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Wdowiak, T. J.

Publications and source records attributed to Wdowiak, T. J..

At least 19 records

Hydrogenation of polycyclic aromatic hydrocarbons as a factor affecting the cosmic 6.2 micron emission band

While many of the characteristics of the cosmic unidentified infrared (UIR) emission bands observed for interstellar and circumstellar sources within the Milky Way and other galaxies, can be best attributed to vibrational modes of the variants of the molecular family known as polycyclic aromatic hydrocarbons (PAH), there are open questions that need to be resolved. Among them is the observed strength of the 6.2 micron (1600 cm(-1)) band relative to other strong bands, and the generally low strength for measurements in the laboratory of the 1600 cm(-1) skeletal vibration band of many specific neutral PAH molecules. Also, experiments involving laser excitation of some gas phase neutral PAH species while producing long lifetime state emission in the 3.3 micron (3000 cm(-1)) spectral region, do not result in significant 6.2 micron (1600 cm(-1)) emission. A potentially important variant of the neutral PAH species, namely hydrogenated-PAH (H(N)-PAH) which exhibit intriguing spectral correlation with interstellar and circumstellar infrared emission and the 2175 A extinction feature, may be a factor affecting the strength of 6.2 micron emission. These species are hybrids of aromatic and cycloalkane structures. Laboratory infrared absorption spectroscopy augmented by density function theory (DFT) computations of selected partially hydrogenated-PAH molecules, demonstrates enhanced 6.2 micron (1600 cm(-1)) region skeletal vibration mode strength for these molecules relative to the normal PAH form. This along with other factors such as ionization or the incorporation of nitrogen or oxygen atoms could be a reason for the strength of the cosmic 6.2 micron (1600 cm(-1)) feature.

Cosmic Dust/analysis

Laboratory investigation of the contribution of complex aromatic/aliphatic polycyclic hybrid molecular structures to interstellar ultraviolet extinction and infrared emission

We have demonstrated by experiment that, in an energetic environment, a simple polycyclic aromatic hydrocarbon (PAH) such as naphthalene will undergo chemical reactions that produce a wide array of more complex species (an aggregate). For a stellar wind of a highly evolved star (post-asymptotic giant branch [post-AGB]), this process would be in addition to what is expected from reactions occurring under thermodynamic equilibrium. A surprising result of that work was that produced in substantial abundance are hydrogenated forms that are hybrids of polycyclic aromatic and polycyclic alkanes. Infrared spectroscopy described here reveals a spectral character for these materials that has much in common with that observed for the constituents of circumstellar clouds of post-AGB stars. It can be demonstrated that a methylene (-CH2-) substructure, as in cycloalkanes, is the likely carrier of the 6.9 microns band emission of dust that has recently been formed around IRAS 22272+5433, NGC 7027, and CPD -56 8032. Ultraviolet spectroscopy previously done with a lower limit of 190 nm had revealed that this molecular aggregate can contribute to the interstellar extinction feature at 2175 angstroms. We have now extended our UV spectroscopy of these materials to 110 nm by a vacuum ultraviolet technique. That work, described here, reveals new spectral characteristics and describes how material newly formed during the late stages of stellar evolution could have produced an extinction feature claimed to exist at 1700 angstroms in the spectrum of HD 145502 and also how the newly formed hydrocarbon material would be transformed/aged in the general interstellar environment. The contribution of this molecular aggregate to the rise in interstellar extinction at wavelengths below 1500 angstroms is also examined. The panspectral measurements of the materials produced in the laboratory, using plasmas of H, He, N, and O to convert the simple PAH naphthalene to an aggregate of complex species, provide insight into possible molecular structure details of newly formed hydrocarbon-rich interstellar dust and its transformation into aged material that becomes resident in the interstellar medium. Specifically the presence of naphthalene-like and butadiene-like conjugated structures as chromophores for the 2175 angstroms ultraviolet extinction feature is indicated.

