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NASA NTRS2018

Detailed Study of the Formation of Sugar Derivatives Produced from the UV Irradiation of Astrophysical Ice Analogs

Carbonaceous meteorites such as Murchison contain a large variety of organic compounds of astrobiological interest such as amino acids, other amphiphilic compounds, functionalized nitrogen heterocycles (including nucleobases), functionalized polycylic aromatic hydro-carbons (including quinones), and sugar derivatives. The presence of such a broad variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is strongly supported by laboratory studies in which astrophysical ice analogs (i.e., mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (less than 15 K) to simulate cold interstellar environments. These studies have shown that the organic residues recovered at room temperature after irradiation contain organic compounds that are very similar to those found in meteorites. No systematic search for the presence of sugar derivatives in laboratory residues had been carried out until the recent detection of ribose, the sugar of RNA, as well as other sugars, sugar alcohols, and sugar acids in one residue produced from the UV irradiation of an ice mixture containing H2O, CH3OH, and NH3 at 80 K. In this work, we present a detailed study of the formation of sugar derivatives contained in organic residues that are produced from the UV irradiation of ice mixtures of different starting compositions (H2O, CH3OH, CO, CO2, and/or NH3) at less than 15 K. While the presence of sugar alcohols, sugars, and sugar acids-in some cases with up to 6 carbon atoms-could be confirmed in all these residues, their distribution was shown to vary with the composition of the starting ices. In particular, only a few ices result in the formation of sugar derivatives displaying a distribution that resembles that of meteorites, in which sugar alcohols and sugar acids are very abundant while sugars are mostly absent.

Photochemistry↗
NASA NTRS2014

Extremely Organic-Rich Coma of Comet C/2010 G2 (HILL) During Its Outburst in 2012

We performed high-dispersion near-infrared spectroscopic observations of comet C/2010 G2 (Hill) at 2.5 AU from the Sun using NIRSPEC (R approx. equal to 25,000) at the Keck II Telescope on UT 2012 January 9 and 10, about a week after an outburst had occurred. Over the two nights of our observations, prominent emission lines of CH4 and C2H6, along with weaker emission lines of H2O, HCN, CH3OH, and CO were detected. The gas production rate of CO was comparable to that of H2O during the outburst. The mixing ratios of CO, HCN, CH4, C2H6, and CH3OHwith respect to H2O were higher than those for normal comets by a factor of five or more. The enrichment of COand CH4 in comet Hill suggests that the sublimation of these hypervolatiles sustained the outburst of the comet. Some fraction of water in the inner coma might exist as icy grains that were likely ejected from nucleus by the sublimation of hypervolatiles. Mixing ratios of volatiles in comet Hill are indicative of the interstellar heritage without significant alteration in the solar nebula.

protoplanetary disks↗
NASA NTRS2017

Habitable Moist Atmospheres on Terrestrial Planets near the Inner Edge of the Habitable Zone Around M Dwarfs

Terrestrial planets in the habitable zones (HZs) of low-mass stars and cool dwarfs have received significant scrutiny recently. Transit spectroscopy of such planets with the James Webb Space Telescope (JWST) represents our best shot at obtaining the spectrum of a habitable planet within the next decade. As these planets are likely tidally locked, improved 3D numerical simulations of such planetary atmospheres are needed to guide target selection. Here we use a 3D climate system model, updated with new water-vapor absorption coefficients derived from the HITRAN 2012 database, to study ocean-covered planets at the inner edge of the HZ around late M to mid- K stars (2600 K less than or equal to T(sub eff) less than or equal to 4500 K). Our results indicate that these updated water-vapor coefficients result in significant warming compared to previous studies, so the inner HZ around M dwarfs is not as close as suggested by earlier work. Assuming synchronously rotating Earth-sized and Earth-mass planets with background 1 bar N2 atmospheres, we find that planets at the inner HZ of stars with T(sub eff) greater than 3000 K undergo the classical ''moist greenhouse'' (H2O mixing ratio greater than 10(exp -3) in the stratosphere) at significantly lower surface temperature (approx. 280 K) in our 3D model compared with 1D climate models (approx. 340 K). This implies that some planets around low-mass stars can simultaneously undergo water loss and remain habitable. However, for stars with T(sub eff) less than or equal to 3000 K, planets at the inner HZ may directly transition to a runaway state, while bypassing the moist greenhouse water loss entirely. We analyze transmission spectra of planets in a moist greenhouse regime and find that there are several prominent H2O features, including a broad feature between 5 and 8 micron, within JWST MIRI instrument range. Thus, relying only on standard Earth-analog spectra with 24 hr rotation period around M dwarfs for habitability studies will miss the strong H2O features that one would expect to see on synchronously rotating planets around M dwarf stars, with JWST.

