Effects of UV and Calcium Perchlorates on Uracil Deposited on Strontium Fluoride Substrates at Mars Pressure and Temperature.

Organic matter is actively searched on Mars with current and future space missions as it is a key to detecting potential biosignatures. Given the current harsh environmental conditions at the surface of Mars, many organic compounds might not be preserved over a long period as they are exposed to energetic radiation such as ultraviolet light, which is not filtered above 190 nm by the martian atmosphere. Moreover, the presence of strong oxidizing species in the regolith, such as perchlorate salts, might enhance the photodegradation of organic compounds of astrobiological interest. Because current space instruments analyze samples collected in the upper surface layer, it is necessary to investigate the stability of organic matter at the surface of Mars. Previous experimental studies have shown that uracil, a molecule relevant to astrobiology, is quickly photolyzed when exposed to UV radiation under the temperature and pressure conditions of the martian surface with an experimental quantum efficiency of photodecomposition (φexp) of 0.30 ± 0.26 molecule·photon-1. Moreover, the photolysis of uracil leads to the formation of more stable photoproducts that were identified as uracil dimers. The present work aims to characterize the additional effect of calcium perchlorate detected on Mars on the degradation of uracil. Results show that the presence of calcium perchlorate enhances the photodecomposition of uracil with φexp = 12.3 ± 8.3 molecule·photon-1. Although some of the photoproducts formed during these experiments are common to those formed from pure uracil only, the Fourier transformation infrared (FTIR) detection of previously unseen chemical functions such as alkyne C ≡ C or nitrile C ≡ N has shown that additional chemical species are formed in the presence of calcium perchlorate in the irradiated sample. This implies that the effect of calcium perchlorate on the photolysis of uracil is not only kinetic but also related to the nature of the photoproducts formed.

Photolysis of Cometary Organic Dust Analogs on the EXPOSE-R2 Mission at the International Space Station.

We describe the results obtained on a set of organic samples that have been part of the experiment "Photochemistry on the Space Station (PSS)" on the EXPOSE-R2 mission conducted on the EXPOSE-R facility situated outside the International Space Station (ISS). The organic samples were prepared in the Catania laboratory by 200 keV He+ irradiation of N2:CH4:CO icy mixtures deposited at 17 K, on vacuum UV (VUV) transparent MgF2 windows. This organic material contains different chemical groups, including triple CN bonds, that are thought to be of interest for astrobiology. It is widely accepted that materials similar to that produced in the laboratory by ion irradiation of frozen ices could be present in some astrophysical environments such as comets. Once expelled from comets, these materials are exposed to solar radiation during their interplanetary journey. In the young Solar System, some of these processed materials could have reached early Earth and contributed to its chemical and prebiotic evolution. The samples were exposed for 16 months to the unshielded solar UV photons. It was found that, if an interplanetary dust particle (IDP) containing organic material (50% vol) is large enough (>20-30 µm), relevant chemical groups, such as those containing the CN triple bond, can survive for many years (>104 years) in the interplanetary medium.

Gas chromatography for in situ analysis of a cometary nucleus: characterization and optimization of diphenyl/dimethylpolysiloxane stationary phases.

The development of a gas chromatograph for the cometary sampling and composition (COSAC) experiment is described in the context of the preparation for the European Space Agency (ESA) Mission Rosetta for investigation of a cometary nucleus. COSAC is one out of ten experiments on the Rosetta Lander. Its scientific goal is to analyze in situ the chemical composition of the volatile constituents of the nucleus of the target comet P/Wirtanen. Constituted of several (up to eight) capillary wall-coated and porous-layer open tubular columns operating in parallel, the GC system is designed to separate and identify both organic and inorganic compounds which evolve from the comet naturally or are obtained from cometary samples through stepwise heating in a miniaturized pyrolizer. In this first part of our study, dimethylpolysiloxane (DMPS) stationary phases with increasing percentages of diphenyl substituted group (DP) have been investigated. A coupled experimental and theoretical approach has been taken in order to predict chromatographic data. By the use of a four-point experimental calibration (0 to 65% diphenyl group) in conjunction with Pro ezGC modeling software, results in prediction of multicomponent chromatograms with a mean error less than 5% for each compound retention time were obtained, irrespective of the stationary phase's diphenyl content and column physical parameters. The possibility to associate such phases is illustrated by the evolution of coelutions obtained on a non-polar (100% DMPS) and a medium polar (65% DP-DMPS) stationary phase, respectively. This study showed that with a small number of well tuned DP-DMPS columns, the separation and identification of most of the targeted compounds can be achieved with a minimum amount of coelutions and within the experiment requirements.