NASA Discipline Exobiology

MALDI for Europa Planetary Science and Exobiology

TOF MS for Europa landed science can identify small molecules of the cryosphere and complex biomolecules upwelling from a subsurface water ocean. A matrix-assisted laser-desorption ionization (MALDI) testbed for cryo-ice mixtures is being developed.

Wdowiak, T. J.

An Impact Tool for In Situ Planetary Geology

A repeating impact tool using the electrolysis of water to produce an oxygen-hydrogen propellant has been developed for in-situ planetary geology by robotic means.

McHone, J. F.

Aqueous Processing in Planetesimals of Interstellar Species

Laboratory experiments suggest interstellar organics were processed in planetesimals under near-critical water conditions of temperature and pressure yielding the kind of organic material found in carbonaceous chondrites.

Arnoult, K. M.

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

NASA Discipline Exobiology

Experimental indication of a naphthalene-base molecular aggregate for the carrier of the 2175 angstroms interstellar extinction feature

Experiments where the simple polycyclic aromatic hydrocarbon (PAH) naphthalene (C10H8) is subjected to the energetic environment of a plasma have resulted in the synthesis of a molecular aggregate that has ultraviolet spectral characteristics that suggest it provides insight into the nature of the carrier of the 2175 angstroms interstellar extinction feature and may be a laboratory analog. Ultraviolet, visible, infrared, and mass spectroscopy, along with gas chromatography, indicate that it is a molecular aggregate in which an aromatic double ring ("naphthalene") structural base serves as the electron "box" chromophore that gives rise to the envelope of the 2175 angstroms feature. This chromophore can also provide the peak of the feature or function as a mantle in concert with another peak provider such as graphite. The molecular base/chromophore manifests itself both as a structural component of an alkyl-aromatic polymer and as a substructure of hydrogenated PAH species. Its spectral and molecular characteristics are consistent with what is generally expected for a complex molecular aggregate that has a role as an interstellar constituent.

NASA Discipline Exobiology

A laboratory analog for the carrier of the 3 micron emission of the protoplanetary nebula IRAS 05341+0852

A mixture of the polycyclic aromatic hydrocarbons (PAHs), acenaphthylene and acenaphthene, when subjected to the energetic environment of a hydrogen plasma, is transformed into a material that exhibits an infrared absorption profile in the 3 micron region that is an excellent match of the protoplanetary nebula IRAS 05341+0852 emission profile in the same wavelength region. Acenaphthylene and acenaphthene were chosen as precursors in the experiment because these molecules have a structure that can be described as a keystone in a process in which carbon atoms in a stellar wind condense into PAH species. The spectral match between experiment and observations appears to validate that scenario.

Non-NASA Center

Inference of a 7.75 eV lower limit in the ultraviolet pumping of interstellar polycyclic aromatic hydrocarbon cations with resulting unidentified infrared emissions

The discrete infrared features known as the unidentified infrared (UIR) bands originating in starburst regions of other galaxies, and in H II regions and planetary nebulae within the Milky Way, are widely thought to be the result of ultraviolet pumped infrared fluorescence of polycyclic aromatic hydrocarbon (PAH) molecules and ions. These UIR emissions are estimated to account for 10%-30% of the total energy emitted by galaxies. Laboratory absorption spectra including the vacuum ultraviolet region, as described in this paper, show a weakening of the intensity of absorption features as the population of cations increases, suggesting that strong pi* <-- pi transitions are absent in the spectra of PAH cations. This implies a lower energy bound for ultraviolet photons that pump infrared emissions from such ions at 7.75 eV, an amount greater than previously thought. The implications include size and structure limitations on the PAH molecules and ions which are apparent constituents of the interstellar medium. Also, this might affect estimations of the population of early-type stars in regions of rapid star formation.

