClO_x⁻) species, although the yields were orders of magnitude lower than those under Martian-relevant conditions. Nanophase-Fe⁰ particles in the lunar regolith and the common photocatalyst TiO₂ can facilitate the ClO_x⁻ formation, but their yields were lower than those with olivine. The oxides ilmenite and magnetite did not efficiently contribute to ClO_x⁻ production. Our results highlight the critical role of H₂O in the oxidation chloride to chlorate and perchlorate, and provide essential insights into the environmental influence on the formation of oxychlorine species on different celestial bodies.