From organic chemistry in small bodies of the solar system to low temperature chemistry in the universe. Preface.

A COSPAR two days Symposium has been dedicated to "Prebiotic chemistry in Space" at the COSPAR Plenary Meeting, (Hamburg, Germany, July 1994). This Symposium was jointly organized by Commissions B (Space studies of the Earth-Moon system, planets and small bodies of the solar system) and F (Life sciences as related to space). Its goal was to review, from an interdisciplinary approach, our knowledge on organic and prebiotic chemistry in small bodies of the Solar System, and on low temperature chemistry and exobiology. The Symposium was sponsored by COSPAR and the IAU (session 1), ESA, NASA, and ISSOL (session 2).     

From the interstellar clouds, through the inner to the outer solar system: a universally distributed complex organic chemistry. Preface.

High molecular weight organic compounds are involved in the chemistry and physics of many astrophysical and planetary objects. They are or should be present in interstellar dust, in comets and meteorites, in the Giant planets and Titan, in asteroids Triton and icy satellites. They represent a class of very complex organic material, part of which may have played a role in the origin of life on Earth. Thus they directly concern prebiotic chemistry and exobiology.     

Production of hydrocarbons and nitriles by electrical processes in Titan's atmosphere.

Although lightning has not been observed in Titan's atmosphere, the presence of methane rain in the troposphere suggests the possibility of electrical activity in the form of corona and/or lightning discharges. Here we examine the chemical effects of these electrical processes on a Titan simulated atmosphere composed of CH4 in N2 at various mixing ratios. Corona discharges were simulated in two different experimental arrays. For the detection of reactive intermediates we used a mass spectrometer to study the main positive ions arising by bombarding low-energy electrons from a hot filament into low-pressure methane. The final stable products, generated by applying a high voltage in a coaxial reactor with either positive or negative polarity, were separated and detected by gas chromatography-Fourier transform infrared spectroscopy and electron impact mass spectrometry (GC-FTIR-MS). Lightning discharges were simulated by a hot and dense plasma generated by a Nd-YAG laser and the final products were separated and detected by GC-FTIR-MS. Corona discharges produce linear and branched hydrocarbons as well as nitriles whereas lightning discharges generate mainly unsaturated hydrocarbons and nitriles. Lightning discharges are about 2 orders of magnitude more efficient in product formation than corona discharges.     

The PROCESS experiment: amino and carboxylic acids under Mars-like surface UV radiation conditions in low-earth orbit

The search for organic molecules at the surface of Mars is a top priority of the next Mars exploration space missions: Mars Science Laboratory (NASA) and ExoMars (ESA). The detection of organic matter could provide information about the presence of a prebiotic chemistry or even biological activity on this planet. Therefore, a key step in interpretation of future data collected by these missions is to understand the preservation of organic matter in the martian environment. Several laboratory experiments have been devoted to quantifying and qualifying the evolution of organic molecules under simulated environmental conditions of Mars. However, these laboratory simulations are limited, and one major constraint is the reproduction of the UV spectrum that reaches the surface of Mars. As part of the PROCESS experiment of the European EXPOSE-E mission on board the International Space Station, a study was performed on the photodegradation of organics under filtered extraterrestrial solar electromagnetic radiation that mimics Mars-like surface UV radiation conditions. Glycine, serine, phthalic acid, phthalic acid in the presence of a mineral phase, and mellitic acid were exposed to these conditions for 1.5 years, and their evolution was determined by Fourier transform infrared spectroscopy after their retrieval. The results were compared with data from laboratory experiments. A 1.5-year exposure to Mars-like surface UV radiation conditions in space resulted in complete degradation of the organic compounds. Half-lives between 50 and 150?h for martian surface conditions were calculated from both laboratory and low-Earth orbit experiments. The results highlight that none of those organics are stable under low-Earth orbit solar UV radiation conditions.     

Astrobiology and habitability of Titan

Largest satellite of Saturn and the only in the solar system having a dense atmosphere, Titan is one of the key planetary bodies for astrobiological studies, due to several aspects. (i) Its analogies with planet Earth, in spite of much lower temperatures, with, in particular, a methane cycle on Titan analogous to the water cycle on Earth. (ii) The presence of an active organic chemistry, involving several of the key compounds of prebiotic chemistry. The recent data obtained from the Huygens instruments show that the complex organic matter in Titan’s low atmosphere is mainly concentrated in the aerosol particles. The formation of biologically interesting compounds may also occur in the deep water ocean, from the hydrolysis of complex organic material included in the chrondritic matter accreted during the formation of Titan. (iii) The possible emergence and persistence of Life on Titan. All ingredients which seem necessary for Life to appear and even develop – liquid water, organic matter and energy – are present on Titan. Consequently, it cannot be excluded that life may have emerged on or in Titan. In spite of the extreme conditions in this environment life may have been able to adapt and to persist. Many data are still expected from the Cassini-Huygens mission and future astrobiological exploration mission of Titan are now under consideration. Nevertheless, Titan already looks like another world, with an active organic chemistry, in the absence of permanent liquid water, on the surface: a natural laboratory for prebiotic-like chemistry.     

