Fluorescent organic matter in carbonaceous chondrites.

Fluorescent organic matter in carbonaceous chondrites was investigated using a microscope equipped with a fluorescence spectrophotometer. Fluorescent particles were observed in powdered CM2 carbonaceous chondrites (Y-74662, Y-7791198, and Murchison) without carbon enrichment by acid treatments. Although it was difficult to find fluorescent particles in powdered sample of C3 chondrites (ALH-77307, Y-791717, and Allende) without acid treatments, many fluorescent particles were observed after carbon enrichment by acid treatments. Fluorescence of coronene and shock-altered graphite were observed using the same microscope and the same conditions as those for carbonaceous chondrites.     

Survivability of biomolecules during extraterrestrial delivery: new results on pyrolysis of amino acids and poly-amino acids.

The hypothesis on exogenous origin of organic matter on the early Earth is strongly supported by the detection of a large variety of organic compounds (including amino acids and nucleobases) in carbonaceous chondrites. Whether such complex species can be successively delivered by other space bodies (comets, asteroids and interplanetary dust particles) is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. Recent simulation experiments on amino acid and nucleic acid base pyrolysis under oxygen-free atmosphere demonstrated that simple representatives of these (considered thermally unstable) compounds can survive at 1-10% level a rapid heating at 500-600 degrees C. In the present work, we report on new data on the pyrolysis of amino acids and their homopolymers and discuss implications of their thermal behavior for extraterrestrial delivery.     

Amino acids in meteorites.

Carbonaceous chondrites carry a record of chemical evolution that is unparalleled among presently accessible natural materials. Within the complex suite of organic compounds that characterize these meteorites, amino acids occur at a total concentration that may reach 0.6 micromole g-1 meteorite (approximately 60 ppm). Both free amino acids and acid-labile amino acid derivatives have been found in hot-water extracts of a CI1 and seven CM2 chondrites. Although the amino acid composition of all CM2 chondrites is not the same, differences may be largely explicable on the basis of spontaneous and biologically-caused decomposition occurring during their terrestrial residence. The amino acids of the Murchison meteorite (CM2) have been extensively analyzed and 52 amino acids have been positively identified. Thirty three of these amino acids are unknown in natural materials other than carbonaceous chondrites. Thus the Murchison meteorite has recently been the major source of new naturally-occurring amino acids. The Murchison amino acids comprise a mixture of C2 through C8 cyclic and acyclic monoamino alkanoic and alkandioic acids of nearly complete structural diversity. Within the acyclic monoamino alkanoic acid series, primary alpha-amino alpha-branched amino acids are predominant. The concentrations of individual amino acids decline exponentially with increasing carbon number within homologous series. Amino acid enantiomers are found in approximately equal amounts. Eight of the terrestrial protein amino acids have been found.     

The origin of organic matter in the Martian meteorite ALH84001.

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta 13C values for the organic matter associated with the carbonate globules averaged -26% and is attributed to terrestrial contamination. In contrast, the delta 13C values for the organic matter associated with the bulk matrix material yielded a value of -15%. The only common carbon sources on the Earth that yield similar delta 13C values, other then some diagenetically altered marine carbonates, are C4 plants. A delta 13C value of -15%, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery of meteoritic or cometary debris to the surface of Mars.     

Transport of extraterrestrial biomolecules to the Earth: problem of thermal stability.

The idea of extraterrestrial delivery of organic matter to the early Earth is especially attractive at present and is strongly supported by the detection of a large variety of organic compounds, including amino acids and nucleobases, in carbonaceous chondrites. Whether these compounds can be delivered by other space bodies is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. In the present study we estimated survivability of simple amino acids (alpha-aminoisobutyric acid, L-alanine, L-valine and L-leucine), purines (adenine and guanine) and pyrimidines (uracil and cytosine) under rapid heating to temperatures of 400 to 1000 degrees C under N2 or CO2 atmosphere. We have found that most of the compounds studied cannot survive the temperatures substantially higher than 700 degrees C; however at 500-600 degrees C, the recovery can be at a per cent level (or even 10%-level for adenine, uracil, alanine, and valine). Implications of the data for extraterrestrial delivery of the biomolecules are discussed.     

