The amino acid and polycyclic aromatic hydrocarbon compositions of the promptly recovered CM2 Winchcombe carbonaceous chondrite

The rapid recovery of the Winchcombe meteorite offers a valuable opportunity to study the soluble organic matter (SOM) profile in pristine carbonaceous astromaterials. Our interests in the biologically relevant molecules, amino acids—monomers of protein, and the most prevalent meteoritic organics—polycyclic aromatic hydrocarbons (PAHs) are addressed by analyzing the solvent extracts of a Winchcombe meteorite stone using gas chromatography mass spectrometry. The Winchcombe sample contains an amino acid abundance of ~1132 parts-per-billion that is about 10 times lower than other CM2 meteorites. The detection of terrestrially rare amino acids, including α-aminoisobutyric acid (AIB); isovaline; β-alanine; α-, β-, and γ-amino-n-butyric acids; and 5-aminopentanoic acid, and the racemic enantiomeric ratios (D/L = 1) observed for alanine and isovaline indicate that these amino acids are indigenous to the meteorite and not terrestrial contaminants. The presence of predominantly α-AIB and isovaline is consistent with their formation via the Strecker-cyanohydrin synthetic pathway. The L-enantiomeric excesses in isovaline previously observed for aqueously altered meteorites were viewed as an indicator of parent body aqueous processing; thus, the racemic ratio of isovaline observed for Winchcombe, alongside the overall high free:total amino acid ratio, and the low amino acid concentration suggest that the analyzed stone is derived from a lithology that has experienced brief episode(s) of aqueous alteration. Winchcombe also contains 2- to 6-ring alkylated and nonalkylated PAHs. The low total PAHs abundance (6177 ppb) and high nonalkylated:alkylated ratio are distinct from that observed for heavily aqueously altered CMs. The weak petrographic properties of Winchcombe, as well as the discrepancies observed for the Winchcombe SOM content—a low total amino acid abundance comparable to heavily altered CMs, and yet the high free:total amino acid and nonalkylated:alkylated PAH ratios are on par with the less altered CMs—suggest that Winchcombe could represent a class of weak, poorly lithified meteorite not been previously studied

A novel organic-rich meteoritic clast from the outer solar system

The Zag meteorite which is a thermally-metamorphosed H ordinary chondrite contains a primitive xenolitic clast that was accreted to the parent asteroid after metamorphism. The cm-sized clast contains abundant large organic grains or aggregates up to 20μm in phyllosilicate-rich matrix. Here we report organic and isotope analyses of a large (~10μm) OM aggregate in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM aggregate has sp2 dominated hydrocarbon networks with a lower abundance of heteroatoms than in IOM from primitive (CI,CM,CR) carbonaceous chondrites, and thus it is distinguished from most of the OM in carbonaceous meteorites. The OM aggregate has high D/H and 15N/14N ratios (δD=2,370±74‰ and δ15N=696±100‰), suggesting that it originated in a very cold environment such as the interstellar medium or outer region of the solar nebula, while the OM is embedded in carbonate-bearing matrix resulting from aqueous activities. Thus, the high D/H ratio must have been preserved during the extensive late-stage aqueous processing. It indicates that both the OM precursors and the water had high D/H ratios. Combined with 16O-poor nature of the clast, the OM aggregate and the clast are unique among known chondrite groups. We further propose that the clast possibly originated from D/P type asteroids or trans-Neptunian Objects

The Winchcombe meteorite, a unique and pristine witness from the outer solar system.

Direct links between carbonaceous chondrites and their parent bodies in the solar system are rare. The Winchcombe meteorite is the most accurately recorded carbonaceous chondrite fall. Its pre-atmospheric orbit and cosmic-ray exposure age confirm that it arrived on Earth shortly after ejection from a primitive asteroid. Recovered only hours after falling, the composition of the Winchcombe meteorite is largely unmodified by the terrestrial environment. It contains abundant hydrated silicates formed during fluid-rock reactions, and carbon- and nitrogen-bearing organic matter including soluble protein amino acids. The near-pristine hydrogen isotopic composition of the Winchcombe meteorite is comparable to the terrestrial hydrosphere, providing further evidence that volatile-rich carbonaceous asteroids played an important role in the origin of Earth's water

The mineralogy and alteration history of the Yamato-type (CY) carbonaceous chondrites

