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Reducing Organic Contamination in NASA JSC Astromaterial Curation Facility

Future robotic and human spaceflight missions to the Moon, Mars, asteroids and comets will require handling and storing astromaterial samples with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. Much was learned from the rigorous attempts to minimize and monitor organic contamination during Apollo, but it was not adequate for current analytical requirements; thus [1]. OSIRIS-REx, Hayabusa-2, and future Mars sample return will require better protocols for reducing organic contamination. Future isolation con-tainment systems for astromaterials, possibly nitrogen enriched gloveboxes, must be able to reduce organic and inorganic cross-contamination. In 2012, a baseline study established the current state of organic cleanliness in gloveboxes used by NASA JSC astromaterials curation labs that could be used as a benchmark for future mission designs [2, 3]. After standard ultra-pure water (UPW) cleaning, the majority of organic contaminates found were hydrocarbons, plasticizers, silicones, and solvents. Hydro-carbons loads (> C7) ranged from 1.9 to 11.8 ng/cm2 for TD-GC-MS wafer exposure analyses and 5.0 to 19.5 ng/L for TD-GC-MS adsorbent tube exposure. Plasticizers included < 0.6 ng/cm2 of DBP, DEP, TXIB, and DIBP. Silicones included < 0.5 ng/cm2 of cyclo(Me2SiO)x (x = 6, 8, 9, 10) and siloxane. Solvents included < 1.0 ng/cm2 of 2-cyclohexen-1-one, 3,5,5-trimethyl- (Isopho-rone), N-formylpiperidine, and 2-(2-butoxyethoxy) ethanol. In addition, DBF, rubber/polymer additive was found at < 0.2 ng/cm2 and caprolactam, nylon-6 at < 0.6 ng/cm2. Reducing Organics: The Apollo program was the last sam-ple return mission to place high-level organic requirements and biological containment protocols on a curation facility. The high vacuum complex F-201 glovebox in the Lunar Receiving Labora-tory used ethyl alcohol (190 proof), 3:1 benzene/methanol (nano grade solution), and heat sterilization at 130degC for 48 hours to reduce organic contamination. In addition, both heat sterilization and peracetic acid sterilization were used in the atmospheric de-contamination (R) cabinets. Later, Lunar curation gloveboxes were degreased with a pressurized Freon 113 wash. Today, UPW has replaced Freon as the standard cleaning procedure, but does not have the degreasing solvency power of Freon. Future Cleaning Studies: Cleaning experiments are cur-rently being orchestrated to study how to degrease and reduce organics in a JSC curation glovebox lower than the established baseline. Several new chemicals in the industry have replaced traditional degreasing solvents such as Freon and others that are now federally restricted. However, these new suites of chemicals remain untested for lowering organics in curation gloveboxes. 3M's HFE-7100DL and DuPont's Vertrel XF are currently being tested as a replacement for Freon 113 as a degreaser at JSC cura-tion facilities. In addition, the use of UPW as a final rinse is be-ing tested, which presumably can maintain a lower total organic carbon load than the filtered purity of chemical solutions. References: [1] Allton J.H. et al. (2012) LPS XLIII, 2439; [2] Calaway M.

Calaway, M. J.↗

Organic Contamination Baseline Study in NASA Johnson Space Center Astromaterials Curation Laboratories

Future robotic and human spaceflight missions to the Moon, Mars, asteroids, and comets will require curating astromaterial samples with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. 21st century sample return missions will focus on strict protocols for reducing organic contamination that have not been seen since the Apollo manned lunar landing program. To properly curate these materials, the Astromaterials Acquisition and Curation Office under the Astromaterial Research and Exploration Science Directorate at NASA Johnson Space Center houses and protects all extraterrestrial materials brought back to Earth that are controlled by the United States government. During fiscal year 2012, we conducted a year-long project to compile historical documentation and laboratory tests involving organic investigations at these facilities. In addition, we developed a plan to determine the current state of organic cleanliness in curation laboratories housing astromaterials. This was accomplished by focusing on current procedures and protocols for cleaning, sample handling, and storage. While the intention of this report is to give a comprehensive overview of the current state of organic cleanliness in JSC curation laboratories, it also provides a baseline for determining whether our cleaning procedures and sample handling protocols need to be adapted and/or augmented to meet the new requirements for future human spaceflight and robotic sample return missions.

