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Mass-spectrometric in situ studies of cometary organics for p/Halley and options for the future.

When the VEGA and GIOTTO spacecrafts flew by comet p/Halley in 1986 the mass-spectrometers Puma and PIA measured the composition of cometary dust particles impacting at speeds of well above 65 km/s. Ion formation upon impact lead to mostly atomic ions. However, a small fraction of the ions measured could be related to molecules. A sophisticated analysis allowed for the first time to point to the chemical nature of cometary organics based on actual mass spectra. With the instrument CoMA for the NASA-BMFT mission CRAF much higher mass-resolution and molecule masses become accessible for in situ measurement, and will yield complementary information to the gas chromatograph CIDEX also onboard CRAF.

Astronomical Phenomena↗

Circular polarisation in star-forming regions: possible implications for homochirality.

Our discovery of high degrees of circular polarisation in some star-forming regions provides an attractive mechanism for the origin of homochirality. The largest degrees of circular polarisation, so far observed at near-infrared wavelengths, are thought to arise from the scattering of stellar radiation from aligned dust grains and are calculated to extend down to UV wavelengths. The extent of the region where circularly polarised light (CPL) of a single handedness originates is very large, and it is likely that the whole of a planetary system would see a single handedness of CPL also. We present the observational data, models of the scattering that leads to the production of CPL, and a model for the origin of homochirality. We also discuss briefly future laboratory and space-based experiments.

Astronomical Phenomena↗

Carbonaceous matter in cometary dust and coma.

The analysis of carbonaceous matter in p/Halley's dust and coma via mass spectrometry of positive ions is reviewed. Dust impact generated ions were analyzed by the PUMA instrument aboard VEGA I, and coma plasma ions by the PICCA instrument aboard GIOTTO. For the organic molecules results an overall C:H:O:N ratio of 1.:1.4:0.6:0.1. Most of this polymer material can formally be understood as an aggregation of monomers C2H2, CH2O, and HCN. Special emphasis is given to possible aromatic, especially heterocyclic, and other unsaturated ions, and their importance for abiotic chemical and prebiotic evolution. Aspects of the potential heterogeneous catalysis in liquid water at the inorganic grain backbone structure found by this analysis, too, are also treated.

Acetylene↗

Detection of soft X-rays and a sensitive search for noble gases in comet Hale-Bopp.

An image of comet Hale-Bopp (C/1995 O1) in soft x-rays reveals a central emission offset from the nucleus, as well as an extended emission feature that does not correlate with the dust jets seen at optical wavelengths. Neon was found to be depleted in the cometary ice by more than a factor of 25 relative to solar abundance, which suggests that ices in Hale-Bopp formed at (or later experienced) temperatures higher than 25 kelvin. A helium line emission at a wavelength of 584 angstroms was detected and may be attributable to charge transfer of solar wind alpha particles in the cometary coma. Ionized oxygen and another helium line contribute to an emission observed at 538 angstroms.

Cosmic Dust↗

Evolution of interstellar ices.

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

Carbon Monoxide↗

Low-temperature crystallization of silicate dust in circumstellar disks.

Silicate dust in the interstellar medium is observed to be amorphous, yet silicate dust in comets and interplanetary dust particles is sometimes partially crystalline. The dust in disks that are thought to be forming planets around some young stars also appears to be partially crystalline. These observations suggest that as the dust goes from the precursor clouds to a planetary system, it must undergo some processing, but the nature and extent of this processing remain unknown. Here we report observations of highly crystalline silicate dust in the disks surrounding binary red-giant stars. The dust was created in amorphous form in the outer atmospheres of the red giants, and therefore must be processed in the disks to become crystalline. The temperatures in these disks are too low for the grains to anneal; therefore, some low-temperature process must be responsible. As the physical properties of the disks around young stars and red giants are similar, our results suggest that low-temperature crystallization of silicate grains also can occur in protoplanetary systems.

Cold Temperature↗

Ground-based thermal infrared observations of comet Hale-Bopp (C/1995 O1) during 1996.

