Light Element (C, N, O) Quantification by EDXS: Application to Meteorite Water Content and Organic Composition.

Quantifying light elements such as carbon, nitrogen, and oxygen in a transmission electron microscope (TEM) is a challenging however essential task in biology, materials, or earth and planetary sciences. We have developed an approach that allows precise quantification by energy-dispersive X-ray spectroscopy (EDXS), using sensitive windowless silicon drift detectors and homemade Python routines for hyperspectral data processing. K-factors were determined using wedge-shaped focused ion beam sections. To correct for X-ray absorption within the sample, the sample mass thickness is determined by the-revisited-two-lines method (Morris, 1980). No beam current measurement is required. Applying this method to the K and L lines of iron, we found that the tabulated mass absorption coefficient at the energy of the iron L lines was too low. This is due to X-ray self-absorption at the iron edge. Using reference material, we experimentally determined an absorption coefficient that gave the expected results. We then analyzed the complex phyllosilicate mixture of the Orgueil meteorite. We show that the N/C ratio of organics can be obtained with an accuracy better than 5 at.% and that oxygen can be quantified accurately enough to infer the hydroxyl content of phyllosilicates.

Compositions of iron-meteorite parent bodies constrain the structure of the protoplanetary disk.

Magmatic iron-meteorite parent bodies are the earliest planetesimals in the Solar System, and they preserve information about conditions and planet-forming processes in the solar nebula. In this study, we include comprehensive elemental compositions and fractional-crystallization modeling for iron meteorites from the cores of five differentiated asteroids from the inner Solar System. Together with previous results of metallic cores from the outer Solar System, we conclude that asteroidal cores from the outer Solar System have smaller sizes, elevated siderophile-element abundances, and simpler crystallization processes than those from the inner Solar System. These differences are related to the formation locations of the parent asteroids because the solar protoplanetary disk varied in redox conditions, elemental distributions, and dynamics at different heliocentric distances. Using highly siderophile-element data from iron meteorites, we reconstruct the distribution of calcium-aluminum-rich inclusions (CAIs) across the protoplanetary disk within the first million years of Solar-System history. CAIs, the first solids to condense in the Solar System, formed close to the Sun. They were, however, concentrated within the outer disk and depleted within the inner disk. Future models of the structure and evolution of the protoplanetary disk should account for this distribution pattern of CAIs.

Laser Engineering Nanocarbon Phases within Diamond for Science and Electronics.

Diamond, as the densest allotrope of carbon, displays a range of exemplary material properties that are attractive from a device perspective. Despite diamond displaying high carbon-carbon bond strength, ultrashort (femtosecond) pulse laser radiation can provide sufficient energy for highly localized internal breakdown of the diamond lattice. The less-dense carbon structures generated on lattice breakdown are subject to significant pressure from the surrounding diamond matrix, leading to highly unusual formation conditions. By tailoring the laser dose delivered to the diamond, it is shown that it is possible to create continuously modified internal tracks with varying electrical conduction properties. In addition to the widely reported conducting tracks, conditions leading to semiconducting and insulating written tracks have been identified. High-resolution transmission electron microscopy (HRTEM) is used to visualize the structural transformations taking place and provide insight into the different conduction regimes. The HRTEM reveals a highly diverse range of nanocarbon structures are generated by the laser irradiation, including many signatures for different so-called diaphite complexes, which have been seen in meteorite samples and seem to mediate the laser-induced breakdown of the diamond. This work offers insight into possible formation methods for the diamond and related nanocarbon phases found in meteorites.

Prebiotic Vitamin B3 Synthesis in Carbonaceous Planetesimals.

Aqueous chemistry within carbonaceous planetesimals is promising for synthesizing prebiotic organic matter essential to all life. Meteorites derived from these planetesimals delivered these life building blocks to the early Earth, potentially facilitating the origins of life. Here, we studied the formation of vitamin B3 as it is an important precursor of the coenzyme NAD(P)(H), which is essential for the metabolism of all life as we know it. We propose a new reaction mechanism based on known experiments in the literature that explains the synthesis of vitamin B3. It combines the sugar precursors glyceraldehyde or dihydroxyacetone with the amino acids aspartic acid or asparagine in aqueous solution without oxygen or other oxidizing agents. We performed thermochemical equilibrium calculations to test the thermodynamic favorability. The predicted vitamin B3 abundances resulting from this new pathway were compared with measured values in asteroids and meteorites. We conclude that competition for reactants and decomposition by hydrolysis are necessary to explain the prebiotic content of meteorites. In sum, our model fits well into the complex network of chemical pathways active in this environment.

