Extraterrestrial Organic Matter Research Articles

Extraterrestrial Organic Matter: An Introduction

Extraterrestrial organic matter forms in a variety of locations in space through different mechanisms. Its nature, distribution, formation mechanisms and locations are of particular interest. Some organic molecules can even be considered as key players for the emergence of life. Although new organic species are continuously detected in the interstellar media, Solar System bodies, and extraterrestrial materials, their formation and evolution are still not fully understood. Ground-based and space observations can detect organic matter in different objects with a range of complexity and diversity, while laboratory investigations of astromaterials allow detailed characterization of extraterrestrial organic matter with high precision. This issue reviews different aspects of extraterrestrial organic matter, including its origin, evolution, diversity, and delivery.

Analytical Techniques for Identification and Characterization of Extraterrestrial Organic Matter

Advances in analytical techniques are essential for understanding the nature, formation, and evolutionary history of extraterrestrial organic matter. In this chapter, we briefly review analytical techniques used to detect and characterize organic matter in extraterrestrial materials. Mass spectrometry is often coupled with gas chromatography or liquid chromatography for elemental and isotopic analysis, and for identifying specific organic compounds. Spectroscopy involves interaction of molecules with electromagnetic radiation at various wavelengths. Almost every wavelength—from X-rays to radio waves—can be used for spectroscopic measurements. The most major microscopic and nanoscopic techniques are scanning and/or transmission electron microscopy. Spectroscopy and mass spectrometry can also be coupled with microscopic analysis for detailed compositional investigations.

High-spatial resolution functional chemistry of nitrogen compounds in the observed UK meteorite fall Winchcombe

Organic matter in extraterrestrial samples is a complex material that might have played an important role in the delivery of prebiotic molecules to the early Earth. We report here on the identification of nitrogen-containing compounds such as amino acids and N-heterocycles within the recent observed meteorite fall Winchcombe by high-spatial resolution spectroscopy techniques. Although nitrogen contents of Winchcombe organic matter are low (N/C ~ 1–3%), we were able to detect the presence of these compounds using a low-noise direct electron detector. These biologically relevant molecules have therefore been tentatively found within a fresh, minimally processed meteorite sample by high spatial resolution techniques conserving the overall petrographic context. Carbon functional chemistry investigations show that sizes of aromatic domains are small and that abundances of carboxylic functional groups are low. Our observations demonstrate that Winchcombe represents an important addition to the collection of carbonaceous chondrites and still preserves pristine extraterrestrial organic matter.

Integrative analytical workflow to enhance comprehensive analysis of organic molecules in extraterrestrial objects.

Molecular identification is a fundamental issue in astrobiology to investigate the routes of emergence of life on our planet involving in particular a potential seeding of extraterrestrial organic matter on the primitive Earth. However, this project encompasses major difficulties due to the low concentration of molecules present in bodies of the Solar System. This work proposes an integrative analytical workflow, no longer based on GC-MS instruments, to enhance comprehensive analysis of organic markers in these objects. Our strategy combines UPLC-HRMS and UPLC-MRM MS methods to bring both a broad molecular mapping and detailed data on indigenous compounds present in any extraterrestrial objects or laboratory analogs. Applied on water extracts from fresh meteorites, our workflow highlights a wide range of free molecules in the non-treated extracts and reveals the wide diversity of amino acid and nucleobase isomers that could lead to misinterpretation as far as the molecular composition of meteorite extracts cannot be anticipated. This strategy, never explored so far, would provide new clues for studying the organic matter in space and should offer new perspectives on its evolution and reactivity.

Speciation of organosulfur compounds in carbonaceous chondrites

Despite broad application of different analytical techniques for studies on organic matter of chondrite meteorites, information about composition and structure of individual compounds is still very limited due to extreme molecular diversity of extraterrestrial organic matter. Here we present the first application of isotopic exchange assisted Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for analysis of alkali extractable fraction of insoluble organic matter (IOM) of the Murchison and Allende meteorites. This allowed us to determine the individual S-containing ions with different types of sulfur atoms in IOM. Thiols, thiophenes, sulfoxides, sulfonyls and sulfonates were identified in both samples but with different proportions, which contribution corroborated with the hydrothermal and thermal history of the meteorites. The results were supported by XPS and thermogravimetric analysis coupled to FTICR MS. The latter was applied for the first time for analysis of chondritic IOM. To emphasize the peculiar extraterrestrial origin of IOM we have compared it with coal kerogen, which is characterized by the comparable complexity of molecular composition but its aromatic nature and low oxygen content can be ascribed almost exclusively to degradation of biomacromolecules.