小行星表面有机物的红外光谱探测方法

小行星的有机物记录了太阳系早期有机物的形成发展历史,为地球早期生命前体出现的研究提供了重要依据,对于研究生命起源和演化具有重要意义.本文综合分析了小行星表面可能存在的有机物成分、种类及其赋存状态,利用红外光谱开展地面模拟实验,探讨有机物的红外光谱特征及其影响因素.结果表明,不同类型有机物的红外光谱特征与其类型、结构、温...     

Structure of high-molecular carbonaceous compound in carbonaceous chondrites and formation of IR-spectroscopically similar compounds in the laboratory.

Main components of carbonaceous matter in carbonaceous chondrites are high molecular organic matter. Examinations of the compounds using pyrolysis GC/MS and FT-IR indicated the structural resemblance of major part of the molecule for all of the compounds from different types of carbonaceous chondrites (8 Antarctic and 2 none-Antarctic meteorites). A carbonaceous matter derived from graphite on a shock experiment using a rail gun (1g projectile at 7 km/s) showed similar IR spectrum to those of the meteoritic high-molecular organic matter. C-60 fullerene also gave a similar compound (with minor differences in IR spectra) on a shock experiment under the same conditions. A shock experiment using coronene also examined.     

Chemical evolution of primitive solar system bodies.

In this paper we summarize some of the most salient observations made recently on the organic molecules and other compounds of the biogenic elements present in the interstellar medium and in the primitive bodies of the solar system. They include the discovery of the first phosphorus molecular species in dense interstellar clouds, the presence of complex organic ions in the dust and gas phase of Halley's coma, the finding of unusual, probably presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites, and new developments on the chemical evolution of Titan, the primitive Earth, and early Mars. Some of the outstanding problems concerning the synthesis of organic molecules on different cosmic bodies are also discussed from an exobiological perspective.     

十块中国球粒陨石元素丰度特征研究

利用仪器中子活化分析方法,对宁强、随州、枣阳、南通、肇东、广南、东台、清镇、武安、导河等陨石进行了多元素分析测定.给出了近40种元素含量结果.并对各类球粒陨石微量元素丰度特征、REE丰度特征以及宁强陨石元素丰度特征进行了讨论.     

Stable isotope analysis at the molecular level: a new approach for determining the origins of amino acids in the Murchison meteorite.

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta 13C values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in 13C relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta 13C values (+5 to +30%, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary results are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.     

Origin of organic compounds in carbonaceous chondrites.

Carbonaceous chondrites, a class of primitive meteorite, have long been known to contain their complement of carbon largely in the form of organic, i.e., hydrocarbon-related, matter. Both discrete organic compounds and an insoluble, macromolecular material are present. Several characteristics of these materials provide evidence for their abiotic origin. The principal formation hypotheses have invoked chemistry occurring either in the solar nebula or on the parent body. However, recent stable isotope analyses of the meteorite carboxylic acids and amino acids indicate that they may be related to interstellar cloud compounds. These results suggest a formation scheme in which interstellar compounds were incorporated into the parent body and subsequently converted to the present suite of meteorite organics by the hydrothermal process believed to have formed the clay minerals of the meteorite matrix.     

Simulated cometary matter as a test for enantiomer separating chromatography for use on comet 46P/Wirtanen.

The Cometary Sampling and Composition Experiment on board of European Space Agency's cornerstone mission ROSETTA is designed to identify organic molecules in cometary matter in situ by a combined pyrolysis gas chromatographic and mass spectrometric technique. Its capillary columns coated with chiral stationary phases received considerable attention, because they are designed for separations of non-complex enantiomers to allow the determination of enantiomeric ratios of cometary chiral organic compounds and consequently to provide information about the origin of molecular parity violation in biomolecules. To get gas chromatographic access to organic compounds on the comet, where macromolecules and complex organic polymers of low volatility are expected to make up the main organic ingredients, the combination of two injection techniques will be applied. The pyrolysis technique performed by heating cometary samples stepwise to defined temperatures in specific ovens resulting in thermochemolysis reactions of polymers and a chemical derivatization technique, in which the reagent dimethylformamide dimethylacetal assists pyrolysis derivatization reactions in producing methyl esters of polar monomers. The combination of the reagent assisted pyrolysis gas chromatographic technique with enantiomer separating chromatography was tested with laboratory-produced simulated cometary matter.     

