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At least 451 records · Page 25

Understanding the Chemistry of PAHs in H2O Ice

Polycyclic aromatic hydrocarbons (PAHs) can be incorporated into H O ice grains and mantles found in dense molecular clouds, comets, interplanetary dust particles (IDPs), and many Solar System objects. However, laboratory infrared (IR) spectroscopic studies of PAHs in ices is still a relatively young field. Early research efforts have shown the rich chemistry of PAHs in H O to be dependent on PAH concentration, with the concentration impacting everything from IR band shifts to the photoproducts produced [1-6]. Similarly, research suggests that a potential top-down synthesis route for complex organic molecules or COMs found within solar systems is possible from PAHs in water ice [7]. In order to fully exploit the observations from the James Webb Space Telescope (JWST) more IR studies of PAHs in H O ice under relevant astrophysical conditions and planetary systems are needed. The NASA ICEE (Institute for Carbon Evolution Experiments), formerly the NASA Ames PAH IR Laboratory, has been at the forefront of this field. Starting in 2019, just before the COVID-19 shutdown, the ICEE laboratory underwent a major renovation, gearing it towards in-depth PAHs in H O ice research under relevant solar systems and interstellar conditions. The ICEE facility enables us to study the processing of PAHs in H O ice using UV photons and charged particle (electron) irradiation either singly or in combination under ultra-high vacuum and low temperature (15K). We use in-situ measurements with IR, Raman, and mass spectra by which we monitor the chemistry of PAHs in H O ice before, during and after the irradiation. This presentation will summarize the past work regarding PAHs in ices and provide an update on the latest ICEE research results in this area, outlining a roadmap for future research efforts.

Andrew Mattioda↗

H2O Electrolysis with Impure Water Source - Final Report

This Phase III final report summarizes the Phase I research and development work performed during the IRAD FY 2018-Cycle 1, Stage C-Phase I project March 15, 2018 through August 17, 2018 and during the Phase II continuation request which funded the research and development November 26, 2018 through September 30, 2019. A Phase III proposal was accepted to continue the technology development, but due to the unavailability of the Principal Investigators to complete the proposed PhasE III work, the Phase III project was re-scoped to complete a final report on the research and development work that was previously completed as a wrap-up of this IRAD project

Electrolysis↗

The H Content of Aubrites: An Evaluation of Bulk Versus in Situ Methods for Quantifying Water in Meteorites

Aubrites and enstatite chondrites (ECs) are isotopically similar to the Earth and therefore may resemble the primary materials that accreted to form our planet. Recent bulk H elemental and isotopic analyses of ECs and the Norton County aubrite suggest that enstatite-rich materials are H-rich and may represent a significant source of terrestrial water, with measured values of 3000±2000 μg/g H2O and 5300±900 μg/g H2O in the bulk and enstatite fractions of Norton County (Piani et al., Science, 2020). Here, we present a detailed investigation of in situ H2O concentrations in enstatite, diopside, forsterite, and plagioclase from a suite of main group aubrites, including Norton County, and Shallowater. We find that enstatite (4±2 μg/g H2O), diopside (4.8±0.5 μg/g H2O), and forsterite (5±3 μg/g H2O) have similar H2O concentrations, and all are significantly lower than plagioclase (24±3 μg/g H2O). We combine our in situ analyses of H2O contents with equilibrium partition coefficients and bulk mineralogies to estimate the bulk H2O content of our samples. We compare these first order estimates with bulk volatile analyses conducted using sample pyrolysis and find that the previous bulk H2O analyses of aubrites predominantly reflect terrestrial contamination and alteration. If our conclusion that the reported bulk H2O analyses of Norton County primarily reflect terrestrial contamination and alteration extends to bulk analyses of ECs, then EC-like material may not be a significant source of terrestrial water. Our results support the hypothesis that thermal metamorphism, melting, and differentiation leads to efficient desiccation of planetesimals relative to chondrites, and that differentiated planetesimals contributed, at most, trace amounts to Earth's water budget.

