ALBERT

Description: 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 H 2 O in the lunar mantle (H 2 O 〉 F 〉〉 Cl) do not directly reflect those of BSM or urKREEP (Cl 〉 H 2 O 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 H 2 O to determine whether or not estimates of F, Cl, and H 2 O 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 H 2 O, 0.26–2.9 ppm Cl, 0.014–0.57 ppm C, and 78.9 ppm S. Our estimates of H 2 O are depleted compared to independent estimates of H 2 O 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, H 2 O) is urKREEP, which we estimate to have 660 ppm F, 300–1250 ppm H 2 O, and 1100–1350 ppm Cl. This urKREEP composition implies a BSM with 7.1 ppm F, 3–13 ppm H 2 O, and 11–14 ppm Cl. An upper bound on the abundances of F, Cl, and H 2 O 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% H 2 O, and 0.98–1.2 wt% Cl and 60 ppm F, 27–114 ppm H 2 O, 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 H 2 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 H 2 O as the primary solvent for alteration fluids on Earth and H 2 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.

Description: 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 IW-1 to IW+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: K d Cl-F Ap-Melt = 0.21 ± 0.03, K d OH-F Ap-Melt = 0.014 ± 0.002, and K d 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 H 2 O content of a silicate melt at the time of apatite crystallization (apatite-based melt hygrometry), the H 2 O 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 H 2 O 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.

Description: The search for water in our solar system is one of the primary driving forces for planetary science and exploration because water plays an important role in many geologic processes and is required for biologic processes as we currently understand them. Excluding Earth, Mars is the most promising destination in the inner solar system to find water, as it is undoubtedly responsible for shaping many geomorphologic features observed on the present-day martian surface; however, the water content of the martian interior is currently unresolved. Much of our information about the martian interior comes from studies of the basaltic martian meteorites (shergottites). In this study we examined the water contents of magmatic apatites from a geochemically enriched shergottite (the Shergotty meteorite) and a geochemically depleted shergottite (the Queen Alexandria Range 94201 meteorite). From these data, we determined that there was little difference in water contents between the geochemically depleted and enriched shergottite magmas. The water contents of the apatite imply that shergottite parent magmas contained 730–2870 ppm H 2 O prior to degassing. Furthermore, the martian mantle contains 73–290 ppm H 2 O and underwent hydrous melting as recently as 327 Ma. In the absence of plate tectonics, the presence of water in the interior of Mars requires planetary differentiation under hydrous conditions. This is the first evidence of significant hydrogen storage in a planetary interior at the time of core formation, and this process could support elevated H abundances in the interiors of other terrestrial bodies like the Moon, Mercury, Venus, large differentiated asteroids, and Earth.

Description: Space weathering alters the surfaces of airless planetary bodies via irradiation from the solar wind and micrometeorite impacts. These processes modify the microstructure, chemical composition, and spectral properties of surface materials, typically resulting in the reddening (increasing reflectance with increasing wavelength), darkening (reducing albedo), and attenuation of characteristic absorption features in reflectance spectra. In lunar samples, these changes in optical properties are driven by the production of reduced nanophase Fe particles (npFe). Our understanding of space weathering has largely been based on data from the Moon and, more recently, near-Earth S-type asteroids. However, the environment at Mercury is significantly different, with the surface experiencing intense solar wind irradiation and higher velocity micrometeorite impacts. Additionally, the composition of Mercurys surface varies significantly from that of the Moon, including a component with very low albedo known as low reflectance material (LRM) which is enriched with up to 4 wt.% carbon over the local mean. Our understanding of how carbon phases, including graphite, are altered as a result of these processes is limited.

Description: New initiatives to begin Lunar and Martian human surface operations within the next few decades are illustrative of the resurgence of interest in human space exploration. However, as with all exploration, there are risks. The previous manned missions to the Moon highlight a major hazard for future human exploration of the Moon and beyond: surface dust. Not only did the dust cause mechanical and structural integrity issues with the suits, the dust 'storm' generated upon reentrance into the crew cabin caused "lunar hay fever" and "almost blindness.". It was further reported that the allergic response to the dust worsened with each exposure. Due to the prevalence of these high exposures, the Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern.