The chemical conditions on the parent body of the murchison meteorite: Some conclusions based on amino, hydroxy and dicarboxylic acids

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 × 10^?3 M. Succinic acid and β-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/β-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10^?3 to 10^?2 M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 10}{}^4\text{yrs}$) this high concentration implies a period of synthesis of organic compounds as short as 10⁴ years on the Murchison meteorite parent body.     

Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature.

Many experiments have already been carried out to simulate organic chemistry on Titan, the largest satellite of Saturn. They can provide fruitful information on the nature of minor organic constituents likely to be present in Titan's atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one already detected in Titan's atmosphere have been identified in simulation experiments. The exception, C4N2, as well as other compounds expected in Titan from theoretical modeling, such as other N-organics, and polyynes, first of all C6H2, have never been detected in experimental simulation thus far. All these compounds are thermally unstable, and the temperature conditions used during the simulation experiments were not appropriate. We have recently started a new program of simulation experiments with temperature conditions close to that of Titan's environment. It also uses dedicated analytical techniques and procedures compatible with the analysis of organics only stable at low temperatures, as well solid products of low stability in the presence of O2 and H2O. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range 100-150 K. Products were analysed by FTIR, GC and GC-MS techniques. GC-peaks were identified by their mass spectrum, and, in most cases, by comparison of the retention time and mass spectrum with standard ones. We report here the first detection in Titan simulation experiments of C6H2 and HC5N. Their abundance is a few percent relative to C4H2 and HC3N, respectively. Preliminary data on the solid products indicate an elemental composition corresponding to (H11C11N)n. These results open new prospects in the modeling of Titan's haze making.     

Catalytic wet-oxidation of human wastes produced in space: the effects of temperature elevation.

The filtrate of non-catalytical wet-oxidation sewage sludge was wet-oxidized again at 290 degrees C and 300 degrees C with a Ru-Rh catalyst. At each temperature, repeated batch tests were carried out. Both oxidation and denitrification efficiency of organic matter in the raw material were studied. In the 16 times batch tests at 300 degrees C, high and stable oxidation occurred. 98.0% of organic carbon in the raw material was oxidized and 98.3% of organic nitrogen was denitrified. At 290 degrees C, though high and stable denitrification occurred, oxidation did not occur highly and stably. A catalytic wet-oxidation system studied at 300 degrees C will be useful as a waste management system for a human life support system, where almost all food is resupplied from the earth. This system can prevent organic waste accumulation in the life support system.     

Decomposition of sodium formate and L- and D-alanine in the Pampas de La Joya soils: Implications as a new geochemical analogue to Martian regolith

The organic compounds on the Martian surface are still undetectable by the previous Viking mission that has been sent to Mars even though they are expected to be there by exogenous and/or endogenous synthesis. The high abiotic reactivity has been the most acceptable explanation for the apparently absence of organic matter in the regolith.     

Subcritical and supercritical water oxidation of CELSS model wastes.

Controlled-Ecological-Life-Support-System (CELSS) model wastes were wet-oxidized at temperatures from 250 to 500 degrees C, i.e., below and above the critical point of water (374 degrees C and 218 kg/cm2 or 21.4 MPa). A solution of ammonium hydroxide and acetic acid and a slurry of human urine, feces, and wipes were used as model wastes. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 degrees C, i.e., above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. Although the extent of nitrogen oxidation to nitrous oxide (N2O) and/or nitrogen gas (N2) increased with reaction temperature, most of the nitrogen was retained in solution as ammonia near 400 degrees C. This important finding suggests that most of the nitrogen in the waste feed can be retained in solution as ammonia during oxidation at low supercritical temperatures and be subsequently used as a nitrogen source for plants in a CELSS while at the same time organic matter is almost completely oxidized to carbon dioxide and water. It was also found in this study the Hastelloy C-276 alloy reactor corroded during waste oxidation. The rate of corrosion was lower above than below the critical temperature for water.     

Solid organic matter in the atmosphere and on the surface of outer Solar System bodies.