Kopparapu, Ravi kumar↗
NASA NTRS2017

Ground-Based Detection of Deuterated Water in Comet C/2014 Q2 (Lovejoy) at IR Wavelengths

We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H2O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H2O and HDO, yielding production rates of 5.9 +/- 0.13 × 10(exp 29) and 3.6 +/- 1.0 × 10(exp 26) molecules/sec, respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water of 3.02 +/- 0.87 × 10(exp −4), i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 +/- 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 +/- 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H2O.

Paganini, L.↗
NASA NTRS2018

Phenolic Polymer Interactions with Water and Ethylene Glycol Solvents

Interactions between pre-cured phenolic polymer chains and a solvent have a significant impact on the structure and properties of the final post-cured phenolic resin. Developing an understanding of the nature of these interactions is important and will aid in the selection of the proper solvent that will lead to the desired final product. Here, we investigate the role of the phenolic chain structure and the solvent type on the overall solvation performance of the system through ab initio techniques and molecular dynamics simulations. Two types of solvents are considered: ethylene glycol (EGL) and H2O. Three phenolic chain structures are considered, including two novolac-type chains with either an ortho-ortho (OON) or an ortho-para (OPN) backbone network and a resole-type (RES) chain with an ortho-ortho network. Each system is characterized through a structural analysis of the solvation shell and the hydrogen-bonding environment as well as through a quantification of the solvation free energy along with partitioned interaction energies between specific molecular species. The combination of simulations and the analyses indicate that EGL provides a higher solvation free energy than H2O due to more energetically favorable hydrophilic interactions as well as favorable hydrophobic interactions between CH element groups. In addition, the phenolic chain structure significantly affects the solvation performance, with OON having limited intermolecular hydrogen-bond formations, while OPN and RES interact more favorably with the solvent molecules. The results suggest that a resole-type phenolic chain with an ortho-para network should have the best solvation performance in EGL, H2O, and other similar solvents.

Haskins, Justin B.↗
NASA NTRS2018

The Volatile Composition of Comet C/2017 E4 (Lovejoy) before its Disruption, as Revealed by High-Resolution Infrared Spectroscopy with iSHELL at the NASA/IRTF

In 2017 April, we acquired comprehensive high-resolution spectra of newly discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the range (2.8-5.3) μm, in four customized instrument settings (L1-c, L3, Lp1-c, and M1) of iSHELL-the new near-IR high-resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified 12 molecular species: nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2, OH). We detected 85 H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho- and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of underabundant methanol and overabundant ammonia in E4.

