Characterization of Regolith And Trace Economic Resources (CRATER): An Orbitrap-based laser desorption mass spectrometry instrument for in situ exploration of the Moon.

RATIONALE: Characterization of Regolith And Trace Economic Resources (CRATER), an Orbitrap™-based laser desorption mass spectrometry instrument designed to conduct high-precision, spatially resolved analyses of planetary materials, is capable of answering outstanding science questions about the Moon's formation and the subsequent processes that have modified its (sub)surface. METHODS: Here, we describe the baseline design of the CRATER flight model, which requires <20 000 cm3  volume, <10 kg mass, and <60 W peak power. The analytical capabilities and performance metrics of a prototype that meets the full functionality of the flight model are demonstrated. RESULTS: The instrument comprises a high-power, solid-state, pulsed ultraviolet (213 nm) laser source to ablate the surface of the lunar sample, a custom ion optical interface to accelerate and collimate the ions produced at the ablation site, and an Orbitrap mass analyzer capable of discriminating competing isobars via ultrahigh mass resolution and high mass accuracy. The CRATER instrument can measure elemental and isotopic abundances and characterize the organic content of lunar surface samples, as well as identify economically valuable resources for future exploration. CONCLUSION: An engineering test unit of the flight model is currently in development to serve as a pathfinder for near-term mission opportunities.

Detection of Short Peptides as Putative Biosignatures of Psychrophiles via Laser Desorption Mass Spectrometry.

Studies of psychrophilic life on Earth provide chemical clues as to how extraterrestrial life could maintain viability in cryogenic environments. If living systems in ocean worlds (e.g., Enceladus) share a similar set of 3-mer and 4-mer peptides to the psychrophile Colwellia psychrerythraea on Earth, spaceflight technologies and analytical methods need to be developed to detect and sequence these putative biosignatures. We demonstrate that laser desorption mass spectrometry, as implemented by the CORALS spaceflight prototype instrument, enables the detection of protonated peptides, their dimers, and metal adducts. The addition of silicon nanoparticles promotes the ionization efficiency, improves mass resolving power and mass accuracies via reduction of metastable decay, and facilitates peptide de novo sequencing. The CORALS instrument, which integrates a pulsed UV laser source and an Orbitrap™ mass analyzer capable of ultrahigh mass resolving powers and mass accuracies, represents an emerging technology for planetary exploration and a pathfinder for advanced technique development for astrobiological objectives. Teaser: Current spaceflight prototype instrument proposed to visit ocean worlds can detect and sequence peptides that are found enriched in at least one strain of microbe surviving in subzero icy brines via silicon nanoparticle-assisted laser desorption analysis.

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.

Composition of cometary particles collected during two periods of the Rosetta mission: multivariate evaluation of mass spectral data.

The instrument COSIMA (COmetary Secondary Ion Mass Analyzer) onboard of the European Space Agency mission Rosetta collected and analyzed dust particles in the neighborhood of comet 67P/Churyumov-Gerasimenko. The chemical composition of the particle surfaces was characterized by time-of-flight secondary ion mass spectrometry. A set of 2213 spectra has been selected, and relative abundances for CH-containing positive ions as well as positive elemental ions define a set of multivariate data with nine variables. Evaluation by complementary chemometric techniques shows different compositions of sample groups collected during two periods of the mission. The first period was August to November 2014 (far from the Sun); the second period was January 2015 to February 2016 (nearer to the Sun). The applied data evaluation methods consider the compositional nature of the mass spectral data and comprise robust principal component analysis as well as classification with discriminant partial least squares regression, k-nearest neighbor search, and random forest decision trees. The results indicate a high importance of the relative abundances of the secondary ions C+ and Fe+ for the group separation and demonstrate an enhanced content of carbon-containing substances in samples collected in the period with smaller distances to the Sun.

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.

Krypton isotopes and noble gas abundances in the coma of comet 67P/Churyumov-Gerasimenko.

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis mass spectrometer Double Focusing Mass Spectrometer on board the European Space Agency's Rosetta spacecraft detected the major isotopes of the noble gases argon, krypton, and xenon in the coma of comet 67P/Churyumov-Gerasimenko. Earlier, it was found that xenon exhibits an isotopic composition distinct from anywhere else in the solar system. However, argon isotopes, within error, were shown to be consistent with solar isotope abundances. This discrepancy suggested an additional exotic component of xenon in comet 67P/Churyumov-Gerasimenko. We show that krypton also exhibits an isotopic composition close to solar. Furthermore, we found the argon to krypton and the krypton to xenon ratios in the comet to be lower than solar, which is a necessity to postulate an addition of exotic xenon in the comet.