Calaway, Michael J.↗

The Astromaterials X-Ray Computed Tomography Laboratory at Johnson Space Center

The Astromaterials Acquisition and Curation Office at NASA's Johnson Space Center (hereafter JSC curation) is the past, present, and future home of all of NASA's astromaterials sample collections. JSC curation currently houses all or part of nine different sample collections: (1) Apollo samples (1969), (2) Lunar samples (1972), (3) Antarctic meteorites (1976), (4) Cosmic Dust particles (1981), (5) Microparticle Impact Collection (1985), (6) Genesis solar wind atoms (2004); (7) Stardust comet Wild-2 particles (2006), (8) Stardust interstellar particles (2006), and (9) Hayabusa asteroid Itokawa particles (2010). Each sample collection is housed in a dedicated clean room, or suite of clean rooms, that is tailored to the requirements of that sample collection. Our primary goals are to maintain the long-term integrity of the samples and ensure that the samples are distributed for scientific study in a fair, timely, and responsible manner, thus maximizing the return on each sample. Part of the curation process is planning for the future, and we also perform fundamental research in advanced curation initiatives. Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of sample collections, or getting new results from existing sample collections [2]. We are (and have been) planning for future curation, including cold curation, extended curation of ices and volatiles, curation of samples with special chemical considerations such as perchlorate-rich samples, and curation of organically- and biologically-sensitive samples. As part of these advanced curation efforts we are augmenting our analytical facilities as well. A micro X-Ray computed tomography (micro-XCT) laboratory dedicated to the study of astromaterials will be coming online this spring within the JSC Curation office, and we plan to add additional facilities that will enable nondestructive (or minimally-destructive) analyses of astromaterials in the near future (micro-XRF, confocal imaging Raman Spectroscopy). These facilities will be available to: (1) develop sample handling and storage techniques for future sample return missions; (2) be utilized by PET for future sample return missions; (3) be used for retroactive PET (Positron Emission Tomography)-style analyses of our existing collections; and (4) for periodic assessments of the existing sample collections. Here we describe the new micro-XCT system, as well as some of the ongoing or anticipated applications of the instrument.

Zeigler, R. A.↗

The Astromaterials X-Ray Computed Tomography Laboratory at Johnson Space Center

The Astromaterials Acquisition and Curation Office at NASA's Johnson Space Center (hereafter JSC curation) is the past, present, and future home of all of NASA's astromaterials sample collections. JSC curation currently houses all or part of nine different sample collections: (1) Apollo samples (1969), (2) Lunar samples (1972), (3) Antarctic meteorites (1976), (4) Cosmic Dust particles (1981), (5) Microparticle Impact Collection (1985), (6) Genesis solar wind atoms (2004); (7) Stardust comet Wild-2 particles (2006), (8) Stardust interstellar particles (2006), and (9) Hayabusa asteroid Itokawa particles (2010). Each sample collection is housed in a dedicated clean room, or suite of clean rooms, that is tailored to the requirements of that sample collection. Our primary goals are to maintain the long-term integrity of the samples and ensure that the samples are distributed for scientific study in a fair, timely, and responsible manner, thus maximizing the return on each sample. Part of the curation process is planning for the future, and we also perform fundamental research in advanced curation initiatives. Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of sample collections, or getting new results from existing sample collections [2]. We are (and have been) planning for future curation, including cold curation, extended curation of ices and volatiles, curation of samples with special chemical considerations such as perchlorate-rich samples, and curation of organically- and biologically-sensitive samples. As part of these advanced curation efforts we are augmenting our analytical facilities as well. A micro X-Ray computed tomography (micro-XCT) laboratory dedicated to the study of astromaterials will be coming online this spring within the JSC Curation office, and we plan to add additional facilities that will enable nondestructive (or minimally-destructive) analyses of astromaterials in the near future (micro-XRF, confocal imaging Raman Spectroscopy). These facilities will be available to: (1) develop sample handling and storage techniques for future sample return missions; (2) be utilized by PET for future sample return missions; (3) be used for retroactive PET (Positron Emission Tomography)-style analyses of our existing collections; and (4) for periodic assessments of the existing sample collections. Here we describe the new micro-XCT system, as well as some of the ongoing or anticipated applications of the instrument.