Faggi, S.↗
NASA NTRS2017

Sugar Derivatives in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety of organic compounds of astrobiological and prebiotic interest have been detected in carbonaceous meteorites. These include amino acids, carboxylic acids, amphiphiles, functionalized nitrogen heterocycles such as nucleobases, functionalized polycylic aromatic hydrocarbons such as quinones, and sugar derivatives. The sugar derivatives identified in the Murchison and Murray meteorites are mainly sugar alcohols and sugar acids, and only the smallest sugar (dihydroxyacetone) has been detected. The presence of such a variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is further supported by laboratory studies in which astrophysical ice analogs (mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (<15 K) to simulate cold interstellar environments. These studies show that the organic residues recovered at room temperature after irradiation contain amino acids, amphiphiles, nucleobases, sugar derivatives, as well as other complex organic compounds. The finding of such compounds under plausible interstellar conditions is consistent with the presence of organic compounds in meteorites. Until very recently, no systematic search for the presence of sugar derivatives in laboratory residues had been carried out. The detection of ribose, the sugar constituent of RNA in all living systems, as well as other sugars, sugar alcohols, and sugar acids have been recently reported in one organic residue produced from the UV irradiation of an H2O:CH3OH:NH3 (10:3.5:1) ice mixture at 80 K. In this work, we present a detailed study of organic residues produced from the UV irradiation ice mixtures of several starting compositions (containing H2O, CH3OH, CO, CO2, and/or NH3) at <15 K for their sugar derivative content. Our results confirm the presence of all 3C‒5C sugar alcohols, several 3C‒5C sugars, and all 3C‒4C sugar acids (in decreasing order of abundances) in the residues. The higher abundances of sugar alcohols in these residues suggest a pathway in which sugar alcohols are formed first, while the formation of sugars and sugar acids require more steps. Finally, our results are compared with the detection of sugars derivatives in primitive meteorites.

Astrophysical Ice Analogs↗
NASA NTRS2015

Search for Sugars and Related Compounds in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety and number of organic compounds of prebiotic interest have been detected in meteorites. Among them, one sugar (dihydroxyacetone) as well as several sugar acids and sugar alcohols have been detected in Murchison and Murray [1]. Their presence in meteorites, along with amino acids, amphiphiles, and nucleobases [2-6], strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is supported by laboratory studies on the formation of complex organic molecules from the ultraviolet (UV) irradiation of astrophysical ice analogs (H2O, CO, CO2, CH3OH, CH4, NH3, etc.). These studies show that the organic residues recovered at room temperature after the UV irradiation of such ice mixtures contain amino acids [7-9], amphiphiles [4], nucleobases [10-13], and other organic complex organic compounds [14-16]. However, no systematic search for the presence of sugars, sugar acids, and sugar alcohols in laboratory residues have been reported to date, despite the fact that those compounds are involved in a large number of biological processes. Only a limited number of small (less than or equal to 3 carbon atoms) sugar derivatives such as glycerol and glyceric acid have been detected in residues [14-16]. In this work, we show results obtained from the systematic search for sugars and sugar-related compounds in organic residues produced from the UV irradiation of simple CH3OH and H2O+CH3OH ices, and more astrophysically relevant ice mixtures containing H2O, CH3OH, CO, and NH3. The results are compared with measurements of sugars and related compounds in primitive meteorites.

Murchison and Murray↗
NASA NTRS2019

Oxidation of the Mantle Wedge by H+ in Aqueous Fluids: A New Interdisciplinary Approach

The observation that arc magmas are the most oxidized on Earth have led petrologists to question whether the subduction process might cause oxidation of the sub-arc mantle source. A strong correlation between the input of slab-derived aqueous fluid and Fe3(+)/ΣFe in arc magmas has led to the hypothesis that slab fluids may facilitiate the transfer of redox potential from oxidized slab material to mantle wedge and subsequently to primary arc melts. Despite this intuitive link, identifying an efficient and ubiquitous chemical process to transfer oxidation state in slab fluids has been challenging. Pure H2O alone is an inefficient oxidizer in the mantle, necessitating another oxidant within the fluid. Commonly invoked components include S or C, which are likely heterogeneously distributed within subducting slabs, and direct transfer of Fe3(+), which is only possible in very solute-rich fluids. Here we present a new mechanism to explain the oxidation of the sub-arc mantle by slab-derived aqueous fluid, wherein dissolved H(+)(aq) is reduced to H2(aq). Redox equilibrium is satisfied by electron transfer from Fe2(+)(s), which is oxidized in the rock to Fe3(+)(s) in the reaction: 2Fe2(+)(s) + 2H(+)(aq) = 2Fe3(+)(s) + H2(aq). This simple reaction was previously overlooked due to the assumption that all H must be bound by H2O molecules (i.e., no dissolved H), applicable to a pure H2O fluid, but not one with a solute load as addressed here. The application of thermodynamic modeling tools from aqueous geochemistry (DEW, EQ3/6) to mantle petrology predicts this reaction between mantle rock and slab fluid with our own experimentally constrained chemistry and fO2 (QFM+2). Mass transfer model results show an increase in Fe3(+)/ΣFe in mantle rock from MORB- like (0.15) to arc-like (0.2–0.3) values at reasonable fluid fluxes, co-incident with increasing H2 activity in the fluid. This can explain the stark correlation between slab fluid input into the mantle wedge and the observed fO2 of arc magmas. Moreover, it does not require diffusion of hydrogen out of the system. Instead, H2 remains dissolved in fluid in equilibrium with oxidized mantle rock.

