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Register a new userIdentification of organic molecules with a laboratory prototype based on the Laser Ablation-CosmOrbitrap
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In the Solar System, extra-terrestrial organic molecules have been found on cometary primitive objects, on Titan and Enceladus icy moons and on Mars. Identification could be achieved for simple organic species by remote sensing based on spectroscopic methods. However in situ mass spectrometry is a key technology to determine the nature of more complex organic matter. A new concept of mass analyser offering ultra-high mass resolving power of more than 50,000 at m/z 56 (under high vacuum condition about 10-9 mbar) is currently being developed for space applications: the CosmOrbitrap (Briois et al., 2016), based on the OrbitrapTM technology. This work challenges the use of LAb-CosmOrbitrap, a space instrument prototype combining Laser Ablation ionisation and the CosmOrbitrap mass analyser, to identify solid organic molecules of relevance to the future space exploration. For this purpose a blind test was jointly organised by the JAXA-HRMS team (Japan Aerospace Exploration Agency-High Resolution Mass Spectrometry) and the CosmOrbitrap consortium. The JAXA team provided two organic samples, whereas the CosmOrbitrap consortium analysed them without prior information. Thanks to the high analytical performances of the prototype and our HRMS data post-processing, we successfully identified the two molecules as HOBt, hydroxybenzotriazole (C6H5N3O) and BBOT, 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene (C26H26N2O2S), with a mass resolving power of, respectively, 123 540 and 69 219. The success of this blind test on complex organic molecules shows the strong potential of LAb-CosmOrbitrap for future space applications.
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RATIONALE: The investigation of cryogenic planetary environments as potential harbors for extant life and/or contemporary sites of organic synthesis represents an emerging focal point in planetary exploration. Next generation instruments need to be capable of unambiguously determining elemental and/or molecular stoichiometry via highly accurate mass measurements and the separation of isobaric interferences. METHODS: An OrbitrapTM analyzer adapted for spaceflight (referred to as the CosmOrbitrap), coupled with a commercial pulsed UV laser source (266 nm), is shown to successfully characterize a variety of planetary analog samples via ultrahigh resolution laser desorption/ablation mass spectrometry. The materials analyzed in this study include: jarosite (a hydrous sulfate detected on Mars); magnesium sulfate (a potential component of the subsurface ocean on Europa); uracil (a nucleobase of RNA); and a variety of amino acids. RESULTS: The instrument configuration tested here enables: measurement of major elements and organic molecules with ultrahigh mass resolution (m/{Delta}m higher than 120,000, FWHM); quantification of isotopic abundances with 1.0% (2{sigma}) precision; and, identification of highly accurate masses within 3.2 ppm of absolute values. The analysis of a residue of a dilute solution of amino acids demonstrates the capacity to detect twelve amino acids in positive ion mode at concentrations as low as 1 pmol/mm2 while maintaining mass resolution and accuracy requirements. CONCLUSIONS: 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 missionenabling technology capable of advancing planetary exploration for decades to come.
Context. Near- and mid-infrared observations have revealed the presence of organic refractory materials in the solar system, in cometary nuclei and on the surface of centaurs, Kuiper-belt and trans-neptunian objects. In these astrophysical environments, organic materials can be formed because of the interaction of frozen volatile compounds with cosmic rays, stellar/solar particles, and favoured by thermal processing. The analysis of laboratory analogues of such materials gives information on their properties, complementary to observations. Aims. We present new experiments to contribute in the understanding of the chemical composition of organic refractory materials in space. Methods. We bombard frozen water, methanol and ammonia mixtures with 40 keV H$^+$ and we warm the by-products up to 300~K. The experiments allow the production of organic residues that we analyse by means of infrared spectroscopy and by Very High Resolution Mass Spectrometry to study their chemical composition and their high molecular diversity, including the presence of hexamethylenetetramine and its derivatives. Results. We find that the accumulated irradiation dose plays a role in determining the residues composition. Conslusions. Based on the laboratory doses, we estimate the astrophysical timescales to be short enough to induce an efficient formation of organic refractory materials at the surface of icy bodies in the outer solar system.
Aluminum monochloride (AlCl) has been proposed as a promising candidate for laser cooling to ultracold temperatures, and recent spectroscopy results support this prediction. It is challenging to produce large numbers of AlCl molecules because it is a highly reactive open-shell molecule and must be generated in situ. Here we show that pulsed-laser ablation of stable, non-toxic mixtures of Al with an alkali or alkaline earth chlorides, denoted XCln, can provide a robust and reliable source of cold AlCl molecules. Both the chemical identity of XCln and the Al:XCln molar ratio are varied, and the yield of AlCl is monitored using absorption spectroscopy in a cryogenic gas. For KCl, the production of Al and K atoms was also monitored. We model the AlCl production in the limits of nonequilibrium recombination dominated by first-encounter events. The non-equilibrium model is in agreement with the data and also reproduces the observed trend with different XCln precursors. We find that AlCl production is limited by the solid-state densities of Al and Cl atoms and the recondensation of Al atoms in the ablation plume. We suggest future directions for optimizing the production of cold AlCl molecules using laser ablation.
(Abridged) Protoplanetary disks are vital objects in star and planet formation, possessing all the material which may form a planetary system orbiting the new star. We investigate the synthesis of complex organic molecules (COMs) in disks to constrain the achievable chemical complexity and predict species and transitions which may be observable with ALMA. We have coupled a 2D model of a protoplanetary disk around a T Tauri star with a gas-grain chemical network including COMs. We compare compare synthesised line intensities and calculated column densities with observations and determine those COMs which may be observable in future. COMs are efficiently formed in the disk midplane via grain-surface chemical reactions, reaching peak grain-surface fractional abundances 1e-6 - 1e-4 that of the H nuclei number density. COMs formed on grain surfaces are returned to the gas phase via non-thermal desorption; however, gas-phase species reach lower fractional abundances than their grain-surface equivalents, 1e-12 - 1e-7. Including the irradiation of grain mantle material helps build further complexity in the ice through the replenishment of grain-surface radicals which take part in further grain-surface reactions. There is reasonable agreement with several line transitions of H2CO observed towards several T Tauri star-disk systems. The synthesised line intensities for CH3OH are consistent with upper limits determined towards all sources. Our models suggest CH3OH should be readily observable in nearby protoplanetary disks with ALMA; however, detection of more complex species may prove challenging. Our grain-surface abundances are consistent with those derived from cometary comae observations providing additional evidence for the hypothesis that comets (and other planetesimals) formed via the coagulation of icy grains in the Suns natal disk.
The discovery and characterization of exoplanets around nearby stars is driven by profound scientific questions about the uniqueness of Earth and our Solar System, and the conditions under which life could exist elsewhere in our Galaxy. Doppler spectroscopy, or the radial velocity (RV) technique, has been used extensively to identify hundreds of exoplanets, but with notable challenges in detecting terrestrial mass planets orbiting within habitable zones. We describe infrared RV spectroscopy at the 10 m Hobby-Eberly telescope that leverages a 30 GHz electro-optic laser frequency comb with nanophotonic supercontinuum to calibrate the Habitable Zone Planet Finder spectrograph. Demonstrated instrument precision <10 cm/s and stellar RVs approaching 1 m/s open the path to discovery and confirmation of habitable zone planets around M-dwarfs, the most ubiquitous type of stars in our Galaxy.
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