Titan's Organic Residue from Benzene Ices: Role of Atmospheric Pressure.

Benzene has been detected in Titan's atmosphere, the Saturn's largest moon, and it is known to condense when it reaches the stratosphere to form ice, which is submitted to low ultraviolet (UV) radiation. In a previous work, we put in evidence that the irradiation of benzene ice at λ > 230 nm induces the formation of volatile photoproducts, in particular, fulvene (a benzene isomer) and a solid residue. In this work, we study the influence of pressure on the residue formation after benzene ice's irradiation and its characterization using infrared (IR), Raman, and gas chromatography-mass spectrometry (GC-MS) methods. We show that the residue obtained during the increase of temperature performed at 1 mbar is dominated by CH sp2 groups, whereas the one obtained at 10-6 mbar contains an equivalent proportion of CH sp2 and sp3. Polyphenyls with up to three rings are unambiguously identified by GC-MS in all of the residues formed.

Gas chromatography coupled-to Fourier transform orbitrap mass spectrometer for enantioselective amino acid analyses: Application to pre-cometary organic analog.

Gas chromatography (GC) is a separation technique commonly developed for targeted in situ analyses in planetary space missions. It is coupled with low-resolution mass spectrometry to obtain additional structural information and allow compound identification. However, ground-based analyses of extraterrestrial samples have shown the presence of large molecular diversities. For future targeted in situ analyses, it is therefore essential to develop new technologies. High resolution mass spectrometry (HRMS) is currently being spatialized using FT-orbitrap-MS technology. In this contribution, the coupling of gas chromatography with FT-orbitrap-MS is studied for targeted amino acid analyses. The method for enantioselective separation of amino acids was optimized on a standard mixture comprising 47 amino acid enantiomers. Different ionization modes were optimized, chemical ionization with three different reactive gasses (NH3, CH4 and NH3/CH4) and electron impact ionization at different electron energies. Single ion and full scan monitoring modes were compared, and detection and quantification limits were estimated by internal calibration under the optimized conditions. The GC-FT-orbitrap-MS demonstrated its ability to separate 47 amino acid enantiomers with minimal co-elution. Furthermore, due to the high mass resolution and accuracy of FT-orbitrap-MS, with mass extraction, the S/N is close to zero, allowing average LOD values of 10⁻7 M, orders of magnitude lower than conventional GC-MS techniques. Finally, these conditions were tested for enantioselective analysis of amino acids on an analog of a pre-cometary organic material showing similarities to that of extraterrestrial materials.

Exploring the link between molecular cloud ices and chondritic organic matter in laboratory.

Carbonaceous meteorites are fragments of asteroids rich in organic material. In the forming solar nebula, parent bodies may have accreted organic materials resulting from the evolution of icy grains observed in dense molecular clouds. The major issues of this scenario are the secondary processes having occurred on asteroids, which may have modified the accreted matter. Here, we explore the evolution of organic analogs of protostellar/protoplanetary disk material once accreted and submitted to aqueous alteration at 150 °C. The evolution of molecular compounds during up to 100 days is monitored by high resolution mass spectrometry. We report significant evolution of the molecular families, with the decreases of H/C and N/C ratios. We find that the post-aqueous products share compositional similarities with the soluble organic matter of the Murchison meteorite. These results give a comprehensive scenario of the possible link between carbonaceous meteorites and ices of dense molecular clouds.

Formaldehyde chemistry in cometary ices: the case of HOCH2OH formation.

Laboratory experiments devoted to simulate the chemistry occurring in interstellar and cometary ice analogues are of paramount importance to understand the formation of complex organic molecules that are detected throughout the universe. These laboratory simulations provide relevant hints on the fundamental physical and chemical steps associated with the increase of the molecular complexity in space and, moreover, give benchmark results for dedicated space missions. In the present work, we study the thermally promoted reactivity of H2O-dominated and D2O-dominated cometary ice analogues that contain various amounts of H2CO and NH3 by means of Fourier-transform infrared spectroscopy (FTIR), mass spectrometry and DFT calculations. Experimental measurements show that methyleneglycol (HOCH2OH) and D2-methyleneglycol (DOCH2OD, the corresponding isotopologue) are formed from the H2O- and D2O-dominated ices, respectively, only if ammonia is present. We also reported for the first time the mass spectrum of methyleneglycol and D2-methyleneglycol. B3LYP calculations have also been used to characterize the potential energy surface of the mechanistic steps associated with the formation of HOCH2OH as well as to simulate the IR spectrum of this compound. The fruitful interplay between theory and experiment has allowed us to elucidate the exact role of ammonia during the warming, which essentially stands for the formation and stabilization of the NH4(+)/OH(-) ion pair, thus enabling the OH(-) species to react with formaldehyde. The present results reproduce the heating of circumstellar ices in star formation regions and can be applied to the late thermal evolution of comets. In addition, the mass spectrum of methyleneglycol represents a benchmark for the analysis of the data coming from the ROSINA on-board instrument of the Rosetta mission.

Kinetics of the NH3 and CO2 solid-state reaction at low temperature.

Ammonia and carbon dioxide play an important role in both atmospheric and interstellar ice chemistries. This work presents a theoretical and experimental study of the kinetics of the low-temperature NH3 and CO2 solid-state reaction in ice films, the product of which is ammonium carbamate (NH4(+)NH2COO(-)). It is a first-order reaction with respect to CO2, with a temperature-dependent rate constant fitted to the Arrhenius law in the temperature range 70 K to 90 K, with an activation energy of 5.1 ± 1.6 kJ mol(-1) and a pre-exponential factor of 0.09-0.08(+1.1) s(-1). This work helps to determine the rate of removal of CO2 and NH3, via their conversion into ammonium carbamate, from atmospheric and interstellar ices. We also measure first-order desorption energies of 69.0 ± 0.2 kJ mol(-1) and 76.1 ± 0.1 kJ mol(-1), assuming a pre-exponential factor of 10(13) s(-1), for ammonium carbamate and carbamic acid, respectively.

Acetaldehyde solid state reactivity at low temperature: formation of the acetaldehyde ammonia trimer.

We focus on low temperature reactivity from 25 to 300 K, in ice containing acetaldehyde, ammonia, and formic acid. We show that the warming of this ice mixture forms the acetaldehyde ammonia trimer (2,4,6-trimethyl-1,3,5-hexahydrotriazine, C(6)H(15)N(3)) after five steps. The reaction is monitored by FTIR spectroscopy and mass spectrometry. We propose a mechanism for its formation that differs from the one proposed in the liquid phase. The reaction intermediates, α-aminoethanol (from 80 K) and ethanimine (formed at 180 K), have been identified by a mechanistic approach: each step of the reaction has been treated separately. The chemical implications and the astrophysical relevance of the study are also discussed.