Identifying Amino Acid Isomers with Mass Spectrometry on Icy Ocean Moons

Enceladus and Europa are compelling targets for astrobiology investigations due to their potentially habitable subsurface oceans connected to the icy surface by geological processes. Both moons emit ice grains either ejected via micrometeoroid surface impacts or erupted from their interiors through plume activity. These grains can be sampled by spacecraft flybys, and their composition can be analyzed by impact ionization mass spectrometers, such as the SUrface Dust Analyzer (SUDA) onboard Europa Clipper, or similar instruments proposed for future Enceladus missions. These instruments can identify potential biomolecules, such as amino acids, down to nanomolar concentrations, as demonstrated through previous laboratory experiments. However, the identical masses of isomeric compounds could hinder the mass spectrometric identification and assignment of molecular biosignatures. Here, we investigate the general capability of impact ionization mass spectrometry to distinguish between isomeric compounds, validated with a test case of eight amino acid isomers with an identical molecular mass of 131.173 u and formula C₆H₁₃NO₂, using quantum chemical calculations. We show that the amino acid isomers (including diastereoisomers) can be uniquely identified due to their distinct mass spectral features and fragmentation patterns, explained through intramolecular hydrogen bonding and other structural specificities of the individual isomers. Importantly, α-amino acids can be clearly differentiated from non-α-amino acids owing to several major mass spectral features. We show that SUDA-type instruments have sufficient capabilities to differentiate certain isomers and to identify biosignatures from ocean worlds with high confidence.