Non-terrestrial Material Agency

We are interested in discussing and exploring the intermingling of non-human agency, degrees of aliveness and alien life. Through the Proto-Alien Project (Proto-A), we investigate the synthesis and use of extraterrestrial organic matter (ETOM) as an active medium for artistic expression. We particularly focus on the ability to self-assemble, the morphogenetic tendencies and the non-linear behaviour of non-terrestrial material assemblages in liquids other than water. Largely, this project is a framework, a multi-disciplinary laboratory of ideas and experiments at the intersection of astrobiology, chemistry and media art. Our aim is to use ETOM to grow soft, kinetic and intelligent agents: autonomous ‘others’ that thrive and avoid equilibrium on extraterrestrial environments —a new type of alien material agency, yet unknown to humankind.

Hydrogen isotopic anomalies in extraterrestrial organic matter: role of cosmic ray irradiation and implications for UCAMMs

Context. Micrometeorites represent, at timescales shorter than a few million years, the dominant source of extraterrestrial matter at the surface of the Earth. Analyses of ultracarbonaceous micrometeorites recovered from Antarctica, known as UCAMMs reveal an exceptionally N-rich organic matter associated with spatially extended high D enrichments. Experiments show that this specific organic matter might have been formed in the outer solar system by energetic irradiation of N-rich icy surfaces. Aims. We experimentally investigate the hydrogen isotopic fractionation resulting from irradiation of normal and D-rich N2-CH4 ices by high energy ions, simulating the exposition to Galactic cosmic rays of icy bodies surfaces orbiting at large heliocentric distances. Methods. Films of N2-CH4 ices and a N2-CH4/CD4/N2-CH4 “sandwich” ice were exposed to 129Xe13+ ion beams at 92 and 88 MeV. The chemical evolution of the samples was monitored using in situ Fourier transform infrared spectroscopy. After irradiation, targets were annealed to room temperature. The solid residues of the whole process left after ice sublimation were characterized in situ by infrared spectroscopy, and the hydrogen isotopic composition measured ex situ by imaging secondary ion mass spectrometry at the sub-micron scale (NanoSIMS). Results. Irradiation leads to the formation of new molecules and radicals. After annealing, the resulting poly-HCN-like macro-molecular residue exhibits an infrared spectrum close to that of UCAMMs. The residue resulting from irradiation of N2-CH4 ices does not exhibit a significant deuterium enrichment comparable to that found in extraterrestrial organic matter. The residue formed by irradiation of D-rich ices shows the formation of isotopic heterogeneities with localised hotspots and an extended contribution likely due to the diffusion of the radiolytic products from the D-rich layer. Conclusions. These results show that high-energy cosmic ray irradiation does not induce the large hydrogen isotopic fractionation observed at small spatial scale in interplanetary organics. By contrast, large D/H ratio heterogeneities at the sub-micron spatial scale in extraterrestrial organic matter can result from isotopically heterogeneous ices mixtures (i.e. condensed with different D/H ratios), which were transformed into refractory organic matter upon irradiation.

Extraterrestrial organic matter preserved in 3.33 Ga sediments from Barberton, South Africa

Electron paramagnetic resonance (EPR) analysis of carbonaceous, volcanic, tidal sediments from the 3.33 Ga-old Josefsdal Chert (Kromberg Formation, Barberton Greenstone Belt), documents the presence of two types of insoluble organic matter (IOM): (1) IOM similar to that previously found in Archean cherts from numerous other sedimentary rocks in the world and of purported biogenic origin; (2) anomalous IOM localized in a 2 mm-thick sedimentary horizon. Detailed analysis by continuous-wave-EPR and pulse-EPR reveals that IOM in this layer is similar to the insoluble component of the hydrogenated organic matter in carbonaceous chondrites, suggesting that this narrow sedimentary horizon has preserved organic matter of extraterrestrial origin. This conclusion is supported by the presence in this thin layer of another anomalous EPR signal at g = 3 attributed to Ni-Cr-Al ferrite spinel nanoparticles, which are known to form during atmospheric entry of cosmic objects. From this EPR analysis, it was deduced that the anomalous sedimentary layer originates from deposition, in a nearshore environment, of a cloud of tiny dust particles originating from a flux of micrometeorites falling through the oxygen-poor Archean atmosphere.

