Compact two-step laser time-of-flight mass spectrometer for in situ 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 UV ionization 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.

Arrayed time-of-flight mass spectrometry for time-critical detection of hazardous agents.

The design and operation of an arrayed time-of-flight (TOF) mass spectrometer for simultaneous data acquisition from multiple samples is described. Versions of the instrument employ sets of two or four linear or reflectron mass analyzers. They are housed in the same vacuum chamber and utilize the same laser for ion desorption. Instrument performance is illustrated in the example of a two-linear-mass-analyzer array using MALDI-MS for mixtures of commercially available proteins as well as intact microorganisms. We also describe the properties of a novel short delay time (<170 ns) pulsed extraction method for linear TOF analyzers. This configuration allows uniform resolution improvements to be achieved in a wide m/z range. In addition, we present multiplexed sample preparation methods, using different reagents prior to mass analysis in the arrayed system, to increase the overall sensitivity of the MS method and to allow wider and more efficient detection across the entire range of potentially hazardous agents. In addition to the multifold increase in data collection rates, arrayed TOF-MS configurations provide a high degree of redundancy, critical for rapid, high confidence agent identification as well as for reduction in false alarm rates.