Iacovino, Kayla↗
NASA NTRS2020

Detection of a Water Tracer in Interstellar Comet 2I/Borisov

We present high spectral resolution optical spectra obtained with the ARCES instrument at Apache Point Observatory showing detection of the [O i] 6300 Å line in interstellar comet 2I/Borisov. We employ the observed flux in this line to derive an H2O production rate of (6.3 ± 1.5) × 1026 mol s−1. Comparing to previously reported observations of CN, this implies a CN/H2O ratio of ~0.3%–0.6%. The lower end of this range is consistent with the average value in comets, while the upper end is higher than the average value for solar system comets, but still within the range of observed values. C2/H2O is depleted, with a value likely less than 0.1%. The dust-to-gas ratio is consistent with the normal value for solar system comets. Using a simple sublimation model we estimate an H2O active area of 1.7 km2, which for current estimates for the size of Borisov suggests active fractions between 1% and 150%, consistent with values measured in solar system comets. More detailed characterization of 2I/Borisov, including compositional information and properties of the nucleus, is needed to fully interpret the observed H2O production rate.

McKay, Adam J.↗
NASA NTRS2019

Earth's Early Reduced Atmospheres

Earth’s early atmosphere evolved in response to cosmic impacts, photochemistry generated by the copious extreme ultraviolet radiation emitted by the young Sun, hydrogen escape, mineral redox buffering, the evolution of iron in the mantle, and the character of crustal weathering and subduction. No single chemical composition, surface pressure, or temperature was typical. After the biggest impacts the temperature likely rose above 3000 K and the atmosphere held rock vapor. As the atmosphere cooled its constituents rained out: first the silicates, then the geochemical volatiles (such as salt), and last the water. Depending on the size of the impact, cooling took thousands to millions of years. Between impacts the atmosphere was thick with gases like CO2, H2, and CH4 that do not condense at Earth but provide greenhouse warming that could easily have maintained surface temperatures in excess of 500 K. At some point the early atmosphere must have been conducive to the evolution of organic chemistry and the origin of life. It was therefore --- at times --- dominated by reduced gases like hydrogen and methane. Hydrogen-methane atmospheres are easily formed thermochemically after major impacts if H2O and CO2 were present on Earth in quantities consistent with their inventories on Earth today – the key is high pressure. Hydrogen-methane atmospheres slowly break down over millions of years by hydrogen escape and photochemistry. At first methane decomposes into tars and nitriles that precipitate, but later as the atmosphere grows more oxidized from hydrogen escape the methane oxidizes to CO and CO2, with a small fraction going to HCN. Impacts can also produce NH3 directly from N2 and H2O, which is expected to rain out with the H2O. As impacts grew infrequent the climate cooled in response to the fixing of CO2 as carbonate and carbonate subduction. Eventually the CO2 was mostly removed to the mantle and the surface mostly frozen.

