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NASA NTRS2001

The Aquarius Mission: Sea Surface Salinity from Space

Aquarius is a new satellite mission concept to study the impact of the global water cycle on the ocean, including the response of the ocean to buoyancy forcing and the subsequent feedback of the ocean on the climate. The measurement objective of Aquarius is sea surface salinity, which reflects the concentration of freshwater at the ocean surface. Salinity affects the dielectric constant of sea water and, consequently, the radiometric emission of the sea surface to space. Rudimentary space observations with an L-band radiometer were first made from Skylab in the mid-70s and numerous aircraft missions of increasing quality and improved technology have been conducted since then. Technology is now available to carry out a global mission, which includes both an accurate L band (1.413 Ghz) radiometer and radar system in space and a global array of in situ observations for calibration and validation, in order to address key NASA Earth Science Enterprise questions about the global cycling of water and the response of the ocean circulation to climate change. The key scientific objectives of Aquarius examine the cycling of water at the ocean's surface, the response of the ocean circulation to buoyancy forcing, and the impact of buoyancy forcing on the ocean's thermal feedback to the climate. Global surface salinity will also improve our ability to model the surface solubility chemistry needed to estimate the air-sea exchange of CO2. In order to meet these science objectives, the NASA Salinity Sea Ice Working Group over the past three years has concluded that the mission measurement goals should be better than 0.2 practical salinity units (psu) accuracy, 100 km resolution, and weekly to revisits. The Aquarius mission proposes to meet these measurement requirements through a real aperture dual-polarized L band radiometer and radar system. This system can achieve the less than 0.1 K radiometric temperature measurement accuracy that is required. A 3 m antenna at approx. 600km altitude in a sun-synchronous orbit and 300 km swath can provide the desired 100 km resolution global coverage every week. Within this decade, it may be possible to combine satellite sea surface salinity measurements with ongoing satellite observations of temperature, surface height, air-sea fluxes; vertical profiles of temperature and salinity from the Argo program; and modern ocean/atmosphere modeling and data assimilation tools, in order to finally address the complex influence of buoyancy on the ocean circulation and climate.

Koblinsky, Chester↗
DOE OSTI2023

Direct observation of coherence transfer and rotational-to-vibrational energy exchange in optically centrifuged CO2 super-rotors

Abstract Optical centrifuges are laser-based molecular traps that can rotationally accelerate molecules to energies rivalling or exceeding molecular bond energies. Here we report time and frequency-resolved ultrafast coherent Raman measurements of optically centrifuged CO 2 at 380 Torr spun to energies beyond its bond dissociation energy of 5.5 eV ( J max = 364, E rot = 6.14 eV, E rot / k B = 71, 200 K). The entire rotational ladder from J = 24 to J = 364 was resolved simultaneously which enabled a more accurate measurement of the centrifugal distortion constants for CO 2 . Remarkably, coherence transfer was directly observed, and time-resolved, during the field-free relaxation of the trap as rotational energy flowed into bending-mode vibrational excitation. Vibrationally excited CO 2 ( ν 2 > 3) was observed in the time-resolved spectra to populate after 3 mean collision times as a result of rotational-to-vibrational (R-V) energy transfer. Trajectory simulations show an optimal range of J for R-V energy transfer. Dephasing rates for molecules rotating up to 5.5 times during one collision were quantified. Very slow decays of the vibrational hot band rotational coherences suggest that they are sustained by coherence transfer and line mixing.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2012

Co2(nu2)-o Quenching Rate Coefficient Derived from Coincidental SABER-TIMED and Fort Collins Lidar Observations of the Mesosphere and Lower Thermosphere

Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(nu2) vibrational levels by collisions with O atoms plays an important role. However, there is a factor of 3-4 discrepancy between the laboratory measurements of the CO2-O quenching rate coefficient, k(sub VT),and its value estimated from the atmospheric observations. In this study, we retrieve k(sub VT) in the altitude region85-105 km from the coincident SABER/TIMED and Fort Collins sodium lidar observations by minimizing the difference between measured and simulated broadband limb 15 micron radiation. The averaged k(sub VT) value obtained in this work is 6.5 +/- 1.5 X 10(exp -12) cubic cm/s that is close to other estimates of this coefficient from the atmospheric observations.However, the retrieved k(sub VT) also shows altitude dependence and varies from 5.5 1 +/-1 10(exp -12) cubic cm/s at 90 km to 7.9 +/- 1.2 10(exp -12) cubic cm/s at 105 km. Obtained results demonstrate the deficiency in current non-LTE modeling of the atmospheric 15 micron radiation, based on the application of the CO2-O quenching and excitation rates, which are linked by the detailed balance relation. We discuss the possible model improvements, among them accounting for the interaction of the non-thermal oxygen atoms with CO2 molecules.

SABER/TIMED↗
NASA NTRS2019

Comparison of Neutral Outgassing of Comet 67P/Churyumov-Gerasimenko Inbound and Outbound Beyond 3 Au From ROSINA/DFMS

Context. Pre-equinox measurements of comet 67P/Churyumov-Gerasimenko with the mass spectrometer ROSINA/DFMS on board the Rosetta spacecraft revealed a strongly heterogeneous coma. The abundances of major and various minor volatile species were found to depend on the latitude and longitude of the nadir point of the spacecraft. The observed time variability of coma species remained consistent for about three months up to equinox. The chemical variability could be generally interpreted in terms of surface temperature and seasonal effects superposed on some kind of chemical heterogeneity of the nucleus. Aims. We compare here pre-equinox (inbound) ROSINA/DFMS measurements from 2014 to measurements taken after the outbound equinox in 2016, both at heliocentric distances larger than 3 AU. For a direct comparison we limit our observations to the southern hemisphere. Methods. We report the similarities and differences in the concentrations and time variability of neutral species under similar insolation conditions (heliocentric distance and season) pre- and post-equinox, and interpret them in light of the previously published observations. In addition, we extend both the pre- and post-equinox analysis by comparing species concentrations with a mixture of CO2 and H2O. Results. Our results show significant changes in the abundances of neutral species in the coma from pre- to post-equinox that are indicative of seasonally driven nucleus heterogeneity. Conclusions. The observed pre- and post-equinox patterns can generally be explained by the strong erosion in the southern hemisphere that moves volatile-rich layers near the surface.

comets↗
NASA NTRS2014

High-Speed On-Board Data Processing for Science Instruments

A new development of on-board data processing platform has been in progress at NASA Langley Research Center since April, 2012, and the overall review of such work is presented in this paper. The project is called High-Speed On-Board Data Processing for Science Instruments (HOPS) and focuses on a high-speed scalable data processing platform for three particular National Research Council's Decadal Survey missions such as Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS), Aerosol-Cloud-Ecosystems (ACE), and Doppler Aerosol Wind Lidar (DAWN) 3-D Winds. HOPS utilizes advanced general purpose computing with Field Programmable Gate Array (FPGA) based algorithm implementation techniques. The significance of HOPS is to enable high speed on-board data processing for current and future science missions with its reconfigurable and scalable data processing platform. A single HOPS processing board is expected to provide approximately 66 times faster data processing speed for ASCENDS, more than 70% reduction in both power and weight, and about two orders of cost reduction compared to the state-of-the-art (SOA) on-board data processing system. Such benchmark predictions are based on the data when HOPS was originally proposed in August, 2011. The details of these improvement measures are also presented. The two facets of HOPS development are identifying the most computationally intensive algorithm segments of each mission and implementing them in a FPGA-based data processing board. A general introduction of such facets is also the purpose of this paper.

