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NASA NTRS2013

Photo-Induced Deuterium Enrichment in Residues Produced from the UV Irradiation of Pyrimidine in H2O and H2O+NH3 Ices

Organic compounds found in meteorites often show isotopic signatures of their interstellar/protosolar heritage as enrichments in D and 15N. Meteoritic organics found to be enriched in D include amino acids, hydroxy and dicarboxylic acids, as well as polycyclic aromatic hydrocarbons (PAHs). Processes that can produce isotopic enrichments in presolar/protosolar materials include gas-phase ion-molecule reactions, gas-grain surface reactions, and unimolecular photo-dissociation reactions involving PAHs. Because many molecules in interstellar clouds are enriched in D, the presence of D anomalies in meteorites is thought to originate from preserved or slightly altered interstellar/protostellar materials. However, the link between isotopic enrichments seen in space and those in meteoritic compounds and their relationship remain unclear. In this work, we present results of hydrogen isotopic fractionation for compounds in organic residues produced from the UV irradiation using an H2- discharge UV lamp of H2O:pyrimidine = 20:1 and H2O:NH3:pyrimidine = 20:2:1 ice mixtures at low temperature (is less than 20 K). After irradiation, the resulting residues are dissolved in H2O and analyzed with gas chromatography-mass spectrometry coupled with isotope ratio mass spectrometry (GC-MS/IRMS) [1], following a protocol similar to that used for previous analyses of comparable samples [2,3]. We used this technique to measure compound-specific D/H isotopic ratios for the initial pyrimidine and for two photo-products present in the residues, namely, 2,2'-bipyrimidine and an unidentified bipyrimidine isomer [2-4]. Measuring D enrichments in bipyrimidines has the advantage that the H atoms on these molecules are not easily exchangeable with other compounds, in particular the H2O and NH3 present in the ices or the solvents used to extract the samples for GC-MS/IRMS measurements. The δD value for the initial pyrimidine, measured with a high-temperature conversion elemental analyzer connected to the IRMS, was found to be -30% per mille. Preliminary measurements made on a residue produced from the UV irradiation of an H2O:NH3:pyrimidine = 20:2:1 ice mixture indicate δD values of +118% per mille for 2,2'- bipyrimidine and +92% per mille for the other bipyrimidine isomer, and therefore show a significant D enrichment during the photo-processing and warm-up that lead to their formation [5]. New measurements are currently being performed on a number of residues produced from simpler H2O:pyrimidine = 20:1 ice mixtures under different experimental conditions and will be presented here.

Laboratory Astrochemistry↗

NASA NTRS2005

Interstellar PAH Analogs in the Laboratory: Comparison with Astronomical Data

Salama, Farid↗

NASA NTRS1988

Aromatic components in cometary materials

The Raman spectra of interplanetary dust particles (IDPs) collected in the stratosphere show that two bands at about 1350 and 1600 delta/cm and a broader feature between 2200 and 3300 delta/cm that are characteristic of aromatic molecular units with ordered domains smaller than 25 A in diameter. This suggests that the carbonaceous material in IDPs may be similar to the polymeric component seen in meteorites, where this material is thought to consist of aromatic molecular units that are randomly interlinked by short aliphatic bridges. The features in the Raman spectra of IDPs are similar in position, and relative strength to interstellar infrared emission features that have been attributed to vibrational transitions in free molecular polycyclic aromatic hydrocarbons. Taken together, these observations suggest that some fraction of the carbonaceous materials in IDPs may have been produced in circumstellar dust shells and only slightly modified in interstellar space.

Allamandola, Louis J.↗

NASA NTRS1996

The infrared spectrum of the Galactic center and the composition of interstellar dust

We have obtained 5-8 micrometers spectra of the Galactic center from the Kuiper Airborne Observatory at resolving powers of approximately 50, approximately 150, and approximately 300. These spectra show absorption features at 5.5, 5.8, 6.1, and 6.8 micrometers. Together with previously observed features in the 3 micrometers region, these features are compared with laboratory spectra of candidate materials. The 3.0 and 6.1 micrometers features are due to the OH stretching and bending variations of H2O and are well fitted by water of hydration in silicates (e.g., talc). The 3.0 micrometer band is equally well fitted by ice mixtures containing 30% H2O, but such mixtures do not provide a good fit to the observed 6.1 micrometer band. The 3.4 and 6.8 micrometers features are identified with the CH stretching and deformation modes in CH2 and CH3 groups in saturated aliphatic hydrocarbons. The 6.1 micrometer band shows a short wavelength shoulder centered on 5.8 micrometer, attributed to carbonyl (C double bond O) groups in this interstellar hydrocarbon dust component. Finally, the narrow 5.5 micrometer feature is also attributed to carbonyl groups, but in the form of metal carbonyls [e.g., Fe(CO)4]. We have derived column densities and abundances along the line of sight toward the Galactic center for the various identified dust components. This analysis shows that hydrocarbon grains contain only 0.08 of the elemental abundance of C and contribute only a relatively minor fraction (0.1) of the total dust volume. Most of the interstellar dust volume is made up of silicates (approximately 0.6). Small graphite grains, responsible for the 2200 angstroms bump, account for 0.07 of the total dust volume. The remaining one-quarter of the interstellar dust volume consists of a material(s) without strong IR absorption features. Likely candidates include large graphite grains, diamonds, or amorphous carbon grains, which all have weak or no IR active modes. Finally, various models for the origin of the hydrocarbon dust component of the interstellar dust are discussed. All of them face some problems in explaining the observations, in particular, the absence of the spectroscopic signature of hydrocrbon grains in sources associated with molecular clouds.

