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NASA NTRS2000

The Composition of Organics and Volatiles in the Interstellar Medium

Tremendous progress has been made in our understanding of the composition of interstellar dust through the combined use of telescopic observations, theoretical models, laboratory studies of analogs, and the analysis of interstellar samples found in meteorites. It is increasingly clear that the interstellar medium (ISM) contains an enormous diversity of materials created by a wide range of chemical and physical processes. This paper reviews some of our current knowledge of the organic and volatile materials thought to exist in the ISM. These compounds supply a significant portion of the material that makes up the interstellar dense molecular clouds from which new stars and planetary systems are formed, and thus represents an important reservoir of material that could play key roles in the formation and evolution of life. This paper will largely focus on solid materials, as opposed to gases, since solids contain a major fraction of the heavier elements in clouds and because solids are most likely to survive incorporation into new planetary systems in identifiable form. The paper concludes with a brief discussion of the astrobiological relevance of some of the compounds now known or suspected to be present in the ISM.

Sandford, Scott A.↗

DOE OSTI2024

In Vitro Antimicrobial Activity of Volatile Compounds from the Lichen Pseudevernia furfuracea (L.) Zopf. Against Multidrug-Resistant Bacteria and Fish Pathogens

Lichens are symbiotic organisms with unique secondary metabolism. Various metabolites from lichens have shown antimicrobial activity. Nevertheless, very few studies have investigated the antimicrobial potential of the volatile compounds they produce. This study investigates the chemical composition and antimicrobial properties of volatile compounds from Pseudevernia furfuracea collected in two regions of Morocco. Hydrodistillation was used to obtain volatile compounds from samples collected in the High Atlas and Middle Atlas. Gas chromatography–mass spectrometry (GC-MS) analysis identified phenolic cyclic compounds as the primary constituents, with atraric acid and chloroatranol being the most abundant. Additionally, eight compounds were detected in lichens for the first time. The antimicrobial activity of these compounds was assessed using disc diffusion and broth microdilution methods. Both samples demonstrated significant antimicrobial effects against multidrug-resistant human bacteria, reference microorganisms, fish pathogens, and Candida albicans, with minimum inhibitory concentrations (MICs) ranging from 1000 µg/mL to 31.25 µg/mL. This study provides the first report on the volatile compounds from Pseudevernia furfuracea and their antimicrobial effects, particularly against fish pathogens, suggesting their potential as novel antimicrobial agents for human and veterinary use. Further research is warranted to explore these findings in more detail.

Essadki, Yasser (ORCID:0009000648460075)↗

DOE OSTI2024

Observation-constrained kinetic modeling of isoprene SOA formation in the atmosphere

Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ~ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ~ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1978

Volatile elements in chondrites - Metamorphism or nebular fractionation

Three of the most highly metamorphosed meteorites of their respective classes, Shaw (LL7), Karoonda (C5), and Coolidge (C4), were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Pd, Rb, Re, Sb, Se, Te, Tl, U, and Zn. Comparison with data by Lipschutz and coworkers (1977) on artificially heated primitive meteorites shows that the natural metamorphism of meteorites cannot have taken place in a system open to volatiles. Shaw, metamorphosed at 1300 C for more than 1 million yr, is less depleted in In, Bi, Ag, Te, Zn, and Tl than Krymka heated at 1000 C for 1 week. Karoonda, metamorphosed at 600 C for many millennia, is less depleted in Bi and Tl than Allende heated at 600 C for 1 week. Data on primordial noble gases also show that the volatile-element patterns of ordinary and carbonaceous chondrites were established by nebular condensation and changed little, if at all, during metamorphism. For enstatite chondrites, the evidence is still incomplete but seems to favor a nebular origin of the volatile pattern.