Search for organic molecules at the Mars surface: The “Martian Organic Material Irradiation and Evolution” (MOMIE) project

The life on Mars remains an open question because of the lack of proof of its past emergence and its current presence. The only indices of a potential Martian life were provided by the Viking Landers, and the study of the Martian meteorite ALH84001 discovered in the Antarctic. In the two case, the results of experiments could be explained either by the presence of life forms or by abiotic processes. The recent data of Mars Express orbiter and Mars Exploration Rovers show different proofs of a past environment favourable for life. Among the targets we seek, the organic molecules are primordial because they are necessary to the origin of life. A key question is to know if they are present, in which concentration and under which form. Within the framework of a search for organic, we are developing an experimental setup simulating as close as possible the environmental conditions of Mars surface in order to determine how organic species evolve. We present here the first step of the development of this experiment which focuses on the study of the impact of the solar UV radiations reaching the Mars surface on glycine. First results show that glycine does not resist if directly exposed to UV radiations.     

HCN formation under electron impact: experimental studies and application to Neptune's atmosphere.

Laboratory experiments simulating organic synthesis in Neptune's atmosphere have been performed. We have submitted to a spark discharge gaseous mixtures containing 9 mbar of molecular nitrogen and 3 mbar of methane (the p(N2)/p(CH4) ratio is compatible with upper limits in Neptune's stratosphere) with varying quantities of molecular hydrogen. The spark discharge is used to model the energetic electrons produced by the impact of cosmic rays on the high atmosphere of Neptune. HCN is synthesized in the described experimental conditions, even with a low mixing ratio of molecular nitrogen. Studying the variation of HCN production with the initial composition of the gas mixture and extrapolating to high mixing ratio of molecular hydrogen allows to estimate HCN production in Neptune's atmosphere. The computed HCN production flux is 7x10(7) m-2 s-1, which is two orders of magnitude lower than the value predicted by chemical models for an internal source of N atoms. The major uncertainty in our extrapolation is the energetic distribution of electrons, implicitly assumed comparable in the discharge and in Neptune's atmosphere. We note that this distribution is also a source of uncertainty in chemical models. The chemical mechanism responsible for the local formation of HCN in the stratosphere probably occurs in the reactor too. We propose a simple characterization of the spark discharge. We thus link the molecular nitrogen dissociation cross section by electron impact to the measured parameters of the experiments (current, voltage, initial partial pressures) and to the resulting HCN partial pressures. However, other laboratory experiments with larger hydrogen pressures, requiring a more powerful electric source, have to be performed to yield a value of the cross section.     

Cosima – High Resolution Time-of-Flight Secondary Ion Mass Spectrometer for the Analysis of Cometary Dust Particles onboard Rosetta

The ESA mission Rosetta, launched on March 2nd, 2004, carries an instrument suite to the comet 67P/Churyumov-Gerasimenko. The COmetary Secondary Ion Mass Anaylzer – COSIMA – is one of three cometary dust analyzing instruments onboard Rosetta. COSIMA is based on the analytic measurement method of secondary ion mass spectrometry (SIMS). The experiment’s goal is in-situ analysis of the elemental composition (and isotopic composition of key elements) of cometary grains. The chemical characterization will include the main organic components, present homologous and functional groups, as well as the mineralogical and petrographical classification of the inorganic phases. All this analysis is closely related to the chemistry and history of the early solar system. COSIMA covers a mass range from 1 to 3500 amu with a mass resolution m/Δm @ 50% of 2000 at mass 100 amu. Cometary dust is collected on special, metal covered, targets, which are handled by a target manipulation unit. Once exposed to the cometary dust environment, the collected dust grains are located on the target by a microscopic camera. A pulsed primary indium ion beam (among other entities) releases secondary ions from the dust grains. These ions, either positive or negative, are selected and accelerated by electrical fields and travel a well-defined distance through a drift tube and an ion reflector. A microsphere plate with dedicated amplifier is used to detect the ions. The arrival times of the ions are digitized, and the mass spectra of the secondary ions are calculated from these time-of-flight spectra. Through the instrument commissioning, COSIMA took the very first SIMS spectra of the targets in space. COSIMA will be the first instrument applying the SIMS technique in-situ to cometary grain analysis as Rosetta approaches the comet 67P/Churyumov-Gerasimenko, after a long journey of 10 years, in 2014.     

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.     

Titan and exobiological aspects of the Cassini-Huygens mission

Titan, the largest satellite of Saturn, has a dense N2-CH4 atmosphere rich in organic compounds, both in gas and in aerosol phases. Its surface is probably covered by oceans of liquid methane-ethane mixtures, with many dissolved organics. This quasi planet appears as a natural laboratory to study chemical evolution toward complex organic systems in a planetary environment over a long time scale. With the Cassini-Huygens mission NASA and ESA will jointly send an orbiter (Cassini) around Saturn and a probe (Huygens) in the atmosphere of Titan. This mission, currently planned to be launched in 1996-1997 for a Saturn - Titan arrival in 2004, offers a unique opportunity to study in detail extra-terrestrial organic processes. Consequently, it has important implications in the field of exobiology and the origins of life.