Accelerating Nature: Induced Atomic Order in Equiatomic FeNi.

The production of locally atomically ordered FeNi (known by its meteoric mineral name, tetrataenite) is confirmed in bulk samples by simultaneous conversion X-ray and backscattered γ-ray 57 Fe Mössbauer spectroscopy. Up to 22 volume percent of the tetragonal tetrataenite phase is quantified in samples thermally treated under simultaneous magnetic- and stress-field conditions for a period of 6 weeks, with the remainder identified as the cubic FeNi alloy. In contrast, all precursor samples consist only of the cubic FeNi alloy. Data from the processed alloys are validated using Mössbauer parameters derived from natural meteoritic tetrataenite. The meteoritic tetrataenite exhibits a substantially higher degree of atomic order than do the processed samples, consistent with their low uniaxial magnetocrystalline anisotropy energy of ≈1 kJ·m-3 . These results suggest that targeted refinements to the processing conditions of FeNi will foster greater atomic order and increased magnetocrystalline anisotropy, leading to an enhanced magnetic energy product. These outcomes also suggest that deductions concerning paleomagnetic conditions of the solar system, as derived from meteoritic data, may warrant re-examination and re-evaluation. Additionally, this work strengthens the argument that tetrataenite may indeed become a member of the advanced permanent magnet portfolio, helping to meet rapidly escalating green energy imperatives.

Rubidium isotopic compositions of angrites controlled by extensive evaporation and partial recondensation.

The planetesimals in the solar system exhibit varying degrees of moderately volatile elements (MVEs) depletion compared to the protosolar composition. Revealing the relevant mechanisms is crucial for exploring early solar system evolution. Most volatile-depleted materials in the solar system exhibit enrichments in the heavier isotopes of MVEs, which have traditionally been attributed to the loss of volatiles through partial evaporation. Angrites are so far an exception as they are enriched in the lighter isotopes of K. This has been interpreted as reflecting condensation processes. Here, we present Rb isotopic data of angrites and find that they have lighter Rb isotopic compositions than Vesta, Mars, and the Moon. The δ87Rb value of the angrite parent body (APB) is estimated to range between -1.19‰ and -0.67‰. The extremely light Rb isotopic composition of the APB is likely a result of the kinetic recondensation of Rb after near-complete evaporation during the magma ocean stage. This finding provides further support for the partial recondensation model to explain the light Rb and K isotopic compositions of the APB. In addition, the APB, alongside other terrestrial planetary bodies (e.g., Earth, Mars, Moon, and Vesta), exhibit a strong correlation between their Rb and K isotopic compositions. This coupling of Rb and K isotopes is indicative of a volatility-driven isotopic fractionation rather than nucleosynthetic anomalies. The extremely light Rb-K isotopic signatures of the APB suggest that beyond evaporation, condensation plays an equally significant role in shaping the planetary-scale distributions of volatile elements.

Shock-Induced Degradation of Guanosine and Uridine Promoted by Nickel and Carbonate: Potential Applications.

Experimental studies of the degradation of two ribonucleosides (guanosine and uridine) were carried out by making use of mechanochemistry. Mechanochemical experiments reveal the decomposition of guanosine and uridine, promoted by nickel(II) and carbonate ions, into guanine and uracil, respectively. These nucleobases were identified by HPLC and 1H NMR spectroscopy (this applied only to uracil). Additionally, density-functional theory (DFT) methodologies were used to probe the energetic viability of several degradation pathways, including in the presence of the abovementioned ions. Three mechanisms were analysed via ribose ring-opening: dry, single-molecule water-assisted, and metal-assisted, wherein the last two mechanisms confirmed the mechanochemical degradation of both ribonucleosides into respective nucleobase moieties. These results can contribute to an astrobiological interpretation of the extraterrestrial sample's contents.

A robust, agnostic molecular biosignature based on machine learning.

The search for definitive biosignatures-unambiguous markers of past or present life-is a central goal of paleobiology and astrobiology. We used pyrolysis-gas chromatography coupled to mass spectrometry to analyze chemically disparate samples, including living cells, geologically processed fossil organic material, carbon-rich meteorites, and laboratory-synthesized organic compounds and mixtures. Data from each sample were employed as training and test subsets for machine-learning methods, which resulted in a model that can identify the biogenicity of both contemporary and ancient geologically processed samples with ~90% accuracy. These machine-learning methods do not rely on precise compound identification: Rather, the relational aspects of chromatographic and mass peaks provide the needed information, which underscores this method's utility for detecting alien biology.