Thermal infrared (IR) imaging and spectroscopy of comet Hale-Bopp (C/1995 O1) during June, August, and September 1996 traced the development of the dust coma several months before perihelion. Images revealed nightly variations in the brightness of the inner coma from 1 to 12 June that were correlated with the appearance of a northward-pointing jet. The central IR flux increased by a factor of 8 between 1 June and 30 September, and the September data showed IR jets that corresponded to similar structures that were visible in reflected sunlight at shorter wavelengths. At all epochs, 8- to 13-micrometer spectra of the central coma revealed a strong silicate emission feature, including an 11.2-micrometer feature indicative of crystalline olivine, even when the comet was at a heliocentric distance of 4.1 astronomical units.

Cosmic Dust↗

The hydrocarbon ring C3H2 is ubiquitous in the Galaxy.

We report the discovery of a strong microwave (lambda 1.6 cm) spectral line, the carrier of which is common and widespread throughout the Galaxy. A survey of a large number of sources shows that the line appears in emission in cold dust clouds, in absorption in the direction of the Galactic center, and exhibits complex profiles toward H II regions. Toward Cas A and distant H II regions, intervening "spiral arm" clouds produce absorption. For almost all cases, the absorption features show a striking 1 : 1 radial velocity correspondence with those seen, e.g., in H2CO spectra of the same objects. The data indicate that the line arises between low-lying energy states of rather polar molecule. Recent work by Thaddeus, Vrtilek, and Gottlieb, reported in 1985 incorporating the present data, shows that the line in question is the 1(10)-1(01) transition of the small hydrocarbon ring C3H2.

Astronomical Phenomena↗

Dust measurements in the coma of comet 81P/Wild 2 by the Dust Flux Monitor Instrument.

We present measurements of the dust particle flux and mass distribution from the Stardust Dust Flux Monitor Instrument (DFMI) throughout the flyby of comet 81P/Wild 2. In the particle mass regime from 10(-14) to 10(-7) kilograms, the spacecraft encountered regions of intense swarms of particles, together with bursts of activity corresponding to clouds of particles only a few hundred meters across. This fine-scale structure can be explained by particle fragmentation. We estimate that 2800 +/- 500 particles of diameter 15 micrometers or larger impacted the aerogel collectors, the largest being approximately 6 x 10(-7) kilograms, which dominates the total collected mass.

Cosmic Dust↗

Spectroscopic diagnostics of organic chemistry in the protostellar environment.

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Amino Acids↗

Supernova olivine from cometary dust.

An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud.

Cosmic Dust↗

Electric interactions between dust and hot plasmas in the solar system.

Interaction of the charged particles of a plasma with a solid body is an old problem which has been investigated under various conditions, in particular by the authors in several papers. However, the electric potential of the grains may be more sensitive than expected to the physical state of grain matter and the physical parameters of plasmas in the solar system. Using a new model accounting for porosity, a characteristic feature of grains observed in the solar system, we have investigated the secondary electron emission under electron impact for porous materials. The conclusion is that porosity has a significant influence on the rate of electron ejection. It follows that the floating potential of porous grains can be different from that of grains made of bulk material, with consequences for grain dynamics in the environment of planets or comets.

Aluminum Oxide↗

Aromatic hydrocarbons, diamonds, and fullerenes in interstellar space: puzzles to be solved by laboratory and theoretical astrochemistry.

New research is presented, and previous research is reviewed, on the emission and absorption of interstellar aromatic hydrocarbons. Emission from aromatic hydrocarbons dominates the mid-infrared emission of many galaxies, including our own Milky Way galaxy. Only recently have aromatic hydrocarbons been observed in absorption in the interstellar medium, along lines of sight with high column densities of interstellar gas and dust. Much work on interstellar aromatics has been carried out, with astronomical observations and laboratory and theoretical astrochemistry. In many cases, the predictions of laboratory and theoretical work are confirmed by astronomical observations but, in other cases, clear discrepancies exist that provide problems to be solved by a combination of astronomical observations, laboratory studies, and theoretical studies. The emphasis of this paper will be on current outstanding puzzles concerning aromatic hydrocarbons that require further laboratory and theoretical astrochemistry to resolve. This paper will also touch on related topics where laboratory and theoretical astrochemistry studies are needed to explain astrophysical observations, such as a possible absorption feature due to interstellar 'diamonds' and the search for fullerenes in space.

Absorption↗

Deflection of the local interstellar dust flow by solar radiation pressure.