Beyon, Jeffrey Y.↗
DOE OSTI2022

Rationally designed negative electrode for selective CO 2 -to-CO conversion in protonic ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) are solid-state electrochemical devices that employ proton-conducting oxides as electrolytes, which offer a promising approach for electrification of chemical manufacturing, including CO 2 reduction to produce value-added chemicals (e.g., CO). The primary advantage of PCECs is their intermediate operating temperatures (300–600 °C), which thermodynamically and kinetically favor the CO 2 reduction chemistry at the negative electrode. However, the conventional negative electrodes of PCECs, such as BaZr 0.8–x Ce x Y 0.2 O 3-δ -Ni or BaZr 0.8–x Ce x Y 0.1 Yb 0.1 O 3-δ -Ni, cannot reduce CO 2 to either CH 4 or CO with a selectivity of >99 %, leading to the production of a CO and CH 4 mixture. Herein, an oxide-supported in-situ exsolved Ni-Fe alloyed nanoparticle electrocatalyst, Sr 2 Fe 1.4 Mo 0.5 O 6-δ -Ni0.175 (SFM-Ni0.175), is first employed as the negative electrode of PCECs. The PCECs equipped with this new negative electrode selectively favor the CO 2 -to-CO conversion. A selectivity of ~100 % toward CO has been demonstrated over a wide range of operating temperatures (400–600 °C) and applied potentials/current densities. The negative electrode demonstrated in this work fully suppresses the CH 4 production. In situ diffuse reflectance infrared spectroscopy (DRIFTS) was performed to probe the CO 2 reduction mechanisms over both SFM-Ni0.175 and the traditional negative electrode (BCZYYb7111 +Ni), which indicates SFM-Ni0.175 inhibits the formation of formate species, leading to selective production of CO. Finally, this work validates that PCECs equipped with the rationally designed negative electrode can selectively manufacture chemicals.

25 ENERGY STORAGE↗
NASA NTRS1992

Lunar surface mining for automated acquisition of helium-3: Methods, processes, and equipment

In this paper, several techniques considered for mining and processing the regolith on the lunar surface are presented. These techniques have been proposed and evaluated based primarily on the following criteria: (1) mining operations should be relatively simple; (2) procedures of mineral processing should be few and relatively easy; (3) transferring tonnages of regolith on the Moon should be minimized; (4) operations outside the lunar base should be readily automated; (5) all equipment should be maintainable; and (6) economic benefit should be sufficient for commercial exploitation. The economic benefits are not addressed in this paper; however, the energy benefits have been estimated to be between 250 and 350 times the mining energy. A mobile mining scheme is proposed that meets most of the mining objectives. This concept uses a bucket-wheel excavator for excavating the regolith, several mechanical electrostatic separators for beneficiation of the regolith, a fast-moving fluidized bed reactor to heat the particles, and a palladium diffuser to separate H2 from the other solar wind gases. At the final stage of the miner, the regolith 'tailings' are deposited directly into the ditch behind the miner and cylinders of the valuable solar wind gases are transported to a central gas processing facility. During the production of He-3, large quantities of valuable H2, H2O, CO, CO2, and N2 are produced for utilization at the lunar base. For larger production of He-3 the utilization of multiple-miners is recommended rather than increasing their size. Multiple miners permit operations at more sites and provide redundancy in case of equipment failure.

Li, Y. T.↗
DOE OSTI2021

Alfven eigenmodes and fast ion transport in negative triangularity DIII-D plasmas

The first energetic particle experiments in negative triangularity tokamak plasmas have been carried out on DIII-D. Alfvén eigenmode (AE) activity and associated fast ion transport comparable to that in positive triangularity is observed during the current ramp portion of all plasmas with early beam heating indicating negative triangularity does not confer a special advantage with respect to AE induced transport. In these discharges, a range of mode activity driven by the sub-Alfvénic (Vbeam/VA < 0.5) 80 kV neutral beams is found including beta induced Alfvén acoustic eigenmodes, beta induced Alfvén eigenmodes, reversed shear Alfvén eigenmodes (RSAEs) and toroidicity induced Alfvén eigenmodes (TAEs). Mode intermittency and possibly chirping appears to be more common than comparable positive triangularity and/or oval discharges but overall, the unstable spectra and mode amplitudes observed on magnetics, CO2 interferometry, and electron cyclotron emission in a set of matched positive and negative triangularity cases at moderate beam power is similar. Large levels of Alfvén eigenmode induced fast ion transport are found in both positive and negative triangularity with up to 70% central fast ion pressure deficits relative to classical predictions early during the current ramp phase for discharges with 3 MW injected 80 kV neutral beam power. The deficit in both cases is reduced toward zero as the current penetrates and eventually reaches classical levels during current flattop with qmin ≈ 1. Fast ion transport in negative triangularity plasmas measured using a beam modulation technique show very similar levels to those measured in oval plasmas over the range of tested beam powers (Pbeam ≈ 2–7 MW). This similarity is found despite quite different unstable spectra in the highest beam power case where a mixture of coherent and quasi-coherent modes in the TAE frequency range are observed in negative triangularity and a spectrum of more typical narrowband TAEs and RSAEs is observed for the oval plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Mechanistic Insights into CO 2 Electroreduction on Ni 2 P: Understanding Its Selectivity toward Multicarbon Products