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.

Mechanical and electrostatic experiments with dust particles collected in the inner coma of comet 67P by COSIMA onboard Rosetta.

The in situ cometary dust particle instrument COSIMA (COmetary Secondary Ion Mass Analyser) onboard ESA's Rosetta mission has collected about 31 000 dust particles in the inner coma of comet 67P/Churyumov-Gerasimenko since August 2014. The particles are identified by optical microscope imaging and analysed by time-of-flight secondary ion mass spectrometry. After dust particle collection by low speed impact on metal targets, the collected particle morphology points towards four families of cometary dust particles. COSIMA is an in situ laboratory that operates remotely controlled next to the comet nucleus. The particles can be further manipulated within the instrument by mechanical and electrostatic means after their collection by impact. The particles are stored above 0°C in the instrument and the experiments are carried out on the refractory, ice-free matter of the captured cometary dust particles. An interesting particle morphology class, the compact particles, is not fragmented on impact. One of these particles was mechanically pressed and thereby crushed into large fragments. The particles are good electrical insulators and transform into rubble pile agglomerates by the application of an energetic indium ion beam during the secondary ion mass spectrometry analysis.This article is part of the themed issue 'Cometary science after Rosetta'.

High-molecular-weight organic matter in the particles of comet 67P/Churyumov-Gerasimenko.

The presence of solid carbonaceous matter in cometary dust was established by the detection of elements such as carbon, hydrogen, oxygen and nitrogen in particles from comet 1P/Halley. Such matter is generally thought to have originated in the interstellar medium, but it might have formed in the solar nebula-the cloud of gas and dust that was left over after the Sun formed. This solid carbonaceous material cannot be observed from Earth, so it has eluded unambiguous characterization. Many gaseous organic molecules, however, have been observed; they come mostly from the sublimation of ices at the surface or in the subsurface of cometary nuclei. These ices could have been formed from material inherited from the interstellar medium that suffered little processing in the solar nebula. Here we report the in situ detection of solid organic matter in the dust particles emitted by comet 67P/Churyumov-Gerasimenko; the carbon in this organic material is bound in very large macromolecular compounds, analogous to the insoluble organic matter found in the carbonaceous chondrite meteorites. The organic matter in meteorites might have formed in the interstellar medium and/or the solar nebula, but was almost certainly modified in the meteorites' parent bodies. We conclude that the observed cometary carbonaceous solid matter could have the same origin as the meteoritic insoluble organic matter, but suffered less modification before and/or after being incorporated into the comet.

Prebiotic chemicals-amino acid and phosphorus-in the coma of comet 67P/Churyumov-Gerasimenko.

The importance of comets for the origin of life on Earth has been advocated for many decades. Amino acids are key ingredients in chemistry, leading to life as we know it. Many primitive meteorites contain amino acids, and it is generally believed that these are formed by aqueous alterations. In the collector aerogel and foil samples of the Stardust mission after the flyby at comet Wild 2, the simplest form of amino acids, glycine, has been found together with precursor molecules methylamine and ethylamine. Because of contamination issues of the samples, a cometary origin was deduced from the (13)C isotopic signature. We report the presence of volatile glycine accompanied by methylamine and ethylamine in the coma of 67P/Churyumov-Gerasimenko measured by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) mass spectrometer, confirming the Stardust results. Together with the detection of phosphorus and a multitude of organic molecules, this result demonstrates that comets could have played a crucial role in the emergence of life on Earth.

Detection of argon in the coma of comet 67P/Churyumov-Gerasimenko.

Comets have been considered to be representative of icy planetesimals that may have contributed a significant fraction of the volatile inventory of the terrestrial planets. For example, comets must have brought some water to Earth. However, the magnitude of their contribution is still debated. We report the detection of argon and its relation to the water abundance in the Jupiter family comet 67P/Churyumov-Gerasimenko by in situ measurement of the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) mass spectrometer aboard the Rosetta spacecraft. Despite the very low intensity of the signal, argon is clearly identified by the exact determination of the mass of the isotope (36)Ar and by the (36)Ar/(38)Ar ratio. Because of time variability and spatial heterogeneity of the coma, only a range of the relative abundance of argon to water can be given. Nevertheless, this range confirms that comets of the type 67P/Churyumov-Gerasimenko cannot be the major source of Earth's major volatiles.

