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Identification of two sources of carbon monoxide in comet Hale-Bopp.

The composition of ices in comets may reflect that of the molecular cloud in which the Sun formed, or it may show evidence of chemical processing in the pre-planetary accretion disk around the proto-Sun. As carbon monoxide (CO) is ubiquitous in molecular clouds, its abundance with respect to water could help to determine the degree to which pre-cometary material was processed, although variations in CO abundance may also be influenced by the distance from the Sun at which comets formed. Observations have not hitherto provided an unambiguous measure of CO in the cometary ice (native CO). Evidence for an extended source of CO associated with comet Halley was provided by the Giotto spacecraft, but alternative interpretations exist. Here we report observations of comet Hale-Bopp which show that about half of the CO in the comet comes directly from ice stored in the nucleus. The abundance of this CO with respect to water (12 per cent) is smaller than in quiescent regions of molecular clouds, but is consistent with that measured in proto-stellar envelopes, suggesting that the ices underwent some processing before their inclusion into Hale-Bopp. The remaining CO arises in the coma, probably through thermal destruction of more complex molecules.

Carbon Monoxide↗

Unaltered cosmic spherules in a 1.4-Gyr-old sandstone from Finland.

Micrometeorites-submillimetre-sized particles derived from asteroids and comets-occur in significant quantities in deep sea sediments, and the ice sheets of Greenland and Antarctica. The most abundant micrometeorites are cosmic spherules, which contain nickel-rich spinels that were crystallized and oxidized during atmospheric entry, therefore recording the oxygen content in the uppermost atmosphere. But the use of micrometeorites for detecting past changes in the flux of incoming extraterrestrial matter, and as probes of the evolution of the atmosphere, has been hampered by the fact that most objects with depositional ages higher than 0.5 Myr show severe chemical alteration. Here we report the discovery of unaltered cosmic spherules in a 1.4-Gyr-old sandstone (red bed) from Finland. From this we infer that red beds, a common lithology in the Earth's history, may contain substantial unbiased populations of fossil micrometeorites. The study of such populations would allow systematic research on variations in the micrometeorite flux from the early Proterozoic era to recent times (a time span of about 2.5 Gyr), and could help to better constrain the time when the atmospheric oxygen content was raised to its present level.

Earth, Planet↗

Early Solar System aqueous activity: Sr isotope evidence from the Orgueil CI meteorite.

The CI meteorites are rare but important objects because they may represent our best sample of chemically unfractionated Solar System material. Despite the fact the these meteorites apparently retain their original chemical composition, they clearly contain secondary mineral phases, some at least believed to have been produced through the action of liquid water on the parent body. The timing of this event, however, was unknown. In an attempt to solve this problem, we have measured the Sr isotopic composition and 87Rb/86Sr in carbonates and sulphate separated from the Orgueil meteorite. Both of these phases probably precipitated from aqueous solution. Our first results, reported here, show that carbonate deposition occurred contemporaneously with parent body formation or shortly after it probably within 100 Myr. On the other hand, at least some of the calcium sulphate seems to have been formed recently.

Calcium Sulfate↗

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite.

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.

Carbon Dioxide↗

Chemical processing in the coma as the source of cometary HNC.

The discovery of hydrogen isocyanide (HNC) in comet Hyakutake with an abundance (relative to hydrogen cyanide, HCN) similar to that seen in dense interstellar clouds raised the possibility that these molecules might be surviving interstellar material. The preservation of material from the Sun's parent molecular cloud would provide important constraints on the processes that took place in the protostellar nebula. But another possibility is that HNC is produced by photochemical processes in the coma, which means that its abundance could not be used as a direct constraint on conditions in the early Solar System. Here we show that the HNC/HCN ratio determined for comet Hale-Bopp varied with heliocentric distance in a way that matches the predictions of models of gas-phase chemical production of HNC in the coma, but cannot be explained if the HNC molecules were coming from the comet's nucleus. We conclude that HNC forms mainly by chemical reactions in the coma, and that such reactions need to be considered when attempting to deduce the composition of the nucleus from observations of the coma.

Cyanates↗

Chemical effects of large impacts on the Earth's primitive atmosphere.