Recently, nickel phosphides (Ni x P y ) have been reported to enable selective electrochemical formation of multicarbon products (C 3 and C 4 ) via the CO 2 reduction reaction (CO 2 RR); nevertheless, their activities remain low. In order to understand the roots of their high selectivity and low activity and to direct the design of more active Ni x P y -based CO 2 RR catalysts, we investigate the CO 2 RR mechanism on Ni 2 P using density functional theory (DFT) calculations. Iin this work, we reveal that the reaction proceeds through the formate pathway, followed by formaldehyde (H 2 CO*) formation and self-condensation. Moreover, we demonstrate that surface hydride transfer steps, along with surface-mediated C–C coupling, are essential in order to avoid C 1 product formation and boost selectivity toward multicarbon products. In addition, we find that the thermal surface hydride transfer from the surface to the physisorbed CO 2 is one of the key rate-limiting steps, and since it is not electroactive, it cannot be accelerated by applying an overpotential. Finally, our results also show that the hydrogen affinity of the surface and the dynamic surface reconstruction via H adsorption facilitate selective CO 2 reduction and C–C coupling on Ni 2 P. These findings provide an impetus for exploring materials design space to identify the physical principles that govern the thermodynamics of rate-limiting thermal steps in electrocatalytic processes.

36 MATERIALS SCIENCE↗
NASA NTRS2008

Assessment of the Quality of the Version 1.07 Temperature-Versus-Pressure Profiles of the Middle Atmosphere from TIMED/SABER

The quality of the retrieved temperature-versus-pressure (or T(p)) profiles is described for the middle atmosphere for the publicly available Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) Version 1.07 (V1.07) data set. The primary sources of systematic error for the SABER results below about 70 km are (1) errors in the measured radiances, (2) biases in the forward model, and (3) uncertainties in the corrections for ozone and in the determination of the reference pressure for the retrieved profiles. Comparisons with other correlative data sets indicate that SABER T(p) is too high by 1-3 K in the lower stratosphere but then too low by 1 K near the stratopause and by 2 K in the middle mesosphere. There is little difference between the local thermodynamic equilibrium (LTE) algorithm results below about 70 km from V1.07 and V1.06, but there are substantial improvements/differences for the non-LTE results of V1.07 for the upper mesosphere and lower thermosphere (UMLT) region. In particular, the V1.07 algorithm uses monthly, diurnally averaged CO2 profiles versus latitude from the Whole Atmosphere Community Climate Model. This change has improved the consistency of the character of the tides in its kinetic temperature (T(sub k)). The T(sub k) profiles agree with UMLT values obtained from ground-based measurements of column-averaged OH and O2 emissions and of the Na lidar returns, at least within their mutual uncertainties. SABER T(sub k) values obtained near the mesopause with its daytime algorithm also agree well with the falling sphere climatology at high northern latitudes in summer. It is concluded that the SABER data set can be the basis for improved, diurnal-to-interannual-scale temperatures for the middle atmosphere and especially for its UMLT region.

