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The THS Experiment: Simulating Titans Atmospheric Chemistry at Low Temperature (200K)

In Titan's atmosphere, composed mainly of N2 (95-98%) and CH4 (2-5%), a complex chemistry occurs at low temperature, and leads to the production of heavy organic molecules and subsequently solid aerosols. Here, we used the Titan Haze Simulation (THS) experiment, an experimental setup developed at the NASA Ames COSmIC simulation facility to study Titan's atmospheric chemistry at low temperature. In the THS, the chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas is cooled to Titan-like temperature ( approximately 150K) before inducing the chemistry by plasma, and remains at low temperature in the plasma discharge (approximately 200K). Different N2-CH4-based gas mixtures can be injected in the plasma, with or without the addition of heavier precursors present as trace elements on Titan, in order to monitor the evolution of the chemical growth. Both the gas- and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed using a combination of complementary in situ and ex situ diagnostics. A recent mass spectrometry[1] study of the gas phase has demonstrated that the THS is a unique tool to probe the first and intermediate steps of Titan's atmospheric chemistry at Titan-like temperature. In particular, the mass spectra obtained in a N2-CH4-C2H2-C6H6 mixture are relevant for comparison to Cassini's CAPS-IBS instrument. The results of a complementary study of the solid phase are consistent with the chemical growth evolution observed in the gas phase. Grains and aggregates form in the gas phase and can be jet deposited on various substrates for ex situ analysis. Scanning Electron Microscopy images show that more complex mixtures produce larger aggregates. A mass spectrometry analysis of the solid phase has detected the presence of aminoacetonitrile, a precursor of glycine, in the THS aerosols. X-ray Absorption Near Edge Structure (XANES) measurements also show the presence of imine and nitrile functional groups, showing evidence of nitrogen chemistry. These complementary studies show the high potential of THS to better understand Titan's chemistry and the origin of aerosol formation.

Laboratory↗

Titan Atmospheric Entry Radiative Heating

Detailed spectrally and spatially resolved radiance has been measured in the Electric Arc Shock Tube for conditions relevant to Titan entry, varying atmospheric composition, free-stream density (equivalent to altitude) and shock velocity. Permutations in atmospheric composition include 1.1, 2, 5 and 8.6 CH4 by mole with a balance of N2 and 1.5 CH4 0.5 Ar 98 N2 by mole, which is consistent with the current understanding of Titan's atmosphere. The effect of gas impurities identified in previous shock tube studies were also examined by testing in pure N2 and deliberate addition of air to the CH4N2 mixtures. The test campaign measured radiation at velocities from 4.7 kms to 8 kms and free-stream pressures from 0.1 to 0.47 Torr. These conditions cover a range of potential trajectories for flight missions, including a direct ballistic trajectory, a fly by or an extremely high speed entry. Radiances measured in this work are substantially larger compared to that reported both in past EAST test campaigns and other shock tube facilities. Depending on the metric used for comparison, the discrepancy can be as high as an order of magnitude. Potential causes for the discrepancy, such as the effect of oxygen due to Air leakage, gas composition and purity are discussed. The present work provides a new benchmark set of data to replace those published in previous studies.

Earth↗

Titan Atmospheric Entry Radiative Heating

Detailed spectrally and spatially resolved radiance has been measured in the Electric Arc Shock Tube for conditions relevant to Titan entry, varying atmospheric composition, free-stream density (equivalent to altitude) and shock velocity. Permutations in atmospheric composition include 1.1, 2, 5 and 8.6 CH4 by mole with a balance of N2 and 1.5 CH4 0.5 Ar 98 N2 by mole, which is consistent with the current understanding of Titan's atmosphere. The effect of gas impurities identified in previous shock tube studies were also examined by testing in pure N2 and deliberate addition of air to the CH4N2 mixtures. The test campaign measured radiation at velocities from 4.7 kms to 8 kms and free-stream pressures from 0.1 to 0.47 Torr. These conditions cover a range of potential trajectories for flight missions, including a direct ballistic trajectory, a fly by or an extremely high speed entry. Radiances measured in this work are substantially larger compared to that reported both in past EAST test campaigns and other shock tube facilities. Depending on the metric used for comparison, the discrepancy can be as high as an order of magnitude. Potential causes for the discrepancy, such as the effect of oxygen due to Air leakage, gas composition and purity are discussed. The present work provides a new benchmark set of data to replace those published in previous studies.

