International audienceIn their late stages of evolution, peraluminous granitic melts exsolve large amounts of fluidswhich can modify the chemical composition of granitic whole-rock samples. The niobium/tantalum (Nb/Ta) ratio is expected to decrease during the magmatic differentiation of graniticmelts, but the behavior of both elements at the magmatic-hydrothermal transition remainsunclear. Using a compilation of whole-rock geochemical data available in the literature, wedemonstrate that fractional crystallization alone is not sufficient to explain the distribution ofNb-Ta in most peraluminous granites. However, we notice that most of the granitic samplesdisplaying evidence of interactions with fluids have Nb/Ta < 5. We propose that the decreaseof the Nb/Ta ratio in evolved melts is the consequence of both fractional crystallization andsub-solidus hydrothermal alteration. We suggest that the Nb/Ta value of ~5 fingerprints themagmatic-hydrothermal transition in peraluminous granites. Furthermore, a Nb/Ta ratio of ~5appears to be a good marker to discriminate mineralized from barren peraluminous granites

Sample return shows late lunar volcanism: Measuring physical samples of Solar System bodies in the laboratory provides more information than is possible from remote sensing alone. In December 2020, the Chang’e-5 mission landed on the Moon, collected samples, and returned them to Earth. Che et al . analyze two fragments of volcanic lunar basalt collected by Chang’e-5. Radiometric dating using lead isotopes indicated that the rocks formed from magma that erupted about 2 billion years ago, later than other volcanic lunar samples. The abundance of extinct radioactive elements in the rock is too low for radioactive heating to have produced the magma. Another, thus far unknown, source must be responsible for the late lunar volcanism. —KTS

Many studies exist on magmatic volatiles (H, C, N, F, S, Cl) in and on the Moon, within the last several years, that have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. However, these recent observations are not the first data on lunar volatiles. When Apollo samples were first returned, substantial efforts were made to understand volatile elements, and a wealth of data regarding volatile elements exists in this older literature. In this review paper, we approach volatiles in and on the Moon using new and old data derived from lunar samples and remote sensing. From combining these data sets, we identified many points of convergence, although numerous questions remain unanswered. The abundances of volatiles in the bulk silicate Moon (BSM), lunar mantle, and urKREEP [last ~1% of the lunar magma ocean (LMO)] were estimated and placed within the context of the LMO model. The lunar mantle is likely heterogeneous with respect to volatiles, and the relative abundances of F, Cl, and H₂O in the lunar mantle (H₂O > F >> Cl) do not directly reflect those of BSM or urKREEP (Cl > H₂O ≈ F). In fact, the abundances of volatiles in the cumulate lunar mantle were likely controlled by partitioning of volatiles between LMO liquid and nominally anhydrous minerals instead of residual liquid trapped in the cumulate pile. An internally consistent model for lunar volatiles in BSM should reproduce the absolute and relative abundances of volatiles in urKREEP, the anorthositic primary crust, and the lunar mantle within the context of processes that occurred during the thermal and magmatic evolution of the Moon. Using this mass-balance constraint, we conducted LMO crystallization calculations with a specific focus on the distributions and abundances of F, Cl, and H₂O to determine whether or not estimates of F, Cl, and H₂O in urKREEP are consistent with those of the lunar mantle, estimated independently from the analysis of volatiles in mare volcanic materials. Our estimate of volatiles in the bulk lunar mantle are 0.54–4.5 ppm F, 0.15–5.3 ppm H₂O, 0.26–2.9 ppm Cl, 0.014–0.57 ppm C, and 78.9 ppm S. Our estimates of H₂O are depleted compared to independent estimates of H₂O in the lunar mantle, which are largely biased toward the “wettest” samples. Although the lunar mantle is depleted in volatiles relative to Earth, unlike the Earth, the mantle is not the primary host for volatiles. The primary host of the Moon’s incompatible lithophile volatiles (F, Cl, H₂O) is urKREEP, which we estimate to have 660 ppm F, 300–1250 ppm H₂O, and 1100–1350 ppm Cl. This urKREEP composition implies a BSM with 7.1 ppm F, 3–13 ppm H₂O, and 11–14 ppm Cl. An upper bound on the abundances of F, Cl, and H₂O in urKREEP and the BSM, based on F abundances in CI carbonaceous chondrites, are reported to be 5500 ppm F, 0.26–1.09 wt% H₂O, and 0.98–1.2 wt% Cl and 60 ppm F, 27–114 ppm H₂O, and 100–123 ppm Cl, respectively. The role of volatiles in many lunar geologic processes was also determined and discussed. Specifically, analyses of volatiles from lunar glass beads as well as the phase assemblages present in coatings on those beads were used to infer that H₂ is likely the primary vapor component responsible for propelling the fire-fountain eruptions that produced the pyroclastic glass beads (as opposed to CO). The textural occurrences of some volatile-bearing minerals are used to identify hydrothermal alteration, which is manifested by sulfide veining and sulfide-replacement textures in silicates. Metasomatic alteration in lunar systems differs substantially from terrestrial alteration due to differences in oxygen fugacity between the two bodies that result in H₂O as the primary solvent for alteration fluids on Earth and H₂ as the primary solvent for alteration fluids on the Moon (and other reduced planetary bodies). Additionally, volatile abundances in volatile-bearing materials are combined with isotopic data to determine possible secondary processes that have affected the primary magmatic volatile signatures of lunar rocks including degassing, assimilation, and terrestrial contamination; however, these processes prove difficult to untangle within individual data sets. Data from remote sensing and lunar soils are combined to understand the distribution, origin, and abundances of volatiles on the lunar surface, which can be explained largely by solar wind implantation and spallogenic processes, although some of the volatiles in the soils may also be either indigenous to the Moon or terrestrial contamination. We have also provided a complete inventory of volatile-bearing mineral phases indigenous to lunar samples and discuss some of the “unconfirmed” volatile-bearing minerals that have been reported. Finally, a compilation of unanswered questions and future avenues of research on the topic of lunar volatiles are presented, along with a critical analysis of approaches for answering these questions.

