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Survival of Organic Materials in Ancient Cryovolcanically-Produced Halite Crystals

Spectroscopic evidence supports the presence of Mg-Na-K salts derived from cryovolcanism on the surface of Europa. Halite (NaCl) is effective at very long-term preservation of organic phases and structures. Collection of salt crystals from Europan plumes would provide solid inclusions of organics, potentially also biomaterials, all suitable for analysis. Two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans 1998 (H5) and Zag (H3-6)) contain fluid and solid inclusion-bearing halite crystals, dated to approximately 4.5 billion years, and thus the trapped aqueous fluids and solids are at least as old. Heating/freezing studies of the aqueous fluid inclusions in these halites demonstrated that they were trapped near 25 degrees Centigrade, and their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid occurred after that body's metamorphism ended, since heating would have dessicated the halite. O and H isotopes of the trapped fluids are consistent with mixing of asteroidal and cometary water. Cryovolcanic Origin of the Halite: We hypothesize that these meteoritic halites derive from ancient cryovolcanism based on the following points. (1) Salts crystals are observed as products of current cryovolcanism on Enceladus. (2) In-situ spacecraft analysis of some of the icy grains associated with the Enceladus salt found minor organic or siliceous components, including methane, also found in the Monahans halite. (3) Cryovolcanic fluids are observed to be in chemical disequilibrium, reflecting incomplete reactions between interior volatiles and rocky materials. The coexistence of N2 and HCN in Enceladus' cryovolcanic fluids requires that the plume consists of a mixture of materials whose sources experienced different degrees of aqueous processing, including primordial material trapped in ice that has not been in contact with liquid water. The observed mineral assemblage within the Monahans and Zag halites is also far from equilibrium. Cryovolcanoes on Ceres are a potential source of our halite, however the processes that form halite should also be operating within Europa. Dissolution of Monahans halite grains has revealed a remarkable variety of organics, which dominate the population of solid inclusions. Thermal alteration of this macromolecular carbon (measured by Raman spectroscopy) shows remarkable diversity. We have identified highly-condensed aromatics, diamond, carbonates and chloromethane. Light organic compounds like methane tend to be water soluble and require cold formation temperatures at high hydrogen fugacity - i.e. require water ice. Another indication that these halites have not been heated is that light organics readily volatilize or aromaticize into PAHs. We are currently analyzing the organics by Raman and C-XANES, and measuring the content and exploring the potential chirality of amino acids in the halite. Implications for Europa Plumes: Organic materials and structures erupted by a Europa cryovolcano should be similarly preserved within halite, and other salts, which will be a convenient form for capture and analysis, since halite will serve to encapsulate and protect the organics from spacecraft contamination. Also, being transparent at many wavelengths halite will permit analysis by spacecraft-mounted spectroscopic techniques. In addition, halite is readily dissolved, permitting further analysis of entrained organics.

Zolensky, M.↗

LIRA: Probing the Lunar Surface for Resources.

The thermal, compositional and electrical properties of the lunar regolith, such as the triboelectric properties of lunar dust, the volatile content and the thermophysical properties of the polar regolith are essential to understand from a scientific perspective as well as for resource extraction and hazard mitigation. Understanding these properties specifically requires in situ measurement, as these properties are inherent in the ambient environment. With the Lunar In situ Regolith Analyzer (LIRA) we will combine mature surface sensor technologies from previous spacecraft missions (TECP) with new sensors (ClO4- ) and battery capability to achieve a compact in situ analysis package. The surface instrument suite is adapted for lunar conditions from a sensor developed as part of the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the 2007 Mars Phoenix mission, as well as supplemental sensors. • The Thermal and Electrical Conductivity Probe (TECP), flown on MECA/Phoenix, which measures heat capacity, thermal conductivity, electrical resistance, and electrical permittivity between needles inserted into the soil. The TECP also measured atmospheric humidity, a capability that will be retained to search for subsurface H2O ice. The Mars TECP weighed 100-gram and by definition was at TRL 9. The lunar version (LIRA) is TRL 4. • The Perchlorate (ClO4) sensor is based on the fluorescence property of perchlorate (Mg, Fe, Na). We added a light source to excite the perchlorate (ClO4) and a photo diode to collect the emission wavelength. A sun-shade over the photo diode blocks out the ambient light during day light hours. The unifying goal of LIRA is to deliver a complete, integrated experiment suite that investigates properties that must be measured in situ, and provides the capability to power the suite at night or in PSRs, as well as a means to simulate aspects of the diurnal transition by delivering an optical pulse to the surface with intensity comparable to sunlight. We describe the scientific context of LIRA, touching on the electrical state of the near-surface environment, the thermal properties of the undisturbed regolith, and the distribution, geochemistry, and mobility of water. We also address the exploration implications of the work, examining hazards and resources in the context of strategic knowledge gaps (SKGs).

