OLYMPIA-LILBID: A New Laboratory Setup to Calibrate Spaceborne Hypervelocity Ice Grain Detectors Using High-Resolution Mass Spectrometry.

The coupling of an Orbitrap-based mass analyzer to the laser-induced 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.

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.

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™ 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 source 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. CONCLUSIONS: The 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 future planetary exploration.

An Orbitrap-based laser desorption/ablation mass spectrometer designed for spaceflight.

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 Orbitrap™ analyzer adapted for spaceflight (referred to as the CosmOrbitrap), coupled with a commercial pulsed UV laser source (266 nm), was used 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/Δm ≥ 120,000, FWHM); quantification of isotopic abundances with <1.0% (2σ) 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 mission-enabling technology capable of advancing planetary exploration for decades to come.

Scattering properties of sands. 2. Results for sands from different origins.

Mineral sand is a major component of aerosols in the atmosphere. It is necessary to have a laboratory database to interpret the remote sensing measurements of light scattered by such grains. For this purpose, the PROGRA2 experiment is dedicated to the retrieval of polarization and brightness phase curves, in the visible wavelength domain, of various grains that can be found in Earth's atmosphere and in space. The measurements of the scattered light by levitating clouds of grains are conducted at two wavelengths, 632.8 and 543.5nm, with PROGRA2-VIS. Large grains (at least tens of micrometers) are studied in microgravity conditions during parabolic flights; smaller (micrometer-sized) grains are lifted by an air draught in ground-based conditions. The PROGRA2-SURF instrument allows measurements on the grains deposited on a plane surface, at the same wavelengths. New data for the scattering properties are presented for sands of various origins, including fine clay. The polarimetric phase curves for levitating grains are close to each other for all the samples (except for black sands); small discrepancies are mainly due to grains' light absorption differences. The polarization curves for levitating grains differ strongly from those of deposited grains (dry or wet). In particular, these curves can be used to interpret remote sensing measurements to distinguish between grains at ground and grains transported by winds.

Scattering properties of sands. 1. Comparison between different techniques of measurements.

Measuring linear polarization of light scattered by a cloud of particles can help retrieve their physical properties. We present an extensive study of polarimetric measurements of sand grains that can be found on the surface and in the atmosphere of the Earth. Different techniques of measurements are compared using the Laboratoire de Météorologie Physique nephelometer on the ground and the Propriétés Optiques des Grains Astronomiques et Atmosphériques on the ground and in microgravity during parabolic flights. The techniques used on the ground bias the measurements. When the grains are lifted by an air draft, differentiation is produced in the size distribution and the nature of the floating particles. When the grains are carried along with the airflow, some grains become oriented along the flow direction at air speeds greater than a few meters per second, producing abnormal negative polarization. On the other hand, measurements conducted under microgravity permit the retrieval of the representative optical properties of the lifted sand grains with sizes greater than tens of micrometers.