Compact two-step laser time-of-flight mass spectrometer for \u3ci\u3ein situ\u3c/i\u3e analyses of aromatic organics on planetary missions

RATIONALE: A miniature time-of-flight mass spectrometer measuring 20 cm in length has been adapted to demonstrate two-step laser desorption/ionization (LDI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional LDI, in order to produce low-fragmentation mass spectra of organic analytes. Tuning the UVionization laser energy would allow control of the degree of fragmentation, which might enable better identification of constituent species. METHODS: A reflectron time-of-flight mass spectrometer prototype was modified to allow a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. RESULTS: The instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. Two-step laser mass spectrometry (L2MS) analysis of a model PAH, pyrene, was demonstrated, including molecular ion identification and the onset of tunable fragmentation as a function of ionizing laser energy. Mass resolution m/Δm=380 at full width at half-maximum was achieved for gas-phase postionization of desorbed neutrals in this highly compact mass analyzer. CONCLUSIONS: Achieving L2MS in a highly miniaturized instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of molecular and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. The selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is proposed