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.     

Formation of bioorganic compounds in planetary atmospheres by cosmic radiation.

Simulated planetary atmospheres (mixtures of simple gases) were irradiated with high energy particles to simulate an action of cosmic rays. When a mixture of carbon monoxide, nitrogen and water was irradiated with 2.8-40 MeV protons, a wide variety of bioorganic compounds including amino acids, imidazole, and uracil were identified in the products. The amount of amino acids was proportional to the energy deposit to the system. Various kinds of simulated planetary atmospheres, such as "Titan type" and "Jovian type", were also irradiated with high energy protons, and gave amino acids in the hydrolyzed products. Since cosmic rays are a universal energy source in space, it was suggested that formation of bioorganic compounds in planetary atmospheres is inevitable in the course of cosmic evolution.     

Possible complex organic compounds on Mars.

It is suggested that primitive Mars had somehow similar environments as primitive Earth. If life was born on the primitive earth using organic compounds which were produced from the early Earth environment, the same types of organic compounds were also formed on primitive Mars. Such organic compounds might have been preserved on Mars still now. We are studying possible organic formation on primitive and present Mars. A gaseous mixture of CO2, CO, N2 and H2O with various mixing ratios were irradiated with high energy protons (major components of cosmic rays). Hydrogen cyanide and formaldehyde were detected among volatile products, and yellow-brown-colored water-soluble non-volatile substances were produced, which gave amino acids after acid-hydrolysis. Major part of "amino acid precursors" were not simple molecules like aminonitriles, but complex compounds which eluted earlier than free amino acids in cation-exchange HPLC. These organic compounds should be major targets in the future Mars mission. Strategy for the detection of the complex organics on Mars will be discussed.     

How primitive are the gases in Titan's atmosphere?

Titan's atmosphere contains a mixture of nitrogen, methane, argon, hydrogen, simple hydrocarbons and nitriles, carbon monoxide, and carbon dioxide. Sources of nitrogen may be as a product of the photodissociation of ammonia or trapped in the ices that formed the satellite. Reasons for the abundance of deuterium are examined and its association with nitrogen on Titan is explained.     

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.     

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N₂/0.1 CH₄ gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (1.65) and k (0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k(λ), including the 4.6 μm nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.     

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 atmospheric greenhouse effect and climates on various planets

The greenhouse effect of the planetary atmospheres is considered and its evolution as a result of variations in the chemical composition and in gas abundances of the atmospheres as well as in the chemical composition, size distribution and concentration of aerosol components. A computer modelling gave the values of the greenhouse effect of the atmospheres of the Earth, Mars, Venus, Jupiter, and Titan. It is shown that the atmospheric greenhouse effect plays a decisive role in the formation of the planetary climates and that it has substantially changed in the process of the planetary evolution. The greenhouse effect mechanism has always been and still is a major factor of the mean global planetary climate.     

The escape of molecular hydrogen and the synthesis of organic nitriles in planetary atmospheres.

What is the influence of hydrogen escape from the atmosphere of small planetary bodies on the synthesis of organic molecules in that atmosphere? To answer this question, laboratory experiments have been performed to study the evolution of different reducing model atmospheres submitted to electrical discharges, with and without the simulation of H₂ escape. A study of mixtures of nitrogen and methane shows a very strong effect of H₂ escape on the formation of organic nitriles, the only nitrogen containing organics detected in the gas phase. These are HCN, CH  CCN, (CN)₂, CH₂CHCN, CH₃ CN and CH₃CH₂CN. The yield of synthesis of most of these compounds is noticeably increased, up to several orders of magnitude, when hydrogen escape is simulated. The escape of H₂ from the atmosphere of the primitive Earth may have played a crucial role in the formation of reactive organic molecules such as CHCCN or (CN)₂, which can be considered as important prebiotic precursors. These experimental results may also explain extant data concerning the nature and relative abundance of organics present in the atmosphere of Titan, a planetary satellite which may be an ideal model within our solar system for the study of organic cosmochemistry and exobiology.     

