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The CAESAR New Frontiers Mission: Comet Surface Sample Acquisition and Preservation

NASA recently selected the Comet Astrobiology Exploration Sample Return (CAESAR) mission for Phase A study in the New Frontiers Program. This mission will acquire and return to Earth for laboratory analysis at least 80 g of surface material from the nucleus of comet 67P/Churyumov-Gerasimenko (hereafter 67P). CAESAR will characterize the surface region sampled, preserve the sample in a pristine state, and return evolved volatiles by capturing them in a separate gas reservoir. The system protects both volatile and non-volatile components from contamination or alteration thatwould hamper their scientific analysis. Laboratory analyses of comet samples provide unparalleled knowledge about the presolar history through the initial stages of planet formation to the origin of life.

CAESAR↗

Pneumatic Sampler (P-Sampler) for the Martian Moons Exploration (MMX)

The Martian Moons eXploration (MMX) mission, led by the Japanese Aerospace Exploration Agency (JAXA), will focus on the exploration of the two Martian moons – Phobos and Deimos (Figure 1). The spacecraft will perform close-up remote sensing and observations of both moons and collect a sample from Phobos for Earth sample return. MMX has set the two mission goals: (1) determining the origin of the Martian moons and (2) observing processes in the circumplanetary environment of Mars, based on remote sensing, in-situ observations, and laboratory analyses of returned samples of Phobos regolith [1-2]. To fulfill the mission goals, MMX employs a double sampling approach: Coring and Pneumatic Samplers (Figure 2).The Coring Sampler (C-Sampler), a core soil tube deployed by a robotic arm, providing access to the building blocks of Phobos beneath the surface (>2 cm), and also collect a mixture of near surface material. The P-Sampler, on the other hand, would selectively sample the surface veneer and provides reference of surface component with the C-Sampler. The double sampling system not only enhances the scientific merits of MMX but also reduces risks associated with the sampling of Phobos. Without enough knowledge of the physical and chemical properties, and the geotechnical conditions of the surface of Phobos (e.g., compositions, temperature gradient/variation, porosity, grain size distribution), having two sampling systems that utilize entirely different sampling approaches is prudent.

Dylan Van Dyne↗

Xylan - A potential contaminant for lunar samples and Antarctic meteorites

The possibility that lunar samples have been contaminated by the proprietary lubricant paint known as Xylan, which has been applied to screw threads in dry-N sample processing cabinets at NASA JSC, is considered. From a sample analysis using sealed-tube and stepped combustion, it is argued that the unexpectedly high concentration of organic materials found in EET A79001 is not due to Xylan contamination. It is considered unlikely that previous C and N analyses of lunar samples have been affected by the introduction of Xylan.

Wright, I. P.↗

Sampling and Chemical Analysis of Potable Water for ISS Expeditions 12 and 13

The crews of Expeditions 12 and 13 aboard the International Space Station (ISS) continued to rely on potable water from two different sources, regenerated humidity condensate and Russian ground-supplied water. The Space Shuttle launched twice during the 12- months spanning both expeditions and docked with the ISS for delivery of hardware and supplies. However, no Shuttle potable water was transferred to the station during either of these missions. The chemical quality of the ISS onboard potable water supplies was verified by performing ground analyses of archival water samples at the Johnson Space Center (JSC) Water and Food Analytical Laboratory (WAFAL). Since no Shuttle flights launched during Expedition 12 and there was restricted return volume on the Russian Soyuz vehicle, only one chemical archive potable water sample was collected with U.S. hardware and returned during Expedition 12. This sample was collected in March 2006 and returned on Soyuz 11. The number and sensitivity of the chemical analyses performed on this sample were limited due to low sample volume. Shuttle flights STS-121 (ULF1.1) and STS-115 (12A) docked with the ISS in July and September of 2006, respectively. These flights returned to Earth with eight chemical archive potable water samples that were collected with U.S. hardware during Expedition 13. The average collected volume increased for these samples, allowing full chemical characterization to be performed. This paper presents a discussion of the results from chemical analyses performed on Expeditions 12 and 13 archive potable water samples. In addition to the results from the U.S. samples analyzed, results from pre-flight samples of Russian potable water delivered to the ISS on Progress vehicles and in-flight samples collected with Russian hardware during Expeditions 12 and 13 and analyzed at JSC are also discussed.