Remsberg, E. E.↗
NASA NTRS2020

Increasing anthropogenic methane emissions arise equally from agricultural and fossil fuel sources

Climate stabilization remains elusive, with increased greenhouse gas concentrations already increasing global average surface temperatures 1.1°C above pre-industrial levels (World Meteorological Organization 2019). Carbon dioxide (CO2) emissions from fossil fuel use, deforestation, and other anthropogenic sources reached ~ 43 billion metric tonnes in 2019 (Friedlingstein et al 2019, Jackson et al 2019). Storms, floods, and other extreme weather events displaced a record 7 million people in the first half of 2019 (IDMC 2019). When global mean surface temperature four million years ago was 2°C–3°C warmer than today (a likely temperature increase before the end of the century), ice sheets in Greenland and West Antarctica melted and parts of East Antarctica’s ice retreated, causing sea levels to rise 10–20 m (World Meteorological Organization 2019). Methane (CH4) emissions have contributed almost one quarter of the cumulative radiative forcings for CO2, CH4, and N2O (nitrous oxide) combined since 1750 (Etminan et al 2016). Although methane is far less abundant in the atmosphere than CO2, it absorbs thermal infrared radiation much more efficiently and, in consequence, has a global warming potential (GWP) ~86 times stronger per unit mass than CO2 on a 20-year timescale and 28- times more powerful on a 100-year time scale (IPCC 2014). Global average methane concentrations in the atmosphere reached ~1875 parts per billion (ppb) at the end of 2019, more than two-and-a-half times preindustrial levels (Dlugokencky 2020). The largest methane sources include anthropogenic emissions from agriculture, waste, and the extraction and use of fossil fuels as well as natural emissions from wetlands, freshwater systems, and geological sources (Kirschke et al 2013, Saunois et al 2016a, Ganesan et al 2019). Here, we summarize new estimates of the global methane budget based on the analysis of Saunois et al (2020) for the year 2017, the last year of the new Global Methane Budget and the most recent year data are fully available. We compare these estimates to mean values for the reference ‘stabilization’ period of 2000–2006 when atmospheric CH4 concentrations were relatively stable. We present data for sources and sinks and provide insights for the geographical regions and economic sectors where emissions have changed the most over recent decades.

fossil fuel sources↗
DOE OSTI2025

Boosting Hydrogenation of CO 2 Using Cationic Cu Atomically Dispersed on 2D γ‐Al 2 O 3 Nanosheets

The continuous development of novel catalytic approaches is crucial for advancing efficient CO 2 hydrogenation processes. Drawing inspiration from single-atom catalysis and 2D materials, we designed a new 2D single-atom catalyst with excellent thermal stability by thermally treating Cu-adsorbed γ-AlOOH nanosheets, which yielded a Cu/γ-Al 2 O 3 catalyst with high activity in the hydrogenation of CO 2 -yielding methanol (CH 3 OH), dimethyl ether (DME), and CO as products. The active Cu sites are monodispersed and highly stable due to their cationic oxidation state and their substitution for pentacoordinated aluminum (Al P ) sites on particle surfaces. This study demonstrates an efficient approach for achieving a high CO 2 hydrogenation rate (30.45 mol mol −1 h −1 ) using a catalyst system that lacks metallic Cu centers, traditionally considered essential for H₂ dissociation, and employs what was previously thought to be an inert metal oxide (γ-Al 2 O 3 ) for CO and CH 3 OH production. Ongoing mechanistic studies aim to elucidate the synergy between cationic Cu single atoms and γ-Al 2 O 3 , a Lewis acid support, in facilitating hydrogen (H 2 ) activation and methanol formation.

