Europlanet Science Congress 2022
Palacio de Congresos de Granada, Spain
18 – 23 September 2022
Europlanet Science Congress 2022
Palacio de Congresos de Granada, Spain
18 September – 23 September 2022

MITM9

MITM
Advances in Mass Spectrometry for Spaceflight Applications 

Since the beginning of planetary exploration in the 1960s, mass spectrometers have been key to the in situ exploration of celestial bodies. These instruments enable the detection and identification of many chemical compounds and reaction chains, leading to a better understanding of extraterrestrial environments. A wide range of samples derived from planetary exospheres, atmospheres, and (sub) surfaces, as well as materials sourced from small bodies and interplanetary dust, have been analyzed to date. Legacy technologies, including heritage spaceflight mass analyzers, often represent the state-of-the-art. However, a suite of next generation mass spectrometry instruments is being developed, improving several analytical performances such as mass resolution, dynamic range and mass range among others. In this frame, High Resolution Mass Spectrometry (HRMS) instruments targeting mass resolving powers up to m/Δm > 100,000 (FWHM) and mass ranges beyond >1000 mass units, aim to provide answers to high-priority science questions previously considered inaccessible.
By increasing their respective TRLs (Technology Readiness Levels), these emerging instruments (including HRMS instruments) can be selected for new and exciting in situ space missions that support the long-term objectives of science programs across the globe, including the ESA Voyage 2050 and the NASA Planetary Science Decadal Survey.
The proposed session solicits contributions that inform on the latest advances in mass spectrometry for planetary exploration. Abstracts are invited to be submitted on the following topics:
- New spaceflight instruments concepts
- Performances characterization of laboratory prototypes of space mass spectrometers under development
- Applications of HRMS operations and analytical techniques germane to evolving community-driven science goals
- Future mission concepts made possible with the new generation of mass spectrometers

Conveners: Laura Selliez, Arnaud Sanderink | Co-conveners: J. Hunter Waite, Ricardo Arevalo, Frank Postberg, Morgan L. Cable, Jean-Pierre Lebreton
Orals
| Fri, 23 Sep, 15:30–17:15 (CEST)|Room Albéniz+Machuca
Posters
| Attendance Thu, 22 Sep, 18:45–20:15 (CEST) | Display Wed, 21 Sep, 14:00–Fri, 23 Sep, 16:00|Poster area Level 1

Session assets

Discussion on Slack

Orals: Fri, 23 Sep | Room Albéniz+Machuca

Chairpersons: Arnaud Sanderink, Laura Selliez
15:30–15:45
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EPSC2022-1075
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ECP
Adeline Garcia, Cornélia Meinert, Pauline Poinot, and Gregoire Danger

Introduction

The organic molecular diversity present in extraterrestrial bodies such as asteroids and comets is of great interest for understanding the origin of life. However, the onboard analytical techniques are essentially low resolution mass spectrometry which, in view of the molecular diversity, quickly present limits both in the identification of compounds and in the comprehensive understanding of the composition of this type of sample. It is therefore interesting to question the interest to develop high resolution mass spectrometry for future space missions. In this context, the cosmorbitrap consortium is developing the spatialization of the Orbitrap. In addition, to optimize the identification of compounds within the samples to be analyzed, the coupling of such a technology to a gas chromatograph would also provide a gain in resolution and thus improve the characterization of the targeted samples.

In this perspective, a first development was carried out for a targeted analysis focusing on the detection of amino acids within analogues of soluble organic matter of meteorites [1] [2]. These molecules are particularly interesting because they have been detected in some meteorites and can be markers of the chemical evolution of the studied object [3]. Moreover, they could have played an important role in the homochirality observed on Earth [4]. In a second step, the same samples were analyzed by pyrolysis and thermal desorption, two sampling techniques usually used for in situ GC-MS analyses.

Materials and methods

Samples were analyzed on a GC-FT-Orbitrap-MS (Trace 1310 gas chromatograph with a Q-Exactive OrbitrapTM MS analyzer from Thermo Fisher Scientific).

Targeted amino acid analyses were performed on a chiral column: Chirasil-L-Val (Agilent). Pyrolysis and thermodesorption were performed on an RXi-5MS column (Restek). Evolved gas analyses (EGA) required the use of an inert column with an isothermal oven temperature.

For the analysis of the amino acid solution within the soluble organic meteorite analogues in GC-Orbitrap, a preliminary derivatization step was performed according to the method of Meinert and Meierhenrich [5].

The analogues were formed using the MICMOC device as described [6]. 

Preliminary results and conclusions

The optimization of the parameters and the realization of the calibration provide values of limit of detection and quantification as well as the sensitivity. A sensitivity in the order of 10-6 M is obtained .

Once optimized, the analysis of the amino acids within the analogues allows to observe about ten amino acids in full scan (see Fig. 1). By mass extractions about fifteen amino acids are identified. The use of GC-orbitrap for the targeted analysis of amino acids presents performances equivalent to those observed by GCxCG-TOFMS on the same samples, with higher detection and quantification limits.

