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Launch Complex 39B, SWMU 009 Air Sparging System Expansion Implementation Work Plan Kennedy Space Center, Florida

This Implementation Work Plan (IWP) for expansion of the Air Sparging (AS) system at Launch Complex 39B (LC39B), presents the design and coordination specifics to expand the existing AS Interim Measure (IM) at LC39B located at Kennedy Space Center (KSC), Florida. The existing AS system at LC39B was installed in 2017 and included 279 AS wells. LC39B has been designated as Solid Waste Management Unit (SWMU) 009 under the KSC Resource Conservation and Recovery Act (RCRA) Corrective Action Program. Expansion of the AS IM will include installation of an additional five AS wells to depths of approximately 13 and 17 feet below land surface (bls) to remediate contaminated groundwater identified northwest of the launch pad, near the liquid oxygen (LOX) tank. The expansion will target concentrations of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) greater than Florida Department of Environmental Protection (FDEP) Natural Attenuation Default Concentrations (NADCs) that were identified during direct push technology (DPT) sampling events between 2019-2022 in shallow intervals between 8 and 16 feet bls. The objective for this expansion is to remediate contaminated groundwater within the treatment zone to below NADCs to support transition to monitored natural attenuation (MNA) through a long-term monitoring (LTM) program. This expansion will treat approximately 0.07-acres of residual groundwater contamination. The IWP design for this expansion will utilize the existing AS system trailer that is already onsite and operating. The five new AS expansion wells will be integrated into the existing Zone Z4 distribution manifold to deliver compressed air to the new AS wells. To deliver airflow, three existing lateral lines will be split in the field at a lateral split junction point (using 2-way or 3-way splits). Each split lateral will supply air to AS wells at the same depth interval to minimize preferential pathways. The trenching layout for the new AS wells was developed to minimize ground disturbance due to the amount of utilities in the area. One new monitoring well will also be installed and added to LC39B’s performance monitoring program to evaluate the effectiveness of the AS system expansion. This well will be sampled on a semi-annual basis for volatile organic compounds, with results evaluated to determine if system adjustments may be required. The main components of this IWP were presented to the KSC Remediation Team (KSCRT) at the October 2022 Meeting (Meeting 2210-M05). DPT delineation data from the LOX area were also presented, which included some inferred boundaries due to physical restrictions of the LOX tank and associated concrete pad and infrastructure. Planned monitoring well sampling in this area will help determine if back-diffusion may be occurring from beneath the pad. Additionally, based on potential petroleum odors and staining identified at two DPT locations during the January 2022 DPT event in the 10-16 feet bls range, a KSCRT action item was assigned during the October 2022 meeting to collect soil samples for petroleum compounds if similar odors or staining are identified during IM implementation. Construction completion and performance monitoring will be incorporated into LC39B’s groundwater monitoring reports, which are currently submitted on an annual basis to FDEP to document operation and maintenance activities and results from the AS IM.

Deborah M. Wilson↗

Nitrogen and xenon isotopic disequilibrium in Bachmut (L6) chondrule J2689 and matrix

Chondrule J2689, a large (8-mm) RP chondrule from Bachmut (L6) was previously found to be in disequilibrium with its host in a variety of features: (1) It has a fine-grained hornfelsic texture; (2) it contains low amounts of metal with a low-Ni taenite composition not found in the matrix; (3) the Ni/Co ratio of that metal is close to the solar ratio, which is equal to the bulk Ni/Co ratio (23) of the chondrule; (4) the bulk alkali content of the chondrule is high and the Na/K ratio is fractionated with respect to the average L chondrite ratio of 8; (5) Cr is depleted in spite of the high pyroxene content; (6) the siderophile elements are strongly depleted but are fractionated with their abundances increasing with volatility; and (7) the O isotopes of the chondrule and the host are out of equilibrium. However, the (Fe,Mg) silicates, feldspar, and chromite have chemical compositions indistinguishable from that of the host chondrite. We have studied a chip of the chondrite and of adjacent matrix by stepwise heating and by combustion in O for N and Xe isotopic abundances. (1) The chondrule preserved distinct bulk, metal, and O isotopic compositional features. It is therefore unlikely that the 'equilibration' of the major silicates Fe/Mg ratios could have taken place after accretion; (2) the chondrule was well equilibrated before break-up and exposure to cosmic rays; (3) two N signatures in the matrix also indicate that the matrix is not equilibrated; and (4) all data collected so far point toward the presence of unequilibrated Bachmut components. Very few reactions took place after accretion.