Heather Smith↗

Effects of Acute Exposures to Carbon Dioxide Upon Cognitive Functions

Large quantities of carbon dioxide (CO2) originate from human metabolism and typically, within spacecraft, remain about 10-fold higher in concentration than at the earth's surface. There have been recurring complaints by crew members of episodes of "mental viscosity" adversely affecting their performance, and there is evidence from the International Space Station (ISS) that associates CO2 levels with reports of headaches by crewmembers. Additionally, there is concern that CO2 may contribute to vision impairment and intracranial pressure that has been observed in some crewmembers. Consequently, flight rules have been employed to control the level of CO2 below 4 mm Hg, which is well below the existing Spacecraft Maximum Allowable Concentration (SMAC) of 10 mm Hg for 24-hour exposures, and 5.3 mm Hg for exposures of 7 to 180 days. However, the flight rule imposed limit, which places additional demands upon resources and current technology, still exceeds the lower bound of the threshold range for reportable headaches (2 - 5 mm Hg). Headaches, while sometime debilitating themselves, are also symptoms that can provide evidence that physiological defense mechanisms have been breached. The causes of the headaches may elicit other subtle adverse effects that occur at CO2 levels well below that for headaches. The concern that CO2 may have effects at levels below the threshold for headaches appears to be substantiated in unexpected findings that CO2 at concentrations below 2 mm Hg substantially reduced some cognitive functions that are associated with the ability to make complex decisions in conditions that are characterized by volatility, uncertainty, complexity, ambiguity, and delayed feedback. These are conditions that could be encountered by crews in off-nominal situations or during the first missions beyond low earth orbit. If findings of the earlier study are confirmed in crew-like subjects, our findings would provide additional evidence that CO2 may need to be controlled at levels that are well below current spacecraft limits. Our study will extend the earlier study to determine if crew-like subjects are similarly effected by CO2. In addition to employing the Strategic Management Simulation tool, we will use the Cognition battery of psychometric measures that are being utilized aboard the ISS. It will be important to learn, by using Cognition, if additional cognitive domains are sensitive to concentrations of CO2 at or below limits currently controlled by flight rules. While spaceflight Cognition data will greatly enhance the knowledge base related to inflight behavioral health and performance, some of the measures may be influenced by fatigue (related to sleep deprivation and or workload) and changes in circadian rhythms. Therefore our use of this battery of tests in a well-controlled, ground-based study that is free of these potential confounding influences will establish a baseline terrestrial data set against which Cognition data collected in flight may be assessed. The findings from this study will be useful to the NASA Toxicology Office and the National Research Council Committee on Toxicology, which assists NASA in setting environmental standards, for revision of the SMAC for CO2, and for designing further studies on effects of CO2 upon cognitive functions.

Scully, R. R.↗

Hydrogen Abundance and Distribution on (101955) Bennu

Asteroids were likely a major source of volatiles and water to early Earth. Quantifying the hydration of asteroids is necessary to constrain models of the formation and evolution of the Solar System and the origin of Life on Earth. The OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer) mission showed that near-Earth asteroid (101955) Bennu contains widespread, abundant hydrated phyllosilicates, indicated by a ubiquitous absorption at ~ 2.7 μm. The objective of this work is to quantify the hydration—that is, the hydrogen content—of phyllosilicates on Bennu's surface and investigate how this hydration varies spatially. We analyse spectral parameters (normalized optical path length, NOPL; effective single-scattering albedo, ESPAT; and Gaussian modeling) computed from the hydrated phyllosilicate absorption band of spatially resolved visible–near-infrared spectra acquired by OVIRS (the OSIRIS-REx Visible and InfraRed Spectrometer). We also computed the same spectral parameters using laboratory-measured spectra of meteorites including CMs, CIs, and the ungrouped C2 Tagish Lake. We estimate the mean hydrogen content of water and hydroxyl groups in hydrated phyllosilicates on Bennu's surface to be 0.71 ± 0.16 wt%. This value is consistent with the hydration range of some aqueously altered meteorites (CMs, C2 Tagish Lake), but not the most aqueously altered group (CIs). The sample collection site of the OSIRIS-REx mission has slightly higher hydrogen content than average. Spatial variations in hydrogen content on Bennu's surface are linked to geomorphology, and may have been partially inherited from its parent body.

