A XANES and Raman investigation of sulfur speciation and structural order in Murchison and Allende meteorites

Insoluble organic matter (IOM) and hydrothermally treated IOM extracted from two carbonaceous chondrites, Murchison and Allende, was studied using sulfur K‐edge XANES (X‐ray absorption near edge structure) and μ‐Raman spectroscopy, with the aim to understand their IOM's sulfur speciation and structural order, and how aqueous alteration or thermal metamorphism may have transformed these materials. We found that the sulfur‐functional group chemistry of both the Murchison IOM and hydrothermally treated IOM samples have a large chemical variability ranging from oxidation states of S^?2 to S⁺⁶, and exhibit a transformation in their oxidation state after the hydrothermal treatment (HT) to produce thiophenes and thiol compounds. Sulfoxide and sulfite peaks are also present in Murchison. Sulfates considered intrinsic to Murchison are most likely preaccretionary in nature, and not a result of reactions with water at high temperatures on the asteroid parent body. We argue that the reduced sulfides may have formed in the CM parent body, while the thiophenes and thiol compounds are a result of the HT. Micro‐Raman spectra show the presence of aliphatic and aromatic moieties in Murchison's material as observed previously, which exhibits no change after HT. Because the Murchison IOM was modified, as seen by XANES analysis, absence of a change observed using micro‐Raman indicated that although the alkyl carbons of IOM were cleaved, the aromatic network was not largely modified after HT. By contrast, Allende IOM contains primarily disulfide and elemental sulfur, no organic sulfur, and shows no transformation after HT. This nontransformation of Allende IOM after HT would indicate that parent body alteration of sulfide to sulfate is not feasible up to temperatures of 300°C. The reduced sulfur products indicate extreme secondary chemical processing from the precursor compounds in its parent body at temperatures as high as 624°C, as estimated from μ‐Raman D band parameters. The Raman parameters in Allende IOM that was interpreted in terms of amorphous carbon with regions of large clusters of benzene rings, was transformed after the HT to those with fewer benzene rings.     

Comparison of the Murchison CM2 and Allende CV3 chondrites

The size distribution, abundance, and physical and chemical characteristics of chondritic inclusions are key features that define the chondrite groups. We present statistics on the size and abundance of the macroscopic components (inclusions) in the Murchison (CM2) and Allende (CV3) chondrites and measure their general chemical trends using established X‐ray mapping techniques. This study provides a fine‐scale assessment of the two meteorites and a semiquantitative evaluation of the relative abundances of elements and their distribution among meteorite components. Murchison contains 72% matrix and 28% inclusions; Allende contains 57% and 43%, respectively. A broad range of inclusion sizes and relative abundances has been reported for these meteorites, which demonstrates the necessity for a more standardized approach to measuring these characteristics. Nonetheless, the characteristic mean sizes of inclusions in Allende are consistently larger than those in Murchison. We draw two significant conclusions (1) these two meteorites sampled distinct populations of chondrules and refractory inclusions, and (2) complementary Mg/Si ratios between chondrules and matrix are observed in both Murchison and Allende. Both support the idea that chondrules and matrix within each chondrite group originated in single reservoirs of precursors with approximately solar Mg/Si ratios, providing a constraint on astrophysical models of the origin of chondrite parent bodies.     

Extraterrestrial amino acids and L‐enantiomeric excesses in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

The abundances, distributions, enantiomeric ratios, and carbon isotopic compositions of amino acids in two fragments of the Aguas Zarcas CM2 type carbonaceous chondrite fall and a fragment of the CM2 Murchison meteorite were determined via liquid chromatography time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. A suite of two‐ to six‐carbon aliphatic primary amino acids was identified in the Aguas Zarcas and Murchison meteorites with abundances ranging from ~0.1 to 158 nmol/g. The high relative abundances of α‐amino acids found in these meteorites are consistent with a Strecker‐cyanohydrin synthesis on these meteorite parent bodies. Amino acid enantiomeric and carbon isotopic measurements in both fragments of the Aguas Zarcas meteorites indicate that both samples experienced some terrestrial protein amino acid contamination after their fall to Earth. In contrast, similar measurements of alanine in Murchison revealed that this common protein amino acid was both racemic (D ≈ L) and heavily enriched in ¹³C, indicating no measurable terrestrial alanine contamination of this meteorite. Carbon isotope measurements of two rare non‐proteinogenic amino acids in the Aguas Zarcas and Murchison meteorites, α‐aminoisobutyric acid and D‐ and L‐isovaline, also fall well outside the typical terrestrial range, confirming they are extraterrestrial in origin. The detections of non‐terrestrial L‐isovaline excesses of ~10–15% in both the Aguas Zarcas and Murchison meteorites, and non‐terrestrial L‐glutamic acid excesses in Murchison of ~16–40% are consistent with preferential enrichment of circularly polarized light generated L‐amino acid excesses of conglomerate enantiopure crystals during parent body aqueous alteration and provide evidence of an early solar system formation bias toward L‐amino acids prior to the origin of life.     