Zahnle, Kevin↗
NASA NTRSDate not supplied

Organic-rich fluids in Pluto’s interior—A source of cryovolcanic activity

The highly variegated surface of Pluto revealed by the New Horizons spacecraft is composed of both volatile ices (N2, CH4, CO) and H2O ice, all of which are intrinsically colorless. The colors on Pluto reveal a non-ice component generally acknowledged to be a refractory complex organic material (tholins) produced by photolysis in the planet’s atmosphere [1], and by photolysis and radiolysis of the surface ices [2-4]. These processes have produced a range of colors from pale yellow to red to brown, and result in a variation of a factor of 10in albedo across the surface. Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups containing carbon. Nitrogen, oxygen, and other elements can be substituted in both the aliphatic and aromatic subunits. The detection of the spectral absorption of an ammoniated compound associated with surface exposures of red-colored H2O ice (herein, RAW) in the LEISA spectral mapping data from New Horizons suggests that a third source of a colored material is ejected from Pluto’s interior as a water-rich fluid(cryomagma) that rapidly freezes at the low temperature (~40K) of the surface [5,6]. The ammoniated compound is thought to be an ammonia hydrate or an ammoniated salt; the spectral data cover a limited wavelength range, resulting in ambiguity in the identification of the form of the ammonia. The distribution of RAW in the vicinity of tectonically stressed and deformed geological structures, particularly graben (fossae), is seen as the result of both fluid effusion and fountaining ejection of cryoclastic materials in Pluto’s Virgil Fossae region [5,6]. RAW is seen elsewhere on Pluto, both in association with graben complexes and on broad expanses of old surface, but primarily in zones of tectonic stress. The nature of the putative subsurface fluid is unknown, but it must have existed at relatively shallow depths such that the graben faulting could reach it. Geochemical modeling of fluids in the interiors of small planetary bodies in the outer Solar System[7] shows that ammonia-bearing H2O in contact with rock and metal components produce a rich chemical soup, including gases that can, in principle, help propel the fluid from shallow reservoirs through crustal fractures to reach the surface. An organic component of the fluid cryomagma is predicted to originate from thermal processing of the components [ref] and may be an example of one-pot synthesis of such complexes as amino acid precursors [ref].

Dale P Cruikshank↗
NASA NTRSDate not supplied

TPSAS-NF1676L-32105-DND

NASA Langley Research Center is developing the High-Altitude Lidar Observatory (HALO) system to address the observational needs of NASA’s weather, climate, carbon cycle, and atmospheric composition focus areas. HALO is a multi-function airborne lidar being developed to measure atmospheric H2O and CH4 mixing ratios and aerosol/cloud/ocean optical properties using the Differential Absorption Lidar (DIAL) and High Spectral Resolution Lidar (HSRL) techniques, respectively. To respond to a wide range of airborne process studies, HALO can be rapidly reconfigured to provide either CH4 DIAL+HSRL, H2O DIAL+HSRL, or CH4 DIAL+H2O DIAL measurements using three different laser transmitters. During spring 2018 NASA Langley demonstrated the world’s first combined airborne CH4 DIAL and HSRL measurements from the Langley King Air aircraft during four test flights. The HALO methane configuration also participated in the Long Island Sound Tropospheric Ozone Study (LISTOS) air quality field campaign on the NASA B200 aircraft. The flown instrument configuration employed the DIAL technique at 1645 nm for column and multi-layer range resolved measurements of CH4 concentrations, and the HSRL technique at 532 nm to make independent, unambiguous retrievals of aerosol extinction and backscatter. It also employed the standard backscatter technique at 1064 nm and is polarization-sensitive at the 1064/532 nm wavelengths. The addition of the HSRL channels provides context to the airborne CH4 DIAL measurements such as source attribution, transport, and vertical mixing through mixed layer height retrievals, as well as providing the critical capability to validate aerosol induced biases from passive space-borne measurements of column CH4. In this presentation we focus on the instrument capabilities, initial CH4 measurements over oil and gas production sites in coordination with the ACT-America campaign, CH4 signatures over the Long Island Sound domain during the LISTOS campaign, and prospects for future airborne campaigns with cohosted payloads consisting of active and passive sensors.