Brandis, A. M↗

Shock Tube Measurements of Radiative Heating for Titan and Nitrogen

Detailed spectrally and spatially resolved radiance has been measured in the Electric Arc Shock Tube at NASA Ames Research Center for conditions relevant to Titan entry, with varying atmospheric composition, free-stream density (equivalently, altitude) and shock velocity. The test campaign measured radiation at velocities from 4.7 km/s to 8 km/s and free-stream pressures of 0.1, 0.28 and 0.47 Torr with a variety of compositions. Radiances measured in this work are substantially larger compared to that reported both in past EAST test campaigns and in other shock tube facilities. Depending on the metric used for comparison, the discrepancy can be as high as an order of magnitude. Due to the difference with previously reported data, a substantial effort was undertaken to provide confidence in the new results. The present work provides a new benchmark set of data to replace those published in previous studies. The effect of gas impurities identified in previous shock tube studies was also examined by testing in pure N2 and deliberate addition of air to the CH4/N2 mixtures. Furthermore, a test campaign in pure N2 was also conducted with the aim of providing data for improving fundamental understanding of high enthalpy flows containing N2, such as high-speed entries into Earth or Titan. These experiments cover conditions from approximately 6 km/s to 11 km/s at an initial pressure of 0.2 Torr. It is the intention of this paper to motivate code comparisons benchmarked against this data set.

Radiation↗

Mapping of Spacecraft Atmosphere Monitor Signal to Major Constituent Abundances

The Spacecraft Atmosphere Monitor (S.A.M.) follows the JPL’s commitment to introduce and develop next-generation instrumentation concepts for sensing the air quality on manned space flights via continuous sampling, measuring, and reporting in 2s intervals on all gaseous pollutants. The S.A.M. will have two modes of operation: the Major Constituent Analysis (MCA) mode and the Trace Gas Analysis (TGA) mode. The MCA mode will report on molecular analytes such as CH4, H2O, N2, O2, Ar, and CO2 while the TGA mode will acquire minute amounts of volatile organic compounds. Both modes assess the composition of the ambient air with twenty full mass spectra per second giving rise to a substantial amount of data to be processed by a set of small footprint software stacks hosted by an on-board computer. Mass spectra will be accumulated as the number of counts recorded in a given mass-to-charge channel and converted into the absolute abundances of detected species using an efficient algorithm. The decomposition algorithm contains four units: peak identification, mass calibration, background and dead time correction, and an abundance analysis unit. The abundance analysis module identifies target species through their characteristic fragmentation patterns in the presence of molecular isobars, such as CO and N2. For example, in order to identify N2 analyte, the code will simultaneously monitor abundance ratios of the 14, 28 and 29 Th signals and will adapt to any instability caused by a decrease in ambient pressure or changes in humidity. This requirement becomes critical for instruments designed to monitor the near real-time quality of cabin air and promptly provide accurate feedbacks.