Compound‐specific carbon,nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

Abstract– Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ¹³C, and δ¹⁵N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound‐specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ¹³C and increasing δD with increasing carbon number in the α‐H, α‐NH₂ amino acids that correspond to predictions made for formation via Strecker‐cyanohydrin synthesis. We also observe light δ¹³C signatures for β‐alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight‐chain, amine‐terminal amino acids (n‐ω‐amino acids). Higher deuterium enrichments are observed in α‐methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent‐body chemistry.     

Cosmogenic helium and neon in individual chondrules from Allende and Murchison: Implications for the precompaction exposure history of chondrules

Abstract– We analyzed cosmogenic He and Ne in more than 60 individual chondrules separated from small chips from the carbonaceous chondrites Allende and Murchison. The goal of this work is to search for evidence of an exposure of chondrules to energetic particles—either solar or galactic—prior to final compaction of their host chondrites and prior to the exposure of the meteoroids to galactic cosmic rays (GCR) on their way to Earth. Production rates of GCR‐produced He and Ne are calculated for each chondrule based on major element composition and a physical model of cosmogenic nuclide production in carbonaceous chondrites ( Leya and Masarik 2009 ). All studied chondrules in Allende show nominal exposure ages identical to each other within uncertainties of a few hundred thousand years. Allende chondrules therefore show no signs of a precompaction exposure. The majority of the Murchison chondrules (the “normal” chondrules) also have nominal exposure ages identical within a few hundred thousand years. However, roughly 20% of the studied Murchison chondrules (the “pre‐exposed” chondrules) contain considerably or even much higher concentrations of cosmogenic noble gases than the normal chondrules, equivalent to exposure ages to GCR at present‐day fluxes in a 4π irradiation of up to about 30 Myr. The data do not allow to firmly conclude whether these excesses were acquired by an exposure of the pre‐exposed chondrules to an early intense flux of solar energetic particles (solar cosmic rays) or rather by an exposure to GCR in the regolith of the Murchison parent asteroid. However, we prefer the latter explanation. Two major reasons are the GCR‐like isotopic composition of the excess Ne and the distribution of solar flare tracks in Murchison samples.     

MALDI analysis of presolar nanodiamonds: Mass spectrometric determination of the mass distribution of nanodiamonds from meteorites and a technique to manipulate individual nanodiamonds

Abstract— This paper describes the use of matrix‐assisted laser desorption and ionization (MALDI) to measure the mass distribution of nanodiamonds extracted from meteorites. The techniques used to prepare and mass analyze nanodiamond samples from the Murchison (CM2) and Allende (CV3) meteorites are described. The mass spectra of nanodiamonds (peaking at between 1 times 10⁴‐1.5 times 10⁴ Daltons) are compared with size distributions obtained by point‐counting transmission electron microscopy (TEM) images obtained elsewhere and reasonable agreement is found. The implications of the ability to produce and mass analyze a beam of nanodiamonds are explored.     

Composition and clues to the origin of refractory metal nuggets extracted from chondritic meteorites

Refractory metal nuggets (RMNs) contain elements, such as Os, Ir, Mo, and Ru, which are predicted to condense from a cooling gas of solar composition simultaneously with CAI‐minerals. Berg et al. ( 2009 ) identified a large number of RMNs in acid‐resistant residues of the Murchison meteorite and suggested that they are pristine condensates. In extending the work of these authors, we have improved the chemical extraction process to enrich the concentration of RMNs in the residue sample and prepared three additional RMN‐rich residues from the chondritic meteorites Murchison, Allende, and Leoville. The results show that, while their origin is clearly solar, the compositions in detail of RMNs from all three meteorites do not match well with a simple condensation model based on equilibrium thermodynamics and ideal solid solution of all metals. Thus, we find that a primary formation by direct condensation, as suggested previously, is unlikely for most of the studied grains and that alternative scenarios should be considered in future work. The results also show that several, but not all, alloys from Allende and Leoville have undergone processes, such as metamorphic oxidation and sulfidization in the meteoritic environment, in which they lost, e.g., W and Mo. For Murchison and several Leoville and Allende RMNs, we propose a pristine nature.     

SIMS studies of Allende projectiles fired into Stardust‐type aluminum foils at 6 km/sec

Abstract— We have explored the feasibility of C, N, and O isotopic measurements by NanoSIMS and of elemental abundance determinations by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) on residues of Allende projectiles that impacted Stardust‐type aluminum foils in the laboratory at 6 km/sec. These investigations are part of a consortium study aimed at providing the foundation for the characterization of matter associated with microcraters that were produced during the encounter of the Stardust space probe with comet 81P/Wild‐2. Eleven experimental impact craters were studied by NanoSIMS and eighteen by TOF‐SIMS. Crater sizes were between 3 and 190