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The motivation behind analyzing gaseous samples from the Permanently Shadowed Regions (PSRs) on the lunar surface is built upon the volatiles observed during the LCROSS mission. Advanced curation techniques under cold conditions are essential to the critical scientific analysis of these returned samples. The detection of various volatiles in returned samples by gas-phase infrared (IR) spectroscopy is known to be a powerful tool to understand the resources present in planetary bodies and Astro-materials. The identification and quantification of volatile compounds in returned planetary samples and regolith simulants by advanced and custom-built analytical devices are areas of primary research interest in our group and the Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility. In this context, we discuss recent advancements and experimental results for quick analysis of the major volatiles detected by the LCROSS (water, CO2, CH3OH, and NH3) by a long-path gas cell/FTIR (Fourier Transform Infrared) spectrometer system. The applicability of this system is demonstrated by qualitative analysis of a series of volatiles measured individually. In addition, the linear dependence of absorption intensity on headspace sample volumes was checked by measuring gas-phase IR absorption spectra of increasing volumes of pure CO2 gas aliquots. Finally, the instrument performance was evaluated by measuring the relative concentration of NH3 (g) in methanol solution.

Mercury’s depletion in O and abundance of S substituting in as S2- has fundamental effects on the physicochemical properties of minerals and melts because O2- is the dominant rock-forming anion. These changes exert a first order effect on planetary body evolution, including the initial distribution of elements, crystallization paths, stability of phases, and mineral chemistry. Experimental and empirical data have revealed that most nominally lithophile elements become more chalcophile and/or siderophile at reducing conditions, which can be visualized through a re-interpreted Goldschmidt classification table prepared for McCubbin & Anzures’s Treatises of Geochemistry 3rd edition chapter under review. Additionally, the S bonding environment influences Mercurian phase equilibria by decreasing the stability of forsterite and anorthite while increasing the stability of enstatite, silica, and albite through re-projection of silicate ternaries.