Zeigler, R. A.↗

The Astromaterials X-Ray Computed Tomography Laboratory at Johnson Space Center

The Astromaterials Acquisition and Cura-tion Office at NASA's Johnson Space Center (hereafter JSC curation) is the past, present, and future home of all of NASA's astromaterials sample collections. JSC curation currently houses all or part of nine different sample collections. Our primary goals are to maintain the long-term integrity of the samples and ensure that the samples are distributed for scientific study in a fair, timely, and responsible manner, thus maximizing the return on each sample. Part of the curation process is planning for the future, thus we also perform funda-mental research in advanced curation initiatives. Ad-vanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of sample collections, or getting new results from existing sample collections [1]. As part of these ad-vanced curation efforts we are augmenting our analyti-cal facilities.

Zeigler, R. A.↗

Development of the Thermal Interface Between the Dragonfly Mass Spectrometer and the DrACO Sample Delivery Carousel

Icy celestial bodies are an exciting new frontier for surface exploration and in-situ sampling and analysis. These destinations are inherently cryogenic in nature, and each body presents unique challenges related to thermal design. The Dragonfly mission to Titan is one such example. One of the most important requirements of a sampling system is to preserve the integrity of the surface material. The interface between the Dragonfly Mass Spectrometer (DraMS) and the Drill for Acquisition of Complex Organics (DrACO) is complicated by several competing requirements. Development of this interface has required the use of new enabling technologies such as 3D printing to achieve a successful design. This overview of the DraMS Cryogenic subsystem will show how the design meets all the requirements of the interface and preserves integrity of Titan surface samples.

Peter W. Barfknecht↗

Magnetic Shield Design Modeling and Validation on SWOT Spacecraft Applied to Mars Flux Pinning Orbiting Sample Design

A modeling methodology was developed for use on the Surface Water and Ocean Topography (SWOT) mission for the computational modeling and design of a magnetic shield for a 63 A-sq m source. Shield options were modeled and tested across various design parameters and validated with measurement. Measurement results fell within 10% of simulation in most cases of concern with sources of error well understood. These methods results informed a subsequent modeling activity for a future Mars Sample Return (MSR) mission concept with stringent magnetic cleanliness requirements to retain geologic integrity of the samples. One option for capturing the sample from orbit requires rare earth magnets in close proximity to the Martian samples. Magnetic modeling with a finite-element method solver estimated the magnetic environment and established the need for shielding. Further modeling then determined the shielding necessary to meet magnetic requirements, followed by the design of a mass-optimized solution.

Gonzales, Edward↗

Using X-Ray Computed Tomography as a Tool for Preliminary Examination Tool of Current and Future Extraterrestrial Sample Return Missions

The Astromaterials Acquisition and Curation Office at the Johnson Space Center is the past, present, and future home of all of NASA’s astromaterials sample collections. The primary goals of the curation office are to maintain the long-term integrity of the samples and ensure that the samples are distributed for scientific study in a fair, timely, and responsible manner, thus maximizing the return on each sample. Part of the curation process is planning for the future. To this end, we perform fundamental research in advanced curation initiatives to better prepared for future sample return missions. Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new sample collections, or getting new results from existing sample collections. As part of these advanced curation efforts, we have installed and are operating a Nikon XTH 320 X-ray Computed Tomography(XCT) system in the JSC curation office with four interchangeable X-ray sources, a large-area detector, and a heavy-duty stage. These instrument characteristics allow us exceptional flexibility to analyze a wide range of sample sizes, from sub-mm soil particles to rocks >10 cm in diameter. The penetrative nature of the XCT scans allows for astromaterials samples to be analyzed within sealed low-density containers (e.g., Teflon bags), preserving the pristinity of the samples. We have begun scanning of the Apollo and Antarctic Meteorite sample suites in order to non-destructively map out lithic clasts (and other features) within the samples. The data from these scans will be made available to scientists via the JSC curation website and the Astromaterials Curation Newsletter. We anticipate sample requests from these “new” lithic clasts identified in these “old” samples. We also anticipate that XCT analyses like these would be useful for future sample return missions, like the OSIRIS REx mission, as well as future sample return missions.