Fig. 1. Full scan GC-orbitrap chromatogram of a derivatized residue for amino acids detection. Aminoacids are numbered as following : 1, Sarcosine; 2, D-Alanine; 3 : L-Alanine; 4, Glycine; 5, β-Alanine; 6, Methionine; 7, 2,3-DAPA.

In a second step, an EGA analysis of the same analogue was performed by thermodesorption (Fig. 2). The direct injection allows the rapid identification of molecules such as hexamethyletetramine (HMT) thanks to the high resolution of the mass spectrometer allowing to obtain the raw formula. Moreover, due to the possibility of obtaining these raw formulas a polymer of CHN composition is observed. To confirm these first results, an analysis via GC of the same sample allowed to confirm these first observations.

 

Fig. 2. EGA analysis of the non-derivatized residue. A) Chromatogram of the thermodesorption analysis. B) HMT derivatives. C) Mass spectrum of a CHN polymer.

These first data show that very high resolution mass spectrometry is an essential tool for the characterization of samples with a large molecular diversity. Coupled or not with a gas chromatograph, it allows to obtain raw formulas improving the identification of compounds in targeted analysis, and allowing to obtain information on the molecular content of a sample in direct analysis. Very high resolution mass spectrometry coupled or not to a GC is thus a promising technology for the future in situ analysis of interplanetary objects such as asteroids and comets.

 

Reference

[1] Muñoz Caro, G., Meierhenrich, U., Schutte, W. et al. Amino acids from ultraviolet irradiation of interstellar ice analogues. Nature, 2002, 416, 403–406

[2] G. Danger, F.-R. Orthous-Daunay, P. de Marcellus, P. Modica, V. Vuitton, F. Duvernay, L. Flandinet, L. Le Sergeant d’Hendecourt, R. Thissen, T. Chiavassa, Characterization of laboratory analogs of interstellar/cometary organic residues using very high resolution mass spectrometry, Geochimica et Cosmochimica Acta, 2013, Volume 118, 184-201

[3] Martins, Z., Modica, P., Zanda, B. and d'Hendecourt, L.L.S., The amino acid and hydrocarbon contents of the Paris meteorite: Insights into the most primitive CM chondrite. Meteorit Planet Sci, 2015, 50, 926-943.

[4] Iuliia Myrgorodska, Cornelia Meinert, Zita Martins, Louis le Sergeant d’Hendecourt, Uwe J. Meierhenrich. Quantitative enantioseparation of amino acids by comprehensive two-dimensional gas chromatography applied to non-terrestrial samples. Journal of Chromatography A, 2016, 1433, 131-136

[5] C. Meinert, U.J. Meierhenrich, Derivatization and multidimensional gas-chromatography resolution of a-alkyl and a-dialkyl amino acid enantiomers, ChemPlusChem, 2014, 79, 781-785

[6] L. d’Hendecourt and E. Dartois, Interstellar matrices: the chemical composition and evolution of interstellar ices as observed by ISO, Spectrochim. Acta A Mol. Biomol. Spectrosc., 2001, 57, 669–684

How to cite: Garcia, A., Meinert, C., Poinot, P., and Danger, G.: Orbitrap and GC-Orbitrap for in situ analyses: clues from laboratory experiments, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1075, https://doi.org/10.5194/epsc2022-1075, 2022.

15:45–16:00
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EPSC2022-705
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ECP
Kelly Miller, Greg Miller, Hunter Waite, Tim Brockwell, Kurt Franke, Paul Hoeper, Rebecca Perryman, Christopher Glein, and Jim Burch and the MASPEX science and engineering teams

The MAss Spectrometer for Planetary EXploration (MASPEX) instrument is a multi-bounce time-of-flight mass spectrometer designed for high mass resolution and sensitivity. MASPEX-Europa will launch as part of the Europa Clipper mission payload in October 2024 to characterize the composition of major, minor, and trace neutral gases in Europa’s exosphere and potential plumes. The instrument has been designed to optimize measurement of complex natural environments with:

  • Variable mass resolution to support compositional reconnaissance with simultaneous measurement of ions from 2 u to 500 u at separation of unit masses, as well as focused analysis with mass resolution capable of separating CHN- and CHO-bearing organics over a more narrow mass range
  • Nearly 100% duty cycle via storage of ions in the source between extraction pulses
  • Exact mass identification via measurement in flight of the FC-43 calibrant gas
  • Measurement of trace compounds via enhancement of abundance with the cryocooler
  • Automated switching triggered in flight between “regular” and “ice grain” measurement parameters for optimization of data collection

These adaptations make MASPEX especially well-suited for data collection in a dynamic environment where measurement speed is important. The capability to provide both general and highly specific data on the composition of volatile and organic mixtures makes MASPEX very powerful to quantify habitability via geochemical indicators, and to search for the first, perhaps tentative signs of life beyond Earth via measurements of agnostic biosignatures such as isotopic ratios.

