The CosmOrbitrap mass analyzer is highly sensitive and delivers mass resolution/accuracy unmatched by any instrument sent into orbit or launched into deep space. This prototype instrument, which maps to a spaceflight implementation, represents a mission-enabling technology capable of advancing planetary exploration for decades to come.
(RATIONALE) Mass spectrometers are regularly boarded on spacecraft for the exploration of the Solar System. A better understanding of the origin, distribution and evolution of organic matter and its relationships with inorganic matter in different extra-terrestrial environments requires the development of innovative space tools, described as Ultra High Resolution Mass Spectrometry (UHRMS) instruments. (METHODS) Analyses of a complex organic material simulating extraterrestrial matter (Titan's tholins) are performed with a homemade space-designed Orbitrap TM equipped with a laser ablation ionization source at 266 nm: the LAb-CosmOrbitrap. Mass spectra are obtained using only one laser shot and transient duration of 838 ms. A comparison is made on the same sample with a laboratory benchmark mass spectrometer: a Fourier Transform Ion Cyclotron Resonance equipped with a laser desorption ionization at 355 nm (LDI-FTICR) allowing accumulation of 20,000 laser shots. (RESULTS) Mass spectra and attributions of molecular formulae based on the peaks detected by both techniques show significant similarities. Detection and identification of the same species are validated. The formation of clusters ions with the LAb-CosmOrbitrap is also presented. This specific feature brings informative and unusual indirect detections about the chemical compounds constituting Titan's tholins. In particular, the detection of HCN confirms previous results obtained with laboratory Electrospray Ionization (ESI)-UHRMS studies about the understanding of polymeric patterns for the formation of tholins. (CONCLUSION) Capabilities of the LAb-CosmOrbitrap to decipher complex organic mixtures using single laser shot and a short transient are highlighted. In agreement with results provided by a commercial FTICR instrument in the laboratory, we demonstrate in this work the relevance of a space laser-CosmOrbitrap instrument for the future planetary exploration.
The coupling of an Orbitrap-based mass analyzer to the laserinduced liquid beam ion desorption (LILBID) technique has been investigated, with the aim to reproduce the mass spectra recorded by Cassini's Cosmic Dust Analyzer (CDA) in the vicinity of Saturn's icy moon Enceladus. LILBID setups are usually coupled with time-of-flight (TOF) mass analyzers, with a limited mass resolution (∼800 m/Δm). Thanks to the Orbitrap technology, we developed a unique analytical setup that is able to simulate hypervelocity ice grains' impact in the laboratory (at speeds in the range of 15−18 km/s) with an unprecedented high mass resolution of up to 150 000 m/Δm (at m/z 19 for a 500 ms signal duration). The results will be implemented in the LILBID database and will be useful for the calibration and future data interpretation of the Europa Clipper's SUrface Dust Analyzer (SUDA), which will characterize the habitability of Jupiter's icy moon Europa.
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A new laboratory OrbitrapTM cell-based mass spectrometer, OLYMPIA (Orbitrap anaLYseur MultiPle IonisAtion), without a C-trap module, has been developed and constructed. The first operation of the OrbitrapTM cell-based device with the continuous ion source and without the C-trap module is reported. OLYMPIA is being developed and used as a workbench platform to test and develop technologies for the next generation of spaceborne mass spectrometers and as a laboratory instrument to perform high-resolution studies of space-relevant chemical processes. This instrument has been used to measure the quantitative composition of CO/N2/C2H4 mixtures of the same nominal mass using an electron ionization ion source. The relative abundance of ions has been measured using a short acquisition time (up to 250 ms) with a precision of better than 10% (for most abundant ions) and a mass resolution of 30,000–50,000 (full width at half maximum) over the mass range of m/z 28–86. The achieved mass accuracy of measurements is better than 20 ppm. This performance level is sufficient to resolve and identify the CO/N2/C2H4 components of the mixtures. The dynamic range and relative ion abundance measurements have been evaluated using a reference normal isotopic distribution of krypton gas. The measurement accuracy is about 10% for the 4 most abundant isotopes; 6 isotopes are detectable.
