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.     

Formation of amino acid precursors in cometary ice environments by cosmic radiation.

Cometary ices are believed to contain water, carbon monoxide, methane and ammonia, and are possible sites for the formation and preservation of organic compounds relating to the origin of life. Cosmic rays, together with ultraviolet light, are among the most effective energy sources for the formation of organic compounds in space. In order to study the possibility of the formation of amino acids in comets or their precursory bodies (interstellar dust grains), several types of ice mixtures made in a cryostat at 10 K ("simulated cometary ices") were irradiated with high energy protons. After irradiation, the volatile products were analyzed with a quadrupole mass spectrometer, while temperature of the cryostat was raised to room temperature. The non-volatile products remaining in the cryostat at room temperature were collected with water. They were acid-hydrolyzed, and analyzed by ion-exchange chromatography. When an ice mixture of carbon monoxide (or methane), ammonia and water was irradiated, some hydrocarbons were formed, and amino acids such as glycine and alanine were detected in the hydrolyzate. These results suggest the possible formation of "amino acid precursors" (compounds yielding amino acids after hydrolysis) in interstellar dust grains by cosmic radiation. We previously reported that amino acid precursors were formed when simulated primitive planetary atmospheres were irradiated with cosmic ray particles. It will be of great interest to compare the amount of bioorganic compounds that were formed in the primitive earth and that brought by comets to the earth.     

The seeding of life by comets.

The evidence that living organisms were already extant on the earth almost 4 Gyr ago and that early bombardment by comets and asteroids created a hostile environment up to about this time has revived the question of how it was possible for prebiotic chemical evolution to have provided the necessary ingredients for life to have developed in the short intervening time. The actual bracketed available temporal space is no more than 0.5 Gyr and probably much less. Was this sufficient time for an earth-based source of the first simple organic precursor molecules to have led to the level of the prokaryotic cell? If not, then the difficulty would be resolved if the ancient earth was impregnated by organic molecular seed from outer space. Curiously, it seems that the most likely source of such seeds was the same a one of the sources of the hostile enviroment, namely the comets which bombarded the earth. With the knowledge of comets gained by the space missions it has become clear that a very large fraction of the chemical composition of comet nuclei consists of quite complex organic molecules. Furthermore it has been demonstrated that comets consist of very fluffy aggregates of interstellar dust whose chemistry derives from photoprocessing of simple ice mixtures in space. Thus, the ultimate source of organics in comets comes from the chemical evolution of interstellar dust. An important and critical justification for assuming that interstellar dust is the ultimate source of prebiotic molecular insertion on the earth is the proof that comets are extremely fluffy aggregates, which have the possibility of breaking up into finely divided fragments when the comet impacts the earth's atmosphere. In the following we will summarize the properties of interstellar dust and the chemical and morphological structure of comets indicated by the most recent interpretations of comet observations. It will be shown that the suitable condition for comets having provided abundant prebiotic molecules as well as the water in which they could have further evolved are consistent with theories of the early earth environment.     

Silicate core-organic refractory mantle particles as interstellar dust and as aggregated in comets and stellar disks.

The principal observational properties of silicate core-organic refractory mantle interstellar dust grains in the infrared at 3.4 microns and at 10 microns and 20 microns are discussed in terms of the cyclic evolution of particles forming in stellar atmospheres and undergoing subsequent accretion, photoprocessing and destruction (erosion). Laboratory plus space emulation of the photoprocessing of laboratory analog ices and refractories are discussed. The aggregated interstellar dust model of comets is summarized. The same properties required to explain the temperature and infrared properties of comet coma dust are shown to be needed to account for the infrared silicate and continuum emission of the beta Pictoris disk as produced by a cloud of comets orbiting the star.     

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.     

Comets and life.

Some of the chemical species which have been detected in comets include H2O, HCN, CH3CN, CO, CO2, NH3, CS, C2 and C3. All of these have also been detected in the interstellar medium, indicating a probable relationship between interstellar dust and gas clouds and comets. Laboratory experiments carried out with different mixtures of these molecules give rise to the formation of the biochemical compounds which are necessary for life, such as amino acids, purines, pyrimidines, monosaccharides, etc. However, in spite of suggestions to the contrary, the presence of life in comets is unlikely. On the other hand, the capture of cometary matter by the primitive Earth is considered essential for the development of life on this planet. The amount of cometary carbon-containing matter captured by the Earth, as calculated by different authors, is several times larger than the total amount of organic matter present in the biosphere (10(18)g). The major classes of reactions which were probably involved in the formation of key biochemical compounds are discussed. Our tentative conclusions are that: 1) comets played a predominant role in the emergence of life on our planet, and 2) they are the cosmic connection with extraterrestrial life.     