In this presentation, we will provide results from the final calibration and performance characterization of the MASPEX-Europa flight model instrument completed in summer 2022. We will also present the science that will be enabled for Europa Clipper, and how new scientific and technical innovations will allow MASPEX to open more windows into planetary evolution, cosmochemistry, and astrobiology for future missions.

How to cite: Miller, K., Miller, G., Waite, H., Brockwell, T., Franke, K., Hoeper, P., Perryman, R., Glein, C., and Burch, J. and the MASPEX science and engineering teams: Onwards to Europa: Results from the final ground calibration of the MASPEX-Europa flight instrument, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-705, https://doi.org/10.5194/epsc2022-705, 2022.

16:00–16:15
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EPSC2022-1254
Ricardo Arevalo, Ashley Hanna, Ziqin Ni, Soumya Ray, Adrian Southard, Ryan Danell, Andrej Grubisic, Jacob Graham, Anthony Yu, Molly Fahey, Cynthia Gundersen, Niko Minasola, Julie Llano, Christelle Briois, Laurent Thirkell, Fabrice Colin, and Alexander Makarov

Critical Need for LDMS Techniques: Laser desorption mass spectrometry (LDMS) enables 2D and/or 3D chemical imaging of organic and inorganic analytes, supporting focused research objectives as well as discovery-based science. Many minerals and (aromatic) organics effectively absorb UV radiation, and photon energies of UV light approximate the first ionization energies of many elements in the Periodic Table. Consequently, UV laser sources, particularly those with controllable output attenuation, serve as effective ionization sources for many materials. In the realm of in situ planetary science, LDMS techniques are valued to detect refractory organic molecules, including prospective biosignatures, and identify the host phases that harbor said compounds. The short pulse widths offered by many solid-state laser systems, such as the 266 nm laser system developed for the Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars rover, have been shown to circumvent the challenges associated with pyrolyzing organic-rich samples in the presence of strong oxidants, like the perchlorates found across the Martian surface [1]. 

Critical Need for Ultrahigh Mass Resolution: Heritage mass spectrometers, such as that flown on the Sample Analysis at Mars (SAM) investigation onboard the Curiosity rover [2], are limited to mass resolving powers of m/Δm < 1000 (FWHM), leading to uncertainty in the identification of molecular signals. Peaks are often assigned based on known isotope abundances, diagnostic fragmentation patterns, and/or corroborative measurements provided by other payload instruments. Alternatively, hardware additions such as gas chromatographs, resonance lasers sources, and/or collision cells can increase the confidence of molecular assignments, albeit at the cost of additional mass, volume, and power requirements.

In contrast, the OrbitrapTM analyzer commercialized by Thermo Scientific [3], adapted for spaceflight by a consortium of French laboratories [4], and miniaturized and ruggedized through a collaboration with the University of Maryland and NASA GSFC [5], enables identification of molecular stoichiometry through mass resolving powers of m/Δm > 100,000 (FWHM) and ppm-level mass accuracies. Unrivaled disambiguation of isobaric interferences and isotopologues across a wide intrascan mass range (e.g., 20 – 600 u) distinguishes the Orbitrap from other high-resolution analyzers.

LDMS with an Orbitrap mass analyzer: The analytical and scientific value of integrating a pulsed UV laser source with an Orbitrap mass analyzer for planetary applications was first recognized with the development of the Ion Laser Mass Analyzer (ILMA) for Marco Polo [6], a joint ESA-JAXA sample return mission targeting a primitive Near-Earth Object (NEO). In response to the Pre-Release of an Announcement of Opportunity for a NASA Europa Lander Mission, a laser-enabled Orbitrap was modified to analyze ice residues and seek out physicochemical signs of life in potentially habitable cryogenic environments [5]. More recently, a permutation of the instrument was adapted for operation on the lunar surface, facilitating investigations into the composition of the bulk silicate Moon, dynamics of the lunar interior, space weathering of the surface, rates of exogenous infall, and the alteration of organic materials due to exposure to cosmic rays [7].

Advanced analytical capabilities with a laser-enabled Orbitrap mass spectrometer: To support the evolving objectives of the planetary community, such as the prioritization of an Enceladus Orbilander in the most recent Decadal Survey [8], advanced LDMS techniques are currently being explored to maximize the science return for a spectrum of mission architectures. The characterization of complex organic materials simulating extraterrestrial matter (e.g., Titan-like tholins), and planetary analog samples doped with organic compounds commonly associated with living systems, such as proteinogenic amino acids and the nucleobase uracil found in RNA, demonstrates the detection of prospective biomarkers, classification of host mineralogy, and establishment of geological context/provenance [9-11]. In order to improve spectral reproducibility and enhance limits of detection, a variety of sample plate materials spanning a range of thermal diffusivities, electrical conductivities, and ionization potentials are being tested. Inorganic chemical matrices, such as Si nanoparticles, are being explored to promote ionization efficiency and the preservation of the molecular ion of a compelling suite of organic macromolecules, including short chain peptides [12] and simple, compound, and derived lipids [13]. 