Zeigler, Ryan↗

Remotely-Sensed Aerosol Optical Properties Retrieved from a High Spectral Resolution Lidar (HSRL) During the FIREX-AQ Field Campaign

The NASA Langley Research Center’s High Spectral Resolution Lidar with Differential Absorption Lidar (HSRL-DIAL) instrument was flown on the NASA DC-8 aircraft during the Fire Influence on Region to Global Environments and Air Quality (FIREX-AQ; https://www.esrl.noaa.gov/csl/projects/firex-aq/) field campaign. The airborne HSRL-DIAL system retrieves aerosol backscatter and depolarization at 3 wavelengths (355, 532, and 1064 nm), aerosol extinction at 532 nm, and ozone concentration (differential at 290 and 300 nm). Additionally, the HSRL-DIAL system incorporates both a zenith and nadir telescope allowing for retrievals from in-smoke sampling to be integrated through the plume. During the first portion of the FIREX-AQ campaign, the DC8 aircraft sampled more than ten large-scale fires with varying fuels, combustion stages, and metrological conditions, with some fires being sampled multiple times across separate days. This presentation focuses on the retrievals of aerosol backscatter (at 532 and 1064 nm), aerosol depolarization (at 532 nm and 1064 nm), aerosol optical thickness (at 532 nm), lidar ratio, and color ratio to examine the changes in these properties in the smoke plume as they are advected downwind.

Taylor Shingler↗

The Acquisition, Containment, and Curation of Mars Samples on Earth

The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center (henceforth AACO) is responsible for receiving and curating all of NASA’s extraterrestrial samples, current and future (as per NASA Policy Directive (NPD) 7100.10E “Curation of Extraterrestrial Materials”). As such, the AACO coordinates sample capture, containment, and transportation to the curation facility as well as documents, preserves, prepares, and distributes all of the samples within NASA’s astromaterial collections for research, education, and public outreach. Since the lunar rock and soil samples returned during the Apollo Program, NASA’s first Class V Restricted Earth Return Missions, the AACO curates six other astromaterials collections. Lessons learned from each collection and respective missions (e.g. Apollo, Genesis, Stardust) as well as advancements in science and technology have informed the AACO’s plan for acquiring and curating Martian samples. Given the nature of the collection, a mobile and modular facility is recommended. The two broad requirements a Mars sample facility must maintain are: 1) the ability to contain the samples to protect the public from exposure of an “unknown unknown” biological agent and 2) ensure the scientific integrity of the samples are maintained (while maximizing scientific outcome). Although Apollo samples were eventually deemed safe and released to the scientific community for evaluation, there is no guarantee that this will be the case for Martian samples. Therefore, the facility in which the samples will be contained and investigated must be modular and able to accommodate an array of instrumentation that could be highly variable depending on the initial scientific outcomes. Furthermore, in order to facilitate proper sample capture and containment upon landing as well as sample distribution to other laboratories with proper containment, a mobile facility is a valuable investment.