A. Praet↗

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗

Overview of Small and Large-Scale Space Solar Power Concepts

An overview of space solar power studies performed at the Boeing Company under contract with NASA will be presented. The major concepts to be presented are: 1. Power Plug in Orbit: this is a spacecraft that collects solar energy and distributes it to users in space using directed radio frequency or optical energy. Our concept uses solar arrays having the same dimensions as ISS arrays, but are assumed to be more efficient. If radiofrequency wavelengths are used, it will necessitate that the receiving satellite be equipped with a rectifying antenna (rectenna). For optical wavelengths, the solar arrays on the receiving satellite will collect the power. 2. Mars Clipper I Power Explorer: this is a solar electric Mars transfer vehicle to support human missions. A near-term precursor could be a high-power radar mapping spacecraft with self-transport capability. Advanced solar electric power systems and electric propulsion technology constitute viable elements for conducting human Mars missions that are roughly comparable in performance to similar missions utilizing alternative high thrust systems, with the one exception being their inability to achieve short Earth-Mars trip times. 3. Alternative Architectures: this task involves investigating alternatives to the traditional solar power satellite (SPS) to supply commercial power from space for use on Earth. Four concepts were studied: two using photovoltaic power generation, and two using solar dynamic power generation, with microwave and laser power transmission alternatives considered for each. All four architectures use geostationary orbit. 4. Cryogenic Propellant Depot in Earth Orbit: this concept uses large solar arrays (producing perhaps 600 kW) to electrolyze water launched from Earth, liquefy the resulting hydrogen and oxygen gases, and store them until needed by spacecraft. 5. Beam-Powered Lunar Polar Rover: a lunar rover powered by a microwave or laser beam can explore permanently shadowed craters near the lunar poles to search for water ice and other frozen volatiles. Near such craters are mountain peaks and highlands that are in near permanent sunlight. Power can be beamed from a collector on a sunlit mountain or crater rim to a rover inside a crater. Near-term applications of space solar power technology can therefore pave the way toward large-scale commercial power from space.

Potter, Seth↗

Revalidation of the Volatile Organic Analyzer Following a Major On-Orbit Maintenance Activity

The Volatile Organic Analyzer (VOA) contributes to the assessment of air quality aboard the International Space Station (ISS) by identifying and quantifying target airborne volatile organic contaminants in the module air. This on-orbit contaminant monitoring capability becomes particularly important during an air quality degradation event such as a system leak. During several ISS air quality degradations, the VOA has generated near real-time data that was used to make decisions or to better understand the contingency. The VOA was operational from January 2002 through June 2003, during which time it was validated by comparing VOA data to simultaneously acquired grab sample containers (GSCs). In January 2003, one of the two analytical channels of the VOA was shutdown because of a component failure, but a redundant channel continued to supply the necessary analytical data. In June 2003, the sole remaining channel was deactivated. Initial assessments of the channel shutdowns pointed to failed fuses or heaters, but neither was considered repairable on orbit. In 2005, it was determined that failed fuses could be replaced on orbit and the crew conducted a diagnostic procedure to identify the failed component. The crew discovered that both channels incurred failed fuses, which lead to a subsequent on orbit maintenance activity and return of the VOA to operational status in December 2005. The VOA has been providing data on the ISS atmosphere since its reactivation in 2005 and this paper will present the VOA data collected during 2006. Special emphasis will be placed upon the revalidation of the repaired VOA using GSCs as well as a summary of the diagnostic and repair procedures.

