The Strecker synthesis as a source of amino acids in carbonaceous chondrites: deuterium retention during synthesis

Deuterium-enriched amino acids occur in the Murchison carbonaceous chondrite. Synthesis from D-enriched interstellar precursors by Strecker reactions during aqueous alteration of the parent body has been proposed. To test this hypothesis, we have measured the retention of deuterium in amino acids produced from HCN, NH3, and formaldehyde-D2, acetaldehyde-D4, and acetone-D6 in H2O. The isotopic label is 50% to 98% retained, with variations in retentivity depending on the amino acid and the reaction conditions. If amino acids, once formed on the parent body by the Strecker synthesis, lose no deuterium by subsequent exchange with water or H-bearing minerals, then the observed deuterium isotopic composition of Murchison amino acids represents as much as 50% or more of the enrichments inherited from their interstellar precursors. Imino diacids are prominent side products of the Strecker synthesis which have not been reported in carbonaceous chondrites. Under the conditions of the Strecker reaction using deuterium labeled aldehydes and ketones, unlabeled amino acids are also formed by an HCN polymerization route indicating multiple pathways for the synthesis of amino acids in meteorites.     

Iminodicarboxylic acids in the Murchison meteorite: Evidence of Strecker reactions

α-Amino acids and α-hydroxy acids are well known constituents of several carbonaceous meteorites. One proposed mechanism of their formation is the reactions of CN⁻, NH₃, aldehydes and ketones in aqueous solution, a Strecker-like synthesis. Iminodicarboxylic acids, relatively unusual in molecular structure, are significant by-products of laboratory Strecker syntheses of α-amino acids. It is therefore notable that an analogous suite of imino acids has not been reported in CM2 chondrites where amino and hydroxy acids are abundant. In this work, aqueous extracts of the Murchison meteorite were examined for the presence of imino acids; GC-MS and HPLC molecular analyses revealed a complex suite of such acids. With the exception of one of the seven-carbon members, all of the C4 through C7 imino acids were observed in Murchison. These observations suggest that the Strecker synthesis made, at least, some contribution to the formation of extraterrestrial amino acids.     

Molecular and compound-specific isotopic characterization of monocarboxylic acids in carbonaceous meteorites

Low molecular weight monocarboxylic acids are the most abundant water soluble organic compounds in the Murchison and many other CM type carbonaceous chondrites. In this study, we examined the monocarboxylic acids in Murchison and EET96029.20 carbonaceous meteorites using a new sample preparation and introduction technique for gas chromatograph recently developed for volatile, water-soluble organic compounds: solid phase micro-extraction (SPME). We identified more than 50 monocarboxylic acids from Murchison compared with the 18 compounds reported previously. Formic acid, a known interstellar molecule, has been fully analyzed in these carbonaceous meteorites, with its δD value suggesting an interstellar origin. We determined both carbon and hydrogen isotopic ratios of individual monocarboxylic acids in Murchison, to better define the origins and genetic relationships of these compounds. The compound-specific isotopic data reveal a large enrichment in ¹³C (δ¹³C up to + 32.5‰) and particularly D (δD up to + 2024‰). The branched acids are substantially enriched in both ¹³C and D relative to the straight chain acids, with those branched acids containing a quaternary carbon showing the greatest isotopic enrichment. The isotopic difference may be attributed to variations in the different synthetic regimes or terrestrial input of straight chain acids.     

A comparative study of the hydroxy acids from the Murchison, GRA 95229 and LAP 02342 meteorites

