Discriminating Aromatic Parent Compounds and Their Derivative Isomers in Ice Grains From Enceladus and Europa Using a Laboratory Analogue for Spaceborne Mass Spectrometers

Khawaja, Nozair; O’Sullivan, T. R.; Klenner, Fabian; Sánchez, Lucía Hortal; Hillier, Jon K.

doi:10.1029/2022ea002807

Cited by 4 publications

(3 citation statements)

References 51 publications

(102 reference statements)

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“…Among the investigated compounds, this chemical family is the one to which anion polarity LILBID-MS is most sensitive in salt-rich matrices, although it is only moderately sensitive in H 2 SO 4 solutions. Generally, we expect highly acidic compounds to be highly responsive in the anion mode analysis thanks to a strong tendency to form deprotonated molecular peaks. typically form highly prominent [M – OH] + fragment peaks, as observed here in MgSO 4 and H 2 SO 4 matrices and by Khawaja et al in similar experiments with pure water matrix. This differs from the case of NaCl matrices where [M – OH] + peaks have a low intensity, but highly prominent disodiated [M – H + 2Na] + peaks are observed …”

Section: Discussionsupporting

confidence: 87%

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Mass Spectrometric Fingerprints of Organic Compounds in Sulfate-Rich Ice Grains: Implications for Europa Clipper

Napoleoni,

Klenner,

Hortal Sánchez

et al. 2023

ACS Earth Space Chem.

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The surface ice of Europa is known to contain high proportions of inorganic material that could heavily influence the compositional analysis of organic compounds in ejecta ice grains by the SUrface Dust Analyzer (SUDA) impact ionization mass spectrometer onboard NASA’s Europa Clipper mission. We previously have analyzed the effects of NaCl on the mass spectral appearance of organic-rich ice grains. Here, we present analogue experiments for SUDA simulating cation and anion mass spectra of organic-rich ice grains together with sulfates, one of the most abundant inorganic compounds on Europa’s surface. Using the Laser Induced Liquid Beam Ion Desorption (LILBID) technique, a diverse range of representative organic species in MgSO4- and H2SO4-rich matrices at concentrations ranging from 0.01 to 1 M were measured. Results show that mass spectrometric signatures of organic species can be detected in MgSO4-rich and H2SO4-rich ice grains via molecular ions, although the mass spectral appearance changes from molecular ions to a range of adducts with Mg2+, OH–, and HSO4 – ions and MgSO4 and H2SO4 molecules depending on the matrix and the matrix concentration. Sensitivity to the organics is typically higher in cation mode than in anion mode in both matrices. Due to suppression effects, the sensitivity to detect the organics decreases with increasing MgSO4 concentration, but it does not decrease in H2SO4 matrices in cation mode. We establish generic rules for the detection of organics in Europan ice grains by SUDA, applicable to a wide range of organic species in complex ice matrices. The recorded mass spectra complement a spectral reference database for Europa Clipper and other ocean world missions.

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Section: Discussionsupporting

confidence: 87%

“…typically form highly prominent [M – OH] + fragment peaks, as observed here in MgSO 4 and H 2 SO 4 matrices and by Khawaja et al in similar experiments with pure water matrix. This differs from the case of NaCl matrices where [M – OH] + peaks have a low intensity, but highly prominent disodiated [M – H + 2Na] + peaks are observed …”

Section: Discussionsupporting

confidence: 87%

Mass Spectrometric Fingerprints of Organic Compounds in Sulfate-Rich Ice Grains: Implications for Europa Clipper

Napoleoni,

Klenner,

Hortal Sánchez

et al. 2023

ACS Earth Space Chem.

