Detecting Complex Organic Compounds Using the SAM Wet Chemistry Experiment on Mars

The search for organic molecules on Mars can provide important first clues of abiotic chemistry and/or extinct or extant biota on the planet. Gas Chromatography Mass Spectrometry (GC-MS) is currently the most relevant space-compatible analytical tool for the detection of organic compounds. Nevertheless, GC separation is intrinsically restricted to volatile molecules, and many molecules of astrobiological interest are chromatographically refractory or polar. To analyze these organics such as amino acids, nucleobases and carboxylic acids in the Martian regolith, an additional derivatization step is required to transform them into volatile derivatives that are amenable to GC analysis. As part of the Sample Analysis at Mars (SAM) experiment onboard Mars Science Laboratory (MSL) Curiosity rover, a single-step protocol of extraction and chemical derivatization with the silylating reagent N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) has been developed to reach a wide range of astrobiology-relevant refractory organic molecules (Mahaffy et al. 2012; Stalport et al. 2012). Seven cups in the SAM instrument are devoted to MTBSTFA derivatization. However, this chemical reaction adds a protective silyl group in place of each labile hydrogen, which makes the molecule non-identifiable in common mass spectra libraries. Therefore, we have created an extended library of mass spectra of MTBSTFA derivatized compounds of interest, considering their potential occurrence in Mars soils. We then looked specifically for MTBSTFA derivatized compounds using the existing and the newly created library, in various Mars analog soils. To enable a more accurate interpretation of the in situ derivatization GC-MS results that will be obtained by SAM, the lab experiments were performed as close as possible to the SAM flight instrument experimental conditions. Our first derivatization experiments display promising results, the laboratory system permitting an extraction and detection of several proteinogenic amino acids and carboxylic acids from Martian analog materials. Preliminary results show a lack of derivatized organic molecules in hydrated solid samples however, where the MTBSTFA reagent possibly reacts preferentially with the water from hydrated minerals (Stalport et al. 2012). This result shows the importance of a complete understanding of the MTBSTFA reaction depending on the nature of the soil and will help guide the selection of optimal samples for the SAM wet chemistry on Mars.