Straub, John E. II↗

A large interlaboratory electron diffraction study of monolayer graphene

Standardisation of data collection and analysis is essential to enable commercialisation of 2D materials in a wide range of technologies. Selected area electron diffraction (SAED) in the transmission electron microscope (TEM) is one of the key methods for distinguishing monolayer from bilayer and few-layer graphene by comparing the 1st and 2nd order diffraction spot intensities. Yet there are many factors that can affect the reliability of data collection and interpretation, causing the measurement of monolayer samples to deviate from the literature boundary condition of $I_{\{\bar{2}110\}}$$/$$I_{\{1\bar{1}00\}}$ < 1 for monolayer graphene (1LG). Here we present the results of a large interlaboratory SAED comparison study, where 15 international laboratories measured and analysed nominally identical samples of chemical vapour deposited graphene. Large variations were observed in the measured ratios of diffraction spot intensities, with the largest variance associated with poor quality SAED data resulting from inadequate specimen handling and storage. To inform the reliable determination of monolayer thickness from SAED patterns we provide a description of best practice for specimen handling, TEM operation, data collection and analysis. This work was undertaken within VAMAS Technical Working Area 41: Graphene and related 2D materials—Project 9, the results of which have been directly incorporated into ISO/TS 21356–2 for the characterisation of graphene sheets. We find that when this methodology is followed, 1LG can be distinguished from bilayer or thicker material with high confidence where analysis of a single SAED pattern gives $I_{\{\bar{2}110\}}$$/$$I_{\{1\bar{1}00\}}$ < 1.2, even in the absence of precise specimen tilting.

2D materials↗

Nondestructive Analysis of Apollo Samples by Micro-CT and Micro-XRF Analysis: A PET Style Examination

An integral part of any sample return mission is the initial description and classification of returned samples by the preliminary examination team (PET). The goal of a PET is to characterize and classify the returned samples, making this information available to the general research community who can then conduct more in-depth studies on the samples. A PET strives to minimize the impact their work has on the sample suite, which often limits the PET work to largely visual measurements and observations like optical microscopy. More modern techniques can also be utilized by future PET to nondestructively characterize astromaterials in a more rigorous way. Here we present our recent analyses of Apollo samples 14321 and 14305 by micro-CT and micro-XRF (respectively), assess the potential for discovery of "new" Apollo samples for scientific study, and evaluate the usefulness of these techniques in future PET efforts.

Zeigler, Ryan A.↗

Development of Machine Learning Algorithms to Segment and Study Images of Astromaterial Samples

Introduction: Micrometer-scale chemical analyses of chondritic meteorites and mission-returned asteroid samples can reveal details of the physical and chemical processes operating in the early solar system, including processes that gave rise to planets, moons, and minor bodies. These primitive astromaterials are comprised of chondrules, calcium- and aluminum-rich inclusions (CAI), and many other silicates, oxides, metals, sulfides, and fine-grained materials. The chemical and mineralogical complexity of these samples, vast populations of different components, and heterogeneity across mm to km scales, all limit our understanding of the origin and evolution of these materials. Here, we describe recent efforts to use machine learning techniques to automate the segmentation of chemical maps of chondritic meteorites, designed to aid studies of asteroid samples returned by spacecraft. By automating the task of segmentation it will become possible to rapidly analyze and interpret the sizes, shapes, mineralogy, chemistry, and other properties of every chondrule, calcium- and aluminum-rich inclusion (CAI) and other clast within and between asteroid samples. Sample return missions significantly accelerate and heighten the need to develop such new data analysis techniques, and associated data repositories. Techniques: Neural networks require abundant training data, i.e. images which have been segmented by a human user. We have manually segmented data available from previous petrologic and chemical work at NASA Johnson Space Center and the American Museum of Natural History [1-4]. These data were derived from energy- and wavelength-dispersive X-ray spectroscopy (EDS, WDS) mapping of samples from many chondrite groups. The Deeplabv3+ [5] neural network architecture was trained on human-labeled masks and used to create machine-labeled masks. Several different algorithms were investigated, with inputs ranging from common RGB image formats through to hyperspectral datasets, with raw data comprising greyscale maps of Mg, Ca, and Al, with or without Si, Fe, Ti for both EDS and WDS data, and extending to other elements in EDS only. Each greyscale image was paired with a binary mask for each labelled particle type. Results: The trained algorithms can segment (Fig 1), classify, and measure the dimensions of thousands of particles in chemical maps of a standard 1-inch round petrographic section in seconds to minutes, rather than many hours needed by a human. Accuracy of the algorithms varied from chondrite to chondrite and across particle types. Further results and details of the algorithms will be presented at the workshop. Future directions: Machine learning has the potential to revolutionize our understanding of complex particle populations contained within primitive astromaterial, with segmentation being a critical first step. Example applications include better understanding of particle transport, nebular reservoirs, parent body accretion, and a deeper understanding of the relationships between particle populations and bulk rock elemental and isotopic compositions. In addition to benefits that machine learning can bring to individual researchers, building a community data repository of thousands to millions of particles across hundreds of samples will open up many other possibilities. For example, with a large enough dataset it will be possible to search for exceptionally closely matching particles across disparate samples. Such a capability would enable a single CAI from OSIRISREx or Hayabusa/II samples to be matched to chondritic CAIs that exhibit near-identical size, texture, and mineralogy, down to the level of similar core phenocrysts, zonation, and rim sequences. Such comparative analyses will help to disentangle precursor chemistry, chronology, gas/dust reservoirs during heating, and accretion. Such an endeavor would be impossible without machine learning and a large community data repository of astromaterial chemical/mineralogic maps.