Takahashi, H.↗

NASA NTRS1973

Artificial meteor ablation studies

Artificial meteor ablation was performed on natural minerals, composed predominately of magnetite and hematite, using an arc heated plasma stream of air. Analysis of the ablated debris indicated most was composed of two or more minerals. The more volatile elements were depleted and the relative abundance of Fe increased as a result of both volatile depletion and a reduction in its oxidation state. Hematite was converted to magnetite in the ablation zone, and quartz and apatite minerals were converted to an Fe-rich glass consisting of varying amounts of Si, P, Cl, and Ca, depending upon the accessory minerals available at the time of melting. Artificially created ablation products from iron oxides exhibited unique properties depending on the composition of the original material and the environmental conditions of formation. In addition to the accepted elemental criteria, these properties were morphologic characteristics, textural parameters, and the existence of metastable minerals.

Blanchard, M. B.↗

NASA NTRS1974

Investigations of electret as a contamination control device

Thermoelectrets of polymers with stable surface charge on either side have been found to attract ions and charged particles to their surfaces. To assess their applicability to the control of atmospheric contamination, polytetraethylene (teflon) electrets are exposed to vapors coming from volatile mixtures over periods up to 90 min. Use is made of mass spectrometry for the analysis of teflon electret characteristics. It is found that even small quantities of the liquids in the mixture gives its characteristic mass spectra and that the peak height represents a measure for the quantity of the material collected over the electret surface, with the collected quantity being proportional to the duration of exposure.

Pillai, P. K. C.↗

NASA NTRS1975

Validity of trace element cosmothermometer

A reply is made to previous criticisms of the claim that the range of accretion of ordinary chondrites can be narrowed to 500-420 K (from 560-405 K) using volatile metals as cosmothermometers. Questions concerning uncertainties in vapor pressure data, entropy of mixing, methods of analysis, uncertainties in condensation curves, metamorphic transport, alloy formation, condensation of Tl, condensation of In, and concordance with other thermometers (FeO contents of silicates) are addressed. It is concluded that the original claim is valid.

Anders, E.↗

NASA NTRS1979

Semiconductor Grade, Solar Silicon Purification Project

A low cost by-product, SiF4, is reacted with mg silicon to form SiF2 gas which is polymerized. The (SiF2)x polymer is heated forming volatile SixFy homologues which disproportionate on a silicon particle bed forming silicon and SiF4. The silicon analysis procedure relied heavily on mass spectroscopic and emission spectroscopic analysis. These analyses demonstrated that major purification had occured and some samples were indistinguishable from semiconductor grade silicon (except possibly for phosphorus). However, electrical analysis via crystal growth reveal that the product contains compensated phosphorus and boron.

Ingle, W. M.↗

NASA NTRS2000

The Geologic History of Mars: An Astrobiology Perspective

Fourteen SNC meteorites contain information which must be incorporated with recent spaceflight data for developing Mars' geologic history. SNCs have crystallization ages of 4500 to 160 m.y. Tle oldest meteorite ALH84001 contains information on the Noachian period of Mars' history. There are no meteorites from the Hesperian period and the remaining 13 meteorites fall into two age groups within the Amazonian: The nakhlites around 1300 m.y. and the shergottites between 800-160 m.y. Oxygen isotopic analysis of Martian samples shows two distinct O2 reservoirs throughout Martian history indicating late additions of volatiles and a lack of plate tectonics prior to 3.9 Gy. Evidence for percolation of aqueous brines through impact-produced fractures in the rocky surface is contained in the 3.9 Gy-old ALH84001 carbonate deposits. These carbonates precipitated at approx. 100 C. At this time life had already evolved on Earth. Early Mars could have hosted life similar to the bacteria that inhabited early Earth. Potential microorganisms could have been transported into fractures by carbonate-bearing waters and their remains could have become incorporated into the precipitated carbonate. Since Mars had a weak magnetic field at this time, it can be hypothesized that some of the Martian microorganisms may have been similar to terrestrial magnetotactic bacteria. Over geologic time episodic cratering, and tectonic events have occurred on Mars along with the periodic release of subsurface waters which may have produced clays within SNC meteorites. The geochemical data contained within SNC meteorites complements previous observational data and the recent Mars Global Surveyor data to provide a geological and environmental history which spans almost the entire lifespan on Mars. One of the outstanding features of this model is the possible creation of an early (about 4 Gy) volatile reservoir distinct from the outgassed Mars volatiles, and the persistence of this reservoir throughout most, if not all of subsequent Mars' history. Within the framework of this history a potential scenario for a possible record of living organisms is provided by suggestive structures and organic signatures trapped within secondary mineral deposits and alteration features of some SNC meteorites. Tracing the differences in oxygen isotopic compositions within Martian components allows us to gain insight in the history of Mars.