A Comparison of Presolar Isotopic Signatures in Laboratory-Studied Primitive Solar System Materials and Comet 67P/Churyumov-Gerasimenko: New Insights from Light Elements, Halogens, and Noble Gases.

Comets are considered the most primitive planetary bodies in our Solar System. ESA's Rosetta mission to Jupiter family comet 67P/Churyumov-Gerasimenko (67P/CG) has provided a wealth of isotope data which expanded the existing data sets on isotopic compositions of comets considerably. In a previous paper (Hoppe et al. in Space Sci. Rev. 214:106, 2018) we reviewed the results for comet 67P/CG from the first four years of data reduction after arrival of Rosetta at the comet in August 2014 and discussed them in the context of respective meteorite data. Since then important new isotope data of several elements, among them the biogenic elements H, C, N, and O, for comet 67P/CG, the Tagish Lake meteorite, and C-type asteroid Ryugu became available which provide new insights into the formation conditions of small planetary bodies in the Solar System's earliest history. To complement the picture on comet 67P/CG and its context to other primitive Solar System materials, especially meteorites, that emerged from our previous paper, we review here the isotopic compositions of H, C, and N in various volatile molecules, of O in water and a suite of other molecules, of the halogens Cl and Br, and of the noble gas Kr in comet 67P/CG. Furthermore, we also review the H isotope data obtained in the refractory organics of the dust grains collected in the coma of 67P/CG. These data are compared with the respective meteoritic and Ryugu data and spectroscopic observations of other comets and extra-solar environments; Cl, Br, and Kr data are also evaluated in the context of a potential late supernova contribution, as suggested by the Si- and S-isotopic data of 67P/CG.

Underground radioactivity measurements of meteorites: Development of methods suitable to determine precise terrestrial age of recent falls.

The L6 chondritic meteorite, HaH-346, fell in Libya. However, neither the exact date of the fall nor the exact size of the original meteoroid or asteroid is known. A specimen of the meteorite, weighing 488 g, was measured using ultra low-background gamma-ray spectrometry in the 225 m deep underground facility HADES. Activation products 22Na, 26Al, 60Co, 57Co, 54Mn and 44Ti were detected. The detection efficiency was determined by 3D scanning the meteorite and introducing this in the computer model of the detector and sample implemented in the MCNP6.2 Monte Carlo code. The activities of 22Na and 26Al support the hypothesis that the fall took place on 26 August 2018. Furthermore, the 60Co and 26Al activities indicate that the original radius of meteoroid was between 50 and 80 cm, which suggests the mass prior to atmospheric entry was between 2400 and 7300 kg.

Cosmogenic radionuclides in the Cavezzo meteorite: Gamma-ray measurement and detection efficiency simulations.

The Cavezzo meteorite was recovered on January 4th, 2020, just three days after the fall observed over Northern Italy by the all-sky cameras of the Italian PRISMA fireball network. Two specimens, weighing 3.1 g (F1) and 52.2 g (F2), were collected in the predicted strewn-field and the meteorite has been classified as an L5 anomalous chondrite. The gamma-activity of the F2 sample was measured at the Monte dei Cappuccini underground Research Station (Torino, Italy) with a large-volume HPGe-NaI(Tl) spectrometer. Thanks to the high efficiency, selectivity, and low background of the spectrometer, we were able to detect fifteen cosmogenic radioisotopes. The presence of nuclides with half-lives down to a few days (47Ca, 52Mn, and 48V) undoubtedly confirmed the recent fall of the sample. The very low activity of 44Ti and 60Co was revealed with a particular coincidence between the HPGe and NaI(Tl) detectors. To obtain the detection efficiency, we have simulated the response of the detector with the GEANT4 toolkit, once the spectrometer's dead layer thickness was estimated using standards of known activity. Moreover, the simulation of the Dhajala meteorite (H3/4 chondrite) measurement allowed us to verify that the self-absorption of the sample is correctly taken into account and validate our simulations. In this contribution, we focus on the coincidence optimization techniques and the detection efficiency computation.

Protective Effects of Halite to Vacuum and Vacuum-Ultraviolet Radiation: A Potential Scenario During a Young Sun Superflare.