 

References:

[1] Li et al. (2015) Astrobio 15 (2), 104 – 110.

[2] Mahaffy et al. (2012) PSS 170, 401 – 478.

[3] Makarov (1999) US Patent 5,886,346.

[4] Briois et al. (2016) PSS 131, 33 – 45.

[5] Willhite et al. (2021) IEEE Aerospace, 1 – 13.

[6] Cottin et al. (2009) 9th Euro Workshop on Astrobio.

[7] Willhite et al. (2020) LSSW, LPI Contrib. No. 2241.

[8] National Academies (2022) Origins, Worlds and Life.

[9] Arevalo Jr. et al. (2018) Rapid Comm 32, 1875 – 1886.

[10] Selliez et al. (2019) PSS 170, 42 – 51.

[11] Selliez et al. (2020) Rapid Comm 34, e8645.

[12] Arevalo Jr. et al. (2022) AbSciCon, 208-03.

[13] Hanna et al. (2022) AbSciCon, 130-011.

How to cite: Arevalo, R., Hanna, A., Ni, Z., Ray, S., Southard, A., Danell, R., Grubisic, A., Graham, J., Yu, A., Fahey, M., Gundersen, C., Minasola, N., Llano, J., Briois, C., Thirkell, L., Colin, F., and Makarov, A.: Laser Desorption Mass Spectrometry (LDMS) with an Orbitrap mass analyzer: a historical perspective and future projection , Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1254, https://doi.org/10.5194/epsc2022-1254, 2022.

16:15–16:30
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EPSC2022-1194
Maria Mora, Miranda Kok, Aaron Noell, and Peter Willis

Ocean worlds in our Solar System have captivated the attention of scientists due to the presence of liquid water that could make it possible for these worlds to harbor life. Because all life on Earth is built from a selected set of organic molecules, clear patterns appear in the relative distribution of organics when a sample has a biotic origin.  A powerful approach in the search for life involves seeking for such chemical patterns. The liquid-based separation technique of capillary electrophoresis (CE) holds unique promise for this task. CE is a high-resolution separation technique for molecules in solution that allows the analysis of a broad range of compounds using a relatively simple instrumental set up. CE separations occur within small diameter glass capillaries (25-100 mm I.D.) filled with a background electrolyte. CE is an ideal candidate for in situ planetary missions, especially to areas where aqueous analysis is required. 

Although CE can be coupled to multiple detectors, mass spectrometry (MS) is particularly attractive for planetary exploration because it adds another separation dimension based on mass-to-charge (m/z) ratios. Although there are multiple ionization techniques to couple CE to MS, the most common one is electrospray ionization (ESI). With ESI, the compounds that are separated by CE can be efficiently transferred from the liquid phase into the gas-phase. The coupling of CE and MS allows detailed characterization of biomolecules, and more importantly the identification of unknowns in complex mixtures. We have recently reported on the development of a CE instrument that can be coupled to multiple detection systems, including MS 1. Other detectors include laser-induced fluorescence for sensitive analysis of amino acids and contactless conductivity detection for analysis of inorganic ions and organic acids. This system is under development for biosignature detection as part of the Europan Molecular Indicators of Life Instrument (EMILI)2 and the Ocean Worlds Life Surveyor (OWLS).

Based on the major constituents potentially expected in the oceans of Enceladus and Europa, we used NaCl and MgSO4 salts to evaluate the effect of Na+, Mg2+, Cl-, and SO42- on the detection of a wide range of organics by CE-MS using a sheathless interface 3. We have selected a mixture of amino acids, peptides, nucleosides, and nucleobases for this study, all of which are building blocks of the main polymers of terrestrial biology and are associated with at least one of the rungs of the Ladder of Life. We demonstrate CE-MS limits of detection for these organics ranging from 0.05 to 1 mM (8 to 8 ppb), in the absence of salts. More importantly, organics in the low mM range (1 to 50 mM) are detected by CE-MS in the presence of 3 M NaCl without desalting, preconcentration or derivatization 3. The applicability of CE-MS for analysis of challenging natural samples was demonstrated by analysis of samples from Mono Lake. Multiple organics were detected in the sample despite the presence of a salt front. These results demonstrate the potential of CE-MS for in situ organic analysis on future missions to ocean worlds.

How to cite: Mora, M., Kok, M., Noell, A., and Willis, P.: Capillary Electrophoresis Coupled to Mass Spectrometry for the Detection of Organics in High Salinity Samples Relevant to Ocean Worlds, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1194, https://doi.org/10.5194/epsc2022-1194, 2022.

