Complex organics in laboratory simulations of interstellar/cometary ices.

We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.     

Consequences of cometary aurora on the carbon chemistry at comet P/Halley.

Various experimental data acquired during the visit of Halley's comet in 1986 have shown that the amount of carbon produced due to photodissociation of parent carbon bearing species is not ample enough to explain the observations. This requires the presence of an additional source of atomic carbon. One of the possible source could be auroral-type activities resulting from the precipitation of high-energy "auroral electrons" of solar wind origin, the evidence of which have been inferred from many observations at comet Halley. We have developed a coupled chemistry-transport model to study the role of auroral and photoelectron impact as well as of chemistry on the modelling of carbon in the inner coma (< or = 10(4) km) of comet Halley. Our study suggest that electron impact dissociation of CO is the major source of carbon production in the inner coma, not the recombination of CO+ as suggested by earlier workers, while transport is the main loss process.     

Dirty ice grains in comets

Based on the computed equilibrium temperature of evaporating dirty water-ice grains, dirty water-ice halo is examined, taking into account of a size dependence of terminal velocity of dust at P/Halley. It is found that due to an enhanced grain's temperature caused by dirtiness, icy halo cannot extend over 100 km from the nucleus when comet approaches inside a solar distance r of 1 AU. Therefore, it is unlikely that the ice bands in the near infrared wavelengths could be detected in the cometary coma at r<1 AU.     

Optical observations of ion tail structures and velocity flows in comet Halley during the period of the five spacecraft encounters

Observations of the distribution and evolution of a number of the major constituents of the neutral coma (CN, C₂, CH, O, H, Na) of Comet Halley were made during two observing periods, each of 3 weeks duration, from the Table Mountain Observatory, California. The first period was pre-perihelion, in late November/December 1985. The second period, from Feb 28 to March 22 1986, covered the five close spacecraft encounters with Halley, and when ICE flew some 20 M Km upstream of Halley. Sodium emission was recorded in early Dec 1985 from the near-nuclear region at a heliocentric distance of 1.4 AU, an observation confirmed with the UCL Doppler Imaging system. The CN coma could be detected to an outer diameter of more than 4M Km in Dec 1985, and 5 – 6M Km in early March 1986, allowing the production of heavy cometary pick-up ions to be estimated. Observations of the cometary ion coma (H₂O⁺ and CO⁺ ions) showed considerable variability from day to day, particularly during the period of the spacecraft encounters. These observations have been used, in conjuction with the neutral coma data, to map the flow field of cometary ions. In early Dec. 1985, Halley developed a traditional “type I” ion tail, which persisted until late April 1986. It has also been possible to evaluate the ion flow fields within the narrow core of the ion tail, and in the surrounding diffuse, low density, regions populated by pick-up and extracted cometary ions, and by slowed solar wind ions. Tail disconnection events were observed on several occasions, particularly between the VEGA 2 and GIOTTO encounters, and with a highly spectacular event on March 19 1986.     

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds.

The prebiotic synthesis of organic compounds using a spark discharge on various simulated prebiotic atmospheres at 25 degrees has been studied. Methane mixtures contained H2 + CH4 + H2O + N2 + NH3 with H2/CH4 molar ratios from 0 to 4 and pNH3 = 0.1 torr. A similar set of experiments without added NH3 was performed. The yields of amino acids (1.2 to 4.7% based on the carbon) are approximately independent of the H2/CH4 ratio and the presence of added NH3, and a wide variety of amino acids are obtained. Mixtures of H2 + CO + H2O + N2 and H2 + CO2 + H2O + N2, with and without added NH3, all give about 2% yields of amino acids at H2/CO and H2/CO2 ratios of 2 to 4. For the H2/CO and H2/CO2 ratios less than 1, the yields fall off drastically to as low as 10(-3)%. Glycine is almost the only amino acid produced from CO and CO2 atmospheres. These results show that the maximum yield is about the same for the three carbon sources at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. In addition, CH4 gives a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these results indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde parallel the amino acid results, with yields of HCN and H2CO as high as 13% based on the carbon. Ammonia is also produced from N2 in experiments with no added NH3 in yields as high as 4.9%. These results show that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges. The amount of ammonia formed by hydrolysis of HCN and various nitriles may have exceeded that formed directly in electric discharges.     