2D catalyst↗
DOE OSTI2026

In Situ Studies of Ru-CeO 2 –TiO 2 Catalysts for Selective CO 2 Hydrogenation to Methane: Importance of Metal ↔ Oxide–Oxide Interactions

Here, this work investigates Ru-CeO 2 -TiO 2 catalysts for the CO 2 methanation reaction and compares their performance with previously studied Ru-CeO 2 systems. Despite the lower Ru loading, the TiO 2 -containing catalysts exhibit significantly higher activity. To understand this behavior, in situ X-ray absorption spectroscopy (XAS) was carried out at the Ru K-edge and Ce L 3 -edge. Unlike Ru-CeO 2 , which displays reversible redox behavior of Ru, the Ru-CeO 2 -TiO 2 catalysts show irreversible Ru reduction and a substantially higher fraction of Ce 3+ species under all tested conditions (H 2 , CO 2 , H 2 /CO 2 ). The stabilization of metallic Ru during methanation, together with the enhanced formation of Ce 3+ promoted by TiO 2 through interfacial electronic transfer, accounts for their superior performance. Complementary in situ DRIFTS measurements reveal the formation and rapid consumption of bidentate carbonates and formates. These species act as a key intermediate in methane formation. Overall, these findings highlight the crucial role of the mixed CeO 2 -TiO 2 oxide in tuning the surface chemistry of the catalysts by stabilizing metallic Ru, enhancing ceria reducibility, and promoting efficient reaction pathways for CO 2 methanation. The manipulation of metal↔oxide-oxide interactions can be a very useful tool when dealing with the valorization of CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

An Efficient Single Frequency Ho:YLF Laser for IPDA Lidar Applications

A highly efficient, versatile, single frequency 2-micron pulsed laser can be used in a pulsed Differential Absorption Lidar (DIAL) / Integrated Path Differential Absorption (IPDA) instrument to make precise, high-resolution measurements to investigate sources and sinks of CO2. For a direct detection IPDA lidar, the desired 2 m Ho:YLF laser should generate 30-40 mJ pulses at the repetition rate of 100 to 200 Hz, with short pulse length (<100 ns) and better than 2% wall plug efficiency. A Tm fiber laser in-band pumped Ho:YLF laser has been developed to meet this technical challenge. This Ho:YLF laser is designed in a four mirror ring resonator with bow tie configuration, which helps to obtain high beam quality. It is end-pumped by a 40 W linearly polarized Tm fiber laser at 1.94μm. The resonator length is 1.10 meters with output coupler reflectivity at 45%. The laser crystal size is 3 x 3 x 60 mm (w, h, l) with a doping concentration of 0.5% Holmium. The laser beam and pump beam are mode-matched in the active medium. Thus, the pump and laser beams have the same confocal parameters. Mode-matching is also helpful for operating the laser in a single transverse mode. The laser beam waist is slightly less than 0.5 mm at the center of the laser crystal. Based on quasi-four level modeling, pump absorption and saturation depend on laser intensity. Laser amplification and saturation also depend on the pump intensity in the crystal. The laser is injection seeded to obtain the single frequency required by an IPDA lidar measurement. The seed beam is entered into the resonator through an output coupler. The laser is mounted on a water cooled optical bench for stable and reliable operation. The size of the optical bench is 22.16 x 9.20 x 1.25 inches. It is stiffened so that the laser can be operated in any orientation of the optical bench. This packaged Ho:YLF laser is designed for either mobile trailer or airborne platform operation. The engineering prototype Ho:YLF laser has been fully characterized to demonstrate laser performance. Figure 1 shows the laser output power as a function of pump power at different pulse repetition rates from 100 Hz to 333 Hz. The threshold of the laser is less than 14 W. The slope efficiencies are 28%, 40%, 41% and 43% for pulse repetition rates of 100, 200, 250 and 333 Hz, respectively. Maximum power increases with the pulse repetition rate. Output power of 4.2 W, 6 W, 6.7 W, and 7.7 W is achieved for pulse repetition rates of 100, 200, 250 and 333Hz, respectively. This represents the optical conversion efficiency of 16.7%, 22.4%, 23.7%, and 26.5% at these various pulse repletion rates. It is the most efficient and compact Ho:YLF laser demonstrated in the high pulse energy (>20mJ) and moderate pulse repetition rate (100's Hz) operation range. As shown in Figure 1, the maximum pulse energy at 100 Hz is 42 mJ. This is limited due to optical damage. The laser stability is characterized and found to be very stable. A relative pulse energy standard deviation of 2% was measured. The beam quality of the Ho:YLF was measured by a Spiricon infrared laser beam camera. Figure 2 shows the beam profile image of the laser. Both the X-profile of the beam (horizontal direction) and the Y-profile of the beam (vertical direction) are well fitted by a Gaussian profile. The qualitative beam quality measurement shows excellent beam quality in both axis. The M-square value for the laser beam is measured at 1.06 and 1.09 for the x and y axis respectively.-