Production and evolution of carbonaceous material by ion irradiation in space.

We review recent experimental studies concerning the evolution, driven by ion irradiation, of carbonaceous material from frozen gas to a refractory molecular solid. Under further irradiation the latter changes to a polymer-like material and ultimately to amorphous carbon. Most of the results have been obtained by "in situ" and remote IR and Raman spectroscopy. The results have been applied to demonstrate that molecular solids may be easily formed by irradiation of frozen mantles in dense interstellar clouds. Polymer-like material and amorphous carbons may result by further irradiation of organic mantles on grains in the diffuse interstellar medium. Those grains, during the aggregation to form extended bodies like comets (T-Tau phase of the Sun), are further modified. These latter are also irradiated, after the comet formation, during their long stay in the Oort cloud. In particular it has been suggested that comet may develop an ion-produced cometary organic crust that laboratory evidences show to be stable against temperature increases experienced during passages near the Sun. The comparison between the Raman spectra of some IDP (Interplanetary Dust Particles) and the Raman spectra of some ion-produced amorphous carbons, is also discussed.     

Organics produced by ion irradiation of ices: some recent results.

Some results, recently obtained from laboratory experiments of ion irradiation of ice mixtures containing H, C, N, and O, are here summarized. They are relevant to the formation and evolution of complex organics on interstellar dust, comets and other small bodies in the external Solar System. In particular the formation of CN-bearing species is discussed. Interstellar dust incorporated into primitive Solar System bodies and subsequently delivered to the early Earth, may have contributed to the origin of life. The delivery of CN-bearing species seems to have been necessary because molecules containing the cyanogen bond are difficult to be produced in an environment that is not strongly reducing as that of the early Earth probably was. Moreover we report on an ongoing research program concerning the interaction between refractory materials produced by ion irradiation of simple ices and biological materials (amino acids, proteins, cells).     

Spectroscopic properties of polycyclic aromatic hydrocarbons (PAHs) and astrophysical implications.

PAHs (polycyclic aromatic hydrocarbons) are probably present as a mixture of neutral and ionized species and are responsible for the set of infrared emission bands in the 2-15 microns regions, which are observed in many different objects like reflection and planetary nebulae and external galaxies. PAHs are suggested to be the most abundant free organic molecules and ubiquitous in space. PAHs might also exist in the solid phase, included in interstellar ices in dense clouds. A complex aromatic network is expected on interstellar grains in the diffuse interstellar medium. The existence of an aromatic kerogen-like structure in carbonaceous meteorites and its similarity with interstellar spectra suggests a link between interstellar matter and primitive Solar System bodies.     

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.     

From the interstellar clouds, through the inner to the outer solar system: a universally distributed complex organic chemistry. Preface.

High molecular weight organic compounds are involved in the chemistry and physics of many astrophysical and planetary objects. They are or should be present in interstellar dust, in comets and meteorites, in the Giant planets and Titan, in asteroids Triton and icy satellites. They represent a class of very complex organic material, part of which may have played a role in the origin of life on Earth. Thus they directly concern prebiotic chemistry and exobiology.     

XANES analysis of organic residues produced from the UV irradiation of astrophysical ice analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogen- and oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.     

Comets in other planetary systems?

Comets in our solar system appear to have provided a bridge between the cold, volatile-rich outer solar system, and the warm, but volatile-poor inner solar system. Excluding tidal and possible extinct radionuclide heating sources, only in the inner solar system are temperatures high enough for liquid water, and therefore life as we know it, to exist for times comparable to the age of the solar system. Comets may have been crucial for providing biogenic volatiles and perhaps organic molecules to this warm environment. It is therefore interesting from an exobiological point of view to ask if comets exist in other planetary systems. Most attempts to detect comets around other stars or in interstellar space have failed. However, there is growing spectroscopic evidence for comet-like bodies orbiting the star Beta Pictoris.     

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.     