Biogeochemical evidence of microbial activity on Mars.

We suggest a new interpretation of the data on so-called SNC meteorites and delta 13C values of the calcium carbonate minerals and organic matter discovered in them. The delta 13C value of calcite (up to 15 ppt) is accounted for by the microbial reaction CO2 + H2 ---> CH4 + H2O. Methane-forming bacteria also synthesize organic carbon (in the form of biomass) from CO2, and this process is accompanied by 12C fractionation. Therefore, the organic carbon of SNC meteorites is enriched with 12C (delta 13C as low as -35 ppt). The environmental conditions under which the calcite of SNC meteorites was formed were favorable for the activity of methanogens.     

The infrared synthetic spectrum of comet Halley

In order to prepare infrared sounding of comet Halley from the flyby VEGA probes, we have computed the synthetic spectrum between 2.5 and 15 μ of a typical comet at a heliocentric distance of ～ 0.8 AU. The present paper is particularly devoted to the contribution from the cometary gases. For a selection of 20 possible parent molecules, the most efficient excitation process is resonant fluorescence by the solar radiation field. The H₂O, CO, CO₂, CH₄, NH₃ and H₂CO molecules are the best candidates for detection by the IKS infrared spectrometers aboard the VEGA probes. For the water molecule, collisions are too rare to ensure thermal equilibrium in the whole coma ; therefore a limited number of fluorescence lines are expected to be present in the H₂O vibrational bands.     

Cometary constraints on the planet forming environment.

Molecular elemental and isotopic abundances of comets provide sensitive diagnostics for models of the primitive solar nebula. New measurements of the N2, NH and NH2 abundances in comets together with the in situ Giotto mass spectrometer and dust analyzer data provide new constraints for models of the comet forming environment in the solar nebula. An inventory of nitrogen-containing species in comet Halley indicates that NH3 and CN are the dominant N carriers observed in the coma gas. The elemental nitrogen abundance in the gas component of the coma is found to be depleted by a factor approximately 75 relative to the solar photosphere. Combined with the Giotto dust analyzer results for the coma dust component, we find for comet Halley Ngas + dust approximately 1/6 the solar value. The measurement of the CN carbon isotope ratio from the bulk coma gas and dust in comet Halley indicates a significantly lower value, 12C/13C = 65 +/- 9 than the solar system value of 89 +/- 2. Because the dominant CN carrier species in comets remains unidentified, it is not yet possible to attribute the low isotope ratio predominantly to the bulk gas or dust components. The large chemical and isotopic inhomogeneities discovered in the Halley dust particles on 1 mu scales are indicative of preserved circumstellar grains which survived processing in the interstellar clouds, and may be related to the presolar silicon carbide, diamond and graphite grains recently discovered in carbonaceous chondrites. Less than 0.1% of the bulk mass in the primitive meteorites studied consists of these cosmically important grains. A larger mass fraction (approximately 5%) of chemically heterogeneous organic grains is found in the nucleus of comet Halley. The isotopic anomalies discovered in the PUMA 1 Giotto data in comet Halley are probably also attributable to preserved circumstellar grains. Thus the extent of grain processing in the interstellar environment is much less than predicted by interstellar grain models, and a significant fraction of comet nuclei (approximately 5%) may be in the form of preserved circumstellar matter. Comet nuclei probably formed in much more benign environments than primitive meteorites.     

Chemical evolution in space--a source of prebiotic molecules.

In Laboratory Astrophysics at Leiden University a laboratory analog for following the chemical evolution of interstellar dust in space shows that the dust contains the bulk of organic material in the universe. We follow the photoprocessing of low temperature (10 K) mixtures of ices subjected to vacuum ultraviolet radiation in simulation of interstellar conditions. The most important, but necessary, difference is in the time scales for photo-processing. One hour in the laboratory is equivalent to one thousand years in low density regions of space and as much as, or greater than, ten thousand to one million years in the depths of dense molecular clouds. The ultimate product of photoprocessing of grain material in the laboratory is a complex nonvolatile residue which is yellow in color and soluble in water and methanol. The molecular weight is greater than the mid-hundreds. The infrared absorption spectra indicate the presence of carboxylic acid and amino groups resembling those of other molecules of presumably prebiological significance produced by more classical methods. One of our residues, when subjected to high resolution mass spectroscopy gave a mass of 82 corresponding to C4H6H2 after release of CO2 and trace ammounts of urea suggesting amino pyroline rings. The deposit of prebiotic dust molecules occurred as many as 5 times in the first 500-700 million years on a primitive Earth by accretion during the passage of the solar system through a dense interstellar cloud. The deposition rate during each passage is estimated to be between 10(9) and 10(10) g per year during the million or so years of each passage; i.e., a total deposition of 1O(9)-10(10) metric tons of complex organic material per passage.     