Yu, J.↗
NASA NTRSDate not supplied

One-Carbon Metabolism and SANS 2022 Update

Spaceflight Associated Neuro-ocular Syndrome, or SANS, affects a subset of astronauts (1, 2), and biochemical evidence has documented differences in those astronauts (3). Specifically, they had higher circulating concentrations of metabolites of the one-carbon metabolic pathway (1C), including homocysteine, and these concentrations were higher before flight (3). After ruling out many potential confounding factors in these otherwise healthy individuals (e.g., sex, kidney function, vitamin status, coffee consumption), a study of genetics was warranted. In an initial pilot effort, we documented a genetic predisposition to develop ophthalmic changes after long-duration space flight (4). That is, from a limited study of 5 single-nucleotide polymorphisms (SNPs), we found that the G allele for the MTRR A66G SNP was associated with a greater risk of choroidal folds and cotton-wool spots after flight, and the C allele for SHMT1 C1420T was protective against optic disc edema (4). These data provide a potential pathway for understanding why some individuals develop SANS, while others do not. The initial pilot study of 5 SNPs yielded striking findings, but the 1C pathway is far more complex. An effort was undertaken to examine more than 500 1C SNPs to see if a broader examination could help illuminate this association. That work is ongoing. The astronaut findings led us to advocate for the inclusion of 1C pathway genetic and biochemistry testing on other SANS-related projects, noting that genetics might help identify responders, non-responders, or outliers. The first such effort yielded evidence of an association of specific forms of the MTRR and SHMT-1 SNPs and vitamin B12 status with end-tidal CO2 after acute carbon dioxide exposure (5). The second such effort led to the identification that individuals exposed to strict head-down tilt and CO2 for 30-d who developed optic disc edema also had risk alleles for the two SNPs described above (6). Additionally, we identified a clinical population with many characteristics either attributed or purported to be involved in the ocular changes seen in affected astronauts: women with polycystic ovary syndrome (PCOS). PCOS is a condition of androgen excess and anovulatory menstrual cycles. The shared characteristics and clinical findings between SANS and PCOS generally include higher circulating homocysteine concentrations, increased retinal nerve fiber layer thickness, increased androgen concentrations (or responses), and altered carbohydrate metabolism. To our knowledge, no study has examined whether women with PCOS have asymptomatic ophthalmic anomalies observed in astronauts with SANS. While researchers have evaluated the one-carbon metabolism pathway polymorphisms of PCOS patients, and initial studies show an association with certain one-carbon polymorphisms, none have looked at the set of SNPs identified in our studies that are associated with ophthalmic changes in astronauts. Accordingly, we designed a study to evaluate the association of one-carbon pathway SNPs and ophthalmic findings in patients with PCOS and/or IIH compared to controls. Subjects provided blood samples for vitamin and one carbon biochemistry analyses, an extensive analysis of >500 SNPs associated with one carbon metabolism and had eye examinations and ocular imaging. Data analysis are underway. The data collected to date have shown associations between one carbon pathway biochemistry and genetics and incidence of SANS. The mechanisms for SANS has yet to be identified, although many hypotheses exist. Based on our data, we have developed (8, 9) and expanded (6) a multi-hit hypothesis for how these seemingly disparate findings could be linked. While intriguing, the hypothesis represents the starting point for further research. We aim to clarify the relationship between B-vitamin status and genetics with regard to the risk of SANS. Ultimately, understanding the mechanism(s) behind this will provide a means to predict, prevent, or treat these ophthalmologic pathologies in astronauts, and terrestrial populations.

S M Smith↗
NASA NTRSDate not supplied

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

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