A fine mist of very small comet dust particles

A comet nucleus considered as an aggregate of interstellar dust would produce a mist of very finely divided (radius ～ 0.01 μm) particles of carbon and metal oxides accompanying the larger dust grains. These small particles which are very abundant in the interstellar dust size spectrum would provide substantial physical effects because of their large surface area. They may show up strongly in particle detectors on the Halley probes. A strong basis for serious consideration of these particles comes from the other evidence that interstellar dust grains are the building blocks of comets; e.g. (1) the explanation of the “missing” carbon in comets; (2) The S₂ molecule detection which suggests that the comet solid ice materials have been previously subjected to ultraviolet radiation (as are interstellar grains) before aggregation into the comet; (3) the predicted dust to gas ratio.     

Chemical and biological evolution in space

Astronomical infrared spectra are used to confirm the existence of complex organic molecules produced by ultraviolet photoprocessing of interstellar grain mantles. This material is shown to be the major component of the interstellar grains between the sun and the galactic center and, by inference, constitutes more than 10 million solar masses — or close to one part in a thousand of the entire mass of the milky way galaxy. It may be demonstrated that the primitive chemistry of the earth's surface was dominated by these extraterrestrial molecules after aggregated into comets if the rate of comet impacts with the earth was comparable with that required to account for the extinction of species over the past 300 million years.

Ultraviolet irradiation of bacterial spores has been studied for the first time under simulated interstellar conditions. The inactivation time predicted for the less dense regions of space is at most several hundred years. Within molecukar clouds it is shown on theoretical and experimental grounds that this t the estimated cloud. However survival of spores during their initial exposure to the solar ultraviolet presents a problem for panspermia because it requires that in the process of ejection from the earth's surface they must be enclosed within a cocoon (or mantle) of ultraviolet absorbing material of 0.6 μm thickness. Thus, although panspermia can not be rejected on the basis of lack of interstellar survival there may remain insurmountable obstacles to its occuring because of the very special protective shield requirements during ejection from its planetary source.     

On the role of meteoritic impacts in the formation of organic molecules

It is suggested that the UV radiation, and shock and plasma phenomena which accompanied the hypervelocity impacts of solid bodies (meteorites and comets) onto the surface of the young Earth may have contributed to the synthesis of prebiotic organic molecules in the primitive atmosphere in a larger amount than was thought previously. The mechanisms responsible for this synthesis are discussed using information obtained from recent experimental and theoretical work on macroscopic hypervelocity impacts.     

Complex organics in meteorites.

Complex macromolecular organic matter is present in carbonaceous chondrites as the most abundant organic matter and may be present in interstellar dusts and comets. With this view, our studies of the complex organic matter isolated from six CM2 chondrites, namely Yamato-74662, Yamato-791198, Yamato-793321, Yamato-86720, Belgica-7904, and Murchison are introduced and discussed in the text. The complex organic matter is acid-insoluble and organic solvent-insoluble, and therefore, it was examined by heating experiments to obtain information on its chemical constituents and characteristics. Three chondrites, Yamato-74662, Yamato-791198, and Murchison which have solvent-extractable organic compounds, such as amino acids, carboxylic acid, hydrocarbons, etc. possess thermally labile organic fraction in the complex organic matter. Organic compounds detected in the pyrolyzate of the complex organic matter number over 130 of which aromatic hydrocarbons are dominant. They appeared around 300 degrees C, and disappeared at about 600 degrees C with a maximum at 400-500 degrees C during the heating. On the other hand, the other three chondrites do not have the extractable organic compounds nor a thermally labile organic fraction. The presence or absence of the fraction in the complex organic matter likely indicates the presence or absence of the solvent-extractable organic compounds and relates to thermal history of the chondrite.     

The formation of organic molecules in astronomical ices.

An absorption feature at 3.4 micrometers has been observed in various lines-of-sight through the diffuse interstellar medium. Its position and width lead to an identification with the C-H stretching mode of solid organic material. A possible mechanism for the production of organic solids in the interstellar medium is UV photoprocessing of icy mantles which accrete on dust grains in dense clouds. Furthermore, thermally induced reactions involving formaldehyde molecules in the mantles could be an important source of organics. Laboratory simulation of these processes shows that a large variety of oxygen- and nitrogen-rich species may be produced. It is shown that the occurrence of periodic transient heating events plays an important role in the production of organic material in the ice mantles. Finally, it is pointed out how future missions like the Infrared Space Observatory (ISO) as well as analysis of comet material by Rosetta may be able to clarify the nature and evolution of interstellar organics.     

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.