Carbon isotope composition of individual amino acids in the Murchison meteorite

A significant portion of prebiotic organic matter on the early Earth may have been introduced by carbonaceous asteroids and comets. The distribution and stable-isotope composition of individual organic compounds in carbonaceous meteorites, which are thought to be derived from asteroidal parent bodies, may therefore provide important information concerning mechanistic pathways for prebiotic synthesis and the composition of organic matter on Earth before living systems developed. Previous studies have shown that meteorite amino acids are enriched in 13C relative to their terrestrial counterparts, but individual species were not distinguished. Here we report the 13C contents of individual amino acids in the Murchison meteorite. The amino acids are enriched in 13C, indicating an extraterrestrial origin. Alanine is not racemic, and the 13C enrichment of its D- and L-enantiomers implies that the excess of the L-enantiomer is indigenous rather than terrestrial contamination, suggesting that optically active materials were present in the early Solar System before life began.     

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.     

Amino acids from ultraviolet irradiation of interstellar ice analogues

Amino acids are the essential molecular components of living organisms on Earth, but the proposed mechanisms for their spontaneous generation have been unable to account for their presence in Earth's early history. The delivery of extraterrestrial organic compounds has been proposed as an alternative to generation on Earth, and some amino acids have been found in several meteorites. Here we report the detection of amino acids in the room-temperature residue of an interstellar ice analogue that was ultraviolet-irradiated in a high vacuum at 12 K. We identified 16 amino acids; the chiral ones showed enantiomeric separation. Some of the identified amino acids are also found in meteorites. Our results demonstrate that the spontaneous generation of amino acids in the interstellar medium is possible, supporting the suggestion that prebiotic molecules could have been delivered to the early Earth by cometary dust, meteorites or interplanetary dust particles.     

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.     

Extraterrestrial amino acids in Cretaceous/Tertiary boundary sediments at Stevns Klint, Denmark

Since the discovery nearly a decade ago that Cretaceous/Tertiary (K/T) boundary layers are greatly enriched in iridium, a rare element in the Earth's crust, there has been intense controversy on the relationship between this Ir anomaly and the massive extinction of organisms ranging from dinosaurs to marine plankton that characterizes the K/T boundary. Convincing evidence suggests that both the Ir spike and the extinction event were caused by the collision of a large bolide (greater than 10 km in diameter) with the Earth. Alternative explanations claim that extensive, violent volcanism can account for the Ir, and that other independent causes were responsible for the mass extinctions. We surmise that the collision of a massive extraterrestrial object with the Earth may have produced a unique organic chemical signature because certain meteorites, and probably comets, contain organic compounds which are either rare or non-existent on the Earth. In contrast, no organic compounds would be expected to be associated with volcanic processes. Here we find that K/T boundary sediments at Stevns Klint, Denmark, contain both alpha-amino-isobutyric acid [AIB,(CH3)2CNH2COOH] and racemic isovaline [ISOVAL, CH3CH2(CH3)CNH2COOH], two amino acids that are exceedingly rare on the Earth but which are major amino acids in carbonaceous chondrites. An extraterrestrial source is the most reasonable explanation for the presence of these amino acids.     

Ultraviolet-radiation-induced methane emissions from meteorites and the Martian atmosphere