Nikolic, D.↗

A Two-Stage Biological Reactor for Treatment of Space Based Waste Waters

Previous works on Membrane Aerobic Biological Reactors (MABR) CoMANDR 1.0, CoMANDR 2.0, and R-CoMANDAR have demonstrated their ability to stabilize various space based waste streams over operating periods of ~1 year. Biological pretreatment by MABR systems can stabilize space based waste streams. Biological stabilization includes reducing the pH, conversion of organic N to NOx- and oxidation of dissolved organic matter to CO2. These processes produce a more stable waste product (brine), facilitate the distillation processes, and enable evaporative or membrane based systems. An alternative to aerobic operation would be to include anoxic operation to promote denitrification and production of N2 gas. This results in a reduced O2 demand and increases ammonia oxidation efficiency. Denitrifictaion can be accomplished in either a single reactor (Simultaneous Nitrification Denitrification) or in a two-stage system with separate aerobic and anoxic reactors. We evaluated the performance of both architectures in pilot scale systems (1-2 crew/d). Each system was continuously operated for over 2 years during which they processed a variety of habitation waste streams (ISS, Transit, and EPB) in both a continuous and on production feed mode. Here we report the results of the two stage system. Results indicate that the two stage system can successfully remove organic carbon, lower pH and convert organic N to N2 gas. Organic carbon and organic N oxidation reaction rates for the two stage system are similar to past studies for single stage aerobic systems. The two stage system is more complex and requires an additional pump. While no maintenance was required on the system during the nearly two year period of operation, the packed bed did produce N2 gas for many operational test points. The performance and comparison of operational conditions are detailed below

Water↗

Seasonal Variations in Atmospheric Composition as Measured in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Mars Science Laboratory Curiosity rover measures the chemical composition of major atmospheric species (CO2, N2, 40Ar,O2, and CO) through a dedicated atmospheric inlet. We report here measurements of volume mixing ratios in Gale Crater using the SAM quadrupole mass spectrometer, obtained over a period of nearly 5 years (3 Mars years) from landing. The observation period spans the northern summer of MY31 and solar longitude (L(sub S)) of 175° through spring of MY 34, L(sub S) = 12°. This work expands upon prior reports of the mixing ratios measured by SAM QMS in the first 105 sols of the mission. The SAM QMS atmospheric measurements were taken periodically, with a cumulative coverage of four or five experiments per season on Mars. Major observations include the seasonal cycle of CO2, N2, and Ar, which lags approximately 20–40° of L(sub S) behind the pressure cycle driven by CO2 condensation and sublimation from the winter poles. This seasonal cycle indicates that transport occurs on faster timescales than mixing. The mixing ratio of O2 shows significant seasonal and interannual variability, suggesting an unknown atmospheric or surface process at work. The O2 measurements are compared to several parameters, including dust optical depth and trace CH4 measurements by Curiosity. We derive annual mean volume mixing ratios for the atmosphere in Gale Crater: CO2 = 0.951 (±0.003), N2 = 0.0259 (±0.0006), 40Ar = 0.0194 (±0.0004), O2 = 1.61 (±0.09) x 10(exp ‐3), and CO = 5.8 (±0.8) x 10(exp ‐4).

Gale Crater↗

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗

Preliminary XANES Analysis of Laboratory Analogs of Titan Tholins

Titan, the largest moon of Saturn, is a fascinating object. It is the only other object in the Solar System, besides Earth, with a dense (1.5 bar at the surface) atmosphere whose composition is dominated by N2, with CH4 as the second most abundant gas. A complex organic chemistry between N2 and CH4, induced by solar UV photons and energetic particles, results in the formation of a large variety of organic compounds, including hydrocarbons (e.g., C2H2, C2H4, C2H6, C3H4, C6H6), nitriles (e.g., HCN, HNC, HC3N, CH3CN, C2N2), as well as larger molecules that include aromatic and heteroaromatic compounds [1]. This complex organic chemistry also leads to the formation of aerosols that play an important role in Titan’s atmospheric dynamics, climate, as well as surface composition and processes. Because of its N2-based dense atmosphere, and its CH4 cycle that resembles the hydrological cycle on Earth, Titan is often considered to be an analog of early Earth. In recent years, Titan’s atmosphere and surface were monitored in detail by the NASA Cassini mission, which orbited the Saturnian system from 2004 to 2017, as well as the ESA Huygens probe, which plunged into Titan’s atmosphere and landed on its surface in 2005.

