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.     

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-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.     

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.     

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth.

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.     

Riverine export of aged terrestrial organic matter to the North Atlantic Ocean

Global riverine discharge of organic matter represents a substantial source of terrestrial dissolved and particulate organic carbon to the oceans. This input from rivers is, by itself, more than large enough to account for the apparent steady-state replacement times of 4,00-6,000 yr for oceanic dissolved organic carbon. But paradoxically, terrestrial organic matter, derived from land plants, is not detected in seawater and sediments in quantities that correspond to its inputs. Here we present natural 14C and 13C data from four rivers that discharge to the western North Atlantic Ocean and find that these rivers are sources of old (14C-depleted) and young (14C-enriched) terrestrial dissolved organic carbon, and of predominantly old terrestrial particulate organic carbon. These findings contrast with limited earlier data that suggested terrestrial organic matter transported by rivers might be generally enriched in 14C from nuclear testing, and hence newly produced. We also find that much of the young dissolved organic carbon can be selectively degraded over the residence times of river and coastal waters, leaving an even older and more refractory component for oceanic export. Thus, pre-ageing and degradation may alter significantly the structure, distributions and quantities of terrestrial organic matter before its delivery to the oceans.     

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.     

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.     

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.     

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.     

Geochemical evidence for terrestrial ecosystems 2.6 billion years ago

Microorganisms have flourished in the oceans since at least 3.8 billion years (3.8 Gyr) ago, but it is not at present clear when they first colonized the land. Organic matter in some Au/U-rich conglomerates and ancient soils of 2.3-2.7 Gyr age has been suggested as remnants of terrestrial organisms. Some 2.7-Gyr-old stromatolites have also been suggested as structures created by terrestrial organisms. However, it has been disputed whether this organic matter is indigenous or exogenic, and whether these stromatolites formed in marine or fresh water. Consequently, the oldest undisputed remnants of terrestrial organisms are currently the 1.2-Gyr-old microfossils from Arizona, USA. Unusually carbonaceous ancient soils--palaeosols--have been found in the Mpumalanga Province (Eastern Transvaal) of South Africa. Here we report the occurrences, elemental ratios (C, H, N, P) and isotopic compositions of this organic matter and its host rocks. These data show that the organic matter very probably represents remnants of microbial mats that developed on the soil surface between 2.6 and 2.7 Gyr ago. This places the development of terrestrial biomass more than 1.4 billion years earlier than previously reported.     

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.     

Whole-lake carbon-13 additions reveal terrestrial support of aquatic food webs

Ecosystems are supported by organic carbon from two distinct sources. Endogenous carbon is produced by photosynthesis within an ecosystem by autotrophic organisms. Exogenous carbon is produced elsewhere and transported into ecosystems. Consumers may use exogenous carbon with consequent influences on population dynamics, predator-prey relationships and ecosystem processes. For example, exogenous inputs provide resources that may enhance consumer abundance beyond levels supported by within-system primary production. Exogenous fluxes of organic carbon to ecosystems are often large, but this material is recalcitrant and difficult to assimilate, in contrast to endogenously produced organic matter, which is used more easily. Here we show, by the experimental manipulation of dissolved inorganic (13)C in two lakes, that internal primary production is insufficient to support the food webs of these ecosystems. Additions of NaH(13)CO(3) enriched the (13)C content of dissolved inorganic carbon, particulate organic carbon, zooplankton and fish. Dynamics of (13)C indicate that 40-55% of particulate organic carbon and 22-50% of zooplankton carbon are derived from terrestrial sources, showing that there is significant subsidy of these ecosystems by organic carbon produced outside their boundaries.     