Almost a decade after methane was first reported in the atmosphere of Mars there is an intensive discussion about both the reliability of the observations--particularly the suggested seasonal and latitudinal variations--and the sources of methane on Mars. Given that the lifetime of methane in the Martian atmosphere is limited, a process on or below the planet's surface would need to be continuously producing methane. A biological source would provide support for the potential existence of life on Mars, whereas a chemical origin would imply that there are unexpected geological processes. Methane release from carbonaceous meteorites associated with ablation during atmospheric entry is considered negligible. Here we show that methane is produced in much larger quantities from the Murchison meteorite (a type CM2 carbonaceous chondrite) when exposed to ultraviolet radiation under conditions similar to those expected at the Martian surface. Meteorites containing several per cent of intact organic matter reach the Martian surface at high rates, and our experiments suggest that a significant fraction of the organic matter accessible to ultraviolet radiation is converted to methane. Ultraviolet-radiation-induced methane formation from meteorites could explain a substantial fraction of the most recently estimated atmospheric methane mixing ratios. Stable hydrogen isotope analysis unambiguously confirms that the methane released from Murchison is of extraterrestrial origin. The stable carbon isotope composition, in contrast, is similar to that of terrestrial microbial origin; hence, measurements of this signature in future Mars missions may not enable an unambiguous identification of biogenic methane.     

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.     

Comet dust as a source of amino acids at the Cretaceous/Tertiary boundary

Large amounts of apparently extraterrestrial amino acids have been detected recently in rocks at the Cretaceous/Tertiary (K/T) boundary at Stevns Klint, Denmark. The amino acids were found a few tens of centimetres above and below the boundary layer, but were absent in the boundary clay itself. If one supposes that these compounds were carried to the Earth by the giant meteorite thought to have impacted at the end of the Cretaceous, some puzzling questions are raised: why weren't the amino acids incinerated in the impact, and why are they not present in the boundary clay itself? Here we suggest that the amino acids were actually deposited with the dust from a giant comet trapped in the inner Solar System, a fragment of which comprised the K/T impactor. Amino acids or their precursors in the comet dust would have been swept up by the Earth both before and after the impact, but any conveyed by the impactor itself would have been destroyed. The observed amino acid layers would thus have been deposited without an impact.     

Amino-acid synthesis in carbonaceous meteorites by aqueous alteration of polycyclic aromatic hydrocarbons

It has been suggested that amino acids and other organic compounds found in carbonaceous meteorites formed by aqueous alteration in the meteorite parent bodies. Observations of carbonaceous material in interstellar grains and interplanetary dust particles indicate that condensed organic compounds may have been present in meteorite parent bodies at the time of aqueous alteration. One group of compounds thought to be representative of this carbonaceous material is the polycyclic aromatic hydrocarbons (PAHs). Recently it was proposed that PAHs condense on SiC grains in the molecular envelopes of carbon-rich red-giant stars, which would allow for their subsequent incorporation into meteorite parent bodies during accretion. This incorporation mechanism is supported by the identification of SiC grains in carbonaceous chondrites. The possibility therefore exists that PAHs, and/or other condensed organic compounds, represent the starting material for aqueous alteration which leads to the formation of amino acids and other water-soluble organic compounds. Here we present calculations of the distribution of aqueous organic compounds in metastable equilibrium with representative PAHs as functions of the fugacities of O2, CO2 and NH3. The results reported here for pyrene and fluoranthene, two PAHs with different structures but the same stoichiometry, differ greatly but indicate that the formation of amino and carboxylic acids is energetically favourable at probable parent-body alteration conditions. The actual reaction mechanisms involved could be revealed by consideration of isotope data for PAHs, amino acids, other organic compounds and carbonates in carbonaceous chondrites.     

Efficient delivery of meteorites to the Earth from a wide range of asteroid parent bodies

Almost all meteorites come from asteroids, but identifying their specific parent bodies, and modelling their transport to the Earth, has proved to be difficult. The usual model of delivery through orbital resonances with the major planets has recently been shown to deplete the supply of meteorites much too rapidly to explain either the observed flux at the Earth, or the length of time the meteorites have spent in space (as measured by cosmic-ray exposure ages). Independently, it has been found that a force arising from anisotropically emitted thermal radiation from asteroidal fragments (the 'Yarkovsky effect') influences the fragments' orbits in important ways. Here we report the results of a detailed model for the transport of meteorites to the Earth, which includes the Yarkovsky effect and collisional evolution of the asteroidal fragments. We find that the Yarkovsky effect significantly increases the efficiency of the delivery of meteorites to the Earth, while at the same time allowing a much wider range of asteroids to contribute to the flux of meteorites. Our model also reproduces the observed distribution of cosmic-ray exposure ages of stony meteorites.     