Non-NASA Center

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

NASA Discipline Exobiology

Ultraviolet Imaging Spectrometer

Wide-field imaging systems equipped with objective prisms or gratings have had a long history of utility in groundbased observations of meteors and comets. Deployment of similar instruments from low Earth orbit would allow the first UV observations of meteors. This instrument can be used for comets and Lyman alpha coronae of Earth-orbit-crossing asteroids. A CaF2 prism imaging spectrograph designed for stellar observations was used aboard Skylab to observe Comet Kohoutek (1973f), but its 1300-A cut-off precluded Lyman alpha images and it was not used for observation of meteors. Because the observation of the UV spectrum of a meteor has never been attempted, researchers are denied the opportunity to obtain composition information from spectra at those wavelengths. We propose construction of a flight instrument functioning in the 1100-3200 A spectral range that is suitable for a dedicated satellite ('Quick Star') or as a space-station-attached payload. It can also be an autonomous package in the space shuttle cargo bay.

Wdowiak, T. J.

Heavy metal toxicity as a kill mechanism in impact caused mass extinctions

Heavy metals that are known to be toxic exist in carbonaceous chrondrites at abundances considerably in excess to that of the terrestrial crust. An impactor of relatively undifferentiated cosmic matter would inject into the terrestrial environment large quantities of toxic elements. The abundances of toxic metals found in the Allende CV carbonaceous chondrite and the ratio of meteoritic abundance to crustal abundance are: Cr, 3630 PPM, 30X; Co, 662 PPM, 23X; ni, 13300 PPm, 134X; se, 8.2 PPM, 164X; Os, 0.828 PPM, 166X. The resulting areal density for global dispersal of impactor derived heavy metals and their dilution with terrestrial ejecta are important factors in the determination of the significance of impactor heavy metal toxicity as a kill mechanism in impact caused mass extinctions. A 10 km-diameter asteroid having a density of 3 gram per cu cm would yield a global areal density of impact dispersed chondritic material of 3 kg per square meter. The present areal density of living matter on the terrestrial land surface is 1 kg per square meter. Dilution of impactor material with terrestrial ejecta is determined by energetics, with the mass of ejecta estimated to be in the range of 10 to 100 times that of the mass of the impactor. Because a pelagic impact would be the most likely case, the result would be a heavy metal rainout.

Wdowiak, T. J.

Formation of particulates by ion bombardment of cryogenic ice mixtures

An analysis of the particulates which form upon the bombardment of a gaseous mixture reflecting cosmic molecular abundances with H2(+) ions accelerated at 350 keV. The model of Black and Dalgarno (1977) for the Zeta Oph cloud and an observational determination of the interstellar Ar abundances (Simpson et al., 1986) are used to determine the abundances of the gas mixture. The characteristics of the resulting residue are examined, including photographs and absorbance spectra. The possible astrophysical implications of the experiment are discussed.

Wdowiak, T. J.

Ultraviolet spectroscopy of meteoric debris: In situ calibration experiments from Earth orbit

It is proposed to carry out slitless spectroscopy at ultraviolet wavelengths from orbit of meteoric debris associated with comets. The Eta Aquarid, Orionid/Halley, and the Persied/1962 862 Swift-Tuttle showers would be principal targets. Low light level, ultraviolet video technique will be used during night side of the orbit in a wide field, earthward viewing mode. Data will be stored in compact video cassette recorders. The experiment may be configured as a GAS package or in the HITCHHIKER mode. The latter would allow flexible pointing capability beyond that offered by shuttle orientation of the GAS package, and doubling of the data record. The 1100 to 3200 A spectral region should show emissions of atomic, ionic, and molecular species of interest on cometary and solar system studies.

Nuth, J. A., III

Ultraviolet spectroscopy of meteoric debris of comets

It is proposed to carry out slitless spectroscopy at ultraviolet wavelengths from orbit of meteoric debris associated with comets. The Eta Aquarid and Orionid/Halley and the Perseid/1962 862 Swift-Tuttle showers would be principal targets. Low light level, ultraviolet video technique will be used during night side of the orbit in a wide field, earthward viewing mode. Data will be stored in compact video cassette recorders. The experiment may be configured as a GAS package or in the HITCHHIKER mode. The latter would allow flexible pointing capability beyond that offered by shuttle orientation of the GAS package, and doubling of the data record. The 1100 to 3200 A spectral region should show emissions of atomic, ionic, and molecular species of interest on cometary and solar system studies.

Wdowiak, T. J.