Prebiotic reactions in a Mars analog iron mineral system: Effects of nitrate, nitrite, and ammonia on amino acid formation

Iron minerals are highly reactive drivers of abiotic/prebiotic organic chemistry, and in the presence of ammonia (NH₃/NH₄⁺) or other reduced nitrogen (N) compounds, have been shown to promote amino acid synthesis from organic precursors. On early Mars, oxidized nitrogen species (NO_x⁻) such as NO₃⁻ and/or NO₂⁻ may have been present, which could be reduced by Fe(II) to form various species including N₂O and/or NH₃/NH₄⁺. The production of NH₃/NH₄⁺ from Fe(II)-driven NO₃⁻ or NO₂⁻ reduction may be able to feed into prebiotic organic reactions including amino acid formation. In this study, we tested whether iron mineral-driven reduction of NO₃⁻ or NO₂⁻ could provide a source of NH₃/NH₄⁺ to form amino acids from two prebiotically relevant precursors (pyruvate and glyoxylate); or, whether an exogeneous source of NH₃/NH₄⁺ would be required. We observed that pyruvate and glyoxylate reacted with Fe-oxyhydroxide minerals in NO_x⁻-containing experiments to form reduced hydroxy acid products; and in experiments containing only NH₃/NH₄⁺, amino acids were also formed. However, significant amino acid formation was not observed in any experiments containing NO₃⁻ or NO₂⁻ unless sufficient NH₄⁺ was also added; furthermore, colorimetric analysis did not show any generation of NH₄⁺ from NO₃⁻/NO₂⁻ reduction at these conditions. NO₂⁻ was observed to be highly reactive with Fe²⁺ and Fe(II)-bearing minerals, resulting in Fe oxidation during mineral precipitation and the formation of oxidized mineral phases (hematite). The Fe(II)/Fe(III) ratio in oxyhydroxide minerals is an important parameter for determining organic product distributions from pyruvate and glyoxylate; therefore, Fe-mediated NO_x⁻ reduction does impact organic chemistry. However, amino acid formation, at least under these conditions, would also require an exogenous source of NH₃/NH₄⁺ or other reduced N species. These results have implications for organic-N chemistry on early Mars, as well as for some early Earth origin of life scenarios regarding organic synthesis in mineral-containing systems.