The hydroxy acid suites extracted from the Murchison (MN), GRA 95229 (GRA) and LAP 02342 (LAP) meteorites have been investigated for their molecular, chiral and isotopic composition. Substantial amounts of the compounds have been detected in all three meteorites, with a total abundance that is lower than that of the amino acids in the same stones. Overall, their molecular distributions mirror closely that of the corresponding amino acids and most evidently so for the LAP meteorite. A surprising l-lactic acid enantiomeric excess was found present in all three stones, which cannot be easily accounted by terrestrial contamination; all other compounds of the three hydroxy acid suites were found racemic. The branched-chain five carbon and the diastereomer six-carbon hydroxy acids were also studied vis-a-vis the corresponding amino acids and calculated ab initio thermodynamic data, with the comparison allowing the suggestion that meteoritic hydroxyacid at these chain lengths formed under thermodynamic control and, possibly, at a later stage than the corresponding amino acids. ¹³C and D isotopic enrichments were detected for many of the meteoritic hydroxy acids and found to vary between molecular species with trends that also appear to correlate to those of amino acids; the highest δD value (+3450‰) was displayed by GRA 2-OH-2-methylbutyric acid. The data suggest that, while the amino- and hydroxy acids likely relate to common presolar precursor, their final distribution in meteorites was determined to large extent by the overall composition of the environments that saw their formation, with ammonia being the determining factor in their final abundance ratios.     

Primitive Earth environments: organic syntheses and the origin and early evolution of life

The Precambrian is the longest and least understood period in the history of our planet. There is no direct evidence which bears on the primitive Earth environment, the synthesis of organic compounds and the origin of life on our planet, since the geological record only goes back to 3.8 Ga ago. To overcome this deficiency it is necessary to extrapolate backwards from 3.8 Ga ago to the time when the Earth was formed, 4.6 Ga ago, and also make use of additional scientific approaches. These include models of the solar nebula and planet formation, comparative observations with other cosmic environments, and experimental simulation studies under plausible primitive Earth conditions, particularly in regard to the prebiological synthesis of organic compounds. A large number of interstellar organic molecules have been detected by radioastronomy in the interstellar medium, particularly in places where other solar systems may be in the process of formation. It is remarkable that 10 of these molecules are known to be the precursors of the most important biochemical monomers. Furthermore, some of these monomers, e.g., amino acids, purines and pyrimidines, have also been detected in carbonaceous chondrites, which were presumably synthesized on the parent bodies of the meteorites or possibly in the solar nebula. Comparative studies on the terrestrial planets indicate that their primitive atmospheres resulted primarily from outgassing of CO₂ and other partially oxidized (CO, N₂) and reduced (H₂, CH₄, NH₃, H₂S) volatiles. Furthermore, comets and meteorites are thought to have made a significant contribution to the reduced carbon precursors for the prebiological synthesis of biochemical compounds. A brief review of the experiments carried out in the laboratory under possible primitive Earth conditions shows that amino acids, purines, pyrimidines, monosaccharides, fatty acids and other compounds are readily obtained using different energy sources. However, the formation of oligopeptides, oligonucleotides and phospholipids requires more restrictive conditions. They have been synthesized by means of condensing agents, such as cyanamide, as well as by heating under relatively dry conditions of less than 100°C. Experiments have been carried out on the formation of liposomes from prebiotically synthesized phospholipids. Also, using 2-methylimidazolide derivatives of nucleotides, the template directed synthesis of polynucleotides has been demonstrated. In the latter experiments a high fidelity of complementary base pairing has been observed, which if further improved would approach that of enzyme catalyzed replication. However, it is not known how the prebiologically synthesized polymers became organized into a self-replicating system. At any rate the first living systems were probably very rudimentary heterotrophic micro-organisms which used organic compounds from the environment for both cell components and energy. They were probably followed by fermenters and eventually by autotrophic CO₂ reducing micro-organisms similar to the methanogenic and photosynthetic bacteria.     

The carbon isotopic distribution of Murchison amino acids

The δ¹³C values of thirty-four individual amino acids and two pyridine carboxylic acids have been obtained fromthe Murchison meteorite. They were found to range from +4.9 to +52.8‰, with statistically significant differences observed both within and between amino acid subgroups. The ¹³C content of α-amino acids declines with increasing chain length, a trend similar to the ones previously observed for carboxylic acids and alkanes. Also 2-methyl-2-amino acids were found to be heavier in ¹³C than the corresponding 2-H homologues. The3-, 4-, and 5-amino acids do not show a comparable declining trend in δ¹³C values and neither do the amino dicarboxylic acids. This variability in δ ¹³C values can be interpreted as to indicate that the synthetic histories of soluble organics in meteorites may have been diverse even within groups of compounds with very similar functional group composition.     