Limero, Thomas↗

Vacuum Sealable Container (VSC) and Astronaut Lunar Drill (ALD) for Artemis

Introduction: NASA’s Artemis Program is under development to send first woman and next man to the Moon. Artemis will utilize a suite of new technology for Lunar exploration, including new space vehicles, new space suits, and new Astronaut Tools. Honeybee Robotics has been working with NASA JSC to develop a new Vacuum Sealable Container (VSC) and new Astronaut Lunar Drill (ALD) for the upcoming Artemis missions. Vacuum Sealable Container: Sample return continues to be the “Holy Grail” of space exploration, allowing for the analysis of materials using Earth-based laboratories instead of needing to miniaturize and ruggedize instrumentation for space. The Apollo missions to the Moon had several kinds of Sealable Containers which brought back Lunar samples for analysis [1]. These samples are still being analyzed, fifty years later. The VSC requirements are different from that for Apollo containers and as such, new development was required. One major difference between Artemis samples and those from Apollo is the desire to bring back volatiles which may be part of lunar regolith. The VSC is designed to withstand a high-pressure differential caused by sublimating volatiles. Because of the new, stricter sealing requirements, additional features have been added to the VSC. For example, the seal on the container is required to be more robust, thus required more force to actuate, and the seal must be locked in place with a secondary mechanism. Astronaut Lunar Drill: The ALD is designed to be a multi-functional platform for Lunar sample acquisition. The drill builds on lessons learned from the Apollo Lunar Surface Drill (ALSD), as well as Honeybee’s long history of mechanized sample acquisition devices for space [2]. The main functionality of the ALD is Deep Core Regolith Drilling. Additional functionality includes Surface Rock Coring (SRC), and GeoTech Tools (GTT). The ALD is a rotary-percussive drill designed with deep drilling in mind. The ALD is currently designed to have decoupled rotary and percussion subsystems to allow for maximum battery life and reduced fatigue on the crewmember. Honeybee drill technology will automatically engage the percussion when needed to drill at maximum efficiency. The mechanized drill stand helps improve drilling efficiency; the system utilizes advanced drilling algorithms which only require the crewmember to hold a single switch. Additionally, the stand aids in extraction of deep cores, something which was a problem on Apollo. The SRC functionality of the ALD utilizes Honeybee’s Eccentric Tube Core Breakoff technology to collect and retain rock core samples. This technology has also been infused into the Perseverance rover mission. The ALD is removable from the stand to allow crewmembers to collect samples from large boulders. Bringing back rock cores samples instead of full rocks allows for a wider variety of samples to be returned to Earth for study and puts them in a uniform form-factor for effective sealing and analysis. SRC bits will utilize the power of the drill’s percussion system to drill hard Lunar rocks and expedite sample acquisition. The mechanized stand on the ALD allows for additional attachments for taking geotechnical measurements with a Static Cone Penetrometer (SCP) and a Shear Vane (SV). With the stand, the ALD can take SCP measurements with the touch of a button, storing data for return to Earth. SV measurements utilize the ALD’s Rotary motor to spin the vanes in a controlled manner, getting clean data untampered by human error. References: [1] Bar Cohen and Zacny (2009), Drilling in Extreme Environments - Penetration and Sampling on Earth and Other Planets, Wiley. [2] Bar-Cohen and Zacny, Advances in Terrestrial and Extraterrestrial Drilling, CRC Press. [3] Myrick (2003), Core Break-off Mechanism. US Patent No. 6,550,549 Acknowledgements: This work has been supported by NASA via SBIR Phase 3.

Artemis↗

The Chlorine-Isotopic Composition of Lunar KREEP From Magnesian-Suite Troctolite 76535

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

Francis M. McCubbin↗

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

The Gas Chromatograph Mass Spectrometer was one of six instruments on the Cassini-Huygens Probe mission to Titan. The GCMS measured in situ the chemical composition of the atmosphere during the probe descent and served as the detector for the pyrolization products for the Aerosol Collector Pyrolyser (ACP) experiment to determine the composition of the aerosol particles. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be N2 and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3x10(exp -5) and of Ar-36 is 2.8x10(exp -7). The other primordial noble gases were below 10(exp -8) mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3x10(exp -4). Carbon dioxide, methane, acetylene and cyanogen were detected evaporating from the surface in addition to methane. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact.

Niemann, H.↗

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

The Gas Chromatograph Mass Spectrometer was one of six instruments on the Cassini-Huygens Probe mission to Titan. The GCMS measured in situ the chemical composition of the atmosphere during the probe descent and served as the detector for the pyrolization products for the Aerosol Collector Pyrolyser (ACP) experiment to determine the composition of the aerosol particles. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of mlz from 2 to 141. The major constituents of the lower atmosphere were confirmed to be N2 and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3x10(exp -5) and of Ar-36 is 2.8x10(exp -7). The other primordial noble gases were below 10(exp -8) mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3x10(exp -4). Carbon dioxide, ethane, acetylene and cyanogen were detected evaporating from the surface in addition to methane. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact.