Interstellar dust grains intercepted by the dust detectors on the Ulysses and Galileo spacecrafts at heliocentric distances from 2 to 4 astronomical units show a deficit of grains with masses from 1 x 10(-17) to 3 x 10(-16) kilograms relative to grains intercepted outside 4 astronomical units. To divert grains out of the 2- to 4-astronomical unit region, the solar radiation pressure must be 1.4 to 1.8 times the force of solar gravity. These figures are consistent with the optical properties of spherical or elongated grains that consist of astronomical silicates or organic refractory material. Pure graphite grains with diameters of 0.2 to 0.4 micrometer experience a solar radiation pressure force as much as twice the force of solar gravity.

Cosmic Dust↗

Identification of molecular-cloud material in interplanetary dust particles.

Interplanetary dust particles (IDPs) collected in the Earth's stratosphere and meteorites are fragments of comets and asteroids. These are 'primitive' meteorites in part because they have preserved materials which predate the formation of the Solar System. The most primitive (least altered) meteorites contain a few parts per million of micrometre-sized dust which formed in the atmospheres of giant stars. Some meteorites have elevated D/H and 15N/14N ratios that are attributed to surviving interstellar organic molecules which have probably been strongly diluted and altered by parent-body processes. Most IDPs are chemically, mineralogically, and texturally primitive in comparison to meteorites. Here I show that H and N isotopic anomalies among fragile 'cluster' IDPs are far larger, more common, and less equilibrated than those previously observed in other IDPs or meteorites. In some cases, the D/H ratios that we measure reach the values of interstellar molecules, suggesting that molecular-cloud material has survived intact. These observations indicate that cluster IDPs are the most primitive class of Solar System materials currently available for laboratory analysis.

Carbon Isotopes↗

A cloud collision model for water maser excitation.

High-velocity collisions between small, dense, neutral clouds or between a dense cloud and a dense shell can provide the energy source required to excite H2O maser emission. The radiative precursor from the surface of the collisional shock front rapidly diffuses through the cloud, heating the dust grains but leaving the H2 molecules cool. Transient maser emission occurs as the conditions for the Goldreich and Kwan "hot-dust cold-gas" maser pump scheme are realized locally within the cloud. In time the local maser action quenches due to the heating of the H2 molecules by collisions against the grains. Although this model cannot explain the very long-lived steady maser features, it is quite successful in explaining a number of the observed properties of the high-velocity features in such sources as Orion, W51, and W49. In particular, it provides a natural explanation for the rapid time variations, the narrow line widths, juxtaposition of high- and low-velocity features, and the short lifetimes which are frequently observed for the so-called high-velocity maser "bullets" thought to be accelerated by strong stellar winds.

Astronomical Phenomena↗

An infrared spectral match between GEMS and interstellar grains.

Infrared spectral properties of silicate grains in interplanetary dust particles (IDPs) were compared with those of astronomical silicates. The approximately 10-micrometer silicon-oxygen stretch bands of IDPs containing enstatite (MgSiO3), forsterite (Mg2SiO4), and glass with embedded metal and sulfides (GEMS) exhibit fine structure and bandwidths similar to those of solar system comets and some pre-main sequence Herbig Ae/Be stars. Some GEMS exhibit a broad, featureless silicon-oxygen stretch band similar to those observed in interstellar molecular clouds and young stellar objects. These GEMS provide a spectral match to astronomical "amorphous" silicates, one of the fundamental building blocks from which the solar system is presumed to have formed.

Cosmic Dust↗

Structure and UV absorption of QCCs: carbonaceous dust analogues.

"Quenched Carbonaceous Composites (QCCs)" are carbonaceous interstellar dust analogues synthesized in the laboratory from a hydrocarbon plasma. We produced new types of carbonaceous condensates from the ejecta of plasma with mixtures of methane and hydrogen as source gases. We find that QCC with an absorbance peak at 220 nm is composed of onion-like spherules, and QCCs with an absorbance peak at 230-240 nm are composed of polyhedral particles. The onion-like QCC contains aromatic hydrogen bonds, and it shows the 3.3 and 11.4 micrometers absorption bands. The QCC with an absorbance peak at 230-240 nm is composed of ribbons with bent graphitic layers. This suggests that the carrier of the interstellar 220 nm extinction band might also be an emitter of the interstellar diffuse emission bands.

Astronomical Phenomena↗