16:30–16:45
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EPSC2022-1257
Christelle Briois, Donia Baklouti, Noémie Comtesse, Cécile Engrand, Jean-Pierre Lebreton, Ricardo Arevalo, Cédric Pilorget, Laurent Thirkell, Fabrice Colin, Oliver Stenzel, and Martin Hilchenbach

Introduction: The Rosetta mission is one of the latest great scientific and technological European successes. The probe and its lander Philae, transported some very audacious and inventive instruments that for some worked beyond expectations, and gave the scientists and engineers involved an expertise and experience that we should try to build on. The COmetary Secondary Ion Mass Analyser (COSIMA) onboard Rosetta, was the first instrument applying in situ analyses of cometary grains [1]. This instrument already combined two techniques: visible microscopy that was crucial to detect routinely the collected dust and characterize its structure [2], and Time-Of-Flight Secondary Ion Mass Spectrometry that mainly allowed us to determine the elemental composition of the dust [3-4]. COSIMA covered a mass range 1–1200 u but was limited to a mass resolution m/Δm of 1400 at mass 100 u at Full Width Half Maximum (FWHM), which made the assignment of molecular signals difficult.

For the next generation of extraterrestrial (especially, primitive) dust analyzers, we are proposing an instrument that combines near infrared (NIR) and visible microscopy with laser ionization mass spectrometry (LIMS). This multi-analysis instrument (named dPCA for dust Particle Composition Analyzer) was part of the Castalia+ mission proposition to the ESA M7 call, but it is potentially suited for any space mission aiming to characterize dusty materials, especially complex ones containing organic and mineral phases.

In the prospect to build a new generation of mass spectrometer offering High Resolution Mass Spectrometry (HRMS) collaborative effort between consortium of French  and Czech laboratories (LPC2E, LATMOS, LISA, IPAG, IJCLab, J. Heyrovsky Institute of Physical Chemistry) and University of Maryland and NASA GSFC, are on-going to settle a pulsed UV laser source with an Orbitrap™ [5] mass analyzer for planetary applications. The spaceflight and ruggedized version of the Orbitrap cell and its electronics (preamplifier, ultra-stable High Voltage), the CosmOrbitrap mass analyzer/detector, is capable of discriminating isobaric interferences with ultrahigh mass resolution m/Δm > 100,000 (FWHM), high mass accuracies and dual polarity measurements [6-10].

The NIR channel of the microscope will be based on the MicrOmega hyperspectral instrument developed at IAS (Orsay, France). Several replicas of this instrument have already flown or are currently working aboard MASCOT/Hayabusa2, on the ExoMars rover [11] and currently in the JAXA curation facility for Ryugu dust analysis [12]).

In this study, we investigated the analytical value of combining these two techniques. We will show through laboratory measurements how combining infrared and mass data could be extremely useful to unambiguously characterize the targeted dust.

Experimental Procedure: The main well known inputs given by the NIR spectra are: the detection and characterization of hydration signatures, especially on silicates, the detection and partial characterization of carbonates and sulfates, the detection of ammoniated compounds, the detection of the presence of organic compounds and the detection and identification of ices (H2O, CO2, etc.). In the context of main belt comets, asteroids and even the Martian moons and surface, the full characterization of hydration signatures is one of the most important information needed to complete the mass spectra characterization. For this reason, we started our set of experiments and measurements on both instruments, a laboratory MicrOmega replica at IAS,  and a laboratory instrument prototype of a laser ablation / ionization Orbitrap™ mass spectrometer, the LAb-CosmOrbitrap, developed at LPC2E (Orléans, France), by focusing on hydrated and anhydrous silicates. The LAb-CosmOrbitrap integrates i) a commercial pulsed Nd-YAG laser used at 266 nm UV wavelength, ii) a set of ion focusing lenses without C-trap, and iii) a spaceflight CosmOrbitrap mass analyzer/detector. Variable output energy of laser beam can be operated thanks to a polarizing prism.

Samples: To explore the capabilities of the LAb-CosmOrbitrap instrument to characterize silicate in both positive and negative ion mode, we started with analyses of a San Carlos olivine, and a natural Mg-rich serpentine dominated by antigorite and chrysotile. Both samples are obviously silicates, but the former is an anhydrous ionic solid (no covalent bond between O and Mg) and the latter is a phyllosilicate (= a hydrated silicate) where Mg is covalently bonded to O and OH. Same samples have been analyzed with MicrOmega replica  instrument.

Results: LAb-CosmOrbitrap measurements in positive ion modes of the serpentine sample enables detection of various oxide and hydroxide magnesium peaks at high mass accuracy (< 2.5 ppm) during a single laser shot experiment, with high mass resolution (for examples m/∆m ~ 160,000 (FWHM) for  24MgOH+ and m/∆m > 130,000 (FWHM) for  24Mg2O+). In this study, we explored the best suitable laser energy and consecutive shot sequences to find reproducible and robust measurements of oxide and hydroxide ions. These results will be presented among those on olivine and the spectra obtained with NIR microscopy.

Conclusions: This study demonstrates the capabilities of a UV Laser-CosmOrbitrap instrument combined with a NIR spectrometer to detect and characterize hydrated signatures of a serpentine with an optimized protocol. Next steps that will be pursued are among others the analyses of other types of silicates and minerals, of silicate doped with organic compounds. In the prospect of a future space instrument, it is obvious that IR microscopy would be of great benefit for a fast screening of the area of the targeted dust in order to further perform LIMS analyses and increase the confidence in the identification of molecular and structural indices.

