Testing Flight-like Pyrolysis Gas Chromatography-Mass Spectrometry as Performed by the Mars Organic Molecule Analyzer Onboard the ExoMars 2020 Rover on Oxia Planum Analog Samples

The Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars 2020 rover (to be landed in March 2021) utilizes pyrolysis gas chromatography-mass spectrometry (GC-MS) with the aim to detect organic molecules in martian (sub-) surface materials. Pyrolysis, however, may thermally destroy and transform organic matter depending on the temperature and nature of the molecules, thus altering the original molecular signatures. In this study, we tested MOMA flight-like pyrolysis GC-MS without the addition of perchlorates on well-characterized natural mineralogical analog samples for Oxia Planum, the designated ExoMars 2020 landing site. Experiments were performed on an iron-rich shale (that is rich in Fe-Mg-smectites) and an opaline chert, with known organic matter compositions, to test pyrolytic effects related to heating in the MOMA oven. Two hydrocarbon standards (n-octadecane and phytane) were also analyzed. The experiments show that during stepwise pyrolysis (300°C, 500°C, and 700°C), (1) low-molecular-weight hydrocarbon biomarkers (such as acyclic isoprenoids and aryl isoprenoids) can be analyzed intact, (2) discrimination between free and complex molecules (macromolecules) is principally possible, (3) secondary pyrolysis products and carryover may affect the 500°C and 700°C runs, and (4) the type of the organic matter (functionalized vs. defunctionalized) governs the pyrolysis outcome rather than the difference in mineralogy. Although pyrosynthesis reactions and carryover clearly have to be considered in data interpretation, our results demonstrate that pyrolysis GC-MS onboard MOMA operated under favorable conditions (e.g., no perchlorates) will be capable of providing important structural information on organic matter found on Mars, particularly when used in conjunction with other techniques on MOMA, including derivatization and thermochemolysis GC-MS and laser desorption/ionization-MS.