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Laser desorption mass spectrometry with an Orbitrap analyser for in situ astrobiology

Nature Astronomy volume 7, pages 359–365 (2023)Cite this article

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Abstract

Laser desorption mass spectrometry (LDMS) enables in situ characterization of the organic content and chemical composition of planetary materials without requiring extensive sample processing. Coupled with an Orbitrap analyser capable of ultrahigh mass-resolving powers and accuracies, LDMS techniques facilitate the orthogonal detection of a wide range of biomarkers and classification of host mineralogy. Here an Orbitrap LDMS instrument that has been miniaturized for planetary exploration is shown to meet the performance standards of commercial systems and exceed key figures of merit of heritage spaceflight technologies, including those baselined for near-term mission opportunities. Biogenic compounds at area densities relevant to prospective missions to ocean worlds are identified unambiguously by redundant measurements of molecular ions (with and without salt adducts) and diagnostic fragments. The derivation of collision cross-sections serves to corroborate assignments and inform on molecular structure. Access to trace elements down to parts per million by weight levels provide insights into sample mineralogy and provenance. These analytical capabilities position the miniaturized LDMS described here for a wide range of high-priority mission concepts, such as those focused on life detection objectives (for example, Enceladus Orbilander) and progressive exploration of the lunar surface (for example, via the NASA Artemis Program).

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Fig. 1: The highly miniaturized LDMS instrument described here leverages an Orbitrap mass analyser to achieve ultrahigh mass resolution and accuracy.
Fig. 2: In both negative and positive mode, the miniaturized Orbitrap LDMS instrument achieves mass-resolving powers (m/Δm > 105, FWHM at m/z 100) comparable to commercial standards.
Fig. 3: A single mass spectrum of an ocean world analogue sample illustrates the capability to detect and identify organic and inorganic components of planetary materials.
Fig. 4: After successful injection into the Orbitrap analyser, the axial motions of the analyte ions are detected via image current in the time domain transient.
Fig. 5: The Orbitrap LDMS instrument can detect trace elements down to ppmw concentrations, as illustrated by the measurement of REEs in NIST SRM610.

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Data availability

Source data are provided with this paper. All other data presented in this study are available in the Supplementary Information.

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Acknowledgements

This study was supported by the University of Maryland Faculty Incentive Program (PI: R.A. Jr), NASA Goddard Space Flight Center Internal Research and Development Program (PIs: A.G. and A.Y.), NASA ROSES ICEE 2 Grant 80NSSC19K0610 (PI: R.A. Jr), ROSES DALI Grant 80NSSC19K0768 (PI: R.A. Jr) and CRESST II Award Number 80GSFC21M0002 (PI: A.S.).

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Authors and Affiliations

  1. University of Maryland, College Park, MD, USA

    Ricardo Arevalo Jr, Lori Willhite, Anais Bardyn, Ziqin Ni & Soumya Ray

  2. CRESST II, College Park, MD, USA

    Adrian Southard

  3. Danell Consulting, Winterville, NC, USA

    Ryan Danell

  4. NASA Goddard Space Flight Center, Greenbelt, MD, USA

    Andrej Grubisic, Anthony Yu, Molly Fahey & Emanuel Hernandez

  5. AMU Engineering, Miami, FL, USA

    Cynthia Gundersen & Niko Minasola

  6. Laboratoire de Physique et Chimie de l’Environnement et de l’Espace, Orléans, France

    Christelle Briois, Laurent Thirkell & Fabrice Colin

  7. Thermo Fisher Scientific, Bremen, Germany

    Alexander Makarov

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Contributions

The dataset presented in this study was collected and analysed by R.A. Jr, L.W., A.B., Z.N. and S.R. The system-level architecture of the miniaturized instrument and the operational sequence of the experiments conducted were defined by R.A. Jr, A.S., R.D., A.G., C.B., L.T., F.C. and A.M. Requirements for the ion optics and SIMION models of ion transmission were provided by A.S. The mechanical design of the mass analyser assembly and custom series of ion optics were led by C.G. and N.M. The design and build of the prototype UV laser system was led by A.Y. and M.F. All authors contributed to the interpretation of the results and editing of the manuscript.

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Correspondence to Ricardo Arevalo Jr.

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Competing interests

A.M. is an employee of Thermo Fisher Scientific, the manufacturer of the Orbitrap device leveraged in the miniaturized instrument described here.

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Nature Astronomy thanks Marek Tulej and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary discussion, Figs. 1–8 and Table 1.

Source data

Source Data Fig. 2

Raw time domain transients for Fig. 2.

Source Data Fig. 3

Raw time domain transient for Fig. 3.

Source Data Fig. 5

Raw time domain transient for Fig. 5.

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Arevalo, R., Willhite, L., Bardyn, A. et al. Laser desorption mass spectrometry with an Orbitrap analyser for in situ astrobiology. Nat Astron 7, 359–365 (2023). https://doi.org/10.1038/s41550-022-01866-x

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