 

Acknowledgement: We thank the Centre National des Etudes Spatiales (CNES) for their financial support.

References:

[1] Hilchenbach et al. (2016) ApJL 816, L32.

[2] Langevin et al. (2016) Icarus 271, 76–97.

[3] Fray et al. (2016) Nature 538, 72–74.

[4] Bardyn, Baklouti et al. (2017) MNRAS 469, S712–S722.

[5] Makarov (1999) US Patent 5, 886, 346.

[6] Briois et al. (2016) PSS 131, 33–45.

[7] Arevalo Jr. et al. (2018) Rapid Comm 32, 1875–1886.

[8] Selliez et al. (2019) PSS 170, 42–51.

[9] Selliez et al. (2020) Rapid Comm 34, e8645.

[10] Cherville et al. (2021) COSPAR2021, Abstract B0.4-0018-21.

[11] Pilorget and Bibring (2014) PSS 99, 7–18.

[12] Pilorget et al. (2021) Nature Astronomy 6, 221–225.

How to cite: Briois, C., Baklouti, D., Comtesse, N., Engrand, C., Lebreton, J.-P., Arevalo, R., Pilorget, C., Thirkell, L., Colin, F., Stenzel, O., and Hilchenbach, M.: A space instrument combining NIR hyperspectral microscopy and Laser-CosmOrbitrap mass spectrometry for the in situ analysis of extraterrestrial dust, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1257, https://doi.org/10.5194/epsc2022-1257, 2022.

16:45–17:00
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EPSC2022-322
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ECP
Rico Fausch and Peter Wurz

Analysing the chemical composition of celestial objects is key for understanding the origin and evolution of the Solar System. Although Earth’s exosphere provides the simplest access compared to other deep space destinations, it is poorly understood. Last measurements were conducted in the 1980s. These measurements lead to some understanding of the scale heights of the major species. The evolution of Earth’s atmosphere was simulated from its initial composition, which was comparable to the composition of Venus and Mars. However, there remains a discrepancy between the model output and the currently observable chemical composition of Earth’s atmosphere. Moreover, the influence of the external drivers of the exosphere and the exospheric loss remains unclear. These drivers, such as, for example, Sun, Moon, night-side transport of species, etc. seem to influence both the temporal and spatial abundance of species considerably. 

An analysis of Earth’s upper atmosphere with mass spectrometers will end this ongoing debate. Regions of interest are low flying satellites at altitudes well below 1,000 km. To study drivers, maintaining such orbits over months, if not years, is key requiring typical relative encounter velocities of about 7 to 8 km/s. Additional requirements are the high sensitivity for species, a high dynamic range and a mass range of about m/z 1 to 150 at an instant. Overcoming the space-time degeneracy necessitates at least two instruments measuring simultaneously, though, a network of several satellites is preferred for almost real-time analysis of the space weather.

For that purpose, we designed a mission concept complying with these requirements enabled by a novel mass spectrometer design. The goal of this Constellation of High-performance Exospheric Science Satellites (CHESS) mission is to provide an inventory of chemical species present in Earth’s exosphere and analyse both its dynamics in response to external drivers. The scientific payload of this mission are neutral gas and ion time-of-flight mass spectrometer in CubeSat format (1U) for chemical composition analysis and a new generation of dual-frequency global navigation satellite system (GNSS) instrument for analysis of the total electron content. A technical goal of this mission is to demonstrate the concept of the novel ion optical system that allows for direct measurements at high relative encounter velocities implying reliable measurements of complex molecules.

Speed limits of mass spectrometers constrain modern deep space mission designs. Fly-by mass spectrometer mostly have two operation modes. In open source mode, the mass spectrometer handles the rapidly incoming stream of gas by (electrostatic) deflection of the ionized species it into the mass analyser. This mode is limited to about 5 km/s. For higher relative encounter velocities, an antechamber is used to thermalise the species arriving at hypervelocities, where incoming species undergo many collisions with the chamber wall until they are thermalized. The collisions cause chemical alteration of complex molecules, and the reconstruction of these chemical reactions is very challenging, if not impossible for heavier species. We designed a novel ion optical system to directly measure the incoming species without deflection or an antechamber at relative encounter velocities of up to 20 km/s while maintaining a mass range of about m/∆m 1,000 (full width half maximum).  Other scientific parameters such as, for example, sensitivity and dynamic range are comparable to the Neutral and Ion Mass spectrometer (NIM) on board ESA’s L-class JUICE mission.

Thus, this next generation of mass spectrometers enables reliable, unambiguous measurements of complex (bio) molecules during hypervelocity fly-bys. Given its mass range of about m/z 1 to 1,000, an application to volcanic active objects such as, for example, Io or ocean worlds become feasible either as a major instrument on board a spacecraft or using the smaller version as a descent probe that is deployed during a fly-by. Such investigations will provide valuable data for understanding their status including their exosphere and possible plumes. In combination with the data collected from Earth’s exosphere, these measurements enable comparative planetology on composition level for objects with and without life.