NASA Discipline Exobiology↗

NASA NTRS1978

Interplanetary dust - Possible implications for comets and presolar interstellar grains

Interplanetary dust is important to studies of the origin of the solar system because it is material from comets and asteroids, the smallest surviving bodies from the early solar system. The fact that comets are the major suppliers of the millimeter meteoroids which produce optical meteors suggests that a significant fraction of the submillimeter portion of the meteoroid complex is also cometary material. While comets are probably the major source, it is important to remember that the dust presently impacting the earth was probably generated by a number of different parent bodies. The collection of interplanetary dust is considered and a description is presented of the physical properties of interplanetary dust, taking into account the structure, elemental composition, and mineralogy.

Brownlee, D. E.↗

NASA NTRS1989

Dust clouds in Orion and the interstellar neutral hydrogen distribution

According to published examples of the far IR observations in the Orion and its surroundings, several well defined dust clouds of different sizes and structure are present. For comparison of these clouds with the neutral hydrogen distribution on the area of approx. 1000 sq degs, the data from Pulkovo Sky Survey in the interstellar neutral Hydrogen Radio Line as well as special observations with the RATAN-600 telescope in 21 cm line were used. From the materials of Pulkovo HI Survey, the data were taken near the line emission at ten velocities between -21.8 and +25.6 km/s LSR for the structural component of the interstellar hydrogen emission. The results given concern mainly the Orion's Great Dust Cloud and the Lambda Orionis region where the information about the situation with the dust and interstellar hydrogen is very essential for interpretation.

Bystrova, N. V.↗

NASA NTRS1992

Grain Spectroscopy

Our fundamental knowledge of interstellar grain composition has grown substantially during the past two decades thanks to significant advances in two areas: astronomical infrared spectroscopy and laboratory astrophysics. The opening of the mid-infrared, the spectral range from 4000-400 cm(sup -1) (2.5-25 microns), to spectroscopic study has been critical to this progress because spectroscopy in this region reveals more about a materials molecular composition and structure than any other physical property. Infrared spectra which are diagnostic of interstellar grain composition fall into two categories: absorption spectra of the dense and diffuse interstellar media, and emission spectra from UV-Vis rich dusty regions. The former will be presented in some detail, with the latter only very briefly mentioned. This paper summarized what we have learned from these spectra and presents 'doorway' references into the literature. Detailed reviews of many aspects of interstellar dust are given.

Allamandola, L. J.↗

NASA NTRS2015

PAHs in the Ices of Saturn's Satellites: Connections to the Solar Nebula and the Interstellar Medium

Aliphatic hydrocarbons and PAHs have been observed in the interstellar medium (e.g., Allamandola et al. 1985, Pendleton et al. 1994, Pendleton & Allamandola 2002, Tielens 2013, Kwok 2008, Chiar & Pendleton 2008) The inventory of organic material in the ISM was likely incorporated into the molecular cloud in which the solar nebula condensed, contributing to the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Additional organic synthesis occurred in the solar nebula (Ciesla & Sandford 2012). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn (Johnson & Lunine 2005). VIMS spectral maps of Phoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and aliphatic hydrocarbon (=CH2, -CH3) absorption bands (3.2-3.6 micrometers). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles ((is) approximately 5-20 micrometers size) spiral inward toward Saturn (Verbiscer et al. 2009). They encounter Iapetus and Hyperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is approximately 10 times as abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, and in carbonaceous meteorites (Cruikshank et al. 2014). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 (is) approximately 4, which is larger than the value found in the diffuse ISM ((is) approximately 2-2.5). Insofar as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key in understanding the content and degree of processing of that nebular material. A dynamical subset of TNOs define the Kuiper Belt, from which the short-period comets originate. Particles collected from comet 81P/Wild contain PAHs with an interstellar signature of deuterium. By inference, the PAHs contained in Phoebe and now dusted on the surfaces of two other Saturn satellites share that interstellar origin. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST will open that possibility for a number of objects.