Halite (NaCl mineral) has exhibited the potential to preserve microorganisms for millions of years on Earth. This mineral was also identified on Mars and in meteorites. In this study, we investigated the potential of halite crystals to protect microbial life-forms on the surface of an airless body (e.g., meteorite), for instance, during a lithopanspermia process (interplanetary travel step) in the early Solar System. To investigate the effect of the radiation of the young Sun on microorganisms, we performed extensive simulation experiments by employing a synchrotron facility. We focused on two exposure conditions: vacuum (low Earth orbit, 10-4 Pa) and vacuum-ultraviolet (VUV) radiation (range 57.6-124 nm, flux 7.14 W/m2), with the latter representing an extreme scenario with high VUV fluxes comparable to the amount of radiation of a stellar superflare from the young Sun. The stellar VUV parameters were estimated by using the very well-studied solar analog of the young Sun, κ1 Cet. To evaluate the protective effects of halite, we entrapped a halophilic archaeon (Haloferax volcanii) and a non-halophilic bacterium (Deinococcus radiodurans) in laboratory-grown halite. Control groups were cells entrapped in salt crystals (mixtures of different salts and NaCl) and non-trapped (naked) cells, respectively. All groups were exposed either to vacuum alone or to vacuum plus VUV. Our results demonstrate that halite can serve as protection against vacuum and VUV radiation, regardless of the type of microorganism. In addition, we found that the protection is higher than provided by crystals obtained from mixtures of salts. This extends the protective effects of halite documented in previous studies and reinforces the possibility to consider the crystals of this mineral as potential preservation structures in airless bodies or as vehicles for the interplanetary transfer of microorganisms.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Results of an Eight-Year Extraction of Phosphorus Minerals within the Seymchan Meteorite.

In-fall of extraterrestrial material including meteorites and interstellar dust particles during the late heavy bombardment are known to have brought substantial amounts of reduced oxidation-state phosphorus to the early Earth in the form of siderophilic minerals, e.g., schreibersite ((FeNi)3P). In this report, we present results on the reaction of meteoritic phosphide minerals in the Seymchan meteorite in ultrapure water for 8 years. The ions produced during schreibersite corrosion (phosphite, hypophosphate, pyrophosphate, and phosphate) are stable and persistent in aqueous solution over this timescale. These results were also compared with the short-term corrosion reactions of the meteoritic mineral schreibersite's synthetic analog Fe3P in aqueous and non-aqueous solutions (ultrapure water and formamide). This finding suggests that the reduced-oxidation-state phosphorus (P) compounds including phosphite could be ubiquitous and stable on the early Earth over a long span of time and such compounds could be readily available on the early Earth.

The Specific Heat of Astro-materials: Review of Theoretical Concepts, Materials, and Techniques.

We provide detailed background, theoretical and practical, on the specific heat of minerals and mixtures thereof, 'astro-materials,' as well as background information on common minerals and other relevant solid substances found on the surfaces of solar system bodies. Furthermore, we demonstrate how to use specific heat and composition data for lunar samples and meteorites as well as a new database of endmember mineral heat capacities (the result of an extensive literature review) to construct reference models for the isobaric specific heat c P as a function of temperature for common solar system materials. Using a (generally linear) mixing model for the specific heat of minerals allows extrapolation of the available data to very low and very high temperatures, such that models cover the temperature range between 10 K and 1000 K at least (and pressures from zero up to several kbars). We describe a procedure to estimate c P (T) for virtually any solid solar system material with a known mineral composition, e.g., model specific heat as a function of temperature for a number of typical meteorite classes with known mineralogical compositions. We present, as examples, the c P (T) curves of a number of well-described laboratory regolith analogs, as well as for planetary ices and 'tholins' in the outer solar system. Part II will review and present the heat capacity database for minerals and compounds and part III is going to cover applications, standard reference compositions, c P (T) curves, and a comparison with new and literature experimental data. Supplementary Information: The online version contains supplementary material available at 10.1007/s10765-022-03046-5.

Deciphering Redox State for a Metal-Rich World.

The Psyche mission's Oxidation-Reduction Working Group is focused on understanding, determining, and applying the redox state of (16) Psyche to understand the origin of a metal-rich world. The oxidation-reduction state of an asteroid, along with its temperature, parent body size, and composition, is a key parameter in determining the history of an asteroid. Determining the redox state from spacecraft data is most easily done by examining potential metal-oxide buffer pairs. The occurrence of Ni, Fe, C, Cr, P and Si, in that order, in the metal or sulfide phase of an asteroidal body indicates increasingly reduced conditions. Key observations by the Imager and Gamma-Ray and Neutron Spectrometer (GRNS) of Psyche can bracket the redox state using metal-oxide buffers. The presence of Fe,Ni metal can be confirmed by the ratios of Fe/O or Fe/Si and the concentration of Ni variability in metal across the asteroid can be determined by GRNS. The FeO concentration of silicates is complementary to the Ni concentration of metal and can be constrained using filters on the Imager. The presence of FeO in silicates from ground-based observations is one of the few measurements we already have of redox state, although available data permit a wide range of silicate compositions and mineralogies. The presence of C, P or Si concentrated in the metallic, Fe-rich portion of the asteroid, as measured by GRNS, or Ca-sulfide, determined by imaging, would indicate increasingly reducing conditions. Linkage to known types of meteorites, whether metal-rich chondrites, stony-irons or irons, expands the mineralogical, chemical and isotopic data not available from remote observations alone. Redox also controls both silicate and metal mineralogy, influencing differentiation, solidification, and subsolidus cooling, including the relative abundance of sulfur in the core and possible magnetic signatures. The redox state of Psyche, if a fully-differentiated metallic core, might constrain the location and timing of both the formation of Psyche and any oxidation it might have experienced.

