Exploring Biosignatures Associated with Thenardite by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (GALDI-FTICR-MS)

Abstract

Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) has been employed to determine how effectively bio/organic molecules associated with the mineral thenardite (Na 2 SO 4 ) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C 2 H 4 NO 2 − at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition of C 18 H 39 O 7 Na−. A natural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination were estimated to be 3 parts per trillion or ∼7 zeptomoles (10 − 21 ) per laser spot. Attempts to improve the signal-to-noise ratio by co-adding FTICR-MS data predetermined to contain the biosignatures of interest revealed problems due to a lack of phase coherence between data sets.