The deuterium enrichment of individual amino acids in carbonaceous meteorites: A case for the presolar distribution of biomolecule precursors

The δD values of over 40 amino acids and two pyridine carboxylic acids of the Murchison and Murray meteorites have been obtained by compound-specific isotopic analyses. For compounds with no known terrestrial distribution, these values range from approximately +330‰ (for cyclic leucine) to +3600‰ (for 2-amino-2,3-dimethylbutyric acid). The latter value is the highest ever recorded for a soluble organic compound in meteorites and nears deuterium to hydrogen ratios observed remotely in interstellar molecules. Deuterium content varies significantly between molecular species and is markedly higher for amino acids having a branched alkyl chain. The δD value of Murray l-isovaline, with an enantiomeric excess of ∼ 6% in the meteorite, was within experimental error of that determined for the combined dl-isovaline enantiomers. Overall, the hydrogen isotope composition of meteoritic amino acids is relatively simple and their δD values appear to vary more with the structure of their carbon chains than with the number and relative distribution of their functionalities or ¹³C content. The magnitude and extent of deuterium enrichment shared by many and varied amino acids in meteorites indicate that cosmic regimes such as those found in the interstellar medium were capable of producing, if not all the amino acids directly, at least a suite of their direct precursors that was abundant, varied, and considerably saturated.     

Rapid biotic molecular transformation of fulvic acids in a karst aquifer

The study of molecular transformation processes of dissolved organic carbon (DOC) in the environment significantly contributes to a better understanding of the global biogeochemical organic matter cycle. In an oxic karst groundwater system, in which the most powerful abiotic DOC degradative reactions, photodegradation and metal-mediated redox chemistry, are at best marginal contributors, a near complete turnover of fulvic acids (FAs) has been observed within decades (∼60 years). Depletion of oxygen for a very extensive range of aliphatic and aromatic carbon chemical environments has been confirmed as well as the formation of novel classes of compounds, suggesting a major contribution from biotic processes. From these results we infer that FAs must be perceived as a rather active participant in the global carbon cycle. Molecular-level alterations of such magnitude and rapidity on such short-time scales ought to be considered as widespread in the processing of “refractory” DOC in the environment.     

Linear and cyclic aliphatic carboxamides of the Murchison meteorite: hydrolyzable derivatives of amino acids and other carboxylic acids

Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatography-mass spectrometry after silylation with N-methyl-N (tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-alpha-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.     

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.     

Nitrogen-heterocyclic compounds in meteorites: significance and mechanisms of formation

Samples of the Murchison (C2), Murray (C2) and Orgueil (C1) carbonaceous meteorites were analyzed for nitrogen-heterocyclic compounds using gas chromatography, cation and anion exclusion liquid chromatography and mass spectrometry. The purines adenine, guanine, hypoxanthine and xanthine were identified in formic acid extracts of all samples, in concentrations ranging from 114–655 ppb. Purines have not previously been found in the Murray meteorite and adenine. hypoxanthine and xanthine have never simultaneously been detected in meteorite extracts. All four biologically significant purines, as well as the pyrimidine uracil have now been identified in these meteorites. A number of other, previously reported N-heterocyclic compounds such as certain hydroxypyrimidines and s-triazines could not be detected in any of the extracts. Laboratory data indicated that both these classes of compounds may be formed from structurally simple precursors (such as guanylurea in the case of s-triazines) during the extraction and analysis of meteorite extracts.We find that the suite of N-heterocyclic compounds identified in meteorites do not, at present, permit a clear distinction to be made between mechanisms of synthesis such as the Fischer-Tropsch type and other candidates. Secondary reactions and conversions in meteorite parent bodies, of HCN and other nitriles produced by Miller-Urey type reactions as well as by Fischer-Tropsch type reactions, must also be considered.     