The CY chondrites are a group of thermally metamorphosed carbonaceous chondrites. Although they share similarities with the CM and CI chondrites, their primary properties argue for a distinct classification. Previous studies have highlighted their isotopically heavy bulk compositions (δ17O = 10 ‰, δ18O = 21 ‰, Δ17O = 0 ‰) and exceptionally high sulphide abundances (10–30 vol%). In this work we explore their petrography and alteration history. The CYs accreted low abundances of chondrules (15–20 area%) with average apparent diameters slightly larger (∼320–340 µm) than the CM chondrites. In contrast to the CMs, the CYs record an early episode of brecciation prior to the main window of aqueous alteration. Subsequent fluid activity produced a range of alteration extents with both CY2 and CY1 chondrites documented. Phyllosilicate minerals in the CYs were a mix of serpentine and saponite (including occurrences of Na-saponite) with minor quantities of chlorite (within chondrules). An initial generation of Fe-sulphides formed by sulfidation of metal, and by precipitation from S-rich fluids. Three generations of carbonates are recognized, an early generation that infilled voids left by brecciation and co-precipitated with sulphide, a later generation that co-precipitated with magnetite and a final Fe-Mg-bearing generation which formed large (>100 µm) clasts. Only the first-generation carbonates are found in the CY2s, while the CY1s preserve all three generations. Phosphates occur as Ca-apatite or rarely as Mg-bearing apatite and have hydroxylapatite compositions, indicating low halogen activities in the alteration fluids. Refractory oxides (ilmenite and Cr-spinel) occur as precipitates adhering to the margins of phyllosilicates. They formed late in the alteration sequence and attest to oxidizing conditions. During the late-stages of aqueous alteration Fe-sulphides were replaced by magnetite. Thermal metamorphism (Stage II-IV: ∼300–750 °C) overprinted aqueous alteration leading to dehydration and recrystallization of the phyllosilicate matrix and the decomposition of some carbonate phases. Most Fe-sulphide grains survived heating without decomposition as initial partial decomposition from pyrrhotite to troilite under closed system conditions led to elevated ƒS2 gas and resulted in a stabilizing effect. Retrograde reactions between trapped S2 gas and metal/magnetite formed a final generation of Fe-sulphides. The survival of Fe-sulphides and their stochiometric troilite compositions are evidence for near-closed system heating. Analysis of organic matter by Raman spectroscopy supports an interpretation of short-duration heating (on the scale of minutes to days), at peak temperatures between 750 and 900 °C. Thus, an impact event was the most likely cause of metamorphic heating.Copyright © 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). The linked file is the published version of the article.NHM Repositor

Characterization of carbonaceous matter in xenolithic clasts from the Sharps (H3.4) meteorite: Constraints on the origin and thermal processing

Primitive xenolithic clasts, often referred to as “dark clasts”, are well known in many regolith breccias. The Sharps H3.4 ordinary chondrite contains unusually large dark clasts up to ∼1 cm across. Poorly-graphitized carbon (PGC), with Fe, Ni metal and described as “carbon-rich aggregates”, has been reported in these clasts (Brearley, 1990). We report detailed analyses of carbonaceous matter in several identical Sharps clasts using FTIR, Raman, C-XANES, and TEM that provide insight on the extent of thermal processing and possible origin of such clasts. We also prepared acid residues of the clasts using the HCl/HF method and conducted mass spectrometric analysis of the entrained noble gases. Carbonaceous matter is often used to infer thermal history due to its sensitivity to thermal processes. The FTIR spectra of the acid residue from the Sharps clast suggest that carbonaceous matter in the clast contains less hydrogen and oxygen compared to acid residues from typical type 3.4 ordinary chondrites. The metamorphic temperatures obtained by Raman spectroscopy ranges between ∼380 °C and ∼490 °C. TEM observations indicate that the clasts experienced a peak temperature of 300 °C to 400 °C, based on the carbon d002 layer lattice spacing of C-rich aggregates. These estimates are consistent with an earlier estimate of 330 ± 50 °C, that is also estimated by the d002 layer lattice spacing (Brearley, 1990). It should be noted that the lattice spacing thermometer is based on terrestrial metamorphose rocks, and thus temperature was probably underestimated. Meanwhile, the C-XANES spectra of the C-rich aggregates show high exciton intensities, indicative of graphene structures that developed at around 700–800 °C following an extensive period of time (millions of years), however, the surrounding matrix areas experienced lower temperatures of less than 300–500 °C. Noble gas analysis of the acid residue from the Sharps clasts shows that the residue is almost identical with some material reported in carbonaceous chondrites, i.e., heavily enriched in the Q-gas component as well as HL-gas from presolar diamonds and Ne-E(H) from presolar SiC. These results indicate that the C-rich aggregates in the Sharps clasts formed under relatively high temperature conditions, up to 800 °C, and were subsequently mixed with lower temperature matrix, probably in a different parent body, before they were incorporated into the final Sharps lithology by collision

