Discriminating Abiotic and Biotic Fingerprints of Amino Acids and Fatty Acids in Ice Grains Relevant to Ocean Worlds.

Identifying and distinguishing between abiotic and biotic signatures of organic molecules such as amino acids and fatty acids is key to the search for life on extraterrestrial ocean worlds. Impact ionization mass spectrometers can potentially achieve this by sampling water ice grains formed from ocean water and ejected by moons such as Enceladus and Europa, thereby exploring the habitability of their subsurface oceans in spacecraft flybys. Here, we extend previous high-sensitivity laser-based analog experiments of biomolecules in pure water to investigate the mass spectra of amino acids and fatty acids at simulated abiotic and biotic relative abundances. To account for the complex background matrix expected to emerge from a salty Enceladean ocean that has been in extensive chemical exchange with a carbonaceous rocky core, other organic and inorganic constituents are added to the biosignature mixtures. We find that both amino acids and fatty acids produce sodiated molecular peaks in salty solutions. Under the soft ionization conditions expected for low-velocity (2-6 km/s) encounters of an orbiting spacecraft with ice grains, the unfragmented molecular spectral signatures of amino acids and fatty acids accurately reflect the original relative abundances of the parent molecules within the source solution, enabling characteristic abiotic and biotic relative abundance patterns to be identified. No critical interferences with other abiotic organic compounds were observed. Detection limits of the investigated biosignatures under Enceladus-like conditions are salinity dependent (decreasing sensitivity with increasing salinity), at the µM or nM level. The survivability and ionization efficiency of large organic molecules during impact ionization appear to be significantly improved when they are protected by a frozen water matrix. We infer from our experimental results that encounter velocities of 4-6 km/s are most appropriate for impact ionization mass spectrometers to detect and discriminate between abiotic and biotic signatures.