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.
With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of bio/organic signatures. This study further investigates the ability of thenardite (Na 2 SO 4 ) to effectively facilitate the ionization and identification of aromatic amino acids (phenylalanine, tyrosine and tryptophan) using a technique called geomatrix-assisted laser desorption/ionization in conjunction with a Fourier transform ion cyclotron resonance mass spectrometry. This technique is based on the ability of a mineral host to facilitate desorption and ionization of bio/organic molecules for detection. Spectra obtained from each aromatic amino acid alone and in combination with thenardite show differences in ionization mechanism and fragmentation patterns. These differences are due to chemical and structural differences between the aromatic side chains of their respective amino acid. Tyrosine and tryptophan when combined with thenardite were observed to undergo cation-attachment ([M+Na] + ), due to the high alkali ion affinity of their aromatic side chains. In addition, substitution of the carboxyl group hydrogen by sodium led to formation of [M-H+Na]Na + peaks. In contrast, phenylalanine mixed with thenardite showed no evidence of Na + attachment. Understanding how co-deposition of amino acids with thenardite can affect the observed mass spectra is important for future exploration missions that are likely to use laser desorption mass spectrometry to search for bio/organic compounds in extraterrestrial environments.
Evidence of microbial activity associated with mineralization of secondary Na-sulphate minerals (thenardite, mirabilite) in the basaltic subsurface of Craters of the Moon National Monument (COM), Idaho were examined by scanning electron microscopy, X-ray diffraction, laser desorption Fourier transform ion cyclotron resonance mass spectrometry (LD-FTICR-MS), Fourier transform infrared spectroscopy (FTIR) and isotope ratio mass spectrometry. Peaks suggestive of bio/organic compounds were observed in the secondary Na-sulphate deposits by LD-FTICR-MS. FTIR provided additional evidence for the presence of bio/organic compounds. Sulphur fractionation was explored to assist in determining if microbes may play a role in oxidizing sulphur. The presence of bio/organic compounds associated with Na-sulphate deposits, along with the necessity of oxidizing reduced sulphur to sulphate, suggests that biological activity may be involved in the formation of these secondary minerals. The secondary Na-sulphate minerals probably form from the overlying basalt through leached sodium ions and sulphate ions produced by bio-oxidation of Fe-sulphide minerals. Since the COM basalts are one of the most comparable terrestrial analogues for their Martian counterparts, the occurrence of biological activity in the formation of sulphate minerals at COM has direct implications for the search for life on Mars. In addition, the presence of caves on Mars suggests the importance of these environments as possible locations for growth and preservation of microbial activity. Therefore, understanding the physiochemical pathways of abiotic and biotic mineralization in the COM subsurface and similar basaltic settings has direct implications for the search for extinct or extant life on Mars.
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