The distribution of water in the Moon’s interior carries implications for the origin of the Moon¹, the crystallization of the lunar magma ocean² and the duration of lunar volcanism². The Chang’e-5 mission returned some of the youngest mare basalt samples reported so far, dated at 2.0 billion years ago (Ga)³, from the northwestern Procellarum KREEP Terrane, providing a probe into the spatiotemporal evolution of lunar water. Here we report the water abundances and hydrogen isotope compositions of apatite and ilmenite-hosted melt inclusions from the Chang’e-5 basalts. We derive a maximum water abundance of 283 ± 22 μg g⁻¹ and a deuterium/hydrogen ratio of (1.06 ± 0.25) × 10^–4 for the parent magma. Accounting for low-degree partial melting of the depleted mantle followed by extensive magma fractional crystallization⁴, we estimate a maximum mantle water abundance of 1–5 μg g⁻¹, suggesting that the Moon’s youngest volcanism was not driven by abundant water in its mantle source. Such a modest water content for the Chang’e-5 basalt mantle source region is at the low end of the range estimated from mare basalts that erupted from around 4.0 Ga to 2.8 Ga (refs. ^5,6), suggesting that the mantle source of the Chang’e-5 basalts had become dehydrated by 2.0 Ga through previous melt extraction from the Procellarum KREEP Terrane mantle during prolonged volcanic activity.

Apatite-melt partitioning experiments were conducted in a piston-cylinder press at 1.0–1.2 GPa and 950–1000 °C using an Fe-rich basaltic starting composition and an oxygen fugacity within the range of ΔIW-1 to ΔIW+2. Each experiment had a unique F:Cl:OH ratio to assess the partitioning as a function of the volatile content of apatite and melt. The quenched melt and apatite were analyzed by electron probe microanalysis and secondary ion mass spectrometry techniques. The mineral-melt partition coefficients (D values) determined in this study are as follows: D_F^Ap-Melt = 4.4–19, D_Cl^Ap-Melt = 1.1–5, D_OH^Ap-Melt = 0.07–0.24. This large range in values indicates that a linear relationship does not exist between the concentrations of F, Cl, or OH in apatite and F, Cl, or OH in melt, respectively. This non-Nernstian behavior is a direct consequence of F, Cl, and OH being essential structural constituents in apatite and minor to trace components in the melt. Therefore mineral-melt D values for F, Cl, and OH in apatite should not be used to directly determine the volatile abundances of coexisting silicate melts. However, the apatite-melt D values for F, Cl, and OH are necessarily interdependent given that F, Cl, and OH all mix on the same crystallographic site in apatite. Consequently, we examined the ratio of D values (exchange coefficients) for each volatile pair (OH-F, Cl-F, and OH-Cl) and observed that they display much less variability: Kd_Cl-F^Ap-Melt = 0.21 ± 0.03, Kd_OH-F^Ap-Melt= 0.014 ± 0.002, and Kd_OH-Cl^Ap-Melt= 0.06 ± 0.02. However, variations with apatite composition, specifically when mole fractions of F in the apatite X-site were low (X_F < 0.18), were observed and warrant additional study. To implement the exchange coefficient to determine the H₂O content of a silicate melt at the time of apatite crystallization (apatite-based melt hygrometry), the H₂O abundance of the apatite, an apatite-melt exchange K_d that includes OH (either OH-F or OH-Cl), and the abundance of F or Cl in the apatite and F or Cl in the melt at the time of apatite crystallization are needed (F if using the OH-F K_d and Cl if using the OH-Cl K_d). To determine the H₂O content of the parental melt, the F or Cl abundance of the parental melt is needed in place of the F or Cl abundance of the melt at the time of apatite crystallization. Importantly, however, exchange coefficients may vary as a function of temperature, pressure, melt composition, apatite composition, and/or oxygen fugacity, so the combined effects of these parameters must be investigated further before exchange coefficients are applied broadly to determine volatile abundances of coexisting melt from apatite volatile abundances.