Titan↗

Annual and Semiannual Oscillations of Thermospheric Composition in TIMED/GUVI Limb Measurements

The Global UltraViolet Imager (GUVI) onboard the Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED) satellite provides a data set of vertical thermospheric composition (O, N2, and O2 densities) and temperature profiles from 2002–2007. Even though GUVI sampling is limited by orbital constraint, we demonstrated that the GUVI data set can be used to derive the altitude profiles of the amplitudes and phases of annual oscillation (AO) and semiannual oscillation (SAO), thereby providing important constraints on models seeking to explain these features. We performed a seasonal and interannual analysis of GUVI limb O, O2, and N2 densities and volume number density ratio O/N2 at constant pressure levels. These daytime observations of O and O/N2 in the lower thermosphere show a strong AO at midlatitudes and a clear SAO at lower latitudes. The global mean GUVI O/N2 number density ratio shows the AO, with slightly larger values in January than in July and a SAO with O/N2 greater during equinoxes than at the solstices. O and N2 densities on fixed pressure levels in the upper thermosphere are anticorrelated with solar extreme ultraviolet flux. On the other hand, O/N2 is smaller during solar minimum and larger during solar maximum. The thermospheric AO and SAO in composition have a constant phase with altitude throughout the thermosphere.

thermosphere composition↗

The Titan Haze Simulation (THS) Experiment on COSmIC. Part III. XANES Study of Laboratory Analogs of Titan Tholins

We have used the Titan Haze Simulation (THS) experimental set-up at NASA Ames’ COSmIC 19 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples 20 were produced from four gas mixtures, representative of Titan’s atmosphere, of initial 21 compositions N2:CH4 (90:10 and 95:5) and N2:CH4:C2H2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, 22 using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex-situ 23 X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin 24 samples. The C- and N-XANES spectra show the presence of various functional groups 25 (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative 26 proportions between N2 and CH4, and (ii) the presence or absence of C2H2 in the initial mixtures. 27 In particular, mixtures containing C2H2 result in the formation of tholins consisting of more 28 aromatic structures and displaying larger relative amounts of imines and nitriles, but lower 29 overall nitrogen content. XANES spectroscopy also allowed for the determination of the 30 elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent 31 with those measured for tholins produced in other, independent experimental set-ups. The C/N 32 ratios of tholins produced from gas mixtures that contained C2H2 (2.2–2.4) were found to be 33 about twice as large as those of tholins produced from gas mixtures that did not contain C2H234 (0.9–1.3). These new experimental results from the COSmIC/THS experiment demonstrate the 35 impact initial precursors have on the nitrogen chemistry during the formation of tholins, which 36 may help in the interpretation of observations and the development of models of Titan’s 37 atmosphere.

Titan↗

Interfacial thermodynamics of cryogenic fluids: The effect on non-condensable gas on fluid storage

Propellant tanks that contain cryogenic fluids (CFs) in low gravity conditions are usually pressurized with non-condensable (NC) gases for fast extraction. Unfortunately, the presence of NC gases causes CFs to exhibit higher boil-offs compared to pure CF systems. For optimal utilization of the cryogenic fuels, these higher boil-off rates must be minimized. Our goal is to quantify the effects NC gases have on the evaporation and condensation dynamics of CFs to develop strategies that mitigate the higher boil-offs. The hypothesis is that the NC gas accumulates around the CF’s liquid vapor interface in the Knudsen layer, creating a kinetic barrier for both evaporation and condensation. Testing this hypothesis with experimental methods is difficult due to the transient nature of the Knudsen layer, which is only a few nanometers thick. Furthermore, experimental capabilities are limited in low gravity conditions and extremely expensive. Accordingly, we approach this problem from a theoretical perspective. In this study, we employ molecular dynamics (MD) simulations to probe the interfacial mechanisms that affect CF’s evaporation and condensation at varying concentrations of NC gases. Specifically, we use nitrogen (N2) and oxygen (O2) as our CFs and neon (Ne) as our NC gas. Using MD simulations, we show that Ne accumulates at N2 liquid vapor interface across a wide range of Ne concentrations, thereby impeding mass transport of N2. Our simulations allow for direct computation of the molar flux as well as the mass accommodation coefficient (MAC) which can then be used as input parameters to continuum fluid dynamics (CFD) models for optimal storage tank design.