Gibson, Everett K.↗

NASA NTRS2000

The Search for Water and Other Volatiles in Martian Surface Materials: The Thermal Evolved Gas Analyzer (TEGA)

Volatile-bearing minerals and phases (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates, sulfates, palagonites, glasses) may be important components of the Martian regolith. However, essentially no information exists on the mineralogical composition of volatile-bearing phases in the regolith. The Thermal Evolved Gas Analyzer (TEGA), which was part of the Mars Polar Lander payload, was to determine the abundances of two of the most important volatile compounds (i.e., water and carbon dioxide) in the martian soil and to identify the minerals or phases that harbor these volatiles. The TEGA instrument was composed of a differential scanning calorimeter (DSC) interfaced with evolved gas analysis (EGA). The EGA consisted of a Herriott cell of a tunable-diode laser (TDL) spectrometer that determines CO2 and H2O abundances. The sample chamber was to operate at about 100 mbar (-76 torr) with a N2 carrier gas flow of 0.4 sccm. Specifications of TEGA are described in detail elsewhere in this volume.

Ming, D. W.↗

NASA NTRS2003

A New Time-dependent Model for the Martian Radiation Environment

Manned space activities have been until present time limited to the near-Earth environment, most of them to low Earth orbit (LEO) scenarios, with only some of the Apollo missions targeted to the Moon. In current times most human exploration and development of space (HEDS) activities are related to the development of the International Space Station (ISS), and therefore take place in the LEO environment. A natural extension of HEDS activities will be going beyond LEO, and reach asteroids, Mars, Jupiter, Saturn, the Kuiper belt and the outskirts of the Solar System. Such long journeys onboard spacecraft outside the protective umbrella of the geomagnetic field will require higher levels of protection from the radiation environment found in the deep space for both astronauts and equipment. So, it is important to have available a tool for radiation shielding which takes into account the radiation environments found all along the interplanetary space and at the different bodies encountered in the Solar System. Moreover, the radiation protection is one of the two NASA highest concerns and priorities. A tool integrating different radiation environments with shielding computation techniques especially tailored for deep space mission scenario is instrumental in view of this exigency. In view of manned missions targeted to Mars, for which radiation exposure is one of the greatest problems and challenges to be tackled, it is of fundamental importance to have available a tool which allows to know which are the particle flux and spectra at any time at any point of the Martian surface. With this goal in mind, a new model for the radiation environment to be found on the planet Mars due to Galactic Cosmic Rays (GCR) has been developed. Solar modulated primary particles rescaled for Mars conditions are transported within the Martian atmosphere, with temporal properties modeled with variable timescales, down to the surface, with altitude and backscattering patterns taken into account. The tool allows analysis for manned Mars landing missions, as well as planetary science studies, e.g. subsurface water and volatile inventory studies. This Mars environmental model is available through the SIREST website, a project of NASA Langley Research Center.