Harrington, Andrea D.↗

Design considerations for high-power VHF radar transceivers: The Poker Flat MST radar phase control system

Sixty-four separate 50-kW peak-power transmitters are distributed throughout the 200 x 200 meter Poker Flat MST radar antenna array. The relative phase of each transmitter is automatically controlled by a 64-channel unit located in the main building at the edge of the antenna. The phase control unit is described. In operation the RF pulse from a transmitter coupler is power divided and compared with the phase reference in a mixer. The mixer output is low-pass filtered and sampled near the center of the resulting video pulse by an amplifying sample-and-hold integrated circuit. Phase control is effected by maintaining the mixer output pulse near zero volts by amplifying the sample-and-hold output which then drives the voltage-controlled phase shifter in the direction to null the mixer output. The voltage-controlled shifter achieves over 360 deg phase shift in the range from 0.7 to 24 volts. When the voltage into the shifter tracks to either voltage limit the wrap-around control resets the voltage so that the shifter is always operating within its control range.

Ecklund, W. L.↗

Sample Acquisition Techniques for Exobiology Flight Experiments

Exobiology Flight Experiments involve complex analyses conducted in environments far different than those encountered in terrestrial applications. A major part of the analytical challenge is often the selection, acquisition, delivery and, in some cases, processing of a sample suitable for the analytical requirements of the mission. The added complications of severely limited resources and sometimes rigid time constraints combine to make sample acquisition potentially a major obstacle for successful analyses. Potential samples come in a wide range including planetary atmospheric gas and aerosols (from a wide variety of pressures), planetary soil or rocks, dust and ice particles streaming off of a comet, and cemetery surface ice and rocks. Methods to collect and process sample are often mission specific, requiring continual development of innovative concepts and mechanisms. These methods must also maintain the integrity of the sample for the experimental results to be meaningful. We present here sample acquisition systems employed from past missions and proposed for future missions.

Kojiro, Daniel R.↗

Advanced Curation of Astromaterials for Planetary Science Over the Next Decade

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

Francis M. McCubbin↗

A controlled rate freeze/thaw system for cryopreservation of biological materials

A system which allows programmable temperature-time control for a 5 cc sample volume of an arbitrary biological material was constructed. Steady state and dynamic temperature control was obtained by supplying heat to the sample volume through resistive elements constructed as an integral part of the sample container. For cooling purposes, this container was totally immersed into a cold heat sink. Sample volume thermodynamic property data were obtained by measurements of heater power and heat flux through the container walls. Using a mixture of dry ice and alcohol at -79 C, sample volume was controlled from +40 C to -60 C at rates from steady state to + or - 65 C/min. Steady state temperature precision was better than 0.2 C while the dynamic capability depends on the temperature rate of change as well as the thermal mass of the sample and the container.

Anselmo, V. J.↗

Programmable temperature control system for biological materials

A system was constructed which allows programmable temperature-time control for a 5 cu cm sample volume of arbitrary biological material. The system also measures the parameters necessary for the determination of the sample volume specific heat and thermal conductivity as a function of temperature, and provides a detailed measurement of the temperature during phase change and a means of calculating the heat of the phase change. Steady-state and dynamic temperature control is obtained by supplying heat to the sample volume through resistive elements constructed as an integral part of the sample container. For cooling purposes, this container is totally immersed into a cold heat sink. Using a mixture of dry ice and alcohol at 79 C, the sample volume can be controlled from +40 to -60 C at rates from steady state to + or - 65 C/min. Steady-state temperature precision is better than 0.2 C, while the dynamic capability depends on the temperature rate of change as well as the mass of both the sample and the container.

Anselmo, V. J.↗

Radiation-Conditioned Ti–hBN Coatings for Space Mechanisms: Bridging Tribology and Irradiation Effects from Laboratory to Low-Earth Orbit