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“…LILBID is proven to accurately simulate the impact ionization mass spectra of ice grains and any embedded compounds as produced by spaceborne instruments like Cassini's CDA, the SUrface Dust Analyzer (SUDA) onboard the upcoming Europa Clipper mission [43,44], and the High Ice Flux Instrument (HIFI) for the Enceladus mission concept, Moonraker [45]. LILBID has been essential in analysing the organic content of ice grains from Enceladus and efforts are ongoing to build a spectral reference library for future missions to icy moons [46], aiding the detection of organic and potential biosignature compounds [47][48][49][50][51][52]. Thousands of mass spectra have already been measured with LILBID, although these experiments have not yet considered the spectral appearance of material that has been hydrothermally processed.…”

Section: Introductionmentioning

confidence: 99%

Laboratory characterization of hydrothermally processed oligopeptides in ice grains emitted by Enceladus and Europa

Khawaja,

Hortal Sánchez,

O’Sullivan

et al. 2024

Phil. Trans. R. Soc. A.

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The Cassini mission provided evidence for a global subsurface ocean and ongoing hydrothermal activity on Enceladus, based on results from Cassini’s mass spectrometers. Laboratory simulations of hydrothermal conditions on icy moons are needed to further constrain the composition of ejected ice grains containing hydrothermally altered organic material. Here, we present results from our newly established facility to simulate the processing of ocean material within the temperature range 80–150°C and the pressure range 80–130 bar, representing conditions suggested for the water–rock interface on Enceladus. With this new facility, we investigate the hydrothermal processing of triglycine (GGG) peptide and, for the first time, analyse the extracted samples using laser-induced liquid beam ion desorption (LILBID) mass spectrometry, a laboratory analogue for impact ionization mass spectrometry of ice grains in space. We outline an approach to elucidate hydrothermally processed GGG in ice grains ejected from icy moons based on characteristic differences between GGG anion and cation mass spectra. These differences are linked to hydrothermal processing and thus provide a fingerprint of hydrothermal activity on extraterrestrial bodies. These results will serve as important guidelines for biosignatures potentially obtained by a future Enceladus mission and the SUrface Dust Analyzer (SUDA) instrument onboard Europa Clipper. This article is part of the theme issue ‘Dust in the Solar System and beyond’.

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How to identify cell material in a single ice grain emitted from Enceladus or Europa

Klenner,

Bönigk,

Napoleoni

et al. 2024

Sci. Adv.

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Icy moons like Enceladus, and perhaps Europa, emit material sourced from their subsurface oceans into space via plumes of ice grains and gas. Both moons are prime targets for astrobiology investigations. Cassini measurements revealed a large compositional diversity of emitted ice grains with only 1 to 4% of Enceladus’s plume ice grains containing organic material in high concentrations. Here, we report experiments simulating mass spectra of ice grains containing one bacterial cell, or fractions thereof, as encountered by advanced instruments on board future space missions to Enceladus or Europa, such as the SUrface Dust Analyzer onboard NASA’s upcoming Europa Clipper mission at flyby speeds of 4 to 6 kilometers per second. Mass spectral signals characteristic of the bacteria are shown to be clearly identifiable by future missions, even if an ice grain contains much less than one cell. Our results demonstrate the advantage of analyses of individual ice grains compared to a diluted bulk sample in a heterogeneous plume.

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Discriminating Aromatic Parent Compounds and Their Derivative Isomers in Ice Grains From Enceladus and Europa Using a Laboratory Analogue for Spaceborne Mass Spectrometers

Abstract: Mass spectrometers on space missions, e.g., Galileo, Stardust, Cassini-Huygens, and Rosetta, have demonstrated the applicability of mass spectrometry for the in situ analysis of dust and ice grains in different planetary environments (

Cited by 4 publications

References 51 publications

Mass Spectrometric Fingerprints of Organic Compounds in Sulfate-Rich Ice Grains: Implications for Europa Clipper

Mass Spectrometric Fingerprints of Organic Compounds in Sulfate-Rich Ice Grains: Implications for Europa Clipper

Laboratory characterization of hydrothermally processed oligopeptides in ice grains emitted by Enceladus and Europa

How to identify cell material in a single ice grain emitted from Enceladus or Europa

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