Kim, Y.↗

A geochemical assessment of possible lunar ore formation

The Moon apparently formed without appreciable water or other relatively volatile materials. Interior concentrations of water or other volatile substances appear to be extremely low. On Earth, water is important to the genesis of nearly all types of ores. Thus, some have reasoned that only abundant elements would occur in ore concentrations. The definition and recognition of ores on the Moon challenge the imaginations and the terrestrial perceptions of ore bodies. Lunar ores included solar-wind soaked soils, which contain abundant but dilute H, C, N, and noble gases (including He-3). Oxygen must be mined; soils contain approximately 45 percent (wt). Mainstream processes of rock formation concentrated Si, Mg, Al, Fe, and Ca, and possibly Ti and Cr. The highland surface contains approximately 70 percent (wt) feldspar (mainly CaAl2Si2O8), which can be separated from some highland soils. Small fragments of dunite were collected; dunite may occur in walls and central peaks of some craters. Theoretical extensions of observations of lunar samples suggest that the Moon may have produced ores of trace elements. Some small fragments have trace-element concentrations 10(exp 4) times higher than the lunar average, indicating that effective geochemical separations occurred; processes included fractional crystallization, silicate immiscibility, vaporization and condensation, and sulfide metamorphism. Operations of these processes acting on indigenous materials and on meteoritic material in the regolith could have produced ores. Infalling carbonaceous meteorites and comets have added water and hydrocarbons that may have been cold-trapped. Vesicles in basalts, pyroclastic beads, and reported transient events suggest gag emission from the lunar interior; such gas might concentrate and transport rare elements. Large impacts may disperse ores or produce them through deposition of heat at depth and by vaporization and subsequent condensation. The main problem in assessing lunar resources is the ignorance about the largely unexplored Moon.

Haskin, Larry A.↗

Estimating Water Ice Abundance from Short-Wave Infrared Spectra of Drill Cuttings at Cryogenic Temperatures

NASA's Resource Prospector (RP) mission intends to visit a lunar polar region to characterize the volatile distribution. Part of the RP payload, the Near-infrared Volatile Spectrometer System (NIRVSS) is a spectrometer operating from 1600-3400 nm that provides sensitivity to water ice, and other volatiles. For multiple years, the NIRVSS system has been incorporated into on-going RP payload testing in a cryogenic vacuum facility at Glenn Research Center. Soil tubes of lunar simulants, prepared with known amounts of water, are placed in the vacuum chamber and cooled to cryogenic temperatures (soil temperatures of 110-170 K) and placed under low vacuum (a few x 10(exp -6) Torr). During these tests NIRVSS continuously measures spectra of soil cuttings emplaced onto the surface by a drill. Real time processing of NIRVSS spectra produces two spectral parameters associated with water ice absorption features near 2000 and 3000 nm that can be used to inform decision making activities such as delivery of the soil to a sealable container. Post-test collection and analyses of the soils permit characterization the water content as a function of depth. These water content profiles exhibit the characteristics of a vacuum desiccation zone to depths of about 40 cm. Subsequent to completion of the tests, NIRVSS spectra are processed to produce two spectral parameters associated with water ice absorption features near 2000 and 3000 nm. These features can be evaluated as a function of time, and correlated with drill depth, and other measurements, throughout the drilling activities. Until now no effort was attempted to quantitatively relate these parameters to water abundance. This is the focus of our efforts to be presented.