Machine Learning↗

Analyses of the MISSE 9-15 Polymers and Composites Experiment 1-4 (PCE 1-4) Contamination Samples

Spacecraft in low Earth orbit (LEO) are subjected to harsh environmental conditions, including radiation (cosmic rays, ultraviolet (UV), x-ray and charged particle radiation), micrometeoroids and orbital debris, temperature extremes, thermal cycling, and atomic oxygen (AO). These environmental exposures can result in erosion, embrittlement and optical property degradation of susceptible materials threatening spacecraft performance and durability. To increase our understanding of environmental effects such as AO erosion and radiation induced embrittlement of spacecraft materials, NASA Glenn Research Center developed a series of experiments that were flown as part of the Materials International Space Station Experiment (MISSE) missions on the exterior of the International Space Station (ISS). Recently, four Glenn experiments with 365 flight samples were flown on ISS’s MISSE-Flight Facility (MISSE-FF). These experiments are the Polymers and Composites Experiment-1 (PCE-1) flown as part of the MISSE-9 mission, the PCE-2 flown as part of the MISSE-10 mission, the PCE-3 flown as part of the MISSE-12 and MISSE-15 missions, and the PCE-4 flown as part of the MISSE-13 mission. Each of these experiments included passive contamination witness samples in each flight direction for post-flight molecular contamination analyses. A total of 13 contamination flight samples were flown. The post-flight analyses of the PCE 1-4 contamination samples include X-ray Photoelectron Spectroscopy (XPS) analyses (surface and ion sputter depth analyses) and optical properties (total reflectance, total transmittance and solar absorptance). This paper provides results of post-flight analyses of the PCE 1-4 contamination samples and their corresponding control samples. Knowledge of on-orbit contamination is important for the PCE 1-4 flight data interpretation.

Atomic Oxygen↗

Trace gas measurements from whole air samples collected over the Antarctic continent

Whole air samples collected aboard the NASA DC-8 and ER-2 aircraft as part of the Airborne Antarctic Ozone Experiment (AAOE) were analyzed in a field laboratory set up at Punta Arenas, Chile, in August and September, 1987. Mixing ratios obtained from gas chromatographic analyses of these samples are presented for N2O, CFCl3, CFCl2, C2F3Cl3, CH3CCl3, CH4, and CO. Variations in the mixing ratios of these gases along the individual flight paths of the aircraft are used as tracers to indicate the history of air masses over and near the Antarctic continent.