<p>In 2005, a new type of mass spectrometer was commercialised for the first time, the Thermo Fisher Scientific Orbitrap<sup>TM</sup>. Using a Quadro-Logarithmic Electrostatic Ion Trap technology, Orbitrap mass spectrometers are able to reach ultra-high mass resolution<sup>1</sup>. For a decade, the Laboratoire de Physique et Chimie de l&#8217;Environnement et de l&#8217;Espace (LPC2E) is developing a spatialised version of the Orbitrap, the CosmOrbitrap<sup>2</sup>, to bring this high resolution in space exploration. The CosmOrbitrap is intended to be the mass analyser and acquisition system of laser ablation mass spectrometers aiming for planetary bodies like Europa or the Moon<sup>3</sup><sup>,4</sup>.</p><p>In this context, OLYMPIA - Orbitrap anaLYser MultiPle IonisAtion &#8211; has been develop to be used as a new laboratory test bench, and is adaptable to different ionisation methods. After a successful study of planetary atmosphere analogues using Electron Ionisation (EI)<sup>5</sup>, we now coupled OLYMPIA with the Laser Induced Liquid Beam Ion Desorption technique to analyse liquid water samples. For example, LILBID is able to accurately reproduce hypervelocity impact ionisation icy grains mass spectra<sup>6</sup>, such as those recorded by the Comic Dust Analyser<sup>7</sup> (CDA) onboard Cassini in the vicinity of Saturn&#8217;s icy moon Enceladus. The LILBID setup is usually coupled with a Time-of-Flight (TOF) mass spectrometer, with a mass resolution of ~800 m/&#916;m. By coupling the LILBID technique to OLYMPIA and its Orbitrap analyser, we are now able to record hypervelocity icy grains analogue mass spectra with ultra-high mass resolution.&#160;The setup is currently able to measure H<sub>2</sub>O<sup>+</sup> and H<sub>3</sub>O<sup>+</sup> ions with a mass resolution of around 150.000 m/&#916;m (FWHM), with the spectral appearance matching mass spectra of icy grains impact ionisation in an impact velocity range of 15 to 20km/s. Future work aims to simulate lower impact velocities below 15 km/s as they are typically expected for flyby or orbiter missions.</p><p>Those results will be implemented in the LILBID database<sup>8</sup>, and will be useful for the calibration and future data interpretation of the SUrface Dust Analyser (SUDA) mass spectrometer<sup>9</sup>, which will be onboard NASA&#8217;s Europa Clipper mission<sup>10</sup> to characterize the habitability of Jupiter&#8217;s icy moon Europa.</p><p>&#160;</p><p>References</p><p>1. Makarov, A. Electrostatic Axially Harmonic Orbital Trapping: A High-Performance Technique of Mass Analysis. <em>Anal. Chem.</em> <strong>72</strong>, 1156&#8211;1162 (2000).</p><p>2. Briois, C. <em>et al.</em> Orbitrap mass analyser for in situ characterisation of planetary environments: Performance evaluation of a laboratory prototype. <em>Planet. Space Sci.</em> <strong>131</strong>, 33&#8211;45 (2016).</p><p>3. Arevalo, R. <em>et al.</em> An Orbitrap-based laser desorption/ablation mass spectrometer designed for spaceflight. <em>Rapid Commun. Mass Spectrom.</em> <strong>32</strong>, 1875&#8211;1886 (2018).</p><p>4. L. Willhite <em>et al</em>. CORALS: A Laser Desorption/Ablation Orbitrap Mass Spectrometer for In Situ Exploration of Europa, <em>2021 IEEE Aerospace Conference (50100)</em>, 2021, pp. 1-13, doi: 10.1109/AERO50100.2021.9438221.</p><p>5. Zymak, I. <em>et al.</em> OLYMPIA - a compact laboratory Orbitrap-based high-resolution mass spectrometer laboratory set-up: Performance studies for gas composition measurement in analogues of planetary environments. https://meetingorganizer.copernicus.org/EGU21/EGU21-8424.html (2021) doi:10.5194/egusphere-egu21-8424.</p><p>6. Klenner, F. <em>et al.</em> Analogue spectra for impact ionization mass spectra of water ice grains obtained at different impact speeds in space. <em>Rapid Commun. Mass Spectrom.</em> <strong>33</strong>, 1751&#8211;1760 (2019).</p><p>7. Srama, R. <em>et al.</em> The Cassini cosmic dust analyser. <em>Space Sci. Rev.</em> <strong>Volume 114</strong>, 465&#8211;518 (2004).</p><p>8. Klenner, F. <em>et al.</em> Developing a Laser Induced Liquid Beam Ion Desorption Spectral Database as Reference for Spaceborne Mass Spectrometers. <em>Earth and Space Science </em><strong>Under<em> </em>Review</strong> (2022).</p><p>9. Kempf, S. <em>et al.</em> SUDA: A Dust Mass Spectrometer for Compositional Surface Mapping for a Mission to Europa. <em>European Planetary Science Congress </em>2014, EPSC2014-229.</p><p>10. Howell, S. M. & Pappalardo, R. T. NASA&#8217;s Europa Clipper&#8212;a mission to a potentially habitable ocean world. <em>Nat. Commun.</em> <strong>11</strong>, 1311 (2020).</p>
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