The longevity of tribological components in extraterrestrial environments is challenged by abrasive regolith, extreme temperatures, and ionizing radiation. This study evaluates the performance of vacuum plasma sprayed (VPS) Ti-2vol.% hexagonal boron nitride (hBN) coatings applied to joint mechanisms such as rod and slot, ball and socket, and hinge assemblies, fabricated from Al6061 and Ti6Al4V for planetary structures. Coated and uncoated samples were tested under vacuum with lunar regolith simulant (JSC-1A), followed by environmental exposures including electron radiation and thermal cycling. Results show that coated samples consistently outperformed uncoated counterparts across all configurations. Wear depth in coated components was reduced by over 80%, as confirmed by 3D profilometry and surface imaging. SEM analysis revealed severe abrasion and localized plastic deformation in uncoated surfaces, while coated samples retained structural integrity due to synergy of hard protective phases formed during deposition and retained hBN providing solid lubrication in the sliding surface. Coated and exposed samples exhibited smoother actuation profiles and reduced friction, indicating a beneficial "conditioning" effect from environmental exposure. The coatings-maintained performance even on complex geometries with minimal delamination. These findings demonstrate the potential of VPS Ti-hBN coatings to extend the operational life of lunar mechanisms, bridging laboratory-scale tribology with flight-relevant mechanical applications.

tribology↗

Production of long-term global water vapor and liquid water data set using ultra-fast methods to assimilate multi-satellite and radiosonde observations

During the next decade, many programs and experiments under the Global Energy and Water Cycle Experiment (GEWEX) will utilize present day and future data sets to improve our understanding of the role of moisture in climate, and its interaction with other variables such as clouds and radiation. An important element of GEWEX will be the GEWEX Water Vapor Project (GVaP), which will eventually initiate a routine, real-time assimilation of the highest quality, global water vapor data sets including information gained from future data collection systems, both ground and space based. The comprehensive global water vapor data set being produced by METSAT Inc. uses a combination of ground-based radiosonde data, and infrared and microwave satellite retrievals. This data is needed to provide the desired foundation from which future GEWEX-related research, such as GVaP, can build. The first year of this project was designed to use a combination of the best available atmospheric moisture data including: radiosonde (balloon/acft/rocket), HIRS/MSU (TOVS) retrievals, and SSM/I retrievals, to produce a one-year, global, high resolution data set of integrated column water vapor (precipitable water) with a horizontal resolution of 1 degree, and a temporal resolution of one day. The time period of this pilot product was to be det3ermined by the availability of all the input data sets. January 1988 through December 1988 were selected. In addition, a sample of vertically integrated liquid water content (LWC) was to be produced with the same temporal and spatial parameters. This sample was to be produced over ocean areas only. Three main steps are followed to produce a merged water vapor and liquid water product. Input data from Radiosondes, TOVS, and SSMI/I is quality checked in steps one and two. Processing is done in step two to generate individual total column water vapor and liquid water data sets. The third step, and final processing task, involves merging the individual output products to produce the integrated water vapor product. A final quality control is applied to the merged data sets.

Vonderhaar, T. H.↗

Geolab in NASA's First Generation Pressurized Excursion Module: Operational Concepts

We are building a prototype laboratory for preliminary examination of geological samples to be integrated into a first generation Habitat Demonstration Unit-1/Pressurized Excursion Module (HDU1-PEM) in 2010. The laboratory GeoLab will be equipped with a glovebox for handling samples, and a suite of instruments for collecting preliminary data to help characterize those samples. The GeoLab and the HDU1-PEM will be tested for the first time as part of the 2010 Desert Research and Technology Studies (DRATS), NASAs annual field exercise designed to test analog mission technologies. The HDU1-PEM and GeoLab will participate in joint operations in northern Arizona with two Lunar Electric Rovers (LER) and the DRATS science team. Historically, science participation in DRATS exercises has supported the technology demonstrations with geological traverse activities that are consistent with preliminary concepts for lunar surface science Extravehicular Activities (EVAs). Next years HDU1-PEM demonstration is a starting point to guide the development of requirements for the Lunar Surface Systems Program and test initial operational concepts for an early lunar excursion habitat that would follow geological traverses along with the LER. For the GeoLab, these objectives are specifically applied to enable future geological surface science activities. The goal of our GeoLab is to enhance geological science returns with the infrastructure that supports preliminary examination, early analytical characterization of key samples, insight into special considerations for curation, and data for prioritization of lunar samples for return to Earth.

Evans, C. A.↗