Isotopic ratios in planetary atmospheres.

Recent progress on measurements of isotopic ratios in planetary or satellite atmospheres include measurements of the D/H ratio in the methane of Uranus, Neptune and Titan and in the water of Mars and Venus. Implications of these measurements on our understanding of the formation and evolution of the planets and satellite are discussed. Our current knowledge of the carbon, nitrogen and oxygen isotopic ratios in the atmospheres of these planets, as well as on Jupiter and Saturn, is also reviewed. We finally show what progress can be expected in the very near future due to some new ground-based instrumentation particularly well suited to such studies, and to forthcoming space missions.     

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.     

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.     

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.     

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.     

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.     

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.     

Biological nitrogen fixation under primordial Martian partial pressures of dinitrogen.

Early Earth and early Mars were similar enough such that past geochemical and climatic conditions on Mars may have also been favorable for the origin of life. However, one of the most striking differences between the two planets was the low partial pressure of dinitrogen (pN2) on early Mars (18 mb). On Earth, nitrogen is a key biological element and in many ecosystems the low availability of fixed nitrogen compounds is the main factor limiting growth. Biological fixation of dinitrogen on Earth is a crucial source of fixed nitrogen. Could the low availability of dinitrogen in the primordial Martian atmosphere have prevented the existence, or evolution of Martian microbiota? Azotobacter vinelandii and Azomonas agilis were grown in nitrogen free synthetic medium under various partial pressures of dinitrogen ranging from 780-0 mb (total atmosphere=1 bar). Below 400 mb the biomass, cell number, and growth rate decreased with decreasing pN2. Both microorganisms were capable of growth at a pN2 as low as 5 mb, but no growth was observed at a pN2 < or = 1 mb. The data appear to indicate that biological nitrogen fixation could have occurred on primordial Mars (pN2=18 mb) making it possible for a biotic system to have played a role in the Martian nitrogen cycle. It is possible that nitrogen may have played a key role in the early evolution of life on Mars, and that later a lack of available nitrogen on that planet (currently, pN2=0.2 mb) may have been involved in its subsequent extinction.     

The low temperature organic chemistry of Titan's geofluid.

Organic chemistry on Titan and prebiotic chemistry on Earth involve the same N-containing organics: nitriles and their oligomers. Couplings of their chemistry in the three parts of Titan's geofluid (atmosphere, aerosols and surface) seem to play a key role in the organic chemical evolution of the planet. If liquid water was present on Titan, then a prebiotic chemistry, involving eutectics, similar to that of the early Earth, may have occurred. However, liquid water is currently absent and a prebiotic chemistry based only on N-organics may be evolving now on Titan. The other consequence of the low temperatures of Titan is the possible formation of organics unstable at room temperature and very reactive. So far, these compounds have not been systematically searched for in experimental studies of Titan's organic chemistry. C4N2 has already been detected on Titan. Powerful reactants in organic chemistry, CH2N2, and CH3N3, may be also present. They exhibit spectral signatures in the mid-IR strong enough to allow their detection at the 10-100 ppb level. They may be detectable on future IR spectra (ISO and Cassini) of Titan.     

Past and future of radio occultation studies of planetary atmospheres

Measurements of radio waves that have propagated through planetary atmospheres have provided exploratory results on atmospheric constituents, structure, dynamics, and ionization for Venus, Mars, Titan, Jupiter, Saturn, and Uranus. Highlights of past results are reviewed in order to define and illustrate the potential of occultation and related radio studies in future planetary missions.     

Comparative atmospheric dynamics for terrestrial planets

A review is presented of theoretical ideas on the general circulations in the atmospheres of Earth, Mars and Venus and also of results of their theoretical modelling. The role of various factors is discussed in the formation of the circulations. These results are compared with observational data obtained by different means. Data of direct local measurements of meteorological parameters in the atmospheres of Venus and Mars are discussed including those obtained at their surfaces.