Very low temperature formaldehyde reactions and the build-up of organic molecules in comets and interstellar ices.

We have investigated thermally promoted reactions of formaldehyde (H2CO) in very low temperature ices. No such reactions occurred in ices of pure formaldehyde. However, addition of trace amounts of ammonia (NH3) were sufficient to catalyze reactions at temperatures as low as 40 K. Similar reactions could take place in interstellar ices and in Comets and produce considerable amounts of organic molecules.     

A quantitative assay of biologically important compounds in simulated primitive Earth experiments.

A CH4-N2-H2OV gas mixture was subjected to a high voltage (20 kV), high frequency (0.3 MHz) electric discharge. The energy input in the electric discharge was varied from 0.016 to 3.048 MJ mol-1. The chemical yields (G), expressed as the number of molecules formed or destroyed per 100 eV of energy input were calculated for several products. The G values calculated at the lowest energy input were (-CH4) = 6.48; (-N2) = 2.51; (C2H2) = 1.16; (HCN) = 0.215; (CH3CHO) = 0.115; (CH3CH2CHO) = 0.00161; (CH3(CH2)2CHO) = 0.0165; ((CH2CO2H)2) = 0.0000339; (CH4 --> Solid material) = 0.196; (N2 --> Solid material) = 0.00355. This is the first report in prebiotic studies in which the G values of various products in electric discharge experiments are determined. This type of study is needed in order to get a better insight into the relative role of electric discharges on the primitive Earth.     

Cometary atmosphere (gas and dust)

There is important progress now in the identifications and measurements of primary (parent) molecules in the inner coma of Comet Halley. H₂O, CO₂ and CO are definitely in the list, CH and some complicate organic molecules are suspected. Gas production rate for water vapor is Q_H2O 10³⁰ s⁻¹. The bulk of data doesn't contradict to the Whipple model of nucleus (with clathrate modification). Pronounced spatial structure of gaseous flow in the coma was observed, but in general measured properties of neutral gas in the coma of Comet Halley are not very different from predicted. Situation for dust is different. In situ dust measurements show that size spectrum and optical properties of particles in coma are substantively declining from predicted on the base of groundbased photometry. However there are discrepancies between Vega and Giotto dust counter data. Dust in the inner coma didn't prevent the succesful imaging of nucleus by TV on Vega 1 and 2.     

Rocket observation of the ultraviolet spectrum of comet Halley

An ultraviolet sounding rocket telescope/spectrograph experiment observed Comet Halley on 26 February 1986, 17 days after perihelion. From the long-slit spectra, the production rates of O, C, and CO are calculated. The derived water production rate is a lower limit of 5.0 × 10²⁹ s⁻¹ and the volume mixing ratio of CO to H₂O is 21%. The predicted brightness distribution from a radial outflow model with H₂O and CO as parent molecules are in accordance with the measured spatial profiles of OI and CO emissions. The ratio of the production rates of CO to C is 2.7 which is consistent with the carbon source being the photodissociation of CO. However, the radial outflow model which best fits the CO data predicts significantly weaker CI emissions than was observed. A better fit to the carbon data is found when an inner coma source of C at a rate of 3% of the water production rate is included in the model.     