Michael Robert DeLyser↗

Spatial and Temporal Trends in Precambrian Nitrogen Cycling: A Mesoproterozoic Offshore Nitrate Minimum

Fixed nitrogen is an essential nutrient for eukaryotes. As N2 fixation and assimilation of nitrate are catalyzed by metalloenzymes, it has been hypothesized that in Mesoproterozoic oceans nitrate was limited in offshore environments by low trace metal concentrations and high rates of denitrification in anoxic and episodically euxinic deep water masses, restricting eukaryotes to near-shore environments and limiting their evolutionary innovation. To date this hypothesis has only been tested in the Belt Supergroup (∼1.4 Ga), with results that support an onshore-offshore nitrate gradient as a potential control on eukaryote ecology. Here we present bulk nitrogen and organic carbon isotopic data from non-isochronous cross-basinal facies across the Bangemall (∼1.5 Ga) and the Roper (∼1.4–1.5 Ga) basins to better understand the extent and variability of onshore-offshore nitrogen isotope gradients in the Mesoproterozoic. Both basins show an average ∼1-2‰ enrichment in δ-15N(sub bulk) from deep to shallow facies, with a maximum range from ~1‰ offshore to +7.5‰ onshore. Unlike the Belt basin, the Bangemall and Roper basins show some offshore δ-15N(sub bulk) values that are enriched beyond the isotopic range associated with biological N2 fixation alone. This suggests a mixture of aerobic and anaerobic metabolisms offshore. In shallow waters, where δ-15N(sub bulk) enrichment peaks, an aerobic nitrogen cycle was evidently operating. Even though isotopic signatures of aerobic nitrogen cycling are seen in all parts of the Bangemall and Roper basins, our data are consistent with a lateral gradient in nitrate availability within the photic zone, with higher concentrations in near-shore environments than offshore. The variability in δ-15N(sub bulk) values in each depositional environment and the consistently low δ-15N(sub bulk) values from Mesoproterozoic units compared to the Paleoproterozoic and Neoproterozoic suggest that nitrate concentrations in the global ocean were likely low. This trend is now seen in all three Mesoproterozoic basins so far examined, and contrasts with the Paleoproterozoic and Neoproterozoic where nearly all δ-15N(sub bulk) data plot above the N2 fixation window. Thus, we propose that the Mesoproterozoic ocean was characterized by a nitrate minimum, with the lowest concentrations in offshore environments. This inference is consistent with a Mesoproterozoic O2 decline following a temporary Paleoproterozoic O2 peak, and it further supports the idea that nitrate limitation offshore may have contributed to the restriction of photosynthetic eukaryotes to near-shore environments, delaying their rise to ecological dominance until the Neoproterozoic Era.

Mesoproterozoic↗

Modeling pN2 Through Geological Time: Implications for Planetary Climates and Atmospheric Biosignatures

Nitrogen is a major nutrient for all life on Earth and could plausibly play a similar role in extraterrestrial biospheres. The major reservoir of nitrogen at Earth’s surface is atmospheric N2, but recent studies have proposed that the size of this reservoir may have fluctuated significantly over the course of Earth’s history with particularly low levels in the Neoarchean—presumably as a result of biological activity. We used a biogeochemical box model to test which conditions are necessary to cause large swings in atmospheric N2 pressure. Parameters for our model are constrained by observations of modern Earth and reconstructions of biomass burial and oxidative weathering in deep time. A 1-D climate model was used to model potential effects on atmospheric climate. In a second set of tests, we perturbed our box model to investigate which parameters have the greatest impact on the evolution of atmospheric pN2 and consider possible implications for nitrogen cycling on other planets. Our results suggest that (a) a high rate of biomass burial would have been needed in the Archean to draw down atmospheric pN2 to less than half modern levels, (b) the resulting effect on temperature could probably have been compensated by increasing solar luminosity and a mild increase in pCO2, and (c) atmospheric oxygenation could have initiated a stepwise pN2 rebound through oxidative weathering. In general, life appears to be necessary for significant atmospheric pN2 swings on Earth-like planets. Our results further support the idea that an exoplanetary atmosphere rich in both N2 and O2 is a signature of an oxygen-producing biosphere.