NASA's Resource Prospector (RP)↗

Biologically Pre-Treated Habitation Waste Water as a Sustainable Green Urine Pre-Treat Solution

The ability to recover water from urine and flush water is a critical process to allow long term sustainable human habitation in space or bases on the moon or mars. Organic N present as urea or similar compounds can hydrolyze producing free ammonia. This reaction results in an increase in the pH converting ammonium to ammonia which is volatile and not removed by distillation. The increase in pH will also cause precipitation reactions to occur. In order to prevent this, urine on ISS is combined with a pretreat solution. While use of a pretreatment solution has been successful, there are numerous draw backs including: storage and use of highly hazardous solutions, limitations on water recovery (less than 85%), and production of brine with pore dewatering characteristics. We evaluated the use of biologically treated habitation wastewaters (ISS and early planetary base) to replace the current pretreat solution. We evaluated both amended and un-amended bioreactor effluent. For the amended effluent, we evaluated "green" pretreat chemicals including citric acid and citric acid amended with benzoic acid. We used a mock urine/air separator modeled after the urine collection assembly on ISS. The urine/air separator was challenged continually for >6 months. Depending on the test point, the separator was challenged daily with donated urine and flushed with amended or un-amended reactor effluent. We monitored the pH of the urine, flush solution and residual pH in the urine/air separator after each urine event. We also evaluated solids production and biological growth. Our results support the use of both un-amended and amended bioreactor effluent to maintain the operability of the urine /air separator. The ability to use bioreactor effluent could decrease consumable cost, reduce hazards associated with current pre-treat chemicals, allow other membrane based desalination processes to be utilized, and improve brine characteristics.

Jackson, W. Andrew↗

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

58 GEOSCIENCES↗

Adaptive Curation at NASA Johnson Space Center: Preparing for Artemis Samples by Leveraging Proven Practices and Innovative Solution

The proper curation of returned astromaterial samples is essential to ensure that high-quality scientific investigations can be conducted for decades, enabling future generations to address evolving research questions. The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center (hereafter JSC Curation) is responsible for curating all of NASA’s extraterrestrial samples. Under the governing document, NASA Procedural Requirement (NPR) 7100.5 “Curation of Extraterrestrial Materials”, JSC Curation is charged with “The curation of all extraterrestrial material under NASA control, including future NASA missions.” The Directive goes on to define Curation as including “...documentation, preservation, preparation, and distribution of samples for research, education, and public outreach.” JSC Curation has a long-standing legacy of curating extraterrestrial materials, including but not limited to Apollo and Luna lunar samples, Genesis solar wind samples, Stardust comet samples, asteroid samples (Hayabusa1, Hayabusa2, and OSIRIS-REx), and Antarctic Meteorite samples from a variety of parent bodies. Building on this foundation, the Artemis program introduces new challenges and opportunities for sample curation, requiring both the application of proven practices and the development of innovative solutions. The Artemis Collection will be curated using established protocols refined through decades of experience with Apollo and subsequent sample collections, including but not limited to the utilization of cleanrooms, custom nitrogen gloveboxes, specialized storage containers and tools; all of which have strict material utilization and prohibition requirements. These practices provide a robust framework for contamination control, documentation, and long-term preservation. However, Artemis samples may present unique scientific and operational requirements, including enhanced contamination control measures (relative to Apollo) driven by evolving science objectives. To meet these needs, JSC Curation is actively developing new technologies and protocols that extend beyond traditional approaches, ensuring that the integrity of samples is maintained under increasingly stringent standards. One critical area of innovation is the development of cold sample curation capabilities. Certain Artemis samples, particularly those from Permanently Shadowed Regions (PSRs) and cold environments, are expected to contain ices and volatile components that require preservation and handling at sub-zero or even cryogenic temperatures. JSC Curation is leveraging best practices from the cold and cryogenic sample industries, as well as other government agencies and academic experts, to design facilities and handling procedures that maintain sample integrity while enabling scientific access. The goal is to develop capabilities to allow researchers to investigate volatiles and other temperature-sensitive materials while minimizing chemical and physical alterations from their returned state. In summary, adaptive curation at JSC combines the reliability of proven methodologies with forward-looking innovations to meet the scientific and operational demands of Artemis. Through enhanced contamination control, advanced cold curation capabilities, and an understanding of known and evolving future science priorities, NASA is preparing to maximize the scientific return from Artemis samples and preserve their value for generations of researchers.