Comet 67P/Churyumov-Gerasimenko sheds dust coat accumulated over the past four years.

Comets are composed of dust and frozen gases. The ices are mixed with the refractory material either as an icy conglomerate, or as an aggregate of pre-solar grains (grains that existed prior to the formation of the Solar System), mantled by an ice layer. The presence of water-ice grains in periodic comets is now well established. Modelling of infrared spectra obtained about ten kilometres from the nucleus of comet Hartley 2 suggests that larger dust particles are being physically decoupled from fine-grained water-ice particles that may be aggregates, which supports the icy-conglomerate model. It is known that comets build up crusts of dust that are subsequently shed as they approach perihelion. Micrometre-sized interplanetary dust particles collected in the Earth's stratosphere and certain micrometeorites are assumed to be of cometary origin. Here we report that grains collected from the Jupiter-family comet 67P/Churyumov-Gerasimenko come from a dusty crust that quenches the material outflow activity at the comet surface. The larger grains (exceeding 50 micrometres across) are fluffy (with porosity over 50 per cent), and many shattered when collected on the target plate, suggesting that they are agglomerates of entities in the size range of interplanetary dust particles. Their surfaces are generally rich in sodium, which explains the high sodium abundance in cometary meteoroids. The particles collected to date therefore probably represent parent material of interplanetary dust particles. This argues against comet dust being composed of a silicate core mantled by organic refractory material and then by a mixture of water-dominated ices. At its previous recurrence (orbital period 6.5 years), the comet's dust production doubled when it was between 2.7 and 2.5 astronomical units from the Sun, indicating that this was when the nucleus shed its mantle. Once the mantle is shed, unprocessed material starts to supply the developing coma, radically changing its dust component, which then also contains icy grains, as detected during encounters with other comets closer to the Sun.

Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans from a mixture of chlorophenols over fly ash: influence of water vapor.

Recent efforts have been made to establish readily measurable surrogate compounds, such as chlorophenols, for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), that would enable plant operations to limit formation. Despite the extensive studies conducted on PCDDs/Fs formation from chlorophenols, very few studies have been carried out in real combustion conditions with a realistic concentration of precursors and the presence of water. In the present study, low (10(-9) M), stable concentrations of chlorinated phenols that are representative of concentrations of such compounds in municipal waste incinerator (MWI) raw flue gas were used in experiments investigating the formation of PCDDs/Fs over fly ash. Different mixtures of the chlorophenols (CPs) studied (2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and 2,3,4,6-tetrachlorophenol) were passed through a bed of oxidized fly ash (carbon-free) and glass beads with and without the presence of water. The chlorophenol reactants used in this study were found to favor PCDD over PCDF formation. The presence of water was observed to considerably reduce the yields of all PCDD/F formed (< 0.3% phenol conversion). The PCDD homologue and isomer distributions were not affected by the presence of water, unlike the PCDF compounds. The major PCDD homologue groups formed were tetra- and penta-, both with or without water in the gas stream. The major PCDF homologue groups were mostly the lower chlorinated ones in the experiments performed in the presence or absence of water. These results contribute to the understanding of PCDD/Fs formation in realistic combustion conditions, including very low concentrations of precursors and the presence of water in the flue gas.

Experimental study on the thermal oxidation of 2-chlorophenol in air over the temperature range 450-900 degrees C.

The thermal oxidation of 2-chlorophenol (2-CP) in air was investigated using a perfectly stirred reactor at 1 atm over the temperature range 450-900 degrees C. The relative concentration of 2-CP was 1,000 ppm V (equivalence ratio Phi=0.03). About fifty organic products were identified as trace species. The concentration profiles of 2-CP, carbon oxides as well as those of seventeen major organic intermediates and six non-to-lower chlorinated dioxins and furans were presented as a function of temperature for a residence time of 2s. The most abundant intermediate products were carbon monoxide, 2H-pyran-2-one, chlorobenzene, 4-cyclopenten-1,3-dione, phenol, benzofuran, 2-chlorohydroquinone and 2-indanone. These concentration profiles have revealed that temperatures of at least 900 degrees C were needed to completely oxidize 2-CP, CO and all other organic byproducts to carbon dioxide. Reaction pathways accounting for the formation of most observed products are proposed.