Characterization of carbonaceous matter in xenolithic clasts from the Sharps (H3.4) meteorite: Constraints on the origin and thermal processing

Primitive xenolithic clasts, often referred to as “dark clasts”, are well known in many regolith breccias. The Sharps H3.4 ordinary chondrite contains unusually large dark clasts up to ∼1 cm across. Poorly-graphitized carbon (PGC), with Fe, Ni metal and described as “carbon-rich aggregates”, has been reported in these clasts (Brearley, 1990). We report detailed analyses of carbonaceous matter in several identical Sharps clasts using FTIR, Raman, C-XANES, and TEM that provide insight on the extent of thermal processing and possible origin of such clasts. We also prepared acid residues of the clasts using the HCl/HF method and conducted mass spectrometric analysis of the entrained noble gases. Carbonaceous matter is often used to infer thermal history due to its sensitivity to thermal processes. The FTIR spectra of the acid residue from the Sharps clast suggest that carbonaceous matter in the clast contains less hydrogen and oxygen compared to acid residues from typical type 3.4 ordinary chondrites. The metamorphic temperatures obtained by Raman spectroscopy ranges between ∼380 °C and ∼490 °C. TEM observations indicate that the clasts experienced a peak temperature of 300 °C to 400 °C, based on the carbon d layer lattice spacing of C-rich aggregates. These estimates are consistent with an earlier estimate of 330 ± 50 °C, that is also estimated by the d layer lattice spacing (Brearley, 1990). It should be noted that the lattice spacing thermometer is based on terrestrial metamorphose rocks, and thus temperature was probably underestimated. Meanwhile, the C-XANES spectra of the C-rich aggregates show high exciton intensities, indicative of graphene structures that developed at around 700–800 °C following an extensive period of time (millions of years), however, the surrounding matrix areas experienced lower temperatures of less than 300–500 °C. Noble gas analysis of the acid residue from the Sharps clasts shows that the residue is almost identical with some material reported in carbonaceous chondrites, i.e., heavily enriched in the Q-gas component as well as HL-gas from presolar diamonds and Ne-E(H) from presolar SiC. These results indicate that the C-rich aggregates in the Sharps clasts formed under relatively high temperature conditions, up to 800 °C, and were subsequently mixed with lower temperature matrix, probably in a different parent body, before they were incorporated into the final Sharps lithology by collision. 002 00

Heating experiments of the Tagish Lake meteorite: Investigation of the effects of short-term heating on chondritic organics

We present in this study the effects of short-term heating on organics in the Tagish Lake meteorite and how the difference in the heating conditions can modify the organic matter (OM) in a way that complicates the interpretation of a parent body's heating extent with common cosmothermometers. The kinetics of short-term heating and its influence on the organic structure are not well understood, and any study of OM is further complicated by the complex alteration processes of the thermally metamorphosed carbonaceous chondrites—potential analogues of the target asteroid Ryugu of the Hayabusa2 mission—which had experienced posthydration, short-duration local heating. In an attempt to understand the effects of short-term heating on chondritic OM, we investigated the change in the OM contents of the experimentally heated Tagish Lake meteorite samples using Raman spectroscopy, scanning transmission X-ray microscopy utilizing X-ray absorption near edge structure spectroscopy, and ultraperformance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry. Our experiment suggests that graphitization of OM did not take place despite the samples being heated to 900 °C for 96 h, as the OM maturity trend was influenced by the heating conditions, kinetics, and the nature of the OM precursor, such as the presence of abundant oxygenated moieties. Although both the intensity of the 1s−σ* exciton cannot be used to accurately interpret the peak metamorphic temperature of the experimentally heated Tagish Lake sample, the Raman graphite band widths of the heated products significantly differ from that of chondritic OM modified by long-term internal heating