How to cite: Fausch, R. and Wurz, P.: Advances in Hypervelocity Sampling with Mass Spectrometers: From Earth to Deep Space, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-322, https://doi.org/10.5194/epsc2022-322, 2022.

17:00–17:15
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EPSC2022-875
Jan Zabka, Miroslav Polášek, Ylja Zymak, Michal Lacko, Nikola Sixtová, Jean-Pierre Lebreton, Arnaud Sanderink, and Marwa Kashkoul

Application of mass spectrometry in the space exploration has recently become a hot topic. It can be used for the analysis of space dust, micrometeorites and particles from larger objects.

For the Czech SLAVIA (Space Laboratory for Advanced Variable Instruments and Applications) satellite project (expected to be launched in 2026 to the SSO 600km orbit) was designed the HANKA (Hmotnostný ANalyzér pre Kozmické Aplikace) space instrument - a high-resolution Orbitrap-based  electrostatic ion trap mass analyser. The instrument is based on a commercial mass analyser1 established in biology and medicine research, the so-called Orbitrap™  and the space CosmOrbitrap prototype (developed by LPC2E Orleans2). HANKA will bring this new technology into space to combine a CubeSat space version (4U) of this ion trap analyzer with an innovative in-situ hypervelocity impact ionization source for micrometeoroids.

A laboratory version of this instrument (CIARA) is currently under construction, where ions can be generated by three different methods:

  • Photons with molecules in the liquid phase (coupled with experiment LILBID
    (Laser Induced Liquid Bead Ion Desorption)
  • Electrons with molecules in the gas phase (EI source)
  • Photons with solid-phase molecules (MALDI or Laser Ablation)


    Based on the results obtained on the laboratory prototype, a CubeSat version of the high-resolution space mass spectrometer - HANKA - will be constructed.

     

    References

    1Makarov, A.; Anal. Chem. 2000, 72, 1156–1162.

    2Briois C, Thissen R, Thirkell L, et al.; Planet Space Sci. 2016, 131, 33‐45.

    3Zymak Y. et al.; article in preparation

How to cite: Zabka, J., Polášek, M., Zymak, Y., Lacko, M., Sixtová, N., Lebreton, J.-P., Sanderink, A., and Kashkoul, M.: HANKA - cubesat space high resolution mass analyser, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-875, https://doi.org/10.5194/epsc2022-875, 2022.

Display time: Wed, 21 Sep 14:00–Fri, 23 Sep 16:00

Posters: Thu, 22 Sep, 18:45–20:15 | Poster area Level 1

Chairperson: Jean-Pierre Lebreton
L1.128
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EPSC2022-1252
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ECP
Arnaud Sanderink, Fabian Klenner, Jan Zabka, Frank Postberg, Jean-Pierre Lebreton, Illia Zymak, Gaubicher Bertrand, Bernd Abel, Ales Charvat, Barnabé Cherville, Laurent Thirkell, and Christelle Briois

In 2005, a new type of mass spectrometer was commercialised for the first time, the Thermo Fisher Scientific OrbitrapTM. Using a Quadro-Logarithmic Electrostatic Ion Trap technology, Orbitrap mass spectrometers are able to reach ultra-high mass resolution1. For a decade, the Laboratoire de Physique et Chimie de l’Environnement et de l’Espace (LPC2E) is developing a spatialised version of the Orbitrap, the CosmOrbitrap2, 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 Moon3,4.

In this context, OLYMPIA - Orbitrap anaLYser MultiPle IonisAtion – 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)5, 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 spectra6, such as those recorded by the Comic Dust Analyser7 (CDA) onboard Cassini in the vicinity of Saturn’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/Δm. 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. The setup is currently able to measure H2O+ and H3O+ ions with a mass resolution of around 150.000 m/Δm (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.

Those results will be implemented in the LILBID database8, and will be useful for the calibration and future data interpretation of the SUrface Dust Analyser (SUDA) mass spectrometer9, which will be onboard NASA’s Europa Clipper mission10 to characterize the habitability of Jupiter’s icy moon Europa.

 

References

1. Makarov, A. Electrostatic Axially Harmonic Orbital Trapping: A High-Performance Technique of Mass Analysis. Anal. Chem. 72, 1156–1162 (2000).

2. Briois, C. et al. Orbitrap mass analyser for in situ characterisation of planetary environments: Performance evaluation of a laboratory prototype. Planet. Space Sci. 131, 33–45 (2016).

3. Arevalo, R. et al. An Orbitrap-based laser desorption/ablation mass spectrometer designed for spaceflight. Rapid Commun. Mass Spectrom. 32, 1875–1886 (2018).

4. L. Willhite et al. CORALS: A Laser Desorption/Ablation Orbitrap Mass Spectrometer for In Situ Exploration of Europa, 2021 IEEE Aerospace Conference (50100), 2021, pp. 1-13, doi: 10.1109/AERO50100.2021.9438221.