Andrea D Harrington↗

Comparing Low-Cost Sensors with Ground-Based and Airborne In-Situ and Column Observations of NO2 and HCHO during the FRAPPE Field Campaign in Colorado, USA

Even in the presence of more reliable air quality tools, low-cost sensors have the benefit of recording data on highly localized spatial and temporal scales, allowing for multiple measurements within a single satellite pixel and on pixel boundaries. However, they are less accurate than their regulatory-grade counterparts, requiring regular co-locations with accepted instruments to ensure their validity. Thus, the addition of low-cost sensors to a field campaign – where reference-grade air quality instruments are abundant – not only provides ample opportunities for low-cost sensor co-location and calibration, but also allows the low-cost instruments to be used for sub-pixel validation, covering more surface area than the regulatory instruments alone with a network of sensors. During the summer of 2014, our low-cost sensor network was deployed during the Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ) campaign conducted to sample the composition of air at and above ground level in northeastern Colorado, USA. The low-cost sensor platform included a suite of gas-phase sensors, notably NO2 and two generalized volatile organic compound (VOC) sensors, which were leveraged together to quantify speciated hydrocarbons such as formaldehyde. These key pollutants were chosen for their impacts on human health and climate change, as well as their inclusion on the TEMPO satellite launching this year. Airborne campaign measurements included slant column optical observations of formaldehyde (HCHO), nitrogen dioxide (NO2), and ozone (O3). Myriad additional in-situ instruments described chemical composition up to approximately 5 km above surface level. Ground-based instrumentation included both stationary and mobile regulatory-grade instruments, which were used for sensor calibration. Machine learning techniques such as artificial neural networks (ANNs) were used to match the low-cost signals to that of the reference-grade instruments. Here, we compare calibrated low-cost sensor data collected at ground level in a variety of locations along Colorado’s Front Range to various data sources from the FRAPPÉ campaign to better understand how well airborne and regulatory ground-based measurements can be extrapolated to other locations. Further, as the slant column measurements act as satellite simulators, we explore how low-cost instruments can be used for satellite validation purposes. Comparisons among these different data types also have important implications in data fusion.

Kristen Okorn↗

Analysis of secondary organic aerosol simulation bias in the Community Earth System Model (CESM2.1)

Organic aerosol (OA) has been considered as one of the most important uncertainties in climate modeling due to the complexity in presenting its chemical production and depletion mechanisms. To better understand the capability of climate models and probe into the associated uncertainties in simulating OA, we evaluate the Community Earth System Model version 2.1 (CESM2.1) configured with the Community Atmosphere Model version 6 (CAM6) with comprehensive tropospheric and stratospheric chemistry representation (CAM6-Chem) through a long-term simulation (1988–2019) with observations collected from multiple datasets in the United States. We find that CESM generally reproduces the interannual variation and seasonal cycle of OA mass concentration at surface layer with a correlation of 0.40 compared to ground observations and systematically overestimates (69%) in summer and underestimates (-19%) in winter. Through a series of sensitivity simulations, we reveal that modeling bias is primarily related to the dominant fraction of monoterpene-formed secondary organic aerosol (SOA), and a strong positive correlation of 0.67 is found between monoterpene emission and modeling bias in the eastern US during summer. In terms of vertical profile, the model prominently underestimates OA and monoterpene concentrations by 37%–99% and 82%–99%, respectively, in the upper air (>500 m) as validated against aircraft observations. Our study suggests that the current volatility basis set (VBS) scheme applied in CESM might be parameterized with monoterpene SOA yields that are too high, which subsequently results in strong SOA production near the emission source area. We also find that the model has difficulty in reproducing the decreasing trend of surface OA in the southeastern US probably because of employing pure gas VBS to represent isoprene SOA which is in reality mainly formed through multiphase chemistry; thus, the influence of aerosol acidity and sulfate particle change on isoprene SOA formation has not been fully considered in the model. This study reveals the urgent need to improve the SOA modeling in climate models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Volatile Organic Compounds Emitted from Air Fresheners: Plug-Ins at Home and Little Trees in Cars

