Pyrolysis of Carboxylic Acids in the Presence of Iron Oxides: Implications for Life Detection on Missions to Mars

The search for, and characterization of, organic matter on Mars is central to efforts in identifying habitable environments and detecting evidence of life in the martian surface and near surface. Iron oxides are ubiquitous in the martian regolith and are known to be associated with the deposition and preservation of organic matter in certain terrestrial environments, thus iron oxide-rich sediments are potential targets for life-detection missions. The most frequently used protocol for martian organic matter characterization (also planned for use on ExoMars) has been thermal extraction for the transfer of organic matter to gas chromatography-mass spectrometry (GC-MS) detectors. For the effective use of thermal extraction for martian samples, it is necessary to explore how potential biomarker organic molecules evolve during this process in the presence of iron oxides. We have thermally decomposed iron oxides simultaneously with (z)-octadec-9-enoic and n-octadecanoic acids and analyzed the products through pyrolysis-GC-MS. We found that the thermally driven dehydration, reduction, and recrystallization of iron oxides transformed fatty acids. Overall detectability of products greatly reduced, molecular diversity decreased, unsaturated products decreased, and aromatization increased. The severity of this effect increased as reduction potential of the iron oxide and inferred free radical formation increased. Of the iron oxides tested hematite showed the least transformative effects, followed by magnetite, goethite, then ferrihydrite. It was possible to identify the saturation state of the parent carboxylic acid at high (0.5 wt %) concentrations by the distribution of n-alkylbenzenes in the pyrolysis products. When selecting life-detection targets on Mars, localities where hematite is the dominant iron oxide could be targeted preferentially, otherwise thermal analysis of carboxylic acids, or similar biomarker molecules, will lead to enhanced polymerization, aromatization, and breakdown, which will in turn reduce the fidelity of the original biomarker, similar to changes normally observed during thermal maturation.