5. Zymak, I. et al. 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.

6. Klenner, F. et al. Analogue spectra for impact ionization mass spectra of water ice grains obtained at different impact speeds in space. Rapid Commun. Mass Spectrom. 33, 1751–1760 (2019).

7. Srama, R. et al. The Cassini cosmic dust analyser. Space Sci. Rev. Volume 114, 465–518 (2004).

8. Klenner, F. et al. Developing a Laser Induced Liquid Beam Ion Desorption Spectral Database as Reference for Spaceborne Mass Spectrometers. Earth and Space Science Under Review (2022).

9. Kempf, S. et al. SUDA: A Dust Mass Spectrometer for Compositional Surface Mapping for a Mission to Europa. European Planetary Science Congress 2014, EPSC2014-229.

10. Howell, S. M. & Pappalardo, R. T. NASA’s Europa Clipper—a mission to a potentially habitable ocean world. Nat. Commun. 11, 1311 (2020).

How to cite: Sanderink, A., Klenner, F., Zabka, J., Postberg, F., Lebreton, J.-P., Zymak, I., Bertrand, G., Abel, B., Charvat, A., Cherville, B., Thirkell, L., and Briois, C.: OLYMPIA-LILBID: High Resolution Mass Spectrometry for the Calibration of Spaceborne Hypervelocity Ice Grain Detector, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1252, https://doi.org/10.5194/epsc2022-1252, 2022.

L1.129
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EPSC2022-1259
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ECP
Laura Selliez, Christelle Briois, Nathalie Carrasco, Laurent Thirkell, Bertrand Gaubicher, Jean-Pierre Lebreton, and Fabrice Colin

How Life has emerged on Earth? Can we find signs of Life on other celestial bodies in the Solar System? Are they harboring liquid water and complex-enough organic matter to initiate Life? What actually complex-enough organic matter means? Among other scientific questions, those related to astrobiology drive the future space missions for decades to come. The search for organic compounds in the Solar System, such as bio- and prebiotic molecules, has been defined as one of the highest priority by the Space Agencies [1, 2].

Significant improvements of the analytical performances of the future instruments will increase our knowledge of targets of interest for the search of Life, present or past, such as comets, asteroids, icy moons or ocean worlds. New generation of High Resolution Mass Spectrometers (HRMS) is currently being developed in order to provide univocal identifications, study of isotopic abundances and determination of mixing ratios with high analytical performances [3-6], including very HRMS-CosmOrbitrap based under collaborative development with University of Maryland/NASA Goddard Space Flight Center. The CosmOrbitrap mass analyzer is mainly funded by CNES, the French space agency, and developed by a consortium of 6 laboratories (LPC2E, LATMOS, LISA, IPAG, IJC lab, J. Heyrovsky Institute of Physical Chemistry) [7].

Here we address the results of a repeatability study based on three organic compounds and obtained with the LAb-CosmOrbitrap (Laser Ablation CosmOrbitrap) equipped with a commercial laser ionization system at 266 nm and no C-trap system. Organics studied are nitrogenous and sulfurous compounds, HOBt (C6H5N3O+H) at m/z 136 and BBOT (C26H26N2O2S+H) at m/z 431; and a prebiotic compound, the well-known adenine (C5H5N5+H) at m/z 136.

Hundreds of mass spectra have been recorded to demonstrate the reproducible analytical performances of the laser-CosmOrbitrap set-up. Mass resolving power has been studied as a function of the acquisition time and the FFT length. Different kind of mass calibrations have been tried to show the effect on the mass accuracy (internal mass calibration on the species of interest and external mass calibration on the metallic sample-holder). Finally, preliminary results on isotopic abundances (13C/12C, 15N/14N and 34S/32S replacements) have been obtained.

This work provides key information for specifying the required performances of future HRMS space instruments.

 

Acknowledgement: We thank the Centre National des Etudes Spatiales (CNES), the French space agency, for their financial support.

References:

[1] National Academies (2022) Origins, Worlds and Life.

[2] ESA (2021) Voyage 2050

[3] Waite et al. (2019) Abstract Vol.13, EPSC-DPS2019-559-1

[4] Shimma et al. (2010) Anal. Chem. 82, 20, 8456-8463

[5] Willhite et al. (2021) IEEE Aerospace, 1 – 13

[6] Willhite et al. (2021) Annual Meeting of the Lunar Exploration Analysis Group, LPI Contribution No. 2635, id.5034

[7] Briois et al. (2016) PSS 131, 33 – 45

How to cite: Selliez, L., Briois, C., Carrasco, N., Thirkell, L., Gaubicher, B., Lebreton, J.-P., and Colin, F.: The potential of the LAb-CosmOrbitrap for future space studies in astrobiology, Europlanet Science Congress 2022, Granada, Spain, 18–23 Sep 2022, EPSC2022-1259, https://doi.org/10.5194/epsc2022-1259, 2022.