Air fresheners contain volatile organic compounds (VOCs), some of which are possible hazardous air pollutants, carcinogens, or chemicals associated with adverse health effects such as asthma. This screening study identifies VOCs emitted from two types of air fresheners. Plug-in air fresheners are household products that release scents from a heated liquid. Little Tree air fresheners are commonly used solid devices designed to hang in from the rear view mirror in cars. VOCs that were released from heated samples of air fresheners were identified by gas chromatography mass spectroscopy (GCMS). Amongst VOCs commonly known to have scent properties, this screening also revealed the presence of compounds that are not associated with fragrances and that may have adverse health effects. In a pilot study to characterize how air fresheners affect air quality in real settings, air samples were collected on solid-phase microextraction (SPME) field samplers in a home setting and inside a vehicle, before and during air-freshener use. This pilot demonstrated some limited potential for SPME field samplers to track changes in VOC levels in real-life settings.

Adriana Pino-Delgado↗

Oxygen Production from Lunar Regolith using Ionic Liquids

The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal stability. The results showed that ILs can be very efficient electrolytes; in particular IL/phosphoric-acid mixtures appear extremely promising for solubilizing lunar simulant. Results from preliminary experiments for distillation of water produced from the oxygen within the metal oxides of the simulant and the hydrogen from the acid indicates that over 75% of the oxygen from the simulant can be harvested as water at a temperature of 150 C. A method for collection of oxygen from electrolysis of the water derived from solubilizing simulant was developed by using a liquid nitrogen trap to liquefy and collect the oxygen. Although precise quantification of the liquid oxygen trapped is difficult to obtain, the amount of hydrogen and oxygen collected from electrolysis of water in this system was greater than 98%. This set-up also included a portable mass spectrometer for the identification of gases released from electrolysis cells. Regeneration of ILs through re-protonation was also demonstrated. Four sequential re-generations of an IL following solubilization of simulant showed no significant differences in amounts of simulant dissolved. Follow-on work for this project should include more studies of IL/phosphoric acid systems. Also, much more work is necessary for defining methods for electrolysis and purification of metals from regolith solubilized in ILs, and for developing a system to use the produced hydrogen to regenerate the spent IL. Finally, design and development of flight breadboard and prototype hardware is required.

Paley, Mark Steven↗

NASA Technology Evaluation for Environmental Risk Mitigation Remediation Technology Collaboration Development