Introduction: Future Artemis missions aim to return the volatile-bearing samples collected near lunar polar craters. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving the integrity of returned samples and the science value those samples contain. The extent to which that preservation is possible, and the trade-offs preservation requires (e.g. monetary costs, sample volume limitations) all must be considered. Even less-than pristine volatile-bearing samples will be of tremendous value to the scientific community seeking to unravel the history of lunar surface volatiles and, more broadly, volatiles in the solar system. A sample collected on the lunar surface will experience at least five distinctive periods during which any changes here referred to as “alteration” will certainly occur at some scale: collection on the lunar surface; transportation back to Earth; long-term storage; curatorial processing; and allocation/distribution. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on returned volatile samples by working with high-fidelity volatile-containing regolith simulants, setting the foundation for the future of cold curation. This abstract is focused on gas-surface interactions between LCROSS volatiles and readily available lunar regolith simulants. Experiments involved analyzing differences in headspace gas composition for various combinations of volatile and regolith simulants using gas chromatography/mass spectrometry (GC/MS). Experimental Procedure: The volatile simulants were chosen based on the molecules detected during the LCROSS mission.1 Stock solutions of condensed lunar volatile analytes were: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. The regolith simulants used were primarily JSC-1A and NU-LHT-4M. Additional regolith simulant control studies were conducted with <150 μm sieved sand and KBr. A nested vial sample preparation approach separated the liquid stock solutions from the regolith, eliminating potential matrix effects between liquid and solid phases. Fifteen microliter aliquots of liquid volatile simulants were added to a 2 mL liquid GC vial and capped in atmosphere. An 18G needle punctured the 2 mL GC vial immediately before being transferred and sealed in a 20 mL GC vial containing 0-0.3 g of regolith simulant, see Figure 1. Separating the analytes ensures any changes observed in the total headspace gases is a result of gas-surface and/or gas-gas interactions. Equipment and Method: Initial GC/MS method development for the separation and identification of relevant headspace gases can be found in Amick, et al. 2023.2 The only hardware change is a different column: a TG-1701MS 30 m × 0.25 mm × 1.00 μm column. The vials were sampled at 10°C, room temperature (~25°C) and 50°C. Low temperature samples were kept in a chilled autosampler stage for at least 1 hour prior to sampling. High temperature samples were agitated at 50°C for 5 minutes immediately prior to injection onto the column. Headspace chromatograms were collected for each combination of temperature, regolith, and volatile simulant, including controls without one or both types of analytes, in triplicate. The chromatogram elution window for each analyte or significant atmospheric gas was identified using the peak mass spectrum cross-referenced with Figure 1.Picture of the nested vial set-up. a NIST MS library search. Each analyte peak was integrated after filtering the mass spectrum trace for the parent or most unique mass-to-charge ratio. For example, the mass-to-charge ratio used to identify, filter for, and integrate the carbon dioxide peak was centered around 44 m/z. Results: Figure 2 shows the integrated peak area for hydrogen sulfide in all combinations of regolith simulants, temperatures, and the addition of ammonia in methanol solution. Multiple repeat experiments with H2S and regolith simulants have confirmed hydrogen sulfide is removed from the headspace within 1 hour when exposed to JSC-1A, NU-LHT-4M and sand (not pictured). The consumption of H2S by lunar regolith simulants at different temperatures indicates surface chemistry will be an integral component in sample integrity and preservation. It is important to note that while the effect of surface chemistry on gaseous hydrogen sulfide is intriguing, further investigation into more chemically accurate regolith simulants is necessary and ongoing. The sulfur in hydrogen sulfide is in its most reduced state while off-the-shelf, terrestrially sourced JSC-1A and NU-LHT-4M are more oxidized than most lunar materials,3which likely leads to different oxidation-reduction reactions than would be expected in lunar regolith. Figure 3 shows the integrated peak area of carbon dioxide for each sample combination that contained ammonia in methanol solution. The addition of ammonia to the GC vials results in a consistent and reproducible decrease in carbon dioxide gas, even at 50°C. The effect became more pronounced when JSC-1A or NU-LHT-4M were present. This set of experiments demonstrated that the sample composition will affect the chemical and physical state of each component present. Future spectroscopic and microscopy experiments will be geared towards identifying the cause for the CO2(g) concentration decrease and the consumption of hydrogen sulfide. As cold and volatile curation scientists, this information provides necessary insight on how to appropriately handle and analyze volatile bearing returned samples, as well as predict the effect chemical composition has on the various sample phases we will analyze upon return to Earth. Unlike traditional curation of geologic materials, the molecules in a sample cannot be identified or processed using the naked eye or even an optical microscope. Volatile curation will require a combination of analytical techniques, including but not limited to highly sensitive gas and solid/condensed phase spectroscopy. This set of experiments has demonstrated the need for more detailed studies of volatile mixtures with mineralogically and geochemically analogous lunar regolith simulants to prepare for the curation of volatile-rich lunar samples from the south polar region of the Moon. References: [1] Colaprete, A., et al. (2010) Science, 330, (463-468). [2] Amick, C. L., et al.(2023) Houston, Texas, [3] Heiken, G. H., et al.(1991) (778-778)

The presence and distribution of preserved organic matter on the surface of Mars can provide key information about the Martian carbon cycle and the potential of the planet to host life throughout its history. Several types of organic molecules have been previously detected in Martian meteorites1 and at Gale crater, Mars. Evaluating the diversity and detectability of organic matter elsewhere on Mars is important for understanding the extent and diversity of Martian surface processes and the potential availability of carbon sources1,5,6. Here we report the detection of Raman and fluorescence spectra consistent with several species of aromatic organic molecules in the Máaz and Séítah formations within the Crater Floor sequences of Jezero crater, Mars. We report specific fluorescence-mineral associations consistent with many classes of organic molecules occurring in different spatial patterns within these compositionally distinct formations, potentially indicating different fates of carbon across environments. Our findings suggest there may be a diversity of aromatic molecules prevalent on the Martian surface, and these materials persist despite exposure to surface conditions. These potential organic molecules are largely found within minerals linked to aqueous processes, indicating that these processes may have had a key role in organic synthesis, transport or preservation.

