Formation of bioorganic compounds in simulated planetary atmospheres by high energy particles or photons.

Various types of organic compounds have been detected in Jupiter, Titan, and cometary coma. It is probable that organic compounds were formed in primitive Earth and Mars atmospheres. Cosmic rays and solar UV are believed to be two major energy sources for organic formation in space. We examined energetics of organic formation in simulated planetary atmospheres. Gas mixtures including a C-source (carbon monoxide or methane) and a N-source (nitrogen or ammonia) was irradiated with the followings: High energy protons or electrons from accelerators, gamma-rays from 60Co, UV light from a deuterium lamp, and soft X-rays or UV light from an electron synchrotron. Amino acids were detected in the products of particles, gamma-rays and soft X-rays irradiation from each gas mixture examined. UV light gave, however, no amino acid precursors in the gas mixture of carbon monoxide, nitrogen and nitrogen. It gave only a trace of them in the gas mixture of carbon monoxide, ammonia and water or that of methane, nitrogen and water. Yield of amino acid precursors by photons greatly depended on their wavelength. These results suggest that nitrogen-containing organic compounds like amino acid precursors were formed chiefly with high energy particles, not UV photons, in Titan or primitive Earth/Mars atmospheres where ammonia is not available as a predominant N-source.     

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.     

The cometary contribution to prebiotic chemistry.

Different estimates based on dynamical considerations, lunar cratering rates, Solar System chemical abundances, and the single-impact theory on the origin of the Earth-Moon system suggest that comets and other related small, volatile-rich primitive minor bodies captured by the Earth during the early Archean must have been a major source of volatiles on our planet. It is likely that a substantial fraction of the organic molecules present in the colliding cometary nuclei, which may have included nitrogen bases and the precursors of amino acids, were destroyed due to the high temperatures and shock wave energy associated with the collision. However, the presence of H2O, CN, CH, CO, CO2 and other carbon-bearing molecules and radicals in the atmosphere of the Sun and in circumstellar shells around carbon-rich stars suggests that at least simple carbon species could have survived the cometary collisions. Under the anoxic conditions thought to prevail in the prebiotic terrestrial paleoatmosphere, the post-collisional formation of a large number of excited molecules and radicals, and the rapid quenching of the expanding gaseous ball may have led, upon rapid cooling, to the formation of molecules of biogenic elements and to their eventual deposition in localized environments where complex organic compounds of biochemical significance may have been produced and accumulated.     

Development of a gas chromatography compatible Sample Processing System (SPS) for the in-situ analysis of refractory organic matter in martian soil: preliminary results

In the frame of the 2009 Mars Science Laboratory (MSL) mission a new sample preparation system (SPS) compatible with gas chromatography–mass spectrometry (GC–MS) has been developed for the in situ analysis of complex organic molecules in the Martian soil. The goal is to detect, if they exist, some of the key compounds that play an important role in life on Earth including carboxylic acids, amino acids and nucleobases.     

Comets and life.

Some of the chemical species which have been detected in comets include H2O, HCN, CH3CN, CO, CO2, NH3, CS, C2 and C3. All of these have also been detected in the interstellar medium, indicating a probable relationship between interstellar dust and gas clouds and comets. Laboratory experiments carried out with different mixtures of these molecules give rise to the formation of the biochemical compounds which are necessary for life, such as amino acids, purines, pyrimidines, monosaccharides, etc. However, in spite of suggestions to the contrary, the presence of life in comets is unlikely. On the other hand, the capture of cometary matter by the primitive Earth is considered essential for the development of life on this planet. The amount of cometary carbon-containing matter captured by the Earth, as calculated by different authors, is several times larger than the total amount of organic matter present in the biosphere (10(18)g). The major classes of reactions which were probably involved in the formation of key biochemical compounds are discussed. Our tentative conclusions are that: 1) comets played a predominant role in the emergence of life on our planet, and 2) they are the cosmic connection with extraterrestrial life.     

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds.

The prebiotic synthesis of organic compounds using a spark discharge on various simulated prebiotic atmospheres at 25 degrees has been studied. Methane mixtures contained H2 + CH4 + H2O + N2 + NH3 with H2/CH4 molar ratios from 0 to 4 and pNH3 = 0.1 torr. A similar set of experiments without added NH3 was performed. The yields of amino acids (1.2 to 4.7% based on the carbon) are approximately independent of the H2/CH4 ratio and the presence of added NH3, and a wide variety of amino acids are obtained. Mixtures of H2 + CO + H2O + N2 and H2 + CO2 + H2O + N2, with and without added NH3, all give about 2% yields of amino acids at H2/CO and H2/CO2 ratios of 2 to 4. For the H2/CO and H2/CO2 ratios less than 1, the yields fall off drastically to as low as 10(-3)%. Glycine is almost the only amino acid produced from CO and CO2 atmospheres. These results show that the maximum yield is about the same for the three carbon sources at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. In addition, CH4 gives a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these results indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde parallel the amino acid results, with yields of HCN and H2CO as high as 13% based on the carbon. Ammonia is also produced from N2 in experiments with no added NH3 in yields as high as 4.9%. These results show that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges. The amount of ammonia formed by hydrolysis of HCN and various nitriles may have exceeded that formed directly in electric discharges.     