Niemann, Hasso↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

W T Wallace↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

W T Wallace↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

William T Wallace↗

Bubble Mass Transport Measurement in the Large-Scale Test Loops at Oak Ridge National Laboratory

Molten salts are complex fluids that incorporate multi-phase behavior depending on the chemistry and the physical properties of the entrained components. These components include the carrier salt, the actinide fuel, and fission, activation, and corrosion products, the concentrations of which depends on the burnup history of the salt. Radionuclide transport from the salt into the cover gas / off-gas system depends on volatility as predicted by thermochemistry, but data from the Molten Salt Reactor Experiment (MSRE) conducted in the late 1960s suggest that bubble formation and transport are also important. Anomalously high fractions of noble metals were found in the off-gas system and were attributed to transportation with parent salt aerosols and their association with rising noble gas bubbles. The prediction of such phenomena requires coupled neutronic, thermal hydraulic, and chemical equilibrium calculations, the framework of which is being developed within the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program supported by the US Department of Energy (DOE) Office of Nuclear Energy (NE). However, separate effects tests and models of experiments using tools such as SAM and Thermochimica can guide model developers through important processes. Conversely, model development guides the choice of experiments and systems to provide data that are relevant for validation. This report describes several experiments that tracked gas transport in molten salts, ranging from small-scale systems to large-scale loops. Gas transportation in a molten salt, LiCl-KCl, has been studied using the shadowgraph technique. Sensors such as residual gas analysis, Raman spectroscopy, and laser-induced breakdown spectroscopy have been tested for off-gas measurements. These data were used to interpret how the gases move through the upstream salt / cover gas and the interface between them. Differential pressure measurements were able to detect individual gas bubbles as they popped at the liquid–gas interface. Salt aerosols were collected on a cascade impactor. Their formation was also observed directly via the shadowgraph method, and most of these aerosols were launched ballistically into the cover gas. Fine mists could also be observed. Convection currents through the salt were visualized and can be used to calculate the thermophysical properties of the salt itself. The apparatuses described in this report and in a previous work (McFarlane et al. 2023) have been commissioned and are available for use in making further measurements of salt/surrogate fission product behavior. Novel approaches using neutron imaging are planned for the study of fluoride salts, which cannot be contained in quartz, so shadowgraph visualization is not available. Bubble transport in convective flow and in a slow-moving salt column are planned. The mobile laser-induced breakdown spectroscopy (LIBS) system is available for several applications, including iodine capture in a molten hydroxide scrubber, H2 transport though molten salts to complement Raman analysis, and online tracking of salt aerosol generation, transport, and deposition. This report summarizes the findings from FY24 and the plans for FY25. The work completes milestone M2AT-24OR0702013 of the DOE-NE Advanced Reactor Technology, Molten Salt Reactor Campaign, DOE-NE-5.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Cometary Coma Chemical Composition (C4) Mission

Cometary exploration remains of great importance to virtually all of space science. Because comets are presumed to be remnants of the early solar nebula, they are expected to provide fundamental knowledge as to the origin and development of the solar system as well as to be key to understanding of the source of volatiles and even life itself in the inner solar system. Clearly the time for a detailed study of the composition of these apparent messages from the past has come. A comet rendezvous mission, the Cometary Coma Chemical Composition (C4) Mission, is now being studied as a candidate for the new Discovery program. This mission is a highly-focussed and usefully-limited subset of the Cometary Rendezvous Asteroid Flyby (CRAF) Mission. The C4 mission will concentrate on measurements that will produce an understanding of the composition and physical makeup of a cometary nucleus. The core science goals of the C4 mission are 1) to determine the chemical, elemental, and isotopic composition of a cometary nucleus and 2) to characterize the chemical and isotopic nature of its atmosphere. A related goal is to obtain temporal information about the development of the cometary coma as a function of time and orbital position. The four short-period comets -- Tempel 1, Tempel 2, Churyumov-Gerasimenko, and Wirtanen -which all appear to have acceptable dust production rates, were identified as candidate targets. Mission opportunities have been identified beginning as early as 1998. Tempel I with a launch in 1999, however, remains the baseline comet for studies of and planning the C4 mission. The C4 mission incorporates two science instruments and two engineering instruments in the payload to obtain the desired measurements. The science instruments include an advanced version of the Cometary Ice and Dust Experiment (CIDEX), a mini-CIDEX with a sample collection system, an X-ray Fluorescence Spectrometer and a Pyrolysis-Gas Chromatograph, and a simplified version of the Neutral Gas and Ion Mass Spectrometer (NIGMS). Both of these instruments have substantial heritage as they are based on those developed for the CRAF Mission. The engineering instruments include a simplified Comet Dust Environmental Monitor (SCODEM) and a navigational Camera, NAVCAM. While neither of the instruments will be permitted to establish science requirements, it is anticipated that significant science return will be accomplished Radio science will also be included.