Heidt, L. E.↗

Degree of Ice Particle Surface Roughness Inferred from Polarimetric Observations

The degree of surface roughness of ice particles within thick, cold ice clouds is inferred from multidirectional, multi-spectral satellite polarimetric observations over oceans, assuming a column-aggregate particle habit. An improved roughness inference scheme is employed that provides a more noise-resilient roughness estimate than the conventional best-fit approach. The improvements include the introduction of a quantitative roughness parameter based on empirical orthogonal function analysis and proper treatment of polarization due to atmospheric scattering above clouds. A global 1-month data sample supports the use of a severely roughened ice habit to simulate the polarized reflectivity associated with ice clouds over ocean. The density distribution of the roughness parameter inferred from the global 1- month data sample and further analyses of a few case studies demonstrate the significant variability of ice cloud single-scattering properties. However, the present theoretical results do not agree with observations in the tropics. In the extra-tropics, the roughness parameter is inferred but 74% of the sample is out of the expected parameter range. Potential improvements are discussed to enhance the depiction of the natural variability on a global scale.

surface↗

Plume Collection Strategies for Icy World Sample Return

Three icy worlds in the solar system display evidence of pluming activity. Water vapor and ice particles emanate from cracks near the south pole of Saturn's moon Enceladus. The plume gas contains simple hydrocarbons that could be fragments of larger, more complex organics. More recently, observations using the Hubble and Herschel space telescopes have hinted at transient water vapor plumes at Jupiter's moon Europa and the dwarf planet Ceres. Plume materials may be ejected directly from possible sub-surface oceans, at least on Enceladus. In such oceans, liquid water, organics, and energy may co-exist, making these environments habitable. The venting of habitable ocean material into space provides a unique opportunity to capture this material during a relatively simple flyby mission and return it to Earth. Plume collection strategies should enable investigations of evidence for life in the returned samples via laboratory analyses of the structure, distribution, isotopic composition, and chirality of the chemical components (including biomolecules) of plume materials. Here, we discuss approaches for the collection of dust and volatiles during flybys through Enceladus' plume, based on Cassini results and lessons learned from the Stardust comet sample return mission. We also highlight areas where sample collector and containment technology development and testing may be needed for future plume sample return missions.

Stardust Collector↗

LDEF materials results for spacecraft applications: Executive summary

To address the challenges of space environmental effects, NASA designed the Long Duration Exposure Facility (LDEF) for an 18-month mission to expose thousands of samples of candidate materials that might be used on a space station or other orbital spacecraft. LDEF was launched in April 1984 and was to have been returned to Earth in 1985. Changes in mission schedules postponed retrieval until January 1990, after 69 months in orbit. Analyses of the samples recovered from LDEF have provided spacecraft designers and managers with the most extensive data base on space materials phenomena. Many LDEF samples were greatly changed by extended space exposure. Among even the most radially altered samples, NASA and its science teams are finding a wealth of surprising conclusions and tantalizing clues about the effects of space on materials. Many were discussed at the first two LDEF results conferences and subsequent professional papers. The LDEF Materials Results for Spacecraft Applications Conference was convened in Huntsville to discuss implications for spacecraft design. Already, paint and thermal blanket selections for space station and other spacecraft have been affected by LDEF data. This volume synopsizes those results.

Whitaker, A. F.↗

Overview of the Results of the Organics PET Study of the Cometary Samples from Comet Wild 2 by the Stardust Mission

STARDUST is the first mission designed to bring samples back to Earth from a known comet. The captured samples were successfully returned to Earth on 15 Jan 2006, after which they were subjected to a preliminary examination by a number of teams of scientists from around the world. This abstract describes the efforts of the Organics Preliminary Examination Team (PET). More detailed discussions of specific analyses of the samples can be found in other papers presented at this meeting by individual members of the Organics PET (see the author list above for team members). The studied Wild 2 gas and dust samples were collected by impact onto aerogel tiles and Al foils when the spacecraft flew through the coma of 81P/Wild 2 on 2 Jan 2004 at a relative velocity of approx.6.1 kilometers per second. After recovery of the Sample Return Capsule (SRC) on 15 Jan 2006, the aerogel collector trays were removed in a clean room at JSC. After documentation of the collection, selected aerogel tiles and aluminum foils were removed and aerogel and cometary samples extracted for study.