We conducted a petrologic study of apatite within one LL chondrite, six R chondrites, and six CK chondrites. These data were combined with previously published apatite data from a broader range of chondrite meteorites to determine that chondrites host either chlorapatite or hydroxylapatite with ≤33 mol% F in the apatite X-site (unless affected by partial melting by impacts, which can cause F-enrichment of residual apatite). These data indicate that either fluorapatite was not a primary condensate from the solar nebula or that it did not survive lower temperature nebular processes and/or parent body processes. Bulk-rock Cl and F data from chondrites were used to determine that the solar system has a Cl/F ratio of 10.5 ± 1.0 (3σ). The Cl/F ratios of apatite from chondrites are broadly reflective of the solar system Cl/F value, indicating that apatite in chondrites is fluorine poor because the solar system has about an order of magnitude more Cl than F. The Cl/F ratio of the solar system was combined with known apatite-melt partitioning relationships for F and Cl to predict the range of apatite compositions that would form from a melt with a chondritic Cl/F ratio. This range of apatite compositions allowed for the development of a crude model to use apatite X-site compositions from achondrites (and chondrite melt rocks) to determine whether they derive from a volatile-depleted and/or differentiated source, albeit with important caveats that are detailed in the manuscript. This study further highlights the utility of apatite as a mineralogical tool to understand the origin of volatiles (including H2O) and the diversity of their associated geological processes throughout the history of our solar system, including at its nascent stage.

Mercury, the innermost planet, formed under highly reduced conditions, based mainly on surface Fe, S, and Si abundances determined from MESSENGER mission data. The minor element Cr may serve as an independent oxybarometer but only very limited Cr data have been previously reported for Mercury. We report Cr/Si abundances across Mercury's surface based on MESSENGER X-Ray Spectrometer data throughout the spacecraft's orbital mission. The heterogeneous Cr/Si ratio ranges from 3.6 × 10-5 in the Caloris Basin to 0.0012 within the high-magnesium region, with an average southern hemisphere value of 0.0008 (corresponding to about 200 ppm Cr). Absolute Cr/Si values have systematic uncertainty of at least 30%, but relative variations are more robust. By combining experimental Cr partitioning data along with planetary differentiation modeling, we find that if Mercury formed with bulk chondritic Cr/Al, Cr must be present in the planet's core and differentiation must have occurred at log ƒO2 in the range of IW-6.5 to IW-2.5 in the absence of sulfides in its interior and a range of IW-5.5 to IW-2 with an FeS layer at the core-mantle boundary. Models with large fractions of Mg-Ca-rich sulfides in Mercury's interior are more compatible with moderately reducing conditions (IW-5.5 to IW-4) owing to the instability of Mg-Ca-rich sulfides at elevated ƒO2. These results indicate that if Mercury differentiated at a log ƒO2 lower than IW-5.5, the presence of sulfides whether in the form of a FeS layer at the top of the core or Mg-Ca-rich sulfides within the mantle would be unlikely.

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) are documented to exceed 80‰ between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history. The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements. This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the modified Middleton ion source of an existing accelerator mass spectrometer. For samples with as little as 1 μg Cl–the equivalent of 2–4 mm3 of a typical lunar rock sample–the average cathode accuracy is ∼1‰. Cathode reproducibility is typically ∼1‰ (2σ) for samples with at least 10 μg of Cl, increasing to ∼3–6‰ for aliquots with ∼1–2 μg Cl, similar to published SIMS results and sufficient to study astromaterials from the Moon, Mars, or 4 Vesta, which have tens of ‰ observed variations.

Dust transported in the martian atmosphere is of intrinsic scientific interest and has relevance for the planning of human missions in the future. The MSR Campaign, as currently designed, presents an important opportunity to return serendipitous, airfall dust. The tubes containing samples collected by the Perseverance rover would be placed in cache depots on the martian surface perhaps as early as 2023–24 for recovery by a subsequent mission no earlier than 2028–29, and possibly as late as 2030–31. Thus, the sample tube surfaces could passively collect dust for multiple years. This dust is deemed to be exceptionally valuable as it would inform our knowledge and understanding of Mars' global mineralogy, surface processes, surface-atmosphere interactions, and atmospheric circulation. Preliminary calculations suggest that the total mass of such dust on a full set of tubes could be as much as 100 mg and, therefore, sufficient for many types of laboratory analyses. Two planning steps would optimize our ability to take advantage of this opportunity: (1) the dust-covered sample tubes should be loaded into the Orbiting Sample container (OS) with minimal cleaning and (2) the capability to recover this dust early in the workflow within an MSR Sample Receiving Facility (SRF) would need to be established. A further opportunity to advance dust/atmospheric science using MSR, depending upon the design of the MSR Campaign elements, may lie with direct sampling and the return of airborne dust.