Submarine hot springs and the origin of life

The discovery of hydrothermal vents at oceanic ridge crests and the appreciation of their importance in the element balance of the oceans is one of the main recent advances in marine geochemistry. It is likely that vents were present in the oceans of the primitive Earth because the process of hydrothermal circulation probably began early in the Earth's history. Here we examine the popular hypothesis that life arose in these vents. This proposal, however, is based on a number of misunderstandings concerning the organic chemistry involved. An example is the suggestion that organic compounds were destroyed on the surface of the early Earth by the impact of asteroids and comets, but at the same time assuming that organic syntheses can occur in hydrothermal vents. The high temperatures in the vents would not allow synthesis of organic compounds, but would decompose them, unless the exposure time at vent temperatures was short. Even if the essential organic molecules were available in the hot hydrothermal waters, the subsequent steps of polymerization and the conversion of these polymers into the first organisms would not occur as the vent waters were quenched to the colder temperatures of the primitive oceans.     

A hydrogen-based subsurface microbial community dominated by methanogens.

The search for extraterrestrial life may be facilitated if ecosystems can be found on Earth that exist under conditions analogous to those present on other planets or moons. It has been proposed, on the basis of geochemical and thermodynamic considerations, that geologically derived hydrogen might support subsurface microbial communities on Mars and Europa in which methanogens form the base of the ecosystem. Here we describe a unique subsurface microbial community in which hydrogen-consuming, methane-producing Archaea far outnumber the Bacteria. More than 90% of the 16S ribosomal DNA sequences recovered from hydrothermal waters circulating through deeply buried igneous rocks in Idaho are related to hydrogen-using methanogenic microorganisms. Geochemical characterization indicates that geothermal hydrogen, not organic carbon, is the primary energy source for this methanogen-dominated microbial community. These results demonstrate that hydrogen-based methanogenic communities do occur in Earth's subsurface, providing an analogue for possible subsurface microbial ecosystems on other planets.     

Where are the dolphins?

Interest in extraterrestrial life has tended to focus on a search for extrasolar planets similar to the Earth. But what of forms of intelligent life that are very different from those found on Earth? Some features of life will not be peculiar to our planet, and alien life will resemble ours in such universals. But if intelligent, non-humanoid aliens exist, where might they be? Would they wish to visit Earth and would we know if they did?     

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.     

A search for life on Earth from the Galileo spacecraft

In its December 1990 fly-by of Earth, the Galileo spacecraft found evidence of abundant gaseous oxygen, a widely distributed surface pigment with a sharp absorption edge in the red part of the visible spectrum, and atmospheric methane in extreme thermodynamic disequilibrium; together, these are strongly suggestive of life on Earth. Moreover, the presence of narrow-band, pulsed, amplitude-modulated radio transmission seems uniquely attributable to intelligence. These observations constitute a control experiment for the serach for extraterrestrial life by modern interplanetary spacecraft.     

Emergence of life——how and where? -An update based on recent ideas

Panspermic origins notwithstanding, life, assuming that it started on Earth, may have taken root as soon as it became geologically permissible. There are multiple possibilities for early biogenesis from complex inorganic/organic geochemistry at diverse geological niches. Recent theoretical calculations have revived the possibility of Earth having a rather reduced early atmosphere, and had refueled arguments for a surface origin of life. Laboratory modeling of possible prebiotic RNA polymerization has seen interesting experimental advances, although a plausible replicator-like molecule has not yet been produced. The hydrothermal origin school of thought has also seen an interesting postulation for life's early emergence and evolution—within contiguous, porous hydrothermal iron-sulfide (FeS) compartments, leading to a non-free living last universal common ancestor (LUCA). A confined LUCA evolving later into free-living archaebacteria and eubacteria could potentially reconcile some problems of molecular divergence between these two kingdoms. There are, however, many unresolved problems, and experimental evidence for such a scheme is lacking. Here, recent updates and refinements to the mainstay hypotheses for the emergence of life on Earth are reviewed and discussed.     