新疆胜利和田探区南部下二叠统烃源岩的有机地化研究

以下二叠统克孜里奇曼组（P1k)海相碳酸盐岩为主要研究对象,对新疆胜利和田探区南部的石炭－二叠系海相烃源岩开展了系统研究。有机岩石学分析表明,该套烃源岩具有陆源和海相有机质双重输入的特点,有机质呈现偏腐殖的特征,干酪根以Ⅲ,Ⅱ型为主,与碳酸盐岩通常具有的较好有机质类型存在一定差别。有机地化分析也支持上述结论,并且指示出沉积环境并非严格的强还原环境。分析认为造成有机质类型较差的原因主要有3种,即陆源有机质输入、宏观藻类的贡献以及沉积环境充氧造成的有机质氧化。根据以上有机岩石学和有机地化分析的结果,结合碳酸盐岩孔隙度低,排烃较晚的特点,确定该套烃源岩以生成轻质烃类为主。塔西南地区广泛发育有石炭－二叠系海相碳酸盐岩沉积,该套气源岩对于区内天然气的勘探具有一定的石油地质意义。     

A light carbon reservoir recorded in zircon-hosted diamond from the Jack Hills

The recent discovery of diamond-graphite inclusions in the Earth's oldest zircon grains (formed up to 4,252 Myr ago) from the Jack Hills metasediments in Western Australia provides a unique opportunity to investigate Earth's earliest known carbon reservoir. Here we report ion microprobe analyses of the carbon isotope composition of these diamond-graphite inclusions. The observed delta(13)C(PDB) values (expressed using the PeeDee Belemnite standard) range between -5 per mil and -58 per mil with a median of -31 per mil. This extends beyond typical mantle values of around -6 per mil to values observed in metamorphic and some eclogitic diamonds that are interpreted to reflect deep subduction of low-delta(13)C(PDB) biogenic surface carbon. Low delta(13)C(PDB) values may also be produced by inorganic chemical reactions, and therefore are not unambiguous evidence for life on Earth as early as 4,250 Myr ago. Regardless, our results suggest that a low-delta(13)C(PDB) reservoir may have existed on the early Earth.     

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.     

RNA evolution and the origins of life

The evolution of RNA is likely to have played an important role in the very early history of life on Earth but it is doubtful that life began with RNA. Consideration of what came before RNA must take into account relevant information from geochemistry, prebiotic chemistry and nucleic acid biochemistry.     

Photosynthetic microbial mats in the 3,416-Myr-old ocean

Recent re-evaluations of the geological record of the earliest life on Earth have led to the suggestion that some of the oldest putative microfossils and carbonaceous matter were formed through abiotic hydrothermal processes. Similarly, many early Archaean (more than 3,400-Myr-old) cherts have been reinterpreted as hydrothermal deposits rather than products of normal marine sedimentary processes. Here we present the results of a field, petrographic and geochemical study testing these hypotheses for the 3,416-Myr-old Buck Reef Chert, South Africa. From sedimentary structures and distributions of sand and mud, we infer that deposition occurred in normal open shallow to deep marine environments. The siderite enrichment that we observe in deep-water sediments is consistent with a stratified early ocean. We show that most carbonaceous matter was formed by photosynthetic mats within the euphotic zone and distributed as detrital matter by waves and currents to surrounding environments. We find no evidence that hydrothermal processes had any direct role in the deposition of either the carbonaceous matter or the enclosing sediments. Instead, we conclude that photosynthetic organisms had evolved and were living in a stratified ocean supersaturated in dissolved silica 3,416 Myr ago.     

Chlorine isotope homogeneity of the mantle, crust and carbonaceous chondrites

Chlorine in the Earth is highly depleted relative to carbonaceous chondrites and solar abundances. Knowledge of the Cl concentrations and distribution on Earth is essential for understanding the origin of these depletions. Large differences in the stable chlorine isotope ratios of meteoritic, mantle and crustal materials have been used as evidence for distinct reservoirs in the solar nebula and to calculate the relative proportions of Cl in the mantle and crust. Here we report that large isotopic differences do not exist, and that carbonaceous chondrites, mantle and crust all have the same 37Cl/35Cl ratios. We have further analysed crustal sediments from the early Archaean era to the Recent epoch and find no systematic isotopic variations with age, demonstrating that the mantle and crust have always had the same delta37Cl value. The similarity of mantle, crust and carbonaceous chondrites establishes that there were no nebular reservoirs with distinct isotopic compositions, no isotopic fractionation during differentiation of the Earth and no late (post-core formation) Cl-bearing volatile additions to the crustal veneer with a unique isotopic composition.