We conducted a petrologic study of apatite within eight unbrecciated, non-cumulate eucrites and two monomict, non-cumulate eucrites. These data were combined with previously published data to quantify the abundances of F, Cl, and H2O in the bulk silicate portion of asteroid 4 Vesta (BSV). Using a combination of apatite-based melt hygrometry/chlorometry and appropriately paired volatile/refractory element ratios, we determined that BSV has 3.0–7.2 ppm F, 0.39–1.8 ppm Cl, and 3.6–22 ppm H2O. The abundances of F and H2O are depleted in BSV relative to CI chondrites to a similar degree as F and H2O in the bulk silicate portion of the Moon. This degree of volatile depletion in BSV is similar to what has been determined previously for many moderately volatile elements in 4 Vesta (e.g., Na, K, Zn, Rb, Cs, and Pb). In contrast, Cl is depleted in 4 Vesta by a greater degree than what is recorded in samples from Earth or the Moon. Based on the Cl-isotopic compositions of eucrites and the bulk rock Cl/F ratios determined in this study, the eucrites likely formed through serial magmatism of a mantle with heterogeneous δ37Cl and Cl/F, not as extracts from a partially crystallized global magma ocean. Furthermore, the volatile depletion and Cl-isotopic heterogeneity recorded in eucrites is likely inherited, at least in part, from the precursor materials that accreted to form 4 Vesta and is unlikely to have resulted solely from degassing of a global magma ocean, magmatic degassing of eucrite melts, and/or volatile loss during thermal metamorphism. Although our results can be reconciled with the past presence of wide-scale melting on 4 Vesta (i.e., a partial magma ocean), any future models for eucrite petrogenesis involving a global magma ocean would need to account for the preservation of a heterogeneous eucrite source with respect to Cl/F ratios and Cl isotopes.

In the fifty years since the first lunar samples were collected on Apollo 11, significant advancements have taken place in laboratory analysis, planetary science, and astromaterials curation. These advances are now being leveraged for the Apollo Next Generation Sample Analysis (ANGSA) Program, which aims to study specially curated Apollo samples that have never been studied before. Since Apollo 17 in 1972, a great deal has been learned about the Moon, including the unique environments of the poles. Building upon Apollo and remote sensing studies since then, the Artemis Program aims to explore the cold environments near the lunar south pole while achieving the concurrent goals of landing the first woman and the next man on the Moon by 2024. Recent developments for ANGSA have significantly accelerated our readiness for Artemis sample return, particularly in the area of cold sample studies. Four science teams were selected to study cold and/or volatile-bearing samples collected during the Apollo program. These samples have special storage and handling requirements that necessitate their processing in a -20°C environment that meets the Apollo materials and cleanliness requirements. NASA has recently undertaken the development and implementation of a cold sample processing facility to support ANGSA. A similar facility will be needed to process the cold, volatile-bearing samples planned to be returned by Artemis missions; therefore, ANGSA provides excellent preparation for Artemis’ future cold sample processing efforts. We will outline the goals of the ANGSA and Artemis programs, illustrating the complementary nature of the work for both. We will describe the efforts to date in designing, testing, and implementing a cold curation facility that meets the requirements of ANGSA and Apollo curation. We will then outline future work for that facility to reach operational readiness. Finally, we will present the sample collection and curation strategies for Artemis, showing how they overlap and build on ANGSA efforts. The development of cold curation at NASA represents a significant leap in the knowledge, experience, and technologies used in astromaterials curation, opening the door for new investigations of lunar volatiles, impacts, formation processes, prebiotic chemistry, and resource utilization, among many others.

Advanced curation is a cross-disciplinary field of research and development aiming to improve curation and sample acquisition practices in existing astromaterials collections and to enable future sample return activities.The primary result of advanced curation is to both reduce and quantify contamination to astromaterials and preserve the scientific integrity of all samples from mission inception to scientific analysis. Over the next decade, NASA should support advanced curation research and monitoring efforts as they pertain to improving our current collections and preparing for samples from current and future astromaterials acquisition activities.We highlight here five advanced curation activities of critical importance for the success of sample science supported by NASA over the coming decade, including: 1) supporting efforts to build contamination knowledge collections as part of sample return missions, which requires curation involvement from the earliest stages of sample return mission planning;2) supporting Earth-based astromaterials collection campaigns of meteorites and cosmic dust as they represent relatively inexpensive sample acquisition activities that continue to grow NASA’s astromaterials collections and enable new discoveries;3) preparing to curate and process samples under “cold” conditions to enable return of samples from volatile-rich Solar System targets like permanently shadowed regions on the lunar surface orcomets;4) determining how best to combine clean room technology and biosafety technology into one infrastructure to support curation of samples from bodies designated as Category V:Restricted Earth Return; and 5) supporting real-time monitoring and testing of curation labs to verify that sample processing environments remain clean from the standpoint of inorganic, organic, and biological contamination