Characterization of complex organic compounds formed in simulated planetary atmospheres by the action of high energy particles.

A wide variety of organic compounds, which are not simple organics but also complex organics, have been found in planets and comets. We reported that complex organics was formed in simulated planetary atmospheres by the action of high energy particles. Here we characterized the experimental products by using chromatographic and mass spectrometric techniques. A gaseous mixture of CO, N2 and H2O was irradiated with high energy protons (major components of cosmic rays). Water-soluble non-volatile substances, which gave amino acids after acid-hydrolysis, were characterized by HPLC and mass spectrometry. Major part of the products were complex compounds with molecular weight of several hundreds. Amino acid precursors were produced even when no water was incorporated with the starting materials. It was suggested that complex molecules including amino acid precursors were formed not in solution from simple molecules like HCN, but directly in gaseous phase.     

Detection of martian amino acids by chemical derivatization coupled to gas chromatography: in situ and laboratory analysis.

If there is, or ever was, life in our solar system beyond the Earth, Mars is the most likely place to search for. Future space missions will have then to take into account the detection of prebiotic molecules or molecules of biological significance such as amino acids. Techniques of analysis used for returned samples have to be very sensitive and avoid any chemical or biological contamination whereas in situ techniques have to be automated, fast and low energy consuming. Several possible methods could be used for in situ amino acid analyses on Mars, but gas chromatography would likely be the most suitable. Returned samples could be analyzed by any method in routine laboratory use such as gas chromatography, already successfully performed for analyses of organic matter including amino acids from martian meteorites. The derivatization step, which volatilizes amino acids to perform both in situ and laboratory analysis by gas chromatography, is discussed here.     

Life in the solar system.

Life, defined as a chemical system capable of transferring its molecular information via self-replication and also capable of evolving, must develop within a liquid to take advantage of the diffusion of complex molecules. On Earth, life probably originated from the evolution of reduced organic molecules in liquid water. Organic matter might have been formed in the primitive Earth's atmosphere or near hydrothermal vents. A large fraction of prebiotic organic molecules might have been brought by extraterrestrial-meteoritic and cometary dust grains decelerated by the atmosphere. Any celestial body harboring permanent liquid water may therefore accumulate the ingredients that generated life on the primitive Earth. The possibility that life might have evolved on early Mars when water existed on the surface marks it as a prime candidate in a search for bacterial life beyond the Earth. Europa has an icy carapace. However, cryovolcanic flows at the surface point to a possible water subsurface region which might harbor a basic life form. The atmosphere and surface components of Titan are also of interest to exobiology for insight into a hydrocarbon-rich chemically evolving world. One-handed complex molecules and preferential isotopic fractionation of carbon, common to all terrestrial life forms, can be used as basic indicators when searching for life beyond the Earth.     

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.     

Bio-markers and the search for extinct life on Mars.

Geologic and climatologic studies suggest that conditions on early Mars were similar to early Earth. Because life on Earth is believed to have originated during this early period (3.5 billion years ago), the Martian environment could have also been conducive to the origin of life. To investigate this possibility we must first define the attributes of an early Martian biota. Then, specific geographic locations on Mars must be chosen where life may have occurred (i.e. areas which had long standing water), and within these distinct locations search for key signatures or bio-markers of a possible extinct Martian biota. Some of the key signatures or bio-markers indicative of past biological activity on Earth may be applicable to Mars including: reduced carbon and nitrogen compounds, CO3(2-), SO4(2-), NO3-, NO2- [correction of NO2(2)], Mg, Mn, Fe, and certain other metals, and the isotopic ratios of C, N and S. However, we must also be able to distinguish abiotic from biologic origins for these bio-markers. For example, abiotically fixed N2 would form deposits of NO3- and NO2-, whereas biological processes would have reduced these to ammonium containing compounds, N2O, or N2, which would then be released to the atmosphere. A fully equipped Mars Rover might be able to perform analyses to measure most of these biomarkers while on the Martian surface.     

Formation of amino acid precursors in cometary ice environments by cosmic radiation.

Cometary ices are believed to contain water, carbon monoxide, methane and ammonia, and are possible sites for the formation and preservation of organic compounds relating to the origin of life. Cosmic rays, together with ultraviolet light, are among the most effective energy sources for the formation of organic compounds in space. In order to study the possibility of the formation of amino acids in comets or their precursory bodies (interstellar dust grains), several types of ice mixtures made in a cryostat at 10 K ("simulated cometary ices") were irradiated with high energy protons. After irradiation, the volatile products were analyzed with a quadrupole mass spectrometer, while temperature of the cryostat was raised to room temperature. The non-volatile products remaining in the cryostat at room temperature were collected with water. They were acid-hydrolyzed, and analyzed by ion-exchange chromatography. When an ice mixture of carbon monoxide (or methane), ammonia and water was irradiated, some hydrocarbons were formed, and amino acids such as glycine and alanine were detected in the hydrolyzate. These results suggest the possible formation of "amino acid precursors" (compounds yielding amino acids after hydrolysis) in interstellar dust grains by cosmic radiation. We previously reported that amino acid precursors were formed when simulated primitive planetary atmospheres were irradiated with cosmic ray particles. It will be of great interest to compare the amount of bioorganic compounds that were formed in the primitive earth and that brought by comets to the earth.     