NASA is committed to finding solutions to agency cleanup problems that are better, cheaper, and more effective than the status quo. Unfortunately, some potential solutions involve innovative technologies for which NASA remediation managers may not have a high level of understanding or confidence. Since 2004, NASA's Stennis Space Center (SSC) in Mississippi has been pumping groundwater contaminated with trichloroethylene (TCE) and other halogenated volatile organic compounds (HVOC) from their cleanup location designated "Area G" through extraction wells to an aboveground treatment system. Over time, however, the effectiveness of this treatment strategy has diminished and an alternative approach is needed. In 2012, professionals from NASA's Principal Center for Technology Evaluation for Environmental Risk Mitigation (TEERM) introduced SSC managers to an innovative technology for enhancing the performance of SSC's existing pump and treat system. The technology, generally referred to as in situ chemical oxidation (ISCO), involves slowly and continuously injecting a strong but safe chemical oxidant into the groundwater. Treatment is enhanced by a "surfactant-type effect" which causes residual contamination from saturated soil to be released into the dissolved-phase where it can be readily oxidized. Any dissolved-phase contamination that was not oxidized can be collected by the extraction well network and treated aboveground. SSC was not familiar with the technology so to increase their confidence, TEERM identified a contractor who was willing to demonstrate their product and process at a significantly reduced price. An initial, small-scale demonstration of ISCO began at sse in March 2012 and completed in August 2012. This successful demonstration was followed by three larger-scale ISCO demonstrations between August and December 2012. The contractor's innovative Continuous Injection System (CIS) incorporated "green" and sustainable technologies and practices. A slow injection rate was maintained autonomously by the CIS, eliminating the need for multiple mobilizations of personnel and powered equipment. The CIS was calibrated to deliver only as much reagent as the formation would accept without "short circuiting", minimizing material waste. Public utility water pressure was used to mix, dilute, and inject the reagent. NASA personnel were trained to operate and maintain the system and remote monitoring and injection control capabilities were developed, further reducing the need for contractor mobilizations to the site. An integrated solar photovoltaic panel was used to power the control valves and web monitoring telemetry. SSC provided hydrogen peroxide for the process using their existing supplier for the aboveground pump and treat systems. The only consumable required from the contractor was their proprietary activator to catalyze SSC's peroxide.

Romeo, James↗

Regolith Evolved Gas Analyzer

The Regolith Evolved Gas Analyzer (REGA) is a high-temperature furnace and mass spectrometer instrument for determining the mineralogical composition and reactivity of soil samples. REGA provides key mineralogical and reactivity data that is needed to understand the soil chemistry of an asteroid, which then aids in determining in-situ which materials should be selected for return to earth. REGA is capable of conducting a number of direct soil measurements that are unique to this instrument. These experimental measurements include: (1) Mass spectrum analysis of evolved gases from soil samples as they are heated from ambient temperature to 900 C; and (2) Identification of liberated chemicals, e.g., water, oxygen, sulfur, chlorine, and fluorine. REGA would be placed on the surface of a near earth asteroid. It is an autonomous instrument that is controlled from earth but does the analysis of regolith materials automatically. The REGA instrument consists of four primary components: (1) a flight-proven mass spectrometer, (2) a high-temperature furnace, (3) a soil handling system, and (4) a microcontroller. An external arm containing a scoop or drill gathers regolith samples. A sample is placed in the inlet orifice where the finest-grained particles are sifted into a metering volume and subsequently moved into a crucible. A movable arm then places the crucible in the furnace. The furnace is closed, thereby sealing the inner volume to collect the evolved gases for analysis. Owing to the very low g forces on an asteroid compared to Mars or the moon, the sample must be moved from inlet to crucible by mechanical means rather than by gravity. As the soil sample is heated through a programmed pattern, the gases evolved at each temperature are passed through a transfer tube to the mass spectrometer for analysis and identification. Return data from the instrument will lead to new insights and discoveries including: (1) Identification of the molecular masses of all of the gases liberated from heated soil samples; (2) Identification of the asteroid soil mineralogy to aid in the selection process for returned samples; (3) Existence of oxygen in the asteroid soil and the potential for in-situ resource utilization (ISRU); and (4) Existence of water and other volatiles in the asteroid soil. Additional information is contained in the original extended abstract.

Hoffman, John H.↗

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu

Abstract Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe 3+ to Fe 2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (–OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss.