G De Angelis↗

NASA NTRS2006

Flight Data Update on Long-Term Compound Stability in Dual Sorbent Tubes

Dual Sorbent Tubes (DSTs) are currently the primary method for collecting volatile organic compounds in the cabin air of the International Space Station (ISS). Data from groundbased analysis of these archival air samplers provide a major component of the assessment of ISS air quality by the NASA toxicologist. At the 2005 ICES conference data from the positive control DSTs, returned on Soyuz 7S and 8S, were presented. Positive control tubes are dosed, preflight, with known concentrations of representative contaminant compounds and they are launched to ISS in the DST kit as trip controls. Upon return of the DST kit to the ground, results from analysis of the trip (positive) and laboratory control tubes are used to determine the recoveries: concentration of dosed compounds retained in the tube. Results from positive controls, returned on 7S and 8S showed substantial losses of some compounds dosed into the tubes 156 to 240 days prior to the analysis. Low recoveries are expected for spacecraft air contaminants with similar properties to the poorly recovered dosed compounds. It was shown that compound losses in the control tubes were consistent, which led to the generation of acceptable correction factors for spacecraft air contaminants. Correction factors decrease the accuracy of derived compound concentrations and substantial error could arise under some conditions. An investigation into the mechanism for compound loss is necessary before design modifications can be implemented to improve the DST performance. This paper will update results from the DSTs returned on Soyuz 9S and 10S missions during the latter part of 2005. The data acquired from these returned DSTs will be compared to the 7S and 8S data presented last year. Discussion will focus on the reliability of correction factors and identify any trends in the data. This paper will describe the experimental design and plans to identify the compound loss mechanism.

James, John T.↗

DOE OSTI2026

Bioremediation Retrospective: DOE Experiences and Lessons Learned – 26131

The U.S. Department of Energy (DOE) has implemented bioremediation strategies for chlorinated volatile organic compounds (cVOCs) for more than three decades across multiple contaminated groundwater sites. A retrospective analysis conducted by the Savannah River National Laboratory (SRNL) and collaborating field sites evaluated the design, performance, and outcomes of bioremediation projects at DOE’s Savannah River, Hanford, Idaho, Mound, and Pinellas sites. This retrospective was based on a series of case studies, leveraging historical documentation and site interviews. Technical approaches employed at the various sites were explored, including active bioremediation, enhanced attenuation (EA), and monitored natural attenuation, with specific sub-sections discussing anaerobic, aerobic, and combined anaerobic-aerobic strategies. Each case study includes detailed descriptions of the site-specific conditions, deployment strategies, regulatory considerations, metrics, and performance. Key findings include general cost savings compared to traditional remedies such as pump and treat (P&T), significant success in applying enhanced attenuation to transition remedies toward a passive site management strategy, and documentation of robust subsurface microbial communities at most sites limiting the need for bioaugmentation. Challenges highlighted in the study include underperformance due to poor amendment delivery in low-permeability zones and unfavorable biogeochemical conditions, emphasizing the importance of site-specific designs. Cost analysis across DOE sites suggests bioremediation may offer long-term economic benefits. The retrospective study underscores valuable lessons that can help inform current and future bioremediation efforts.

Newby, Deborah T. [Savannah River National Laborat↗

NASA NTRS1991

Long term isothermal aging and thermal analysis of N-CYCAP polyimides

The N-CYCAP polyimides utilize a (2,2) paracyclophane endcap that polymerizes and does not generate volatile gases during the cure process. These polyimides have both high glass temperatures (390 C) and an onset of decomposition in air of 560 C. Thermal oxidative stability (TOS) weight loss studies show that replacing 25 percent by weight of the paraphenylene diamine in the polymer backbone with metaphenylene diamine improves the weight loss characteristics. N-CYCAP neat resin samples performed better than PMR-II-50 when exposed at 343 and 371 C in air for up to 1000 hours. Preliminary composite studies show that both PMR-II-50 and N-CYCAP have better thermal stability when fabricated on T-40R. Higher isothermal aging temperatures of longer aging times are needed to determine the differences in TOS between composite samples of PMR-II-50 and N-CYCAP polyimides.