Possible Ribose Synthesis in Carbonaceous Planetesimals.

The origin of life might be sparked by the polymerization of the first RNA molecules in Darwinian ponds during wet-dry cycles. The key life-building block ribose was found in carbonaceous chondrites. Its exogenous delivery onto the Hadean Earth could be a crucial step toward the emergence of the RNA world. Here, we investigate the formation of ribose through a simplified version of the formose reaction inside carbonaceous chondrite parent bodies. Following up on our previous studies regarding nucleobases with the same coupled physico-chemical model, we calculate the abundance of ribose within planetesimals of different sizes and heating histories. We perform laboratory experiments using catalysts present in carbonaceous chondrites to infer the yield of ribose among all pentoses (5Cs) forming during the formose reaction. These laboratory yields are used to tune our theoretical model that can only predict the total abundance of 5Cs. We found that the calculated abundances of ribose were similar to the ones measured in carbonaceous chondrites. We discuss the possibilities of chemical decomposition and preservation of ribose and derived constraints on time and location in planetesimals. In conclusion, the aqueous formose reaction might produce most of the ribose in carbonaceous chondrites. Together with our previous studies on nucleobases, we found that life-building blocks of the RNA world could be synthesized inside parent bodies and later delivered onto the early Earth.

Focused ultrasound extraction versus microwave-assisted extraction for extraterrestrial objects analysis.

Search for organic bioindicators in the solar system is a fundamental challenge for the space research community. If tremendous improvements have been achieved in detection, little or no research has been dedicated to extraction of the targets from the studied mineral matrices. Apart from thermodesorption, no extraction step was ever performed in situ within the context of biomarker detection experiments. This work presents an extraction protocol compatible with in situ space constraints. Two extraction methods, i.e., microwave-assisted extraction (MAE) and focused ultrasonic extraction (FUSE), were optimized with the aim of extracting molecules having an astrobiological interest (amino acids, nucleobases, polyaromatic carboxylic acids) and that are included in mineral matrices representative of the Martian soil. Higher efficiency was obtained with the FUSE method (20 kHz, amplitude 80%, pulse and relaxation 1 s each, for 10 min) with yields ranging from 30 to 95%. It was then applied on an Atacama Desert soil sample and Aguas Zarcas meteorite fragment. Both water-soluble and organic-soluble compounds present at trace levels were extracted using this short extraction time, and small amounts of sample and solvent compliant with in situ requirements (50 mg, 500 µL). This unique FUSE/derivatization-GC-MS approach gave similar yields to usual 24 h hot water extraction and increased the recovery of the target molecules compared to the derivatization-GC-MS method already used for in situ space experiments by a factor from 2 to 8. The data highlighted the suitability of a focused ultrasonic method for the extraction of trace organic compounds from extraterrestrial samples.

Reviewing in situ analytical techniques used to research Martian geochemistry: From the Viking Project to the MMX future mission.

The study of space has always been a field of great interest and thus space missions are becoming more and more ambitious with time. Therefore, with the 50th anniversary of the first spacecraft to land on Mars, a review about how traditional analytical techniques have been adapted to the era of in situ space exploration is presented. From the Viking Project to the future MMX mission, the techniques used for the in situ study of the geochemistry of the Martian surface is described. These techniques have been differentiated according to the type of analysis: elemental and molecular. On the one hand, among the elemental analytical techniques the XRF, APXS, ISE and LIBS stand out. On the other hand, GCMS, TEGA, MBS, XRD, Raman and IR spectroscopy have been the molecular techniques used in the missions to Mars. Miniaturization, real-time measurements, automation, low power consumption and reliability of operation under extreme conditions are some of the major challenges that analytical chemistry has faced as a result of the technological and scientific requirements of space missions. In this way, this review gathers all the in situ analytical techniques that have reached the surface of Mars onboard landers or rovers with the aim of studying its geochemistry.