Biosignatures↗

First Optical Constants of Laboratory-Generated Organic Refractory Materials (Tholins) Produced in the NASA Ames COSmIC Facility from the Visible to the Near Infrared (0.4–1.6 μm): Application to Titan’s Aerosols

We have measured the complex refractive indices, from 0.4 to 1.6μm, of five laboratory-generated organic refractory materials (tholins) produced at low temperature(150 K)using plasma chemistry in the stream of a supersonic expansion in NASA Ames’ COsmic SImulation Chamber(COSmIC)facility. Three samples were produced from N2:CH4gas precursors(with different voltages inducing different degrees of ionization in the plasma), one sample was produced from N2:CH4:C2H2, and one sample was produced from Ar:CH4in order to produce a purely carbonaceous sample. The optical constants, n and k, of the samples were determined using spectral reflectance measurements. We observe that both n and k appear to be correlated with the nitrogen content in the solid sample, with samples containing more nitrogen having higher n and k. Comparisons to previous laboratory studies and Titan aerosol optical constants derived from observations show that the COSmIC tholins with a higher nitrogen content (higher n and k)are closer analogs of Titan aerosols. We also present a new analysis of Cassini Visible Infrared Mapping Spectrometer observations of Titan’s atmosphere in the visible to near infrared using the COSmIC tholin optical constants in a radiative transfer model. The COSmIC tholin sample produced from N2:CH4with the lowest energy level has a spectral behavior that appears well suited to reproduce the observed Titan aerosol properties. This study has therefore demonstrated that this COSmIC tholin sample has valuable and promising optical properties for the analysis of Cassini’s Titan atmospheric observations.

Optical Constants↗

Development, Validation and Approval of A Planetary Extravehicular Activity Prebreathe Protocol: NASA Exploration Atmosphere Tests 1 & 2

INTRODUCTION: Denitrogenation prebreathe protocols used to mitigate DCS risk for Space Shuttle and International Space Station EVAs are validated for the microgravity environment, but the significantly increased risk of DCS during equivalent ambulatory surface EVAs make these protocols inapplicable to planetary/Lunar missions as planned by the Artemis program. Living in an “Exploration Atmosphere” of 56.5 kPa (8.2 psia), 34% O2, 66% N2 has been recommended by NASA for future Moon and Mars missions as a compromise that balances pre-EVA prebreathe duration, hypoxia, and flammability risk, assuming a 29.6 kPa (4.3 psi) spacesuit. A prebreathe validation campaign at NASA’s Johnson Space Center in 2022–2023 has aimed to validate the prebreathe durations and is being operationalized by NASA for use in upcoming Lunar EVAs. METHODS: Twelve volunteers lived in a hyboparic chamber for 11 days with an “exploration atmosphere” of 56.6kPa/34% O2 66% N2. Subjects acclimated to this atmosphere for 48 hrs and thereafter participated in five 6-hour simulated EVAs at 34kPa/85% O2 / 15% N2 over the course of 11 days. Prior to each simulated EVA, subjects underwent a 20-minute prebreathe at 85% O2. The EVA simulation was designed to include tasks that are physically and ergonomically representative of future planetary EVAs, proportionate to the subject’s VO2max. Decompression stress was evaluated during the simulated EVA by serial doppler and echocardiographs alternating every 15 min, as well as clinical monitoring for DCS signs/symptoms. Venous gas emboli (VGE) and DCS outcomes were verified against NASA Standard 3001, which guides allowable prebreathe protocol acceptance criteria. RESULTS AND DISCUSSION: Venous gas emboli (VGE) were identified during EVAs. No Grade IV VGE were observed. Two cases of mild, Type I DCS were identified in the subjects over the course of 50 EVA exposures. Ten planned EVA exposures were eliminated due to mask fit, metabolic rate, or subject safety concerns. One subject was removed from the study due to presence of left ventricular VGE. Additionally, two doppler techs also experienced DCS, and one case of hypoxia was noted. All cases of DCS resolved with treatment. No cases of severe DCS were observed. The observed incidence (4%, 1.1–13.5% at 95% confidence) met the NASA Standard 3001 criteria leading to the transition of this protocol from research to operational use for upcoming Lunar missions.