Description: The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. Among the many discoveries about Mercury made by MESSENGER, several surprising compositional characteristics of the surface were observed. These discoveries include elevated sulfur abundances (up to 4 wt.%), elevated abundances of graphitic carbon (0-4.1 wt.% across the surface with an additional 1-3 wt.% graphite above the global average in low reflectance materials), low iron abundances (less than 2 wt.%), and low oxygen abundances (O/Si weight ratio of 1.20+/-0.1). These exotic characteristics likely have important implications for the thermochemical evolution of Mercury and point to a planet that formed under highly reducing conditions. In the present study, we focus specifically on the low O/Si ratio of Mercury, which is anomalous compared to all other planetary materials. A recent study that considered the geochemical implications of the low O/Si ratio reported that 12-20% of the surface materials on Mercury are composed of Si-rich, Si-Fe alloys. They further postulated that the origin of the metal is best explained by a combination of space weathering and graphite-induced smelting that was facilitated by interaction of graphite with boninitic and komatiitic parental liquids. The goal of the present study is to assess the plausibility of smelting on Mercury through experiments run at the conditions that McCubbin et al. indicated would be favorable for Si-smelting.

Description: New initiatives to send humans to Mars within the next few decades are illustrative of the resurgence of interest in space travel. However, as with all exploration, there are risks. The Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern. Extended human exploration will further increase the probability of inadvertent and repeated exposures to celestial dusts.

Description: The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite.

Description: The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. The X-Ray Spectrometer (XRS) and Gamma-Ray Spectrometer (GRS) onboard MESSENGER provided the first detailed chemical analyses of Mercury's surface. Among the many discoveries included several surprising characteristics about the surface of Mercury, including elevated S abundances (up to 4 percent by weight), low Fe abundances (less than 4 percent by weight), and relatively low O abundances (O/Si ratio of 1.40 plus or minus 0.03). The surface chemistry as determined by MESSENGER has been used to identify up to nine distinct geochemical terranes on Mercury. Numerous modeling and experimental efforts have been undertaken to infer the mineralogy and petrology of mercurian lavas and surface materials. However, all of these efforts have presumed valence states for each of the elements according to the following: Si4+, Ti4+, Al3+, Cr2+, Fe2+, Mn2+, Mg2+, Ca2+, Na+, K+, S2-, Cl-. Based on these valence assignments, cations are charged balanced with the anions O2-, S2-, and Cl- and the compositions are recast in terms of oxides, sulfides, and chlorides. Based on these assumptions, the geochemical terranes that have been identified on Mercury yield O/Si wt. ratios ranging from 1.61 to 1.84, which is substantially higher than the preliminary O/Si ratio of 1.40 plus or minus 0.03 determined by the MESSENGER GRS]. We have re-evaluated the O/Si ratio using the entire MESSENGER dataset to reassess its implications for the geochemistry of Mercury.

Description: The Astromaterials Acquisition and Curation Office (henceforth referred to herein as NASA Curation Office) at NASA Johnson Space Center (JSC) is responsible for curating all of NASA's extraterrestrial samples. JSC presently curates 9 different astromaterials collections: (1) Apollo samples, (2) LUNA samples, (3) Antarctic meteorites, (4) Cosmic dust particles, (5) Microparticle Impact Collection [formerly called Space Exposed Hardware], (6) Genesis solar wind, (7) Star-dust comet Wild-2 particles, (8) Stardust interstellar particles, and (9) Hayabusa asteroid Itokawa particles. In addition, the next missions bringing carbonaceous asteroid samples to JSC are Hayabusa 2/ asteroid Ryugu and OSIRIS-Rex/ asteroid Bennu, in 2021 and 2023, respectively. The Hayabusa 2 samples are provided as part of an international agreement with JAXA. The NASA Curation Office plans for the requirements of future collections in an "Advanced Curation" program. Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of collections as envisioned by NASA exploration goals. Here we review the science value and sample curation needs of some potential targets for sample return missions over the next 35 years.