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PubMed1999

The composition of interstellar molecular clouds.

We consider four-aspects of interstellar chemistry for comparison with comets: molecular abundances in general, relative abundances of isomers (specifically, HCN and HNC), ortho/para ratios for molecules, and isotopic fractionation, particularly for the ratio hydrogen/deuterium. Since the environment in which the solar system formed is not well constrained, we consider both isolated dark clouds where low mass stars may form and the "hot cores" that are the sites of high mass star formation. Attention is concentrated on the gas phase, since the grains are considered elsewhere in this volume.

Astronomical Phenomena↗
PubMed1999

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↗
PubMed1999

Formation and processing of organics in the early solar system.

Until pristine samples can be returned from cometary nuclei, primitive meteorites represent our best source of information about organic chemistry in the early solar system. However, this material has been affected by secondary processing on asteroidal parent bodies which probably did not affect the material now present in cometary nuclei. Production of meteoritic organic matter apparently involved the following sequence of events: Molecule formation by a variety of reaction pathways in dense interstellar clouds; Condensation of those molecules onto refractory interstellar grains; Irradiation of organic-rich interstellar-grain mantles producing a range of molecular fragments and free radicals; Inclusion of those interstellar grains into the protosolar nebula with probable heating of at least some grain mantles during passage through the shock wave bounding the solar accretion disc; Agglomeration of residual interstellar grains and locally produced nebular condensates into asteroid-sized planetesimals; Heating of planetesimals by decay of extinct radionuclides; Melting of ice to produce liquid water within asteroidal bodies; Reaction of interstellar molecules, fragments and radicals with each other and with the aqueous environment, possibly catalysed by mineral grains; Loss of water and other volatiles to space yielding a partially hydrated lithology containing a complex suite of organic molecules; Heating of some of this organic matter to generate a kerogen-like complex; Mixing of heated and unheated material to yield the meteoritic material now observed. Properties of meteoritic organic matter believed to be consistent with this scenario include: Systematic decrease of abundance with increasing C number in homologous series of characterisable molecules; Complete structural diversity within homologous series; Predominance of branched-chain isomers; Considerable isotopic variability among characterisable molecules and within kerogen-like material; Substantial deuterium enrichment in all organic fractions; Some fractions significantly enriched in nitrogen-15; Modest excesses of L-enantiomers in some racemisation-resistant molecules but no general enantiomeric preference. Despite much speculation about the possible role of Fischer-Tropsch catalytic hydrogenation of CO in production of organic molecules in the solar nebula, no convincing evidence for such material has been found in meteorites. A similarity between some meteoritic organics and those produced by Miller-Urey discharge synthesis may reflect involvement of common intermediates rather than the operation of electric discharges in the early solar system. Meteoritic organic matter constitutes a useful, but not exact, guide to what we shall find with in situ analytical and sample-return missions to cometary nuclei.

Amino Acids↗
PubMed1999

Cometary deuterium.

Deuterium fractionations in cometary ices provide important clues to the origin and evolution of comets. Mass spectrometers aboard spaceprobe Giotto revealed the first accurate D/H ratios in the water of Comet 1P/Halley. Ground-based observations of HDO in Comets C/1996 B2 (Hyakutake) and C/1995 O1 (Hale-Bopp), the detection of DCN in Comet Hale-Bopp, and upper limits for several other D-bearing molecules complement our limited sample of D/H measurements. On the basis of this data set all Oort cloud comets seem to exhibit a similar (D/H)H2O ratio in H2O, enriched by about a factor of two relative to terrestrial water and approximately one order of magnitude relative to the protosolar value. Oort cloud comets, and by inference also classical short-period comets derived from the Kuiper Belt cannot be the only source for the Earth's oceans. The cometary O/C ratio and dynamical reasons make it difficult to defend an early influx of icy planetesimals from the Jupiter zone to the early Earth. D/H measurements of OH groups in phyllosilicate rich meteorites suggest a mixture of cometary water and water adsorbed from the nebula by the rocky grains that formed the bulk of the Earth may be responsible for the terrestrial D/H. The D/H ratio in cometary HCN is 7 times higher than the value in cometary H2O. Species-dependent D-fractionations occur at low temperatures and low gas densities via ion-molecule or grain-surface reactions and cannot be explained by a pure solar nebula chemistry. It is plausible that cometary volatiles preserved the interstellar D fractionation. The observed D abundances set a lower limit to the formation temperature of (30 +/- 10) K. Similar numbers can he derived from the ortho-to-para ratio in cometary water, from the absence of neon in cometary ices and the presence of S2. Noble gases on Earth and Mars, and the relative abundance of cometary hydrocarbons place the comet formation temperature near 50 K. So far all cometary D/H measurements refer to bulk compositions, and it is conceivable that significant departures from the mean value could occur at the grain-size level. Strong isotope effects as a result of coma chemistry can be excluded for molecules H2O and HCN. A comparison of the cometary (D/H)H2O ratio with values found in the atmospheres of the outer planets is consistent with the long-held idea that the gas planets formed around icy cores with a high cometary D/H ratio and subsequently accumulated significant amounts of H2 from the solar nebula with a low protosolar D/H.