Exploration Atmosphere↗

Trace Oxygen Measurements of Asteroid Sample Storage Desiccators

The Astromaterials Curation facility at the NASA Johnson Space Center is currently curating more than 120 g of carbonaceous asteroid Bennu material as well as over 500 mg of asteroid Ryugu [1 and 2]. These astromaterials are stored in isolating desiccators and gloveboxes under a continuous purge of pure (<1 ppm O 2 ) gaseous nitrogen. The oxygen and moisture concentrations in our OSIRIS-REx sample processing gloveboxes are continuously monitored via integrated sensors; however, our sample storage desiccators lack integrated oxygen and humidity sensors. In previous studies, we used PreSens Fibox 4 trace oxygen meters and optochemical PSt9 spot sensors to measure the oxygen concentrations in candidate asteroid sample containers that had been sealed in nitrogen; we determined that Eagle stainless steel containers inhibit the ingress of external oxygen for several weeks [3]. This optochemical sensor technology allowed us to take precise, contactless measurements within a trace range of 0 to 200 ppmv O 2 . The effectiveness of the trace oxygen sensors in our container experiments inspired us to utilize them to assess the performance of our desiccators that previously lacked trace oxygen monitoring. In this study, our goal was to determine the quality of the nitrogen purge in the isolating desiccator under normal operating conditions by measuring the trace oxygen content. Utilizing optochemical sensor technology, we determined how long the oxygen concentration takes to reach an equilibrium in the desiccator; that is, determine the rate at which the oxygen diffusion into the desiccator equals the rate at which oxygen diffuses out of the desiccator via N2 purge. Additionally, we wanted to determine the oxygen concentration at this equilibrium, the state in which our desiccators are in during normal operating conditions. We tested a custom three chamber desiccator manufactured by Germfree using a PSt9 trace oxygen sensor spot that was mounted into a ¼” National Pipe Tapered (NPT) metal flow-through cell and attached it to the desiccator exhaust. The desiccator consists of top, middle, and bottom isolating chambers. The top chamber door was opened for several minutes to simulate a sample exchange, it was sealed, and then purged ~15 Standard Cubic Feet per Hour (SCFH). Oxygen measurements were automatically recorded via the Fibox 4 trace oxygen meter in 5-minute intervals over the course of a 24-hour period. Our results indicate the desiccator reached an equilibrium value of 10-15 ppm O 2 after ~5 hours (Fig. 1). This data allows us to explore standards for purging and exchange protocols that can be applied to similar types of desiccators in Hayabusa2, OSIRIS-REx, and for sample return collections. The assessment of the internal gaseous compositions of desiccators also allows us to share with the community the N 2 environment in which many of our asteroid samples and hardware are securely curated. Future measurements will include other nitrogen flow rates and measuring the trace oxygen concentration as a function of time for the levels of the previous commercial desiccator in which the Hayabusa2 sample collection was stored. We will also analyze how long the desiccators hold N2 after being disconnected from their N2 source, an extended measurement for sample security reassurance.

Curation↗

Membranes for fluid separation

Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membranes can comprise a gas permeable support and a continuous phase comprising a selective inorganic material disposed within the gas permeable support. In some embodiments, the membranes can exhibit a CO2:N2 selectivity of at least 10 at 24° C. The membranes can be bendable, such that when the membranes are wrapped around a 1.5-inch diameter cylinder and returned to a planar conformation, the CO2:N2 selectivity of the membranes is at least 25% of the CO2:N2 selectivity of the membranes prior to having been wrapped around the cylinder.

36 MATERIALS SCIENCE↗