High‐resolution mass spectrometry for future space missions: Comparative analysis of complex organic matter with LAb‐CosmOrbitrap and laser desorption/ionization Fourier transform ion cyclotron resonance

Abstract

(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.

Suggested plausible structures for Titan's haze analogs using tandem mass spectrometry

“…Finally, in a previous work, tholins sample were analysed comparatively with FTICR and the LAB-Cosmorbitrap, an Orbitrap that is intended to be boarded in a space probe (Selliez et al, 2019). Large differences were observed between each analysis: higher masses were detected by FTICR compared to LAB-Cosmorbitrap, but the ions detected in the 100-200 u mass range were found the same.…”

Laser Ionization Mass Spectrometry at 55: Quo Vadis?

“…Mass resolving powers m/Δm above 100,000 (FWHM) were achieved. Later, the same group reported successful performance of the LAb-CosmOrbitrap in a blind test of a sample containing two unknown organic molecules (Selliez et al, 2019) and the comparison of its performance with that of an LI-FTICR mass spectrometer (Selliez et al, 2020). In this last study, the LAb-CosmOrbitrap configuration was the only one able to detect organic species at m/z < 100, thanks to its ability to acquire data over m/z from 8 u to a few thousands.…”

“…LI was initially performed using a UV nitrogen laser (Laser Science Inc.) operating at the wavelength of 337 nm with 300 μJ energy per pulse and 4 ns pulse duration (Briois et al, 2016). In a later stage, it was replaced by a more practical solid-state Brilliant Q-switched Nd:YAG laser source (Quantel, France) operating at the fourth harmonic (266 nm) and 4 ns pulse width with 100 μJ energy per pulse and average energy density of 15 J•cm −2 on the sample surface (Arevalo et al, 2018b;Selliez et al, 2019Selliez et al, , 2020. The low-pressure sample stage was maintained at pressures below 1 × 10 −7 mbar, representative of atmospheric conditions on surfaces of gas giant planet icy moons, such as Europa, Ganymede, and Enceladus.…”

Detecting the elemental and molecular signatures of life: Laser-based mass spectrometry technologies

“…Measurements conducted on Martian mudstone analog material allowed the identification of the elemental signatures of single microbes that were inoculated artificially at low number density 16 . Moreover, LIMS systems, such as LAb-CosmOrbitrap 4 , have been able to successfully characterize the chemical composition of organics and tholins mixed with minerals 17,18 , making use of metal-organic clusters for identification and the high mass resolving power of Orbitrap to disentangle isobaric interferences of possible biogenic and non-biogenic molecular fragments. In combination with a microscope camera system, features of micrometer dimensions can be localized and targeted with the laser beam with high accuracy, which allows for the chemical investigation of the feature with minimal contribution of the host material that may obscure the faint life signature.…”