Many bodies in the outer Solar System display the presence of low albedo materials. These materials, evident on the surface of asteroids, comets, Kuiper Belt objects and their intermediate evolutionary step, Centaurs, are related to macromolecular carbon bearing materials such as polycyclic aromatic hydrocarbons and organic materials such as methanol and related light hydrocarbons, embedded in a dark, refractory, photoprocessed matrix. Many planetary rings and satellites around the outer gaseous planets display such component materials. One example, Saturn's largest satellite, Titan, whose atmosphere is comprised of around 90% molecular nitrogen N2 and less than 10% methane CH4, displays this kind of low reflectivity material in its atmospheric haze. These materials were first recorded during the Voyager 1 and 2 flybys of Titan and showed up as an optically thick pinkish orange haze layer. These materials are broadly classified into a chemical group whose laboratory analogs are termed "tholins", after the Greek word for "muddy". Their analogs are produced in the laboratory via the irradiation of gas mixtures and ice mixtures by radiation simulating Solar ultraviolet (UV) photons or keV charged particles simulating particles trapped in Saturn's magnetosphere. Fair analogs of Titan tholin are produced by bombarding a 9:1 mixture of N2:CH4 with charged particles and its match to observations of both the spectrum and scattering properties of the Titan haze is very good over a wide range of wavelengths. In this paper, we describe the historical background of laboratory research on this kind of organic matter and how our laboratory investigations of Titan tholin compare. We comment on the probable existence of polycyclic aromatic hydrocarbons in the Titan Haze and how biological and nonbiological racemic amino acids produced from the acid hydrolysis of Titan tholins make these complex organic compounds prime candidates in the evolution of terrestrial life and extraterrestrial life in our own Solar System and beyond. Finally, we also compare the spectrum and scattering properties of our resulting tholin mixtures with those observed on Centaur 5145 Pholus and the dark hemisphere of Saturn's satellite Iapetus in order to demonstrate the widespread distribution of similar organics throughout the Solar System.     

Catalysis of peptide formation by inorganic oxides: high efficiency of alumina under mild conditions on the Earth-like planets.

Amino acid condensation catalyzed by inorganic oxides is a widely recognized way for prebiotic peptide formation. Silica and alumina are widely distributed in the Earth-like planets' crust as minerals of different complexity, and thus are attractive model catalysts for the studies of abiotic peptide synthesis. Experiments performed in other laboratories have shown that this process can be efficient at > 80 degrees C, which is not easy to find on the planetary surface in combination with sufficient concentrations of amino acids and necessary catalysts. In the present work we tested catalytic activity of three forms of alumina (which proved to be an efficient catalyst for this process) in the intermolecular condensation of L-alanine. We expanded the temperature interval down to 55 degrees C and used the simplest permanent heating procedure, without employing fluctuating drying/wetting conditions. The most important finding is that even under the lowest temperature considered (i.e. 55 degrees C), short peptide formation can be detected already after 10-30 days of heating. This fact implies that the abiotic peptide formation might occur in a wide variety of planetary environments, without need for high temperatures, given the presence of amino acid building blocks and alumina-containing minerals.     

Characterization of microbial and chemical composition of shuttle wet waste with permanent gas and volatile organic compound analyses.

Solid-waste treatment in space for Advanced Life Support, ALS, applications requires that the material can be safely processed and stored in a confined environment. Many solid-wastes are not stable because they are wet (40-90% moisture) and contain levels of soluble organic compounds that can contribute to the growth of undesirable microorganisms with concomitant production of noxious odors. In the absence of integrated Advanced Life Support systems on orbit, permanent gas, trace volatile organic and microbiological analyses were performed on crew refuse returned from the volume F "wet" trash of three consecutive Shuttle missions (STS-105, 109, and 110). These analyses were designed to characterize the short-term biological stability of the material and assess potential crew risks resulting from microbial decay processes during storage. Waste samples were collected post-orbiter landing and sorted into packaging material, food waste, toilet waste, and bulk liquid fractions deposited during flight in the volume F container. Aerobic and anaerobic microbial loads were determined in each fraction by cultivation on R2A and by acridine orange direct count (AODC). Dry and ash weights were performed to determine both water and organic content of the materials. Experiments to determine the aerobic and anaerobic biostability of refuse stored for varying periods of time were performed by on-line monitoring of CO2 and laboratory analysis for production of hydrogen sulfide and methane. Volatile organic compounds and permanent gases were analyzed using EPA Method TO15 by USEPA et al. [EPA Method TO15, The Determination of Volatile Organic Compounds (VOCs) in Ambient Air using SUMMA, Passivated Canister Sampling and Gas Chromatographic Analysis,1999] with gas chromatography/mass spectrometry and by gas chromatography with selective detectors. These baseline measures of waste stream content, labile organics, and microbial load in the volume F Shuttle trash provide data for waste subsystem analysis and atmospheric management within the ALS Project.