Remote infrared observations of parent volatiles in comets: A window on the early solar system

Organic volatiles and water in Oort Cloud comets were investigated at infrared wavelengths. The detected species include H₂O, CO, CH₃OH, CH₄, C₂H₂, C₂H₆, OCS, HCN, NH₃, and H₂CO. Several daughter fragments (CN, OH, NH₂, etc.) are also measured, and OH prompt emission provides a proxy for water. Long-slit spectra are taken at high spectral dispersion and high spatial resolution, eliminating several sources of systematic error. The resulting parent volatile production rates are highly robust, permitting a sensitive search for compositional diversity among comets. Here, seven OC comets are compared. Six (including Halley) exhibit similar compositions (excepting CO and CH₄). Their low formation temperatures (30 K) suggest this group probably formed beyond 30 AU from the young sun. However, C/1999 S4 is severely depleted in hypervolatiles and also in methanol, and it likely formed near 5–10 AU. C/2001 A2 is discussed briefly to illustrate future prospects.     

A study of chemical systems using signal flow graph theory.

Photochemistry of giant planets and their satellites is characterized by numerous reactions involving a lot of chemical species. In the present paper, chemical systems are modeled by signal flow graphs. Such a technique evaluates the transmission of any input into the system (solar flux, electrons ... ) and gives access to the identification of the most important mechanisms in the chemical system. This method is applied to the production of hydrocarbons in the atmospheres of giant planets. In particular, the production of C2H6 in the atmosphere of Neptune from the photodissociation of CH4 is investigated. Different pathways of dissociation of CH4 are possible from L alpha radiation. A chemical system containing 14 species and 30 reactions including these different pathways of dissociation is integrated. The main mechanism of production of C2H6 is identified and evaluated for each model of dissociation. The importance of various reaction pathways as a function of time is presented.     

Organic chemistry by irradiation in space

The irradiation of grains and/or ices by particles from solar or stellar winds, as well as cosmic rays, induces the synthesis of molecular species. We have shown by in-situ infrared spectroscopy of irradiated samples that this chemistry may be responsible for the presence of organic compounds in a large variety of astrophysical sites such as: lunar and asteroidal regoliths, cometary nucleus, rings and satellites of outer planets, circumstellar shells, interstellar clouds. We present our experimental results concerning the nature and efficiency of C and N irradiation chemistries, and give plausible astrophysical implications.     

Titan: some new results.

New analyses of Voyager spectra of Titan have led to improvements in the determination of abundances of minor constituents as a function of latitude and altitude. Ground-based microwave observations have extended the Voyager results for HCN, and have demonstrated that CO is mysteriously deficient in the stratosphere. The origin of the CH4, CO, and N2 in Titan's atmosphere is still unresolved. Both primordial and evolutionary sources are compatible with the available evidence.     

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands.

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these PAHs absorb in the visible. C10H8+ has 12 discrete absorption bands which fall between 6800 and 5000 angstroms. The strongest band at 6741 angstroms falls close to the weak 6742 angstroms diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8+ is responsible for some of the DIBs can be tested by searching for new DIBs at 6520, 6151, and 5965 angstroms, other moderately strong naphthalene cation band positions. If C10H8+ is indeed responsible for the 6742 angstroms feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10+ is dominated by a strong band at 4435 angstroms in an Ar matrix and 4395 angstroms in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 angstroms. If C16H10+, or a closely related pyrene-like ion is indeed responsible for the 4430 angstroms feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.     

VEGA three-channel spectrometer experiment: Spectroscopy of comet Halley in the visible and near-ultraviolet ranges

A total of 3600 spectra of Comet Halley in the 275–710 nm were obtained on March, 8, 9, 10 and 11, 1986, from the VEGA 2 spacecraft. The emissions of OH, NH, CN, C₃, CH, C₂, NH₂ and H₂O⁺ are identified. From the OH intensity in the (0,0) band: 1.1 Megarayleigh at 5400 km from the nucleus, it can be inferred that the OH production rate was (1.4 ± 0.5)×10³⁰ molecules s⁻¹. The NH, C₃, CH and NH₂ bands became comparatively more intense at distances from the nucleus shorter than 3000km. At 06:40 U.T. when the instrument field of view was 6000×4500 km, two jets were observed. Spectra from the jets show significant differences with other spectra. Inside a jet NH, C₃ and NH₂ are comparatively more intense and the rotational distributions of OH, CN and C₂ are strongly distorted. This shows that part of the observed emissions probably comes from radicals directly produced in the excited state during the initial process of photolysis of the parent molecules.