Astronomy & Astrophysics↗

Comparing Analysis of Hydrogen Concentration in Astromaterials Nominally Anhydrous Minerals by Multiple SIMS

Secondary Ion Mass Spectrometry (SIMS) is utilized to determine hydrogen (H) concentration in astromaterials nominally anhydrous minerals (NAMs) and their inclusions [e.g., 1]. This data is interpreted to refine the volatile history of planetary bodies. Four instruments are being used to compare H concentration analysis: a large geometry SIMS (The University of Hawaiʻi Cameca IMS 1280), a compact SIMS (Arizona State University (ASU) Cameca IMS 6f), and two Cameca NanoSIMS 50L at ASU and NASA-Johnson Space Center (JSC). Results on the first three instruments are available. Although fundamentally similar, SIMS instruments and their modifications [2] may produce different values or pose advantages for H analysis, especially for shocked samples that are susceptible to contamination filling their fractures. New data from the IMS 1280 is reported, using its microchannel plate (MCP) to image high H signals in grain fractures during pre-sputtering to avoid them as much as possible. Between fractures, 16 OH/ 30 Si was measured with a Cs + 4 nA primary beam, 30 micron spot size, and central ~5x5 micron collection area. First order comparison of H concentration (reported in ppm H 2 O) is achieved on a terrestrial gem quality clinopyroxene (SLP114, 162±12 ppm H 2 O [3]), with 157±7 and 215±40 ppm H 2 O by the IMS 1280 and 6f respectively. SIMS comparison is then extended to analysis of two Martian shergottites: RBT 04262 and NWA 5789. Due to a dense fracture network (< 20 micron) in RBT 04262, only one clinopyroxene hosted glassy inclusion was analyzed (n=6, ≤1 ppm H 2 O), while six olivine grains in NWA 5789 (n=12, ≤ 2 ppm H 2 O) (1s ±0.21) were analyzed. Higher concentrations were obtained for RBT 04262 olivine by the ASU NanoSIMS 50L (up to 350 ppm H 2 O [4]), and IMS 6f (300+ ppm H 2 O, [5]), for which contamination in fractures could not be avoided. Work on the JSC NanoSIMS 50L will further develop the SIMS comparison.

J.-M. Dudley↗

Lunar Flashlight: Mapping Lunar Surface Volatiles Using a Cubesat

Water ice and other volatiles may be located in the Moon's polar regions, with sufficient quantities for in situ extraction and utilization by future human and robotic missions. Evidence from orbiting spacecraft and the LCROSS impactor suggests the presence of surface and/or nearsurface volatiles, including water ice. These deposits are of interest to human exploration to understand their potential for use by astronauts. Understanding the composition, quantity, distribution, and form of water/H species and other volatiles associated with lunar cold traps is identified as a NASA Strategic Knowledge Gap (SKG) for Human Exploration. These polar volatile deposits could also reveal important information about the delivery of water to the Earth- Moon system, so are of scientific interest. The scientific exploration of the lunar polar regions was one of the key recommendations of the Planetary Science Decadal Survey. In order to address NASA's SKGs, the Advanced Exploration Systems (AES) program selected three lowcost 6-U CubeSat missions for launch as secondary payloads on the first test flight (EM1) of the Space Launch System (SLS) scheduled for 2017. The Lunar Flashlight mission was selected as one of these missions, specifically to address the SKG associated with lunar volatiles. Development of the Lunar Flashlight CubeSat concept leverages JPL's Interplanetary Nano- Spacecraft Pathfinder In Relevant Environment (INSPIRE) mission, MSFC's intimate knowledge of the Space Launch System and EM-1 mission, small business development of solar sail and electric propulsion hardware, and JPL experience with specialized miniature sensors. The goal of Lunar Flashlight is to determine the presence or absence of exposed water ice and its physical state, and map its concentration at the kilometer scale within the permanently shadowed regions of the lunar south pole. After being ejected in cislunar space by SLS, Lunar Flashlight deploys its solar panels and solar sail and maneuvers into a low-energy transfer to lunar orbit. The solar sail and attitude control system work to bring the satellite into an elliptical polar orbit spiraling down to a perilune of 30-10 km above the south pole for data collection. Lunar Flashlight uses its solar sail to shine reflected sunlight into permanently shadowed regions, measuring surface albedo with a four-filter point spectrometer at 1.1, 1.5 1.9, and 2.0 microns. Water ice will be distinguished from dry regolith from these measurements in two ways: 1) spatial variations in absolute reflectance (water ice is much brighter in the continuum channels), and 2) reflectance ratios between absorption and continuum channels. Derived reflectance and reflectance ratios will be mapped onto the lunar surface in order to distinguish the composition of the PSRs from that of the sunlit terrain. Lunar Flashlight enables a low-cost path to in-situ resource utilization (ISRU) by identifying operationally useful deposits (if there are any), which is a game-changing capability for expanded human exploration.