Kinetics of White Soft Minerals (WSMs) Decomposition under Conditions of Interest for Astrobiology: A Theoretical and Experimental Study

In this paper, the thermal decomposition kinetics of a class of minerals that we call White Soft Minerals (WSMs) is studied by means of theoretical and experimental methods, in connection to the transport of extraterrestrial organic matter to Earth and the possible use of the decomposition reaction in the characterization of these minerals in space. WSMs include, under a single denomination, carbonates and sulphates of Mg, Fe, and Ca. To improve the present knowledge of the properties of such materials, we use the following techniques: kinetic models for chemical decomposition, atmospheric entry models, spectroscopy, and gravimetric analyses. Model results show that the atmospheric entry of WSM grains is strongly affected by their thermal decomposition. The decomposition reaction, being strongly endothermic, tends to significantly lower the grain temperature during the atmospheric entry, especially at high altitudes and for grazing entries. A previously proposed infrared spectroscopic technique to evaluate the degree of advancement of the reaction is found to be in good agreement with gravimetric measurements for calcium carbonate. The numerical model developed for the atmospheric entry scenarios is used to interpret experimental results. These main findings show that an additional contribution to the reaction enthalpy is needed to reproduce the experimental results, suggesting that the present theoretical model needs improvements such as the account of gas diffusion in the materials.

Bulk chemical characteristics of soluble polar organic molecules formed through condensation of formaldehyde: Comparison with soluble organic molecules in Murchison meteorite

Carbonaceous chondrites contain up to 2 wt% organic carbon, which is present as acid and solvent insoluble solid organic matter (IOM) and solvent soluble organic matter (SOM). The extraterrestrial organic matter should record chemical processes occurred in different environments in the early history of the Solar System, and the role of parent body aqueous alteration in the synthesis or subsequent modification of IOM and SOM still requires accurate constraints. We conducted hydrothermal experiments to simulate the synthesis of organic molecules during aqueous alteration on small bodies. Bulk chemical characteristics of soluble organic matter synthesized from formaldehyde in aqueous solutions were studied to compare them with that of chondritic SOM. We found that the redox state of synthesized organic molecules depends on temperature; the molecules become richer in hydrogen at higher temperatures. This can be explained by a cross-disproportionation reaction between organic molecules and formic acid, which occurs as a side reaction of the aldol condensation and works more effectively at higher temperatures. Comparison of the bulk chemical characteristics between the synthesized molecules and SOM extracted from the Murchison meteorite with methanol shows that the soluble organic molecules in Murchison are more reduced than the synthesized molecules. Considering the temperature condition for aqueous alteration on the CM parent body that is lower than or equivalent to the experimental temperatures, the reduced nature of Murchison organic molecules requires a reducing environment for them to be formed during hydrothermal alteration or imply that processes other than hydrothermal alteration were responsible for their synthesis. In case of hydrothermal synthesis, reducing conditions might be established by the interaction between water and iron-bearing silicates or metals on the parent body.

In situ organic compound analysis on a meteorite surface by desorption electrospray ionization coupled with an Orbitrap mass spectrometer.

Since extraterrestrial organic matter in meteorites is a very complex mixture that is hard to ionize due to its association with minerals, in situ analysis of polar organic compounds has never been performed. In addition, when studying powdered samples, spatial information of organic compounds is lost. In situ molecular analysis and chemical imaging of polar organic compounds were performed on a meteorite surface by desorption electrospray ionization coupled with high-resolution mass spectrometry (DESI-HRMS) using an Orbitrap mass spectrometer. Many CHN compounds, including alkylated pyridine and imidazole homologues, were identified from the complex peaks by HRMS using a spray of electrically charged methanol with a spatial resolution of approximately 50μm. The same alkylated homologues have the same spatial distribution in the meteorite matrix, while alkylpyridines occur in a different location from alkylimidazoles. The compound distribution suggests a different source for each compound series or a chromatographic separation effect associated with fluid movement in the meteorite parent body. The DESI-HRMS imaging will further our understanding of organic compound distribution with respect to mineral and water interactions in meteorites.

Effects of Pressure on Model Compounds of Meteorite Organic Matter

Extraterrestrial organic matter has been widely studied; however, its response to pressure has not. Primitive organic matter bearing meteorites, such as CI and CM carbonaceous chondrites, have experienced variable pressures, up to 10 GPa. To appreciate the effects of these pressures on the organic content of these bodies, the model compounds isophthalic acid, vanillin, and vanillic acid were subjected to pressures of up to 11.5 GPa and subsequently decompressed. High-resolution synchrotron source Fourier transform infrared spectroscopy was used to determine the effects of different benzene substituents at high pressure on both the vibrational assignments of the benzene core of the molecules and the ability of the aromatic compounds to form intermolecular hydrogen bonds. The presence of additional peaks at high pressure was found to coincide with molecules that contain carboxyl groups; these features are interpreted as C–H···O intermolecular hydrogen bonds. The formation of these hydrogen bonds has implications for the origination of macromolecular organic matter (MOM), owing to the importance of such attractive forces during episodes of cross-linking, such as esterification. Pressure-induced hydrogen-bond formation is a process by which aromatic MOM precursors could have cross-linked to generate the organic polymers found within extraterrestrial bodies today.