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.

The PROCESS experiment: exposure of amino acids in the EXPOSE-E experiment on the international space station and in laboratory simulations.

To understand the chemical behavior of organic molecules in the space environment, amino acids and a dipeptide in pure form and embedded in meteorite powder were exposed in the PROCESS experiment in the EXPOSE-E facility mounted on the European Technology Exposure Facility (EuTEF) platform on board the International Space Station (ISS). After exposure to space conditions for 18 months, the samples were returned to Earth and analyzed in the laboratory for reactions caused by solar UV and cosmic radiation. Chemical degradation and possible racemization and oligomerization, the main reactions caused by photochemistry in the vacuum ultraviolet domain (VUV, wavelength range 100-200 nm for photon energy from 6.2 to 12.4 eV) were examined in particular. The molecules were extracted and derivatized by silylation and analyzed by gas chromatograph coupled to a mass spectrometer (GC-MS) to quantify the rate of the degradation of the compounds. Laboratory exposure in several wavelength ranges from UV to VUV was carried out in parallel in the Cologne Deutsches Zentrum für Luft- und Raumfahrt (DLR) Center and Centre de biophysique moléculaire (CBM) laboratories. The results show that resistance to irradiation is a function of the chemical nature of the exposed molecules and the wavelengths of the UV light. The most altered compounds were the dipeptide, aspartic acid, and aminobutyric acid. The most resistant were alanine, valine, glycine, and aminoisobutyric acid. Our results also demonstrate the protective effect of meteorite powder, which reemphasizes the importance of exogenic contribution to the inventory of prebiotic organics on early Earth.

Investigating the photostability of carboxylic acids exposed to Mars surface ultraviolet radiation conditions.

The detection and identification of organic molecules on Mars are of primary importance to establish the existence of a possible ancient prebiotic chemistry or even biological activity. The harsh environmental conditions at the surface of Mars could explain why the Viking probes-the only efforts, to date, to search for organics on Mars-detected no organic matter. To investigate the nature, abundance, and stability of organic molecules that could survive such environmental conditions, we developed a series of experiments that simulate martian surface environmental conditions. Here, we present results with regard to the impact of solar UV radiation on various carboxylic acids, such as mellitic acid, which are of astrobiological interest to the study of Mars. Our results show that at least one carboxylic acid, mellitic acid, could produce a resistant compound-benzenehexacarboxylic acid-trianhydride (C(12)O(9))-when exposed to martian surface radiation conditions. The formation of such products could contribute to the presence of organic matter in the martian regolith, which should be considered a primary target for in situ molecular analyses during future surface missions.

Darwin--a mission to detect and search for life on extrasolar planets.

The discovery of extrasolar planets is one of the greatest achievements of modern astronomy. The detection of planets that vary widely in mass demonstrates that extrasolar planets of low mass exist. In this paper, we describe a mission, called Darwin, whose primary goal is the search for, and characterization of, terrestrial extrasolar planets and the search for life. Accomplishing the mission objectives will require collaborative science across disciplines, including astrophysics, planetary sciences, chemistry, and microbiology. Darwin is designed to detect rocky planets similar to Earth and perform spectroscopic analysis at mid-infrared wavelengths (6-20 mum), where an advantageous contrast ratio between star and planet occurs. The baseline mission is projected to last 5 years and consists of approximately 200 individual target stars. Among these, 25-50 planetary systems can be studied spectroscopically, which will include the search for gases such as CO(2), H(2)O, CH(4), and O(3). Many of the key technologies required for the construction of Darwin have already been demonstrated, and the remainder are estimated to be mature in the near future. Darwin is a mission that will ignite intense interest in both the research community and the wider public.