We conducted in-situ Cl isotopic measurements of apatite within intercumulus regions and within a holocrystalline olivine-hosted melt inclusion in magnesian-suite troctolite 76535 from Apollo 17. These data were collected to place constraints on the Cl-isotopic composition of the last liquid to crystallize from the lunar magma ocean (i.e., urKREEP, named after its enrichments in incompatible lithophile trace elements like potassium, rare earth elements, and phosphorus). The apatite in the olivine-hosted melt inclusion and within the intercumulus regions of the sample yielded Cl-isotopic compositions of 28.3 ± 0.9 ‰ (2σ) and 30.3 ± 1.1 ‰ (2σ), respectively. The concordance of these values from both textural regimes we analyzed indicates that the Cl-isotopic composition of apatites in 76535 likely represents the Cl-isotopic composition of the KREEP-rich magnesian-suite magmas. Based on the age of 76535, these results imply that the KREEP reservoir attained a Cl-isotopic composition of 28–30 ‰ by at least 4.31 Ga, consistent with the onset of Cl-isotopic fractionation at the time of lunar magma ocean crystallization or shortly thereafter. Moreover, lunar samples that yield Cl-isotopic compositions higher than the value for KREEP are likely affected by secondary processes such as impacts and/or magmatic degassing. The presence of KREEP-rich olivine-hosted melt inclusions within one of the most pristine and ancient KREEP-rich rocks from the Moon provides a new opportunity to characterize the geochemistry of KREEP. In particular, a broader analysis of stable isotopic compositions of highly and moderately volatile elements could provide an unprecedented advancement in our characterization of the geochemical composition of the KREEP reservoir and of volatile-depletion processes during magma ocean crystallization, more broadly.

Data from Mariner 10, MESSENGER, and ground-based telescopic observations have facilitated great advancements towards understanding the geochemistry, geology, internal structure, and space environment (exosphere/magnetosphere) of Mercury. Future exploration efforts by BepiColombo, landed science, and sample return will revolutionize our understanding of this planet. However, to enhance the scientific return of past, present, and future data collection at Mercury, it is imperative that laboratory and field-based studies be conducted over the next decade. This white paper gives examples of laboratory and field studies, including instrument testing, which should take place over the next decade to facilitate the interpretation of data and preparation of future missions to the inner-most planet. By no means are the topics in this paper exhaustive, but rather are meant to demonstrate the immense amount of work that needs to be completed ahead of, or in conjunction with, current and future exploration efforts of Mercury. This work would amplify the benefits from additional data obtained from the planet’s surface to the fullest extent possible, and to aid in decision making of future instrument payloads. We have chosen to focus our inputs here on geochemistry, geology, and space environment related efforts, but we emphasize that extensive research in the areas of geophysics and other geosciences-related disciplines will benefit from additional studies.

The composition of a planet’s core has important implications for the thermal and magmatic evolution of that planet. Here, we conducted carbon (C)solubility experiments on iron-silicon (Fe-Si)metal mixtures (up to 35 wt%(~52 atom%)Si) at 1 GPa and 800–1800°C to determine the carbon concentration at graphite saturation (CCGS) in metallic melt and crystalline metal with varying proportions of Fe and Si to constrain the C content of Mercury’s core. Our results, combined with those in the literature, show that composition is the major controlling factor for carbon solubility in Fe-rich metal with minimal effects from temperature and pressure. Moreover, there is a strong anti-correlation between the abundances of carbon and silicon in iron-rich metallic systems. Based on the previous estimates of <1–25 wt% Si in Mercury’s core, our results indicate that a carbon-saturated mercurian core has 0.5–6.4wt% C, with 6.4wt% C corresponding to an Si-free, Fe core and 0.5wt% C corresponding to an Fe-rich core with 25 wt% Si. The upper end of estimated FeO abundances in the mantle(up to 2.2 wt%)are consistent with a core that has <1 wt% Siand up to 6.4 wt% C, which would imply that bulk Mercury has a superchondritic Fe/Si ratio. However,the lower end of estimated FeO (≤ 0.05 wt%) support CB-chondrite like bulk compositions of Mercury with core Si abundances in the range of 5–18.5 wt% 33 and C abundances in the range of 0.8–4.0 wt%.