ChemInform Abstract: Enantioselective Gas Chromatography in Search of the Origin of Biomolecular Asymmetry in Outer Space

AbstractReview: [67 refs.

A porosity gradient in 67P/C-G nucleus suggested from CONSERT and SESAME-PP results: an interpretation based on new laboratory permittivity measurements of porous icy analogues

The Rosetta spacecraft made a rendezvous with comet 67P/Churyumov-Gerasimenko (67P) in August 2014, soon after the Philae module landed on the small lobe of the nucleus on 12 November 2014. The CONSERT instrument, onboard Rosetta and Philae, sounded the upper part of the interior of 67P with radiowaves at 90 MHz and determined an average of the real part of the permittivity (hereafter ϵ′) equal to about 1.27. The SESAME-PP instrument, onboard Philae, sounded the near-surface of the small lobe in the 400–800 Hz range and determined a lower limit of ϵ′ equal to 2.45. We use a semi-empirical formula obtained from measurements of ϵ′ performed in the laboratory at 243 K on water ice and ice-basaltic dust mixtures, with a controlled porosity in the 31–91% range and a dust-to-ice volumetric ratio in the 0.1–2.8 range, to interpret the results of the two instruments, taking into account the temperature and frequency dependencies. A graphical method is proposed to derive ranges of porosity and dust-mass fraction from a value of ϵ′ derived from observations. The non-dispersive behaviour of ϵ′ below 175 K, allows us to compare the values of ϵ′ obtained by CONSERT and SESAME-PP. We show that the porosity of the small lobe of 67P increases with depth. Based on new measurements of analogues of complex extraterrestrial organic matter, the so-called tholins, we also suggest that, for the dust component in the cometary material, the presence of silicates has more effect on ϵ′ than organic materials.

Enantioselective Gas Chromatography in Search of the Origin of Biomolecular Asymmetry in Outer Space

AbstractSince the pioneering work of Emanuel Gil‐Av and his associates at the Weizmann Institute of Science the direct gas chromatographic resolution of enantiomers has found its application in different fields of natural sciences, even expanding to space research and astrobiology. In these domains the resolution of chiral molecules of prebiotic relevance is of particular interest, since the determination of ratios between l‐ and d‐enantiomers within non‐terrestrial samples is assumed to shed light on the origin of biomolecular homochirality and the beginnings of life itself. According to an astrophysical scenario, the first molecular symmetry breaking event occurred upon irradiation of chiral organic molecules with circularly polarized light present in the interstellar medium. To examine this hypothesis, among others, chiral gas chromatographic stationary phases have been widely used to provide the differentiation of enantiomers in extracts of meteorites, samples of simulated interstellar ices and Mars soil analogues. Moreover several chiral capillary columns have been selected for in situ analyses of extraterrestrial organic matter by Mars missions and the cometary Rosetta mission. This review will highlight current advances of enantioselective gas chromatography applied to space science.

Sublimation of ice–tholins mixtures: A morphological and spectro-photometric study

Sublimation, the direct transition from solid to gas phase, is a process responsible for shaping and changing the reflectance properties of many Solar System surfaces. In this study, we have characterized the evolution of the structure/texture and of the visible and near-infrared (VIS–NIR) spectral reflectance of surfaces made of water ice mixed with analogues of complex extraterrestrial organic matter, named tholins, under low temperature (<−70°C) and pressure (10−5mbar) conditions. The experiments were carried out in the SCITEAS simulation setup recently built as part of the Laboratory for Outflow Studies of Sublimating Materials (LOSSy) at the University of Bern (Pommerol, A. et al. [2015a]. Planet. Space Sci. 109–110, 106–122). As the water ice sublimated, we observed in situ the formation of a sublimation lag deposit made of a water-free porous (>90% porosity) network of organic filaments on top of the ice. The temporal evolution of the tholins and water ice spectral features (reflectance at the absorption bands wavelengths, red slope, from 0.40 to 1.90μm) are analyzed throughout the sublimation of the samples. We studied how different mixtures of tholins with water (0.1wt.% tholins as coating or inclusions within the water particles), and different ice particle sizes (4.5±2.5 or 67±31μm) influence the morphological and spectral evolutions of the samples. The sublimation of the ice below the mantle produces a gas flow responsible for the ejection of mm to cm-sized fragments of the deposit in outbursts-like events. The results show remarkable differences between these samples in term of mantle structure, speed of mantle building, rates and surface area of mantle ejections. These data provide useful references for interpreting remote-sensing observations of icy Solar System surfaces, in particular the activity of comet nuclei where sublimation of organic-rich ices and deposition of organic-dust particles likely play a major role. Consequently, the data presented here could be of high interest for the interpretation of Rosetta, and also New Horizons, observations.

