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.

In situ laser-Raman imagery of precambrian microscopic fossils.

Laser-Raman imagery is a sensitive, noninvasive, and nondestructive technique that can be used to correlate directly chemical composition with optically discernable morphology in ancient carbonaceous fossils. By affording means to investigate the molecular makeup of specimens ranging from megascopic to microscopic, it holds promise for providing insight into aspects of organic metamorphism and biochemical evolution, and for clarifying the nature of ancient minute fossil-like objects of putative but uncertain biogenicity.

Technology considerations relevant to an exobiology surface-science approach for Europa.

If Europa is to be of primary exobiological interest, namely, as a habitat for extant life, it is obvious that (a) a hydrosphere must prevail beneath the cryosphere for a long time, (b) internal energy sources must be present in a sufficient state of activity, and (c) a reasonable technical means must be available for assessing if indeed life does exist in the hypothesized hydrosphere. This discussion focuses on the last point, namely, technological issues, because the trend of the compounding evidence about Europa indicates that the first two points are likely to be true. First, we present a consideration of time-of-flight mass spectroscopy conducted in situ on the cryosphere surface of Europa during a first landed robotic mission. We assert that this is a reasonable technical means not only for exploring the composition of the cryosphere itself, but also for locating any biomolecular indicators of extant life brought to the surface through cryosphere activity. Secondly, this work also addresses practical issues inherent in any kind of instrumental interrogation of a surface whose properties are governed by radiation chemistry. This includes advocating the construction of a Europan surface simulator to familiarize instrumental system developers with the spacecraft- and instrument-scale conditions under which such an interrogation would take place on Europa. Such a simulator is mandatory in certification of the functional utility of a flight instrument.

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.

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.

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.

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.

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.

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.

Origin of the hydrocarbon component of carbonaceous chondrites: the star-meteorite connection.

We report the results of an experiment that produced a residue which closely matches the hydrocarbon component of the Murchison carbonaceous chondrite. This experiment suggests that the parent material of the meteoritic component originated as polycyclic aromatic hydrocarbon species in carbon stars during their later stages of evolution. The experiments also indicate that the pathway from those formation sites to eventual incorporation into the meteorite parent body involved hydrogenation in a plasma in the solar nebula or in H II regions prior to the solar nebula. This model is consistent with what is known about the meteoritic hydrocarbon component including deuterium abundance, the observation of cosmic infrared emission bands best attributed to polycyclic aromatic hydrocarbon molecules, and the inherent stability of these molecules that allows their formation in stars and subsequent survival in the interstellar medium.

Insoluble organic material of the Orgueil carbonaceous chondrite and the unidentified infrared bands.

Deuterium abundance measurements and the 13C NMR spectrum of the HF/HCl insoluble residue of the Orgueil carbonaceous chondrite indicate the presence of an extensive component of polycyclic aromatic hydrocarbons (PAH) that is of possible interstellar origin or is similar to PAH hypothesized to exist in interstellar space. Infrared spectra have been obtained using an FTIR spectrometer of the acid insoluble residue, the residue after heating in vacuum, and condensate. Bulk acid insoluble residue was pressed into KBr pellets and also heated under high vacuum to sublimate a volatile component onto KBr disks. The remaining non-volatile organic component of the Orgueil meteorite from such evaporations pressed into KBr pellets exhibits a spectral signature similar to that observed in emission from the Orion Nebula and found in Raman spectra of interplanetary dust particles (IDPs). In addition it has an 11.3 microns (885 cm-1) band indicating PAH having single hydrogens per peripheral aromatic ring. We conclude the nonvolatile material is similar to interstellar PAH because the observed 11.3 microns (885 cm-1) unidentified infrared (UIR) emission suggests interstellar PAH have single hydrogens per peripheral aromatic ring. The volatile fraction of the Orgueil shows an aliphatic CH stretch feature and its spectrum in the 2-25 microns range is similar to that of the bulk residue.