Effects of secondary alteration on the composition of free and IOM-derived monocarboxylic acids in carbonaceous chondrites

Monocarboxylic acids (MCAs) are important astrobiologically because they are often the most abundant soluble compounds in carbonaceous chondrites (CCs) and are potential synthetic end products for many biologically important compounds. However, there has been no systematic study on the effect of parent body alteration on molecular and isotopic variability of MCAs. Since MCAs in meteorites are dominated by low molecular weight (C1-C8), highly volatile compounds, their distributions are likely to be particularly sensitive to secondary alteration processes. In contrast, the aliphatic side chains of insoluble organic matter (IOM) in CCs, whose composition has been shown to be closely related to the MCAs, may be far more resistant to secondary alteration. In the present study, we determined the distributions and isotopic ratios of free and IOM-derived MCAs in six carbonaceous chondrites with a range of classifications: Murchison (CM2), EET 87770 (CR2), ALH 83034 (CM1), ALH 83033 (CM2), MET 00430 (CV3) and WIS 91600 (C2). We compare mineralogical and petrological characteristics to the MCAs distributions to better define the processes leading to the synthesis and alteration of meteoritic MCAs. Our results show that aqueous and especially thermal alteration in the parent bodies led to major loss of free MCAs and depletion of straight relative to branched chain compounds. However, the MCAs derived from aliphatic side chains of IOM are well preserved despite of secondary alterations. The molecular and isotopic similarities of IOM-derived MCAs in different chondrite samples indicate very similar synthetic histories for organic matter in different meteorites.     

湖北清江和尚洞洞顶植物叶片和土壤的类脂物对比及其意义

用GC-MS对湖北清江岩溶地区和尚洞洞顶植物叶片与该洞上覆土壤层中的类脂物进行了分析和对比。在植物叶片中检测出了一系列直链烷烃、脂肪酸、以及丙三醇、植醇和甾醇等类脂物,其中直链烷烃的碳数分布范围大体在C21～C36之间,以C29或C31为主峰且具有奇偶优势;脂肪酸的分布主要集中在中、短链脂肪酸内（C数<23）,以C16为主峰呈单峰型分布且具有偶奇优势;醇的分布很不规则,仅检测出丙三醇,植醇和三种甾醇,没有检测到脂肪酮类化合物。与之相比,洞顶上覆土壤层中检测出更加丰富的类脂物。类脂物具有如下特征:正构烷烃以C31为主峰,还存在低碳数正构烷烃和异构烷烃,如2-甲基、3-甲基、4-甲基、5-甲基、6-甲基、7-甲基、8-甲基等一系列的单甲基支链烷烃,这些支链烷烃显示了微生物的贡献;脂肪酸分布也以低碳数的C16为主峰,且低碳数脂肪酸的含量较植物叶片中明显的增加,同时一些异构和反异构脂肪酸（C14∶0,C15∶0和C17∶0）以及一些单不饱和脂肪酸（C16∶1,C17∶1,C18∶1和C20∶1）也被检测到,也表明土壤中的脂肪酸不仅存在高等植物的贡献,还存在微生物的来源;没有植醇,但出现姥鲛烷和植烷并检测到了一系列脂肪醇化合物,碳数分布在C21～C36之间;检测到一系列的酮,具有奇偶优势,碳数分布范围在C23～C30和C33。高等植物叶片和土壤的差异反映了微生物对高等植物类脂物输入到土壤过程的重要贡献。本研究工作不仅提供了该岩溶地区植物叶片的类脂物信息,还为研究土壤有机质的来源和植物叶片中类脂物在地质过程中的转变提供信息,更为研究岩溶地区滴水和石笋中类脂物的来源提供一定的参考。     

Calculation of Si NMR shifts of silicate complexes with carbohydrates, amino acids, and muhicarboxylic acids: potential role in biological silica utilization