Nontarget analysis of Murchison soluble organic matter by high-field NMR spectroscopy and FTICR mass spectrometry.

High-field NMR spectra of Murchison meteorite methanolic extracts revealed primarily aliphatic extraterrestrial organic matter (EOM) with near statistical branching of commonly C(3-5) units separated by heteroatoms and aromatic units. The ratios of CCH, OCH and C(sp2)H units were 89 : 8 : 3, whereas carbon-based aliphatic chain termination was in the order methyl > -COOH > -CH(CH3)COOH. Aliphatic methine carbon was abundant, but its weak NMR signatures were primarily deduced from JRES (J-resolved) NMR spectra. Carbon NMR spectra were dominated by methylene and methyl carbon; strong apodization revealed methine carbon, of which about 20% was aromatic. Extrapolation provided 5-7% aromatic carbon present in Murchison soluble EOM. Compositional heterogeneity in Murchison methanolic extracts was visible in NMR and Fourier transform ion cyclotron (FTICR) mass spectra obtained from a few cubic millimeters of solid Murchison meteorite; increasing sample size enhanced uniformity of NMR spectra. Intrinsic chemical diversity and pH-dependent chemical shift variance contributed to the disparity of NMR spectra. FTICR mass spectra provided distinct clustering of CHO/CHOS and CHNO/CHNOS molecular series and confirmed the prevalence of aliphatic/alicyclic (73%) over single aromatic (21%) and polyaromatic (6%) molecular compositions, suggesting extensive aliphatic substitution of aromatic units as proposed by NMR. Murchison soluble EOM molecules feature a center with enhanced aromatic and heteroatom content, which provides rather diffuse and weak NMR signatures resulting from a huge overall chemical diversity. The periphery of Murchison EOM molecules comprises flexible branched aliphatic chains and aliphatic carboxylic acids. These project on narrow ranges of chemical shift, facilitating observation in one-dimensional and two-dimensional NMR spectra. The conformational entropy provided by these flexible surface moieties facilitates the solubility of EOM.

Clues to the early solar system: Extraterrestrial organic molecules in meteorites

Meteorites are extraterrestrial objects that survive the impact on the Earth's surface. A particular class of meteorites, carbonaceous chondrites, are very old, having remained nearly unaltered since the formation of the solar system approximately 4.6 billion years ago. They contain a rich organic inventory of abiotic molecules with important roles in present day biochemistry. The present article describes the organic compounds present in meteorites, their sources and how to distinguish extraterrestrial organic matter from their terrestrial counterparts.

Effects of high pressure and temperature on carbon isotope compositions of some acyclic alkanes and preservation of organic matter

The effects of high pressure and temperature on carbon isotopic compositions of acyclic alkanes and the stability of the acyclic alkanes were experimentally investigated. The pyrolysis of lignite with water in a closed system was conducted at 400–700°C and 1–3 GPa. The carbon isotope data, variations of peak carbon and evident odd–even predominance of acyclic alkanes indicated that: (1) the high pressure retarded the maturation of organic matter and destruction of hydrocarbons, (2) n-C12+ hydrocarbons from biogenic sources could be preserved in the cool slab subducted into the upper mantle, and (3) some organic compounds might preserve the carbon isotope signals inherited from biogenic sources. The results favor tracing the origins of organic matter in mantle rocks and extraterrestrial organic matter in meteorites and the process of deep carbon cycle.

Raman Spectroscopy on Cometary and Meteoritic Organic Matter

ABSTRACT Extraterrestrial organic matter (OM) is an important component of meteorites that originate from asteroids and from cometary dust collected from comet Wild 2 and the Earth's atmosphere. Some of this OM was incorporated into the first planetary bodies during the formation of the solar system, 4.56 Ga ago, and did not experience significant alteration. Here, we summarize our efforts in the comparative C Raman spectroscopy of this OM. We aim for the identification of the most primitive OM that might be of solar nebula origin and a better understanding of the modifying processes on parent bodies, during transport in space and sample collection. We (i) determine the degree of order of meteoritic OM and hence the metamorphism experienced on their parent bodies; (ii) assess potential effects during sample collection of comet Wild 2 dust, and (iii) compare possibly cometary interplanetary dust particles (IDPs) with primitive meteorites.