Deuterium↗
PubMed1996

Comets, meteorites and atmospheres.

The relatively low value of Xe/Kr in the atmospheres of Earth and Mars seems to rule out meteorites as the major carriers of noble gases to the inner planets. Laboratory experiments on the trapping of gases in ice forming at low temperatures suggest that comets may be a better choice. It is then possible to develop a model for the origin of inner planet atmospheres based on volatiles delivered by comets added to volatiles originally trapped in planetary rocks. The model will be tested by results from the Galileo Entry Probe.

Argon↗
PubMed1996

The delivery of organic matter from asteroids and comets to the early surface of Mars.

Carbon delivered to the Earth by interplanetary dust particles may have been an important source of pre-biotic organic matter (Anders, 1989). Interplanetary dust is shown to deliver an order-of-magnitude higher surface concentration of carbon onto Mars than onto Earth, suggesting interplanetary dust may be an important source of carbon on Mars as well.

Carbon↗
PubMed1991

Isotopic analysis of cometary organic matter.

Carbon isotope ratios have been measured for CN in the coma of comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of 13C/12C values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus. The next decade should substantially improve our understanding of the distribution of C, H, N, and O isotopes in cometary organics. The isotopic composition of meteoritic organic matter is better understood and can serve as a useful analog for the cometary case.

Carbon↗
PubMed1993

Surficial geology of the Chicxulub impact crater, Yucatan, Mexico.

The Chicxulub impact crater in northwestern Yucatan, Mexico is the primary candidate for the proposed impact that caused mass extinctions at the end of the Cretaceous Period. The crater is buried by up to a kilometer of Tertiary sediment and the most prominent surface expression is a ring of sink holes, known locally as cenotes, mapped with Landsat imagery. This 165 +/- 5 km diameter Cenote Ring demarcates a boundary between unfractured limestones inside the ring, and fractured limestones outside. The boundary forms a barrier to lateral ground water migration, resulting in increased flows, dissolution, and collapse thus forming the cenotes. The subsurface geology indicates that the fracturing that created the Cenote Ring is related to slumping in the rim of the buried crater, differential thicknesses in the rocks overlying the crater, or solution collapse within porous impact deposits. The Cenote Ring provides the most accurate position of the Chicxulub crater's center, and the associated faults, fractures, and stratigraphy indicate that the crater may be approximately 240 km in diameter.

Earth, Planet↗
PubMed1988

Photochemical fractionation of 16O in the space medium modeled by resonance excitation of CO by H-Lyman alpha.

Inferences about the formation of primordial matter in our solar system rest on analysis of the earliest preserved materials in meteorites, of the structure of the solar system today, and of matter in evolving stellar systems elsewhere. The isotope distribution in meteorites suggests that molecular excitation processes similar to those observed today in circumstellar regions and dark interstellar clouds were operating in the early solar nebula. Laboratory model experiments together with these observations give evidence on the thermal state of the source medium from which refractory meteoritic dust formed. They indicate that resonance excitation of the broad isotopic bands of molecules such as 12C16O, MgO, O2, AlO, and OH by strong UV line sources such as H-L alpha, Mg II, H beta, and Ca II may induce selective reactions resulting in the anomalous isotopic composition of oxygen and possibly other elements in refractory oxide condensates in meteorites.

Carbon↗
PubMed1983

Chemical evolution and the origin of life: bibliography supplement 1981.

This bibliography is the twelfth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2 (1970), 225-295; 3 (1972), 293-304; 4 (1973), 309-329 and in Origins of Life 5 (1974), 505-527; 6 (1975), 285-300; 7 (1976), 75-85; 8 (1977), 59-66; 9 (1978), 67-74; 10 (1980), 69-87; 10 (1980), 379-404; 11 (1981), 273-288; 12 (1982), 93-118.

Amino Acids↗
PubMed1981

Chemical evolution and the origin of life: bibliography supplement 1979.

This bibliography is the tenth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2 (1970), 225-295; 3 (1972), 293-304; 4 (1973), 309-329 and in Origins of Life 5 (1974), 505-527; 6 (1975), 285-300; 7 (1976), 75-85; 8 (1977), 59-66; 9 (1978), 67-74; 10 (1980), 69-87; 10 (1980), 379-404.

Amino Acids↗
PubMed1994

The search for other planets: clues from the solar system.

Studies of element abundances and values of D/H in the atmospheres of the outer planets and Titan support a two-step model for the formation of these bodies. This model suggests that the dimensions of Uranus provide a good index for the sensitivity required to detect planets around other stars. The high proportion of N2 on the surfaces of Pluto and Triton indicates that this gas was the dominant reservoir of nitrogen in the early solar nebula. It should also be abundant on pristine comets. There is evidence that some of these comets may well have brought a large store of volatiles to the inner planets, while others were falling into the sun. In other systems, icy planetesimals falling into stars should reveal themselves through high values of D/H.

Astronomical Phenomena↗
PubMed1994

Possible consequences of absence of "Jupiters" in planetary systems.