Rory Barton-Grimley↗
NASA NTRS2019

Millimeter/Submillimeter Spectroscopic Detection of Desorbed Ices: A New Technique in Laboratory Astrochemistry

A new laboratory technique has been developed that utilizes gas-phase, direct-absorption millimeter and submillimeter spectroscopy to detect and identify desorbed species from interstellar and cometary ice analogs. Rotational spectroscopy is a powerful structure-specific technique for detecting isomers and other species possessing the same mass that are indistinguishable with mass spectrometry. Furthermore, the resultant laboratory spectra are directly comparable to observational data from far-infrared and millimeter telescopes. Here we present the proof-of-concept measurements of the detection of thermally desorbed H2O, D2O, and CH3OH originating in a solid film created at low temperature (~12 K). The surface binding energy of H2O is reported and compared to results from traditional techniques, including mass spectrometry and quartz-crystal microbalance measurements of mass loss. Lastly, we demonstrate that this technique is capable of deriving thermodynamic values including the sublimation enthalpy and entropy of H2O.

Katarina M. Yocum↗
NASA NTRS2020

Corrigendum to: Volatiles in Lunar Felsite Clasts: Impact-related Delivery of Hydrous Material to an Ancient Dry Lunar Crust

Hydrous components were measured in nominally anhydrous minerals, primarily lunar feldspar, and reported by Simon et al. (2020). In the feldspar mineral structure, these components are contained in the form of OH, H2O, and/or NH4+molecules (Johnson, 2006 and references therein). The advantages of the ion microprobe technique employed by Simon et al. (2020) include high spatial resolution, apparent insensitivity to crystal orientation, high precision, and low detection limits, but unlike complementary spectroscopy techniques (i.e., FTIR) they preclude assignment of molecular species(Mosenfelder et al. 2015). Convention in the lunar sample community is to report major elemental abundances and hydrogen as oxides, H2O is the oxide for H. This convention was not followed by Simon et al. (2020), but rather the measured hydrogen component was reported as H to avoid the appearance of assigning the measured hydrogen concentration to a specific molecular species. The speciation of the hydrous component in terrestrial feldspars varies predominantly between OH and H2O, with no apparent correlation to feldspar composition, and only slight correlation to volcanic-to-plutonic igneous rock type (Johnson and Rossman, 2004).

J. I. Simon↗
NASA NTRS2021

Residual Temperature Bias Effects in Stratospheric Species Distributions from LIMS

The Nimbus 7 Limb Infrared Monitor of theStratosphere (LIMS) instrument operated from 25 Octo-ber 1978 through 28 May 1979. Its version 6 (V6) profileswere processed and archived in 2002. We present severaldiagnostic examples of the quality of the V6 stratospheric species distributions based on their level 3 zonal Fourier co-efficient products. In particular, we show that there are smalldifferences in the ascending (A) minus descending (D) or-bital temperature–pressure orT(p) profiles (theirA−Dval-ues) that affect (A−D) species values. SystematicA−Dbi-ases inT(p) can arise from small radiance biases and/or fromviewing anomalies along orbits. There can also be (A−D)differences inT(p) due to not resolving and correcting forall of the atmospheric temperature gradient along LIMS tan-gent view-paths. An error inT(p) affects species retrievalsthrough (1) the Planck blackbody function in forward calcu-lations of limb radiance that are part of the iterative retrievalalgorithm of LIMS, and (2) the registration of the measuredLIMS species radiance profiles in pressure altitude, mainlyfor the lower stratosphere. There are clearA−Ddifferencesfor ozone, H2O, and HNO3but not for NO2. Percentage differences are larger in the lower stratosphere for ozone andH2O because those species are optically thick. We evaluateV6 ozone profile biases in the upper stratosphere with the aid of comparisons against a monthly climatology of UV–ozone soundings from rocketsondes. We also provide resultsof time series analyses of V6 ozone, H2O, and potential vor-ticity for the middle stratosphere to show that their average(A+D) V6 level 3 products provide a clear picture of the evolution of those tracers during Northern Hemisphere win-ter. We recommend that researchers use the average V6 level3 product for their science studies of stratospheric ozone andH2O, while keeping in mind that there are uncorrected non-local thermodynamic equilibrium effects in daytime ozone inthe lower mesosphere and in daytime H2O in the uppermoststratosphere. We also point out that the present-day Soundingof the Atmosphere using Broadband Emission Radiometry(SABER) experiment provides measurements and retrievalsof temperature and ozone that are nearly free of anomalousdiurnal variations and of effects from gradients at low and middle latitudes.