Solar nebula↗

NASA NTRS1972

Elemental and isotopic abundances in the solar wind

The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

Geiss, J.↗

NASA NTRS1980

Excitation mechanisms for the unidentified infrared emission features

Infrared and radio observations of various objects are analyzed to put observational constraints on the mechanism which gives rise to the unidentified emission features at 3.3, 3.4, 6.2, 7.7, 8.6, and 11.3 microns. The results show that gas-grain collisions or fluorescence is not likely to be the excitation mechanism responsible for the observed features. Thermal emission by dust is reanalyzed and it is concluded that this mechanism can explain the emission features. A simple model in which the emission features arise in a population of small, hot, interstellar grains is constructed. These grains are very efficient radiators, and the emitting materials only need be a minor grain constituent to provide the power that is emitted in the features. The model offers, therefore, a simple explanation for the absence of these features in absorption.

Dwek, E.↗

NASA NTRS1982

OB associations and the nonuniversality of the cosmic abundances - Implications for cosmic rays and meteorites

The formation of the solar system inside an OB association is examined with particular attention to the elemental abundances which would have been ejected by the association's first few supernovae. It is found that the solar system material may have been significantly contaminated by these supernovae and thus the average interstellar composition may differ from the solar system composition. In particular, we find that many of the so-called isotopic and elemental abundance anomalies (e.g., Ne, C, O, s-process/r-process, etc.) found in meteoritic inclusions and in cosmic rays may be more representative of the average interstellar abundance. In other words, it may be that the average solar system abundances are what is 'anomalous'.

Olive, K. A.↗

NASA NTRS1984

Interstellar absorption lines in the spectrum of supernova Evans in M83 (NGC 5236)

It is pointed out that supernovae in other galaxies create spontaneous opportunities to probe spectroscopically the gaseous material in galactic halos. Because of their brightness, supernovae offer an unparalleled chance to obtain spectra with high wavelength resolution and/or signal-to-noise ratio. The present investigation is concerned with observations of visual interstellar lines in the spectrum of a supernova discovered on July 3, 1983, and identified as Type I. The supernova was located 124 arc sec south and 122 arc sec west of the nucleus of M83. Evidence is obtained that for velocities near that of M83, the line of sight toward the supernova contains a complex array of absorption features of Ca II. In both Ca II and Na I, the absorptions associated with M83 are far more prominent than those halfway through the disk (and halo) of the Milky Way Galaxy. It is felt that many of the displaced velocity components in the M83 system arise from a gaseous halo.

Rodgers, A. W.↗

NASA NTRS2001

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Exploring the Links Between the Interstellar Medium and Meteorites

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds can be detected and identified in space via their vibrational transitions. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Furthermore, the presence of D-enriched organics in meteorites suggests that a portion of these materials survives incorporation into protosolar nebulae. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to HII regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. In addition, ABE will attempt to detect and quantify deuterium enrichments in a select set of these materials and environments. This should assist both with understanding the chemical processes that occur in these environments and with establishing any links that exist between interstellar and meteoritic organics.

Sandford, Scott A.↗

NASA NTRS1976

Radical formation, chemical processing, and explosion of interstellar grains

The ultraviolet radiation in interstellar space is shown to create a sufficient steady-state density of free radicals in the grain mantle material consisting of oxygen, carbon, nitrogen, and hydrogen to satisfy the critical condition for initiation of chain reactions. The criterion for minimum critical particle size for maintaining the chain reaction is of the order of the larger grain sizes in a distribution satisfying the average extinction and polarization measures. The triggering of the explosion of interstellar grains leading to the ejection of complex interstellar molecules is shown to be most probable where the grains are largest and where radiation is suddenly introduced; i.e., in regions of new star formation. Similar conditions prevail at the boundaries between very dark clouds and H II regions. When the energy released by the chemical activity of the free radicals is inadequate to explode the grain, the resulting mantle material must consist of extremely large organic molecules which are much more resistant to the hostile environment of H II regions than the classical dirty-ice mantles made up of water, methane, and ammonia.

Greenberg, J. M.↗

NASA NTRS1982

Chemical evolution of OB associations

It is determined that the existence of Al-26 and Pd-107 in meteorites in the early solar system indicates that our solar system probably formed inside an OB association that had been contaminated by the debris of at least one supernova. In addition to these radioactive tracers, the contamination of the material out of which the solar system formed would have significantly enriched the heavy element composition of the solar system relative to that of the average interstellar medium. It is found that the solar system would be enriched in those isotopes which are produced by the more massive stars, such as O-16, C-12, Ne-20, and some other r-process material. It is proposed that specific isotopic ratios and elemental ratios reflecting these differences would include the Ne-20/Ne-22 ratio, which would be higher in the solar system than in the interstellar medium and the cosmic rays, the C-12/C-13 ratio which would be higher in the solar system than in the interstellar medium, and the oxygen-to-carbon ratio, which would also be higher in the solar system than in the typical interstellar medium.