Sutter, James K.↗

DOE OSTI2021

The TESS-Keck Survey. II. An Ultra-short-period Rocky Planet and Its Siblings Transiting the Galactic Thick-disk Star TOI-561

We report the discovery of TOI-561, a multiplanet system in the galactic thick disk that contains a rocky, ultra-short-period planet. This bright (V = 10.2) star hosts three small transiting planets identified in photometry from the NASA TESS mission: TOI-561 b (TOI-561.02, P = 0.44 days, R {sub p} = 1.45 ± 0.11 R {sub ⊕}), c (TOI-561.01, P = 10.8 days, R {sub p} = 2.90 ± 0.13 R {sub ⊕}), and d (TOI-561.03, P = 16.3 days, R {sub p} = 2.32 ± 0.16 R {sub ⊕}). The star is chemically ([Fe/H] = −0.41 ± 0.05, [α/Fe] = +0.23 ± 0.05) and kinematically consistent with the galactic thick-disk population, making TOI-561 one of the oldest (10 ± 3 Gyr) and most metal-poor planetary systems discovered yet. We dynamically confirm planets b and c with radial velocities from the W. M. Keck Observatory High Resolution Echelle Spectrometer. Planet b has a mass and density of 3.2 ± 0.8 M {sub ⊕} and 5.5{sub −1.6}{sup +2.0} g cm{sup −3}, consistent with a rocky composition. Its lower-than-average density is consistent with an iron-poor composition, although an Earth-like iron-to-silicates ratio is not ruled out. Planet c is 7.0 ± 2.3 M {sub ⊕} and 1.6 ± 0.6 g cm{sup −3}, consistent with an interior rocky core overlaid with a low-mass volatile envelope. Several attributes of the photometry for planet d (which we did not detect dynamically) complicate the analysis, but we vet the planet with high-contrast imaging, ground-based photometric follow-up, and radial velocities. TOI-561 b is the first rocky world around a galactic thick-disk star confirmed with radial velocities and one of the best rocky planets for thermal emission studies.

47 OTHER INSTRUMENTATION↗

NASA NTRS1985

A field gas chromatograph using technology developed for solar system exploration

Trace gas analysis is an integral part of biospheric studies. Analytical instruments, primarily gas chromatographs (GC), are capable of measuring gases and volatiles to the ppb-level in real time. Trace gases significant in the study of biocycles include nitrous oxide, hydrogen sulfide, other nitrogen and sulfur species, as well as methane and ethylene. The concept of a field gas chromatograph is derived from technology being pursued in the design of ultra-compact instruments for solar system exploration. The instrument breadboard incorporates the specialized porous column packings and the highly sensitive metastable ionization detector developed by the Solar System Exploration Office. These parts ensure a broad capability for which the analysis of ambient N2O is one example. A commercial, portable gas chromatograph is currently being extensively modified to incorporate analytical concepts and components derived from flight GC technology. Data storage devices suitable for field use are presently being studied.

Woeller, F. H.↗

NASA NTRS2012

The Influence of Mineralogy on Recovering Organic Acids from Mars Analogue Materials Using the One-Pot Derivatization Experiment on the Sample Analysis at Mars(SAM) Instrument Suite

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids, will require a chemical extraction and a derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed a ''one-pot'' extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment instrument suite on NASA's the Mars Science Laboratory (MSL) mission. The temperature and duration of the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 1C for several minutes of a variety of terrestrial Mars analog materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analog materials that contained high abundances of hydrated minerals, and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA. The combination of pyrolysis and two different wet-chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars.

MSL↗

NASA NTRS2015

Preliminary Radiation Analysis of the Total Ionizing Dose for the Resource Prospector Mission

NASA's Resource Prospector (RP) is a collaborative project between multiple centers and institutions to search for volatiles at the polar regions of the Moon as a potential resource for oxygen and propellant production. The mission is rated Class D and will be the first In-Situ Resource Utilization (ISRU) demonstration on the lunar surface and at the lunar poles. Given that this mission is rated Class D, the project is considering using commercial off the shelf (COTS) electronics parts to reduce cost. However, COTS parts can be more susceptible to space radiation than typical aerospace electronic parts and carry some additional risk. Thus, prior to parts selection, having a better understanding of the radiation environment can assist designers in the parts selection process. The focus of this paper is to provide a preliminary analysis of the radiation environment from launch, through landing on the surface, and some surface stay as an initial step in determining worst case mission doses to assist designers in screening out electronic parts that would not meet the potential dose levels experienced on this mission.

Rojdev, Kristina↗