Ellis Remsberg↗
NASA NTRS2019

Mars Atmospheric Chemistry Simulations with the GEM-Mars General Circulation Model

General Circulation Models with interactive physical and chemistry processes are the state-of-the-art tools for an integrated view and understanding of the Martian atmosphere and climate system. The GEM-Mars model currently includes 16 tracers for chemical composition and applies a fully online, interactive calculation of the photo- and gas phase chemistry of carbon dioxide (CO2) and water vapor (H2O). These species largely control the chemical composition of the neutral Mars atmosphere through their photolysis products and their subsequent interactions. Water vapor undergoes a complex cycle on Mars as it is transported and interacts with ice reservoirs both at the planet's surface and at water ice clouds, which in turn provide radiative feedbacks. In the photochemical cycles involving CO2 and H2O, the abundances of 5 species have been reported by previous investigations with significant spatio-temporal coverage: CO2, H2O, CO, O3 and H2O2. This paper presents the current status of the atmospheric chemistry simulations in GEM-Mars by comparing them to a selection of these observational datasets as well as to oxygen dayglow emission from O2(a1∆g). The results are consistent with previous model-data comparisons and illustrate that the water cycle and the photochemistry are well implemented in the model. In particular, the simulation of the key reservoir species H2O2 provides a good match to the available data. Model-data biases for ozone columns and oxygen airglow are related to the simulated water vapor vertical profile, as these species have important column contributions from vertical layers at the top of the hygropause.

F Daerden↗
NASA NTRS2021

Hydroxylation of Apollo 17 Soil Sample 78421 by Solar Wind Protons

Hydroxylation by solar wind protons has been simulated in our laboratory on Apollo 17 lunar sample 78421, a very mature regolith sample that is rich with agglutinates (68%). The goal of this study was to determine the rate of hydroxyl formation and their thermal stability by monitoring changes in the SiOH (hydroxyl) stretching band near 3 μm using diffuse reflectance FTIR spectroscopy (DRIFTS). A 2 keV H2+ ion beam was used to simulate proton implantation on 78421 and on a crushed fused silica sample. We find that the OH band does not change unless the samples have been annealed in vacuum prior to irradiation. Qualitatively, the OH bands for the fused silica and 78421 are very different. The OH band for fused silica is centered at 2.74 μm and is relatively sharp ranging from 2.67 - 3.1 μm at full-width-at-half-maximum (FWHM), while the OH band for 78421 is centered at 3.0 μm and ranges from 2.74 - 3.37 μm at FWHM. The increase in wavelength and broadened nature of the OH band in 78421 may be associated with the OH’s proximity to surface defects and/or lattice vacancies. The lack of the H2O bending mode at 6.1 μm indicates that any adsorbed terrestrial H2O is below our detection limit, and therefore the H2O stretching mode at 2.9 μm is not significantly contributing to the broad 3 μm OH band and implies that proton implantation by itself does not lead to water formation. To simulate the maximum dayside temperature on the lunar surface, the lunar sample was heated after proton irradiation. The proton induced OH concentration was reduced by as much as 25% after heating to 400 K (127 °C).

Apollo 17↗