Intense bombardment of the moon and terrestrial planets approximately 3.9-4.0 x 10(9) years ago could have caused the chemical reprocessing of the Earth's primitive atmosphere. In particular, the shock heating and rapid quenching caused by the impact of large bodies into the atmosphere could produce molecules such as HCN and H2CO4 which are important precursors for the abiotic synthesis of complex organic molecules. Here we model the production of HCN and H2CO by thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures and initial compositions. For atmospheres with C/O > or = 1, our results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10(-3) to 10(-5) in the impact region and global average ratios of 10(-5) to 10(-12). The corresponding H2CO mixing ratios in the impact region are 10(-7) to 10(-9); no-global mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15% of the HCN produced can provide approximately (3-14) x 10(11) mol HCN per year. This is somewhat larger than other predicted sources of HCN and H2CO on the primitive Earth.

Atmosphere↗

Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite.

Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.

Amino Acids↗

Impact frustration of the origin of life.

One possible definition for the origin of life on Earth is the time at which the interval between devastating environmental insults by impact exceeded the timescale for establishing self-replicating proto-organisms. A quantitative relationship for the Hadean (pre-3,800 Myr ago) and Early Archean (3,800 to 3,400 Myr) impact flux can be derived from the lunar and terrestrial impact records. Also, the effects of impact-related processes on the various environments proposed for abiogenesis (the development of life through chemical evolution from inorganic materials) can be estimated. Using a range of plausible values for the timescale for abiogenesis, the interval in time when life might first have bootstrapped itself into existence can be found for each environment. We find that if the deep marine hydrothermal setting provided a suitable site, abiogenesis could have happened as early as 4,000 to 4,200 Myr ago, whereas at the surface of the Earth abiogenesis could have occurred between 3,700 and 4,000 Myr.

Earth, Planet↗

The nature and origin of interstellar diamond.

Microscopic diamond was recently discovered in oxidized acid residues from several carbonaceous chondrite meteorites (for example, the C delta component of the Allende meteorite). Some of the reported properties of C delta seem in conflict with those expected of diamond. Here we present high spatial resolution analytical data which may help to explain such results. The C delta diamond is an extremely fine-grained (0.5-10 nm) single-phase material, but surface and interfacial carbon atoms, which may comprise as much as 25% of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the interstellar medium although a low-pressure mechanism of formation cannot be ruled out.

Carbon↗

S-process krypton of variable isotopic composition in the Murchison meteorite.

Current theories on the origin of the chemical elements explain the abundance of medium-heavy and heavy nuclides to be due to the capture by pre-existing lighter nuclides of free neutrons on either a slow timescale (s-process) or a rapid timescale (r-process). Experimental evidence in support of these theories comes from the analysis of carbonaceous chondrites. In acid-resistant residues of these meteorites a kind of xenon has been found, the isotopic composition of which matches almost perfectly that predicted for s-process xenon. We report data that allow us, for the first time, to derive with reasonable precision the full isotopic spectrum of s-process krypton as well. We show that this s-Kr in a residue from Murchison meteorite did not originate in one single s-process but rather is a mixture of contributions from stellar environments where the density of free neutrons was not the same. The astrophysical conditions under which this Krypton has been produced were distinct from those that have been invoked to explain the Solar System s-process abundance. Similar to the 13C-rich carbon component in an aliquot of the same residue, the s-process Kr from different astrophysical sites has retained its identity during the accumulation and subsequent history of the meteorite.

Extraterrestrial Environment↗

Pre-biotic organic matter from comets and asteroids.

Several authors have suggested that comets or carbonaceous asteroids contributed large amounts of organic matter to the primitive Earth, and thus possibly played a vital role in the origin of life. But organic matter cannot survive the extremely high temperatures (>10(4) K) reached on impact, which atomize the projectile and break all chemical bonds. Only fragments small enough to be gently decelerated by the atmosphere--principally meteors of 10(-12)-10(-6) g--can deliver their organic matter intact. The amount of such 'soft-landed' organic carbon can be estimated from data for the infall rate of meteoritic matter. At present rates, only approximately 0.006 g cm-2 intact organic carbon would accumulate in 10(8) yr, but at the higher rates of approximately 4 x 10(9) yr ago, about 20 g cm-2 may have accumulated in the few hundred million years between the last cataclysmic impact and the beginning of life. It may have included some biologically important compounds that did not form by abiotic synthesis on Earth.

Atmosphere↗