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  • 1
    Publication Date: 2023-07-27
    Description: 〈title xmlns:mml="http://www.w3.org/1998/Math/MathML"〉Abstract〈/title〉〈p xmlns:mml="http://www.w3.org/1998/Math/MathML" xml:lang="en"〉Results from the Cassini‐Huygens space mission at Enceladus revealed a substantial inventory of organic species embedded in plume and E ring ice grains originating from a global subsurface and putative habitable ocean. Compositional analysis by the Cosmic Dust Analyzer indicated the presence of aromatic species and constrained some structural features, although their exact nature remains unclear. As indicated by many studies, among other organic species, low‐mass aromatics likely played a role in the emergence of life on Earth and may be linked to potential prebiotic or biogenic chemistry on icy moons. Here, we study the behavior of single‐ringed aromatic compounds—benzoic acid and two isomeric derivatives, 2,3‐dihydroxybenzoic acid and 2,5‐dihydroxybenzoic acid—using Laser‐Induced Liquid Beam Ion Desorption (LILBID), an analogue setup to simulate the impact ionization mass spectra of ice grains in space. These compounds share common structural features but also exhibit differences in functional groups and substituent positions. We investigate the fragmentation behavior and spectral appearance of each molecule over three simulated impact velocities, in both positive and negative ion modes. Parent compounds can be distinguished easily from their derivatives due to various spectral differences, including the (de)protonated molecular ion peaks appearing at different 〈italic〉m〈/italic〉/〈italic〉z〈/italic〉 values. We conclude that distinction between structural isomers in LILBID is more challenging, but some insights can be revealed by considering intermolecular bonding regimes. This work will guide future investigations into elucidating the composition of isomeric biosignatures in ice grains, relevant for future space missions to Enceladus and Europa.〈/p〉
    Description: Plain Language Summary: The Cassini‐Huygens space mission discovered a plume at Enceladus that ejects gases and frozen ice grains originating from an ocean of liquid water below its icy shell. In these ice grains, a range of interesting organic molecules were discovered by Cassini's Cosmic Dust Analyzer mass spectrometer. Organic molecules are important in the search for life beyond Earth as they form the basis of all known Earth life, and active biology elsewhere would likely have a discernible effect on the local inventory of organic species. One class of organic, with a ring structure of carbon atoms, called aromatics, were discovered in the plume. We investigate the spectral appearance of one example of aromatic compound, benzoic acid, as well as two similar compounds with additional chemical groups attached to the aromatic ring. The two similar compounds have the same mass and general structure, but slightly different arrangements of the additional groups, known as isomers. We find that it is simple to distinguish mass spectral features between benzoic acid and its related compounds, but more difficult to explain the differences between the isomers. This work will assist the analysis of mass spectrometry data from future habitability‐investigating space missions to ocean‐bearing icy moons.〈/p〉
    Description: Key Points: Cassini revealed a variety of organic compounds including clear evidence of aromatics in the plume of Enceladus. Identifying mass spectral features of isomeric organics enhances our ability to assess the astrobiological potential of Enceladus/Europa. Parent aromatic compounds can be easily distinguished from their derivatives in ice grains with impact ionization mass spectrometry.
    Description: European Research Council Consolidator
    Description: http://dx.doi.org/10.17169/refubium-37960
    Description: https://lilbid-db.planet.fu-berlin.de/
    Keywords: ddc:523 ; mass spectrometry ; LILBID and impact ionization ; aromatics and isomeric derivatives ; Enceladus and Europa ; space missions ; habitability
    Language: English
    Type: doc-type:article
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  • 2
    Publication Date: 2019-10-02
    Description: Saturn’s moon Enceladus is erupting a plume of gas and ice grains from its south pole. Linked directly to the moon’s subsurface global ocean, plume material travels through cracks in the icy crust and is ejected into space. The subsurface ocean is believed to be in contact with the rocky core, with ongoing hydrothermal activity present. The Cassini spacecraft’s Ion and Neutral Mass Spectrometer (INMS) detected volatile, gas phase, organic species in the plume and the Cosmic Dust Analyser (CDA) discovered high-mass, complex organic material in a small fraction of ice grains. Here, we present a broader compositional analysis of CDA mass spectra from organic-bearing ice grains. Through analogue experiments, we find spectral characteristics attributable to low-mass organic compounds in the Enceladean ice grains: nitrogen-bearing, oxygen-bearing, and aromatic. By comparison with INMS results, we identify low-mass amines [particularly (di)methylamine and/or ethylamine] and carbonyls (with acetic acid and/or acetaldehyde most suitable) as the best candidates for the N- and O-bearing compounds, respectively. Inferred organic concentrations in individual ice particles vary but may reach tens of mmol levels. The low-mass nitrogen- and oxygen-bearing compounds are dissolved in the ocean, evaporating efficiently at its surface and entering the ice grains via vapour adsorption. The potentially partially water soluble, low-mass aromatic compounds may alternatively enter ice grains via aerosolization. These amines, carbonyls, and aromatic compounds could be ideal precursors for mineral-catalysed Friedel–Crafts hydrothermal synthesis of biologically relevant organic compounds in the warm depths of Enceladus’ ocean.
    Print ISSN: 0035-8711
    Electronic ISSN: 1365-2966
    Topics: Physics
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