Carle, Glenn C.↗

US Navy Submarine Sea Trial of the NASA Air Quality Monitor

For the past four years, the Air Quality Monitor (AQM) has been the operational instrument for measuring trace volatile organic compounds on the International Space Station (ISS). The key components of the AQM are the inlet preconcentrator, the gas chromatograph (GC), and the differential mobility spectrometer. Most importantly, the AQM operates at atmospheric pressure and uses air as the GC carrier gas, which translates into a small reliable instrument. Onboard ISS there are two AQMs, with different GC columns that detect and quantify 22 compounds. The AQM data contributes valuable information to the assessment of air quality aboard ISS for each crew increment. The U.S. Navy is looking to update its submarine air monitoring suite of instruments, and the success of the AQM on ISS has led to a jointly planned submarine sea trial of a NASA AQM. In addition to the AQM, the Navy is also interested in the Multi-Gas Monitor (MGM), which was successfully flown on ISS as a technology demonstration to measure major constituent gases (oxygen, carbon dioxide, water vapor, and ammonia). A separate paper will present the MGM sea trial results. A prototype AQM, which is virtually identical to the operational AQM, has been readied for the sea trial. Only one AQM will be deployed during the sea trial, but it is sufficient to detect the compounds of interest to the Navy for the purposes of this trial. A significant benefit of the AQM is that runs can be scripted for pre-determined intervals and no crew intervention is required. The data from the sea trial will be compared to archival samples collected prior to and during the trial period. This paper will give a brief overview of the AQM technology and protocols for the submarine trial. After a quick review of the AQM preparation, the main focus of the paper will be on the results of the submarine trial. Of particular interest will be the comparison of the contaminants found in the ISS and submarine atmospheres, as both represent closed environments. In U.K. submarine trials in the early 2000s, the submarine and ISS atmospheres were found to be remarkably similar.

Limero, Thomas↗

Effects of dose rate on the microstructure and deuterium retention in γ-LiAlO 2 pellets

This report presents experimental findings obtained from November 2024 to September 2025. Defect accumulation and microstructural evolution during ion irradiation at elevated temperatures are governed by two competing processes: defect production, driven by dose rate, and defect recovery, controlled by defect diffusion, interaction, and annihilation. At a given dose, the resulting microstructural evolution depends on both the dose rate and irradiation temperature. As a continuation of our FY24 tritium science project, which investigated temperature effects at a fixed dose rate, this study focuses on dose-rate effects at a fixed temperature to provide deeper insights into the irradiated microstructure and compositional changes in γ-LiAlO 2 pellets. The study aims to elucidate the impact of dose rate on microstructure, precipitate morphology, deuterium retention, and lithium volatility in γ-LiAlO 2 pellets under sequential 120 keV He + and 80 keV D 2 + ion irradiation. Three dose rates of 7.3×10 4 , 2.9×10 4 and 6.8×10 5 dpa/s were applied to achieve the same total ion fluence of 2×10 17 (He + +D + )/cm 2 at 500 °C, corresponding to a maximum combined dose of 7.55 dpa at ~255 nm. The irradiated pellets were subsequently characterized using scanning transmission electron microscopy (STEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural response of γ-LiAlO 2 to ion irradiation was found to be strongly dose-rate dependent. At medium and high dose rates, irradiation produced a surface amorphized layer and an underlying crystalline layer containing LiAl 5 O 8 precipitates, with implanted gases accumulating and forming blisters at the crystalline-amorphous interface. It remains to be investigated whether the amorphized layer was produced by He + ion irradiation prior to D 2 + ion irradiation. In contrast, at low dose rates, the material remained crystalline, with cavities, likely gas-filled, distributed around precipitates, within the γ-LiAlO 2 matrix, and along grain boundaries. While precipitate morphology exhibited anisotropy, their size showed little sensitivity to dose rate in the applied range of this study. This result, however, does not rule out the possibility that further reductions in dose rate could influence precipitate size. High dose-rate irradiation enhanced protonium–deuterium isotopic exchange and lithium depletion in the amorphized region. Collectively, the results show that dose rate governs amorphization, gas redistribution, isotopic exchange, and lithium depletion, providing important insights into the mechanisms underlying structural evolution in γ-LiAlO 2 pellets under reactor-relevant irradiation conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