Sandford, S. A.↗

Convective Transport to the Upper Troposphere and Lower Stratosphere Over the Asian Summer Monsoon as Observed During the 2022 ACCLIP Airborne Campaign

Deep convection in the Asian summer monsoon (ASM) rapidly transports boundary layer pollutants including ozone-depleting substances into the upper troposphere and lower stratosphere (UTLS). The confinement of the seasonal anticyclonic circulation in the UTLS over Asia initially traps the pollutants near the tropopause level, but air masses are subsequently transported throughout the global stratosphere and impact Earth’s climate. Characterizing the transport pathways and processes of these pollutants are critical for identifying source regions and quantifying regional contributions to global stratospheric concentrations. The Asian summer monsoon Chemical and Climate Impact Project (ACCLIP) was conducted in summer 2022 using two high-altitude aircraft (NSF NCAR Gulfstream V and the NASA WB-57) to obtain UTLS chemical composition and aerosol distribution for characterizing the impact of the ASM on global chemistry and climate. Backward trajectories from ACCLIP flight tracks were traced through time-varying, satellite-derived global convective cloud top altitude fields to investigate the convective air mass origins of the sampled air parcels. Analyses reveal that air masses lofted by convection within the ASM (South Asian summer monsoon) and near the edge of the of the ASM anticyclone (East Asian summer monsoon) contributed to the airborne observations. In this study, we present a summary of the transport statistics of UTLS air masses sampled during ACCLIP and discuss the implications of these results on our understanding of the role of ASM in global constituent transport.

Convective↗

A Novel Hybrid Ultramicrotomy/FIB-SEM Technique: Preparation of Serial Electron-Transparent Thin Sections of a Hayabusa Grain

The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.

Berger, Eve L.↗

Nondestructive Analysis of Astromaterials by Micro-CT and Micro-XRF Analysis for PET Examination

An integral part of any sample return mission is the initial description and classification of returned samples by the preliminary examination team (PET). The goal of the PET is to characterize and classify returned samples and make this information available to the larger research community who then conduct more in-depth studies on the samples. The PET tries to minimize the impact their work has on the sample suite, which has in the past limited the PET work to largely visual, nonquantitative measurements (e.g., optical microscopy). More modern techniques can also be utilized by a PET to nondestructively characterize astromaterials in much more rigorous way. Here we discuss our recent investigations into the applications of micro-CT and micro-XRF analyses with Apollo samples and ANSMET meteorites and assess the usefulness of these techniques in future PET. Results: The application of micro computerized tomography (micro-CT) to astromaterials is not a new concept. The technique involves scanning samples with high-energy x-rays and constructing 3-dimensional images of the density of materials within the sample. The technique can routinely measure large samples (up to approx. 2700 cu cm) with a small individual voxel size (approx. 30 cu m), and has the sensitivity to distinguish the major rock forming minerals and identify clast populations within brecciated samples. We have recently run a test sample of a terrestrial breccia with a carbonate matrix and multiple igneous clast lithologies. The test results are promising and we will soon analyze a approx. 600 g piece of Apollo sample 14321 to map out the clast population within the sample. Benchtop micro x-ray fluorescence (micro-XRF) instruments can rapidly scan large areas (approx. 100 sq cm) with a small pixel size (approx. 25 microns) and measure the (semi) quantitative composition of largely unprepared surfaces for all elements between Be and U, often with sensitivity on the order of a approx. 100 ppm. Our recent testing of meteorite and Apollo samples on micro-XRF instruments has shown that they can easily detect small zircons and phosphates (approx. 10 m), distinguish different clast lithologies within breccias, and identify different lithologies within small rock fragments (2-4 mm soil Apollo soil fragments).

Zeigler, R. A.↗

Contamination measurements on experiment M0003

The contamination monitors on the M0003 experiment consisted of passive sample collectors to measure molecular and particulate deposition. The collectors were placed in the leading and trailing edge trays of M0003. The objective was to quantify the contaminants and determine how contamination affected the other materials in the trays. Duplicate collectors were placed inside the vacuum canisters that provided protection from the launch, ascent, deployment, and recovery environments. Analyses of the samples show small quantities of molecular deposition on both the leading and trailing edge trays. Silicone deposits are negligible. The aluminized fused silica, second surface mirrors showed small changes in solar absorptances. This is consistent with the small quantities of molecular deposits deduced from the FTIR measurements. The results of particle deposition, light scatter, and a micrometeoroid (or debris) impact are presented.

Borson, Eugene N.↗