The existence of ether or ester-like complexes of silicate with organic compounds has long been debated in the literature on biological utilization of silicon. Comparison of theoretically calculated ²⁹Si NMR chemical shifts for such complexes with experimentally measured values in biological systems could provide a diagnostic tool for identifying which, if any of these molecules exist under physiological conditions. Results are presented here for ab initio molecular orbital calculations of ²⁹Si NMR shifts and formation energies of silicate complexes with polyalcohols, sugar-acids, pyranose sugars, amino acids and multicarboxylic acids. The effects of functional group and molecular structure including ligand size, denticity, ring size, silicon polymerization and coordination number on calculated ²⁹Si shifts were considered. The potential role of such compounds in biological silica utilization pathways is discussed.²⁹Si NMR shifts and energies were calculated at the HF/6-311+G(2d,p)//HF/6-31G* level. The main result is that only five-membered rings containing penta- and hexa-coordinated Si can explain experimentally observed resonances at ∼ −101 and −141 ppm. Further, the heptet observed in ¹H-²⁹Si coupled spectra can only be explained by structures where Si bonds to oxygens atoms in H-C-O-Si linkages with six symmetrically equivalent H atoms.While compounds containing quadra-coordinated silicon may exist in intracellular silicon storage pools within diatoms, calculated reaction energies suggest that the organism has no thermodynamic advantage in taking up extracellular organ-silicate compounds, instead of silicic acid, from the ambient aqueous environment. Hyper-coordinated complexes are deemed unlikely for transport and storage, though they may exist as transient reactive intermediates or activated complexes during enzymatically- catalyzed silica polymerization, as known previously from sol-gel silica synthesis studies.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

微生物磷脂脂肪酸单体碳同位素示踪碳循环过程

碳循环对于维持地球生命和调控气候变化具有重要意义。微生物是碳循环的关键驱动者之一,微生物群落结构和碳代谢活动的变化,能够影响温室气体的释放和碳储量,并进一步对气候变化产生反馈作用。在当前全球变化和人类活动加剧的背景下,需要进一步了解不同环境中的微生物群落组成和碳代谢活动的特征和响应。磷脂脂肪酸（PLFA）因其快速的周转速率和多样的分子结构,已经被广泛用于原位识别不同环境中活体微生物的生物量和群落结构。在此基础上,PLFA的单体碳同位素组成进一步指示了微生物利用哪些碳源,以及通过何种方式同化这些碳源,从而揭示微生物介导的碳流通和碳循环过程。本文综述了PLFA单体稳定碳同位素组成（δ¹³C）和放射性碳同位素组成（Δ¹⁴C）在示踪微生物碳循环过程中的应用。对比了农田、草地、森林、湿地以及海洋沉积物中活体微生物的碳源利用和碳同化途径的差异,这些差异可能与不同微生物对碳源的偏好以及不同环境中底物碳的可用性有关。对比了岩石、地下水、表层和深层土壤环境中微生物对化石碳源和年轻碳源的差异利用,化石碳是岩石和地下水环境中活体微生物碳源的重要组成部分,表明现代活体微生物可以直接利用部分老碳;相反,表层和深层土壤微生物倾向于利用现代碳源,这些碳源可能来自根系分泌物和从表面垂直输送的溶解有机碳。随着加速器质谱和单个化合物制备技术的进一步发展,预计PLFA单体放射性碳同位素将在微生物碳循环过程中发挥更重要的作用,值得在不同环境中进一步探索。

     

Amino acids in the Murchison meteorite

Continued investigation of the Murchison meteorite by gas chromatography combined with mass spectrometry has led to the characterization of at least 17 amino acids in addition to the 18 identified in earlier work. The total population consists of a wide variety of linear and cyclic difunctional and polyfunctional amino acids, of which the linear difunctional amino acids show a general decrease in concentration as the number of carbon atoms in the amino acid molecule increases. These results are consistent with the hypothesis that the amino acids are present as the result of an extraterrestrial, abiotic synthesis.     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Formation of meteorite hydrocarbons from thermal decomposition of siderite (FeCO3)

Thermal decomposition of siderite has been proposed as a source of magnetite in martian meteorites. Laboratory experiments were conducted to evaluate the possibility that this process might also result in abiotic synthesis of organic compounds. Siderite decomposition in the presence of water vapor at 300°C generated a variety of organic products dominated by alkylated and hydroxylated aromatic compounds. The results suggest that formation of magnetite by thermal decomposition of siderite on the precursor rock of the martian meteorite ALH84001 would have been accompanied by formation of organic compounds and may represent a source of extraterrestrial organic matter in the meteorite and on Mars. The results also suggest that thermal decomposition of siderite during metamorphism could account for some of the reduced carbon observed in metasedimentary rocks from the early Earth.