Cohen, B. A.↗

Quick-Connect Windowed Non-Stick Penetrator Tips for Rapid Sampling

Standard penetrator sampling systems were designed in order to allow for sampling via penetrators to produce a full set of sample acquisitions including volatile liquids, fine powders, and solid fragments. A gravity harpoon sampler has been designed with a removable tip and a quick coupling. The separation allows for sample handling and eliminates sample cross-contamination. Also, this design allows for multiple use of the penetrator body, which is the largest and heaviest part of the penetrator, while allowing for multiple changes of the light-mass, penetrator tip to avoid sample cross-contamination. The penetrator tip design has been improved by adding a spring trap to retain the sample, as well as a means for connecting to a quick coupling. Quick connect tips have been demonstrated in a sample handling carousel. The penetrator was released and rewound and the tips were released into a circular platter for rotation into instrument stations. The pyro-harpoon sampler was fabricated and tested with a NASA Standard Initiator (NSI) pyrotechnic charge. Initial tests collected cryogenic ice, but removal of the small pyro-harpoon from the ice was difficult. A brass metal sheath was then fitted over the harpoon tip, and removal from the ice was greatly alleviated by leaving the sheath in the ice. Quartz windows in the tips allow direct optical and spectral imaging and gas chromatography-mass spectrometer (GCMS) pyrolysis, and were found to survive impact. All systems were successfully tested by dropping into sand and into cryogenic ice.

Sherritt, Stewart↗

Changes in Anthropogenic Precursor Emissions Drive Shifts in the Ozone Seasonal Cycle Throughout the Northern Midlatitude Troposphere

Simulations by six Coupled Model Intercomparison Project Phase 6 (CMIP6) Earth system models indicate that the seasonal cycle of baseline tropospheric ozone at northern midlatitudes has been shifting since the mid-20th century. Beginning in ∼ 1940, the magnitude of the seasonal cycle increased by ∼10 ppb (measured from seasonal minimum to maximum), and the seasonal maximum shifted to later in the year by about 3 weeks. This shift maximized in the mid-1980s, followed by a reversal – the seasonal cycle decreased in amplitude and the maximum shifted back to earlier in the year. Similar changes are seen in measurements collected from the 1970s to the present. The timing of the seasonal cycle changes is generally concurrent with the rise and fall of anthropogenic emissions that followed industrialization and the subsequent implementation of air quality emission controls. A quantitative comparison of the temporal changes in the ozone seasonal cycle at sites in both Europe and North America with the temporal changes in ozone precursor emissions across the northern midlatitudes found a high degree of similarity between these two temporal patterns. We hypothesize that changing precursor emissions are responsible for the shift in the ozone seasonal cycle; this is supported by the absence of such seasonal shifts in southern midlatitudes where anthropogenic emissions are much smaller. We also suggest a mechanism by which changing emissions drive the changing seasonal cycle: increasing emissions of NOx allow summertime photochemical production of ozone to become more important than ozone transported from the stratosphere, and increasing volatile organic compounds (VOCs) lead to progressively greater photochemical ozone production in the summer months, thereby increasing the amplitude of the seasonal ozone cycle. Decreasing emissions of both precursor classes then reverse these changes. The quantitative parameter values that characterize the seasonal shifts provide useful benchmarks for evaluating model simulations, both against observations and between models.

Ozone↗