Early emergence of protein precursors.

For the emergence of protein precursors essential to primitive cells three prerequisites must have been fulfilled: selective aqueous polymerization of proteinaceous amino acids from a complex mixture of small organic compounds, selection of homochiral amino acid sequences and catalytic activity with respect, more precisely, to information transfer processes.     

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.     

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.     

Organics produced by ion irradiation of ices: some recent results.

Some results, recently obtained from laboratory experiments of ion irradiation of ice mixtures containing H, C, N, and O, are here summarized. They are relevant to the formation and evolution of complex organics on interstellar dust, comets and other small bodies in the external Solar System. In particular the formation of CN-bearing species is discussed. Interstellar dust incorporated into primitive Solar System bodies and subsequently delivered to the early Earth, may have contributed to the origin of life. The delivery of CN-bearing species seems to have been necessary because molecules containing the cyanogen bond are difficult to be produced in an environment that is not strongly reducing as that of the early Earth probably was. Moreover we report on an ongoing research program concerning the interaction between refractory materials produced by ion irradiation of simple ices and biological materials (amino acids, proteins, cells).     

The use of mineral crystals as bio-markers in the search for life on Mars.

Photographs that depict presumed fluvial features on the martian surface have led geologists to hypothesize that water flowed across the early martian terrain. From this, it has been further hypothesized that the surface and atmospheric conditions on early Mars were similar to those on early Earth. Because the oldest fossil evidence of life on Earth dates back to this early period, at least 3.5 billion years ago, the possibility exists that the early Martian environment could have also been conducive to the origin of life. To investigate this possibility, universal signatures or bio-markers indicative of past (or present) biological activity must be identified for use in the search for life on Mars. Several potentially applicable biomarkers have been identified and include: organics (e.g., specific classes of lipids and hopanes), suites of specific inorganic and organic compounds, as well as the isotopic ratios of C, N, and S. Unfortunately, all of these bio-markers may be of biologic or abiotic origin; these origins are often difficult to distinguish. Thus, the discovery of any one of these compounds alone is not a bio-marker. Because minerals produced under biologic control have distinctive crystallographies, morphologies, and isotopic ratios that distinguishable from abiotically produced minerals with the same chemical composition, and are stable through geologic time, we propose the use of minerals resulting from biologically controlled mineralization processes as bio-markers.     

Chemical evolution in space--a source of prebiotic molecules.

In Laboratory Astrophysics at Leiden University a laboratory analog for following the chemical evolution of interstellar dust in space shows that the dust contains the bulk of organic material in the universe. We follow the photoprocessing of low temperature (10 K) mixtures of ices subjected to vacuum ultraviolet radiation in simulation of interstellar conditions. The most important, but necessary, difference is in the time scales for photo-processing. One hour in the laboratory is equivalent to one thousand years in low density regions of space and as much as, or greater than, ten thousand to one million years in the depths of dense molecular clouds. The ultimate product of photoprocessing of grain material in the laboratory is a complex nonvolatile residue which is yellow in color and soluble in water and methanol. The molecular weight is greater than the mid-hundreds. The infrared absorption spectra indicate the presence of carboxylic acid and amino groups resembling those of other molecules of presumably prebiological significance produced by more classical methods. One of our residues, when subjected to high resolution mass spectroscopy gave a mass of 82 corresponding to C4H6H2 after release of CO2 and trace ammounts of urea suggesting amino pyroline rings. The deposit of prebiotic dust molecules occurred as many as 5 times in the first 500-700 million years on a primitive Earth by accretion during the passage of the solar system through a dense interstellar cloud. The deposition rate during each passage is estimated to be between 10(9) and 10(10) g per year during the million or so years of each passage; i.e., a total deposition of 1O(9)-10(10) metric tons of complex organic material per passage.     

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.     

Life on Mars? I. The chemical environment.

The origin of life at its abiotic evolutionary stage, requires a combination of constituents and environmental conditions that enable the synthesis of complex replicating macromolecules from simpler monomeric molecules. It is very likely that the early stages of this evolutionary process have been spontaneous, rapid and widespread on the surface of the primitive Earth, resulting in the formation of quite sophisticated living organisms within less than a billion years. To what extent did such conditions prevail on Mars? Two companion-papers (Life on Mars? I and II) will review and discuss the available information related to the chemical, physical and environmental conditions on Mars and assess it from the perspective of potential exobiological evolution.