Data-Driven UPLC-Orbitrap MS Analysis in Astrochemistry

Abstract

Meteorites have been found to be rich and highly diverse in organic compounds. Next to previous direct infusion high resolution mass spectrometry experiments (DI-HR-MS), we present here data-driven strategies to evaluate UPLC-Orbitrap MS analyses. This allows a comprehensive mining of structural isomers extending the level of information on the molecular diversity in astrochemical materials. As a proof-of-concept study, Murchison and Allende meteorites were analyzed. Both, global organic fingerprint and specific isomer analyses are discussed. Up to 31 different isomers per molecular composition are present in Murchison suggesting the presence of ≈440,000 different compounds detected therein. By means of this time-resolving high resolution mass spectrometric method, we go one step further toward the characterization of chemical structures within complex extraterrestrial mixtures, enabling a better understanding of organic chemical evolution, from interstellar ices toward small bodies in the Solar System.

Sulfur ion irradiation experiments simulating space weathering of Solar System body surfaces

“…m/z signals that correspond to organosulfur (CHNOS) compounds were absent in the Ar 7+ -irradiated ice. From 35,000 experimental m/z signals, ranging from 100 to 800 amu (atomic mass unit), 5822 C-, H-, N-, O-, or S-bearing molecular formulas could be unequivocally assigned in the S 7+ -over-irradiated residue (5.3% CHO, 76.6% CHNO, 2.6% CHOS and 15.5% CHNOS, Figure B.1, Table C.1, available in electronic form at the CDS), along with the m/z signals of both the global organic fingerprint and organosulfur (CHNOS) compounds, appear as regular patterns reflecting a chemosynthetic process as previously observed in UV-photonirradiated ices (Danger et al 2016;Fresneau et al 2017;Gautier et al 2020), ion-irradiated ices (Ruf et al 2019a;Urso et al 2020), or meteorites (Schmitt-Kopplin et al 2010;Ruf et al 2017Ruf et al , 2019c.…”

“…ESI-FT-ICR-MS (Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry) was used for in-depth molecular characterization of the organic matter formed within the residue, resulted from irradiated ices. High resolution mass spectrometry has been widely used for in-depth molecular characterization of extraterrestrial organic matter (Schmitt-Kopplin et al 2010;Danger et al 2013Danger et al , 2016Ruf et al 2017;Fresneau et al 2017;Ruf et al 2018Ruf et al , 2019cGautier et al 2020;Danger et al 2020). FT-ICR-MS represents the highest performance in mass resolving power and mass precision among all mass spectrometers (Ruf et al 2018).…”

Exploring the link between molecular cloud ices and chondritic organic matter in laboratory

“…All these reactions likely led to a high molecular diversity, which could have been available in the solid phase. As observed here with the pre-accretional organic residue, more than 10,000 different molecules can be produced, including isomers 20 .…”

“…Laboratory simulations, conducted to investigate the chemical evolution of ices during this phase showed that a rich chemistry can occur and do form a significant molecular diversity 15 – 17 . Solid organic residues obtained after ice processing contain thousands of species with masses up to 4000 u 18 , 19 , including a high number of different isomers 20 . Depending on the local environment and the distance to the sun or the central star, some molecules would stay on grains being then agglomerated in cometary and asteroid parent bodies during the accretion phase.…”

Organosulfur Compounds Formed by Sulfur Ion Bombardment of Astrophysical Ice Analogs: Implications for Moons, Comets, and Kuiper Belt Objects

“…Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), ran in negative ionization mode, was used for in-depth molecular characterization of the organic matter formed within the residue, resulted from irradiated ices. High resolution mass spectrometry has been widely used for in-depth molecular characterization of extraterrestrial organic matter (Schmitt-Kopplin et al 2010;Ruf et al 2017Ruf et al , 2018Ruf et al , 2019Danger et al 2016;Fresneauetal.2017).FT-ICR-MS represents the highest performance in mass resolving power and mass precision among all mass spectrometers.…”