ESA's Cometary Mission Rosetta-Re-Characterization of the COSAC Mass Spectrometry Results.

The most pristine material of the Solar System is assumed to be preserved in comets in the form of dust and ice as refractory matter. ESA's mission Rosetta and its lander Philae had been developed to investigate the nucleus of comet 67P/Churyumov-Gerasimenko in situ. Twenty-five minutes after the initial touchdown of Philae on the surface of comet 67P in November 2014, a mass spectrum was recorded by the time-of-flight mass spectrometer COSAC onboard Philae. The new characterization of this mass spectrum through non-negative least squares fitting and Monte Carlo simulations reveals the chemical composition of comet 67P. A suite of 12 organic molecules, 9 of which also found in the original analysis of this data, exhibit high statistical probability to be present in the grains sampled from the cometary nucleus. These volatile molecules are among the most abundant in the comet's chemical composition and represent an inventory of the first raw materials present in the early Solar System.

Investigating the Effect of Perchlorate on Flight-like Gas Chromatography-Mass Spectrometry as Performed by MOMA on board the ExoMars 2020 Rover.

The Mars Organic Molecule Analyzer (MOMA) instrument on board ESA's ExoMars 2020 rover will be essential in the search for organic matter. MOMA applies gas chromatography-mass spectrometry (GC-MS) techniques that rely on thermal volatilization. Problematically, perchlorates and chlorates in martian soils and rocks become highly reactive during heating (>200°C) and can lead to oxidation and chlorination of organic compounds, potentially rendering them unidentifiable. Here, we analyzed a synthetic sample (alkanols and alkanoic acids on silica gel) and a Silurian chert with and without Mg-perchlorate to evaluate the applicability of MOMA-like GC-MS techniques to different sample types and assess the impact of perchlorate. We used a MOMA flight analog system coupled to a commercial GC-MS to perform MOMA-like pyrolysis, in situ derivatization, and in situ thermochemolysis. We show that pyrolysis can provide a sufficient overview of the organic inventory but is strongly affected by the presence of perchlorates. In situ derivatization facilitates the identification of functionalized organics but showed low efficiency for n-alkanoic acids. Thermochemolysis is shown to be an effective technique for the identification of both refractory and functional compounds. Most importantly, this technique was barely affected by perchlorates. Therefore, MOMA GC-MS analyses of martian surface/subsurface material may be less affected by perchlorates than commonly thought, in particular when applying the full range of available MOMA GC-MS techniques.

The Mars Organic Molecule Analyzer (MOMA) Instrument: Characterization of Organic Material in Martian Sediments.

The Mars Organic Molecule Analyzer (MOMA) instrument onboard the ESA/Roscosmos ExoMars rover (to launch in July, 2020) will analyze volatile and refractory organic compounds in martian surface and subsurface sediments. In this study, we describe the design, current status of development, and analytical capabilities of the instrument. Data acquired on preliminary MOMA flight-like hardware and experimental setups are also presented, illustrating their contribution to the overall science return of the mission. Key Words: Mars-Mass spectrometry-Life detection-Planetary instrumentation. Astrobiology 17, 655-685.

Habitability on Early Mars and the Search for Biosignatures with the ExoMars Rover.

The second ExoMars mission will be launched in 2020 to target an ancient location interpreted to have strong potential for past habitability and for preserving physical and chemical biosignatures (as well as abiotic/prebiotic organics). The mission will deliver a lander with instruments for atmospheric and geophysical investigations and a rover tasked with searching for signs of extinct life. The ExoMars rover will be equipped with a drill to collect material from outcrops and at depth down to 2 m. This subsurface sampling capability will provide the best chance yet to gain access to chemical biosignatures. Using the powerful Pasteur payload instruments, the ExoMars science team will conduct a holistic search for traces of life and seek corroborating geological context information. Key Words: Biosignatures-ExoMars-Landing sites-Mars rover-Search for life. Astrobiology 17, 471-510.

COMETARY SCIENCE. Organic compounds on comet 67P/Churyumov-Gerasimenko revealed by COSAC mass spectrometry.

Comets harbor the most pristine material in our solar system in the form of ice, dust, silicates, and refractory organic material with some interstellar heritage. The evolved gas analyzer Cometary Sampling and Composition (COSAC) experiment aboard Rosetta's Philae lander was designed for in situ analysis of organic molecules on comet 67P/Churyumov-Gerasimenko. Twenty-five minutes after Philae's initial comet touchdown, the COSAC mass spectrometer took a spectrum in sniffing mode, which displayed a suite of 16 organic compounds, including many nitrogen-bearing species but no sulfur-bearing species, and four compounds­methyl isocyanate, acetone, propionaldehyde, and acetamide­that had not previously been reported in comets.

Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

Comparison of prototype and laboratory experiments on MOMA GCMS: results from the AMASE11 campaign.

The characterization of any organic molecules on Mars is a top-priority objective for the ExoMars European Space Agency-Russian Federal Space Agency joint mission. The main instrument for organic analysis on the ExoMars rover is the Mars Organic Molecule Analyzer (MOMA). In preparation for the upcoming mission in 2018, different Mars analog samples are studied with MOMA and include samples collected during the Arctic Mars Analog Svalbard Expedition (AMASE) to Svalbard, Norway. In this paper, we present results obtained from two different Mars analog sites visited during AMASE11, Colletthøgda and Botniahalvøya. Measurements were performed on the samples during AMASE11 with a MOMA gas chromatograph (GC) prototype connected to a commercial mass spectrometer (MS) and later in home institutions with commercial pyrolysis-GCMS instruments. In addition, derivatization experiments were performed on the samples during AMASE11 and in the laboratory. Three different samples were studied from the Colletthøgda that included one evaporite and two carbonate-bearing samples. Only a single sample was studied from the Botniahalvøya site, a weathered basalt covered by a shiny surface consisting of manganese and iron oxides. Organic molecules were detected in all four samples and included aromatics, long-chained hydrocarbons, amino acids, nucleobases, sugars, and carboxylic acids. Both pyrolysis and derivatization indicated the presence of extinct biota by the detection of carboxylic acids in the samples from Colletthøgda, while the presence of amino acids, nucleobases, carboxylic acids, and sugars indicated an active biota in the sample from Botniahalvøya. The results obtained with the prototype flight model in the field coupled with repeat measurements with commercial instruments within the laboratory were reassuringly similar. This demonstrates the performance of the MOMA instrument and validates that the instrument will aid researchers in their efforts to answer fundamental questions regarding the speciation and possible source of organic content on Mars.