Schramm, D. N.↗

NASA NTRS2005

PAHs and the Diffuse Interstellar Bands. What have we Learned from the New Generation of Laboratory and Observational Studies?

Polycyclic Aromatic Hydrocarbons (PAHs) are an important and ubiquitous component of carbon-bearing materials in space. PAHs are the best-known candidates to account for the IR emission bands (UIR bands) and PAH spectral features are now being used as new probes of the ISM. PAHs are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). In the model dealing with the interstellar spectral features, PAHs are present as a mixture of radicals, ions and neutral species. PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge for laboratory astrophysics is to reproduce (in a realistic way) the physical conditions that exist in the emission and/or absorption interstellar zones, An extensive laboratory program has been developed at NASA Ames to characterize the physical and chemical properties of PAHs in astrophysical environments and to describe how they influence the radiation and energy balance in space and the interstellar chemistry. In particular, laboratory experiments provide measurements of the spectral characteristics of interstellar PAH analogs from the ultraviolet and visible range to the infrared range for comparison with astronomical data. This paper will focus on the recent progress made in the laboratory to measure the direct absorption spectra of neutral and ionized PAHs in the gas phase in the near-W and visible range in astrophysically relevant environments. These measurements provide data on PAHs and nanometer-sized particles that can now be directly compared to astronomical observations. The harsh physical conditions of the IS medium - characterized by a low temperature, an absence of collisions and strong V W radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature (of the order of 100 K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS). These experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase. Intrinsic band profiles and band positions of cold gas-phase PAHs can now be measured with high- sensitivity spectroscopy and directly compared to the astronomical data. The electronic bands measured for ionized PAH are found to be intrinsically broad (about 20/cm) while the bands associated with the neutral precursors are narrower (of the order of 2 - 10/cm).

Salama, Farid↗

NASA NTRS2004

NASA STARDUST Sample Return Mission

This viewgraph presentation reviews the Stardust mission. The objectives of the mission is to rendezvous with the Wild 2 comet, and using a specially designed aerogel capture some of the cometary material, and then return a capsule with the material to Earth. Other objectives are to provide images of the comet, and capture interstellar dust. There is a description of the aerogel, the trajectory, and views of the Stardust Sample Return Capsule (SRC), Cometary and Interstellar Dust Analyzer (CIDA) instrument, and the JPL designed camera. Also included is a timeline of the projected release of data to the Planetary Data System.

Wild 2↗

NASA NTRSDate not supplied

A New Coordinated NanoSIMS, Transmission Electron Microscopy and Atom Probe Tomography Approach For the Characterization of Primitive Astromaterials

Presolar grains are remnants of evolved stellar systems preserved within primitive extraterrestrial materials. They are important for studying physical and chemical processing, and formation mechanisms occurring within the interstellar medium, Solar Nebula and their parent stellar environments [1]. Our recent work has shown coordinated nano-scale Secondary Ion Mass Spectrometry (NanoSIMS) and Atom Probe Tomography (APT) can show isotopic and chemical signatures at major to trace levels, morphological signatures, and regional contextual relationships [2,3]. Previous studies have shown Transmission Electron Microscopy (TEM) of Focus Ion Beam (FIB) TEM lamella, can provide localized contextual relationships, crystallographic information and chemical information [1]. Coordinating NanoSIMS, TEM, and APT could gain access to almost all contextual, structural and geochemical signatures within each presolar grain. However, this has proved challenging owing to the preparation requirements for TEM and APT. For example, studying specimen prepared as APT needles in TEM removes the local context, the higher degree of surface exposure can alter the chemistry of beam sensitive materials, and the shank angle of the needle can impact the quality of TEM diffraction images. We designed a new FIB method which takes a 100 nm thick FIB-TEM lamella and sandwiches it between two indium slices (5 μm x ~300 nm x 3 μm). The indium is melted onto the lamella surface using the electron beam (Fig 1). This process adds bulk to the lamella, making it more amenable to APT needle formation (Fig 2). Consequently, samples can be prepared per the optimal requirements for each technique improving data quality, acquisition stability, and access to the signatures and relationships summarised earlier. This technique can be used for measuring multiple phases across a TEM lamella and targeting an individual phase. For example, a presolar grain identified in NanoSIMS could be targeted, studied in TEM and then indium sandwiched with its precise location in the TEM lamella marked using a Pt button for preparation of an APT needle and atomic scale acquisition. [1] A. M. Davis (2014) Meteorites and cosmochemical processes, 1. [2] Nevill N. et al. (2023) LPSC, 54, #1707. [3] Nevill N. et al. (2023) LPSC, 54, #1714.

NanoSIMS↗