The formation of the gas giant planets Jupiter and Saturn probably required the growth of massive approximately 15 Earth-mass cores on a time scale shorter than the approximately 10(7) time scale for removal of nebular gas. Relatively minor variations in nebular parameters could preclude the growth of full-size gas giants even in systems in which the terrestrial planet region is similar to our own. Systems containing "failed Jupiters," resembling Uranus and Neptune in their failure to capture much nebular gas, would be expected to contain more densely populated cometary source regions. They will also eject a smaller number of comets into interstellar space. If systems of this kind were the norm, observation of hyperbolic comets would be unexpected. Monte Carlo calculations of the orbital evolution of region of such systems (the Kuiper belt) indicate that throughout Earth history the cometary impact flux in their terrestrial planet regions would be approximately 1000 times greater than in our Solar System. It may be speculated that this could frustrate the evolution of organisms that observe and seek to understand their planetary system. For this reason our observation of these planets in our Solar System may tell us nothing about the probability of similar gas giants occurring in other planetary systems. This situation can be corrected by observation of an unbiased sample of planetary systems.

Astronomy↗
PubMed1995

Probing the structure of cometary ice.

Computer simulations of bulk and vapor deposited amorphous ices are presented. The structure of the bulk low density amorphous ice is in good agreement with experiments on pressure disordered amorphous ice. Both the low density bulk ice and the vapor deposited ices exhibit strong ordering. Vapor deposition of hot (300 K) water molecules onto a cold (77 K) substrate yields less porous ices than deposition of cold (77 K) water molecules onto a cold substrate. Both vapor deposited ices are more porous than the bulk amorphous ice. The structure of bulk high density amorphous ice is only in fair agreement with experimental results. Attempts to simulate high density amorphous ice via vapor deposition were not successful. Electron diffraction results on vapor deposited amorphous ice indicate that the temperature of the nucleation of the cubic phase depends upon the amount of time between the deposition and the onset of crystallization, suggesting that freshly deposited ice layers reconstruct on times of the order of hours. The temperature dependence of the microporosity of the vapor deposited amorphous ices might affect laboratory experiments that are aimed at simulating astrophysical ices in the context of the origin of prebiotic organic material and its transport to the Earth.

Computer Simulation↗
PubMed1995

Chirality and life.

The crucial role of homochirality and chiral homogeneity in the self-replication of contemporary biopolymers is emphasized, and the experimentally demonstrated advantages of these chirality attributes in simpler polymeric systems are summarized. The implausibility of life without chirality and hence of a biogenic scenario for the origin of chiral molecules is stressed, and chance and determinate abiotic mechanisms for the origin of chirality are reviewed briefly in the context of their potential viability on the primitive Earth. It is concluded that all such mechanisms would be nonviable, and that the turbulent prebiotic environment would require an ongoing extraterrestrial source for the accumulation of chiral molecules on the primitive Earth. A scenario is described wherein the circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae engenders asymmetric photolysis of the racemic constituents in the organic mantles on interstellar dust grains, whereupon these chiral constituents are transported repetitively to the primitive Earth by direct accretion of the interstellar dust or through impacts of comets and asteroids.

Adsorption↗
PubMed1993

Laboratory simulation of organic grain mantles.

The most relevant conditions in interstellar space for grain mantle evolution are being simulated at Laboratory Astrophysics. In particular we have photoproduced in the laboratory a material resembling the organic refractory mantle on interstellar grains. These organic refractory samples are being analyzed by several methods, and they have been found to consist of a very complex mixture of long chains, cross-linked and probably aromatic carbon molecules.

Ammonia↗
PubMed1995

Dust in the Universe: implications for terrestrial prebiotic chemistry.

In the present review we analyze the available literature on the distribution of dust in the Universe, methods of its observation and determination of the chemical composition, and the roles for terrestrial prebiotic chemistry. The most plausible natural sources of dust on the Earth in the prebiotic era are sedimentation of interplanetary dust, meteoritic and cometary impacts, volcanic eruptions, and soil microparticulates; the interplanetary medium being among the most powerful supplier of the dust matter. Two fundamental roles of dust particles for the origins of life are considered: (1) catalytic formation of prebiotic compounds; and (2) delivery of organic matter to the Earth by space dust particles. Due to the fact that there is only approximate information on the chemical composition and properties of interstellar, circumstellar, and major part of interplanetary dust, even the simulating experiments are difficult to perform. Until these gaps are filled, it seems reasonable to focus efforts of the scientists dealing with dust-driven catalytic formation of prebiotically important compounds on the volcanic and meteoritic/cometary impact environments.

Cosmic Dust↗
PubMed1985

Photochemical reactions in interstellar grains photolysis of CO, NH3, and H2O.

A simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH2:H2O gas mixture on an Al block at 10 K, with concomitant irradiation with vacuum UV. The residues were analyzed by GC-MS, HPLC, and near IR; a reaction pathway leading from NH3 to complex alcohol, fatty acid, and amide products in 27 stages is postulated. The astronomical relevance and significance of the observations are discussed.

Ammonia↗