Achondrite↗

Unidentified ions in comets

Optical spectra were taken of comets Halley, West, and Brorsen-Metcalf in the wavelength region 3200 to 6400 A. These spectra were offset approximately 10(exp -5) to 10(exp -6) km tailward from the nucleus so that the features detected were all ions with the exception of a very small residual C2 emission at 5165 A. The full labeled tail spectrum of comet Halley is given. While most of the features detected are attributable to CO(+), H2O(+), CO2(+), CH(+), and OH(+), there are three moderately strong bands in the spectra of comets Halley and Brorsen-Metcalf which remain unidentified. These features were not detected in comet West. All three spectra in the 4800 to 5400 A region are presented, Brorsen-Metcalf is the gassiest of the three. The central wavelengths of the unidentified features are 4930, 5300, and 6000 A. In an effort to identify the ions responsible for these features as well as to confirm previous identifications, laboratory spectra of ions were compared with the comet spectra. H2O(+) and CO(+) are known to have extensive emission in the 4800 to 6200 A region. Therefore, the possibility that these unidentified features are due to H2O(+) and CO(+) was investigated. A search for the following bands was conducted: H2O(+) (11-0), H2O(+) (12-0), H2O(+) (13-1), CO(+) (1-1), and CO(+) (0-0). CO(+) (1-1) and CO(+) (0-0) were previously identified and are present in all the spectra examined. The H2O(+) (11-0) band was identified. Comparison of the H2O(+) (11-0) synthetic spectrum with comet Brorsen-Metcalf data is presented. The relative fluxes of the blended H2O(+) lines in the synthetic spectrum match those of the cometary data. After eliminating H2O(+) and CO(+) as significant contributors to the stronger unidentified features, spectra of ions which are not yet identified in the optical region of comets were compared to the data. These ions are NH(+), CS(+), and C2(+). None of these ions appears to be a significant contributor to the optical spectra of these three comets. In conclusion, H2O(+) (11-0) was unabiguously identified in cometary optical spectra. No other molecular ion for which there are laboratory spectra can explain the unidentified features found in the ion tails of comets Halley and Brorsen-Metcalf.

Engel, Lisa↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Five-Year (2004-2009)Observations of Upper Tropospheric Water Vapor and Cloud Ice from MLS and Comparisons with GEOS-5 Analyses

This paper gives an overview of August 2004 through July 2009 upper tropospheric (UT) water vapor (H2O) and ice water content (IWC) from the Aura Microwave Limb Sounder (MLS) and comparisons with outputs from the NASA Goddard Earth Observing System Version 5 (GEOS-5) data assimilation system. Both MLS and GEOS-5 show that high values of H2O and IWC at 215 to 147 hPa are associated with areas of deep convection. They exhibit good (within approximately 15%) agreement in IWC at these altitudes, but GEOS-5 H2O is approximately 50% (215 hPa) to approximately 30% (147 hPa) larger than MLS, possibility due to its higher temperatures at these altitudes. GOES-5 produces a weaker intertropical convergence zone than MLS, while a seasonally-migrating band of tropical deep convection is clearly evident in both the MLS and GEOS-5 UT H2O and IWC. MLS and GEOS-5 both show spatial anti-correlation between IWC and H2O at 100 hPa, where less H2O is associated with low temperatures in regions of tropical convection. At 100 hPa, GEOS-5 produces 50% less IWC and 15% less H2O in the tropics, and approximately 20% more H2O in the extra-tropics, than does MLS. Behavior of the 100 hPa H2O, which exhibits a quasi-biennial oscillation, appears consistent with it being controlled by temperature. The seasonal cycle in the vertical transport of tropical mean H2O from approximately 147 hPa to approximately 10 hPa appears much stronger in MLS than in GEOS-5. The UT IWC and H2O interannual variations, from both MLS and GEOS-5, show clear imprints of the El Nino-Southern Oscillation.

Jiang, Jonathan H.↗

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures < 500 C, and an evolution peak at higher temperatures near approx 750 C. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples

McAdam, Amy↗

Mechanism of Thirst Attenuation During Head-Out Water Immersion in Men

The purpose was to determine whether extracellular volume or osmolality was the major contributing factor for reduction of thirst in air and head-out water immersion in hypohydrated subjects. Eight males (19 - 25 yr) were subjected to thermoneutral immersion and thermoneutral air under two hydration conditions without further drinking: euhydration in water (Eu-H2O) and euhydration in air, and hypohydration in water (Hypo-H2O) and hypohydration in air (3.7% wt loss after exercise in heat). The increased thirst sensation with Hypo-H2O decreased (P less than 0.05) within 10 min of immersion and continued thereafter. Mean plasma osmolality (288 +/- 1 mosmol/kg H2O) and sodium (140 +/- 1 meq/1) remained elevated, and plasma volume increased by 4.2 +/- 1.0% (P less than 0.05) throughout Hypo-H2O. A sustained increase (P less than 0.05) in stroke volume accompanied the prompt and sustained decrease in plasma renin activity and sustained increase (P less than 0.05) in plasma atrial natriuretic peptide during Eu-H2O and Hypo-H2O. Plasma vasopressin decreased from 5.3 +/- 0.7 to 2.9 +/- 0.5 pg/ml (P less than 0.05) during Hypo-H2O but was unchanged in Eu-H2O. These findings suggest a sustained stimulation of the atrial baroreceptors and reduction of a dipsogenic stimulus without major alterations of extracellular osmolality in Hypo-H2O. Thus it appears that vascular volume induced stimuli of cardiopulmonary baroreceptors play a more important role than extracellular osmolality in reducing thirst sensations during immersion in hypohydrated subjects. Thus the purpose for this study was to determine the relative importance of volume and osmotic stimuli, and associated hormonal interaction, for attenuation of thirst during immersion.

Wada, F.↗