Isotopic homogeneity of iron in the early solar nebula.

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.     

Iron meteorites as remnants of planetesimals formed in the terrestrial planet region

Iron meteorites are core fragments from differentiated and subsequently disrupted planetesimals. The parent bodies are usually assumed to have formed in the main asteroid belt, which is the source of most meteorites. Observational evidence, however, does not indicate that differentiated bodies or their fragments were ever common there. This view is also difficult to reconcile with the fact that the parent bodies of iron meteorites were as small as 20 km in diameter and that they formed 1-2 Myr earlier than the parent bodies of the ordinary chondrites. Here we show that the iron-meteorite parent bodies most probably formed in the terrestrial planet region. Fast accretion times there allowed small planetesimals to melt early in Solar System history by the decay of short-lived radionuclides (such as 26Al, 60Fe). The protoplanets emerging from this population not only induced collisional evolution among the remaining planetesimals but also scattered some of the survivors into the main belt, where they stayed for billions of years before escaping via a combination of collisions, Yarkovsky thermal forces, and resonances. We predict that some asteroids are main-belt interlopers (such as (4) Vesta). A select few may even be remnants of the long-lost precursor material that formed the Earth.     

The evolution of the marine phosphate reservoir

Phosphorus is a biolimiting nutrient that has an important role in regulating the burial of organic matter and the redox state of the ocean-atmosphere system. The ratio of phosphorus to iron in iron-oxide-rich sedimentary rocks can be used to track dissolved phosphate concentrations if the dissolved silica concentration of sea water is estimated. Here we present iron and phosphorus concentration ratios from distal hydrothermal sediments and iron formations through time to study the evolution of the marine phosphate reservoir. The data suggest that phosphate concentrations have been relatively constant over the Phanerozoic eon, the past 542 million years (Myr) of Earth's history. In contrast, phosphate concentrations seem to have been elevated in Precambrian oceans. Specifically, there is a peak in phosphorus-to-iron ratios in Neoproterozoic iron formations dating from ～750 to ～635?Myr ago, indicating unusually high dissolved phosphate concentrations in the aftermath of widespread, low-latitude 'snowball Earth' glaciations. An enhanced postglacial phosphate flux would have caused high rates of primary productivity and organic carbon burial and a transition to more oxidizing conditions in the ocean and atmosphere. The snowball Earth glaciations and Neoproterozoic oxidation are both suggested as triggers for the evolution and radiation of metazoans. We propose that these two factors are intimately linked; a glacially induced nutrient surplus could have led to an increase in atmospheric oxygen, paving the way for the rise of metazoan life.     

5-木糖酯类衍生物的合成及其卷烟加香应用

 为了开发新型烟用香料,将各种挥发性香味酸做成糖酯添加到卷烟中,并对其卷烟加香效果进行评价。本文以1,2-O-丙叉基-?琢-D-呋喃木糖和一系列具有香味的有机酸为原料,无水碳酸钠和4-二甲氨基吡啶（4-DMAP）为催化剂,N,N'-二环己基碳二亚胺（DCC）为缩合剂,经过酯化反应合成出15种5-木糖酯类衍生物,其中13种化合物为新化合物。所有化合物结构均经IR、1H NMR、MS和元素分析得到确证。该15种化合物的卷烟加香实验结果表明,加入各糖酯前体的卷烟评吸结果与对照卷烟相比,均可使香气质改善,香气量增加,达到烟香协调、余味净化、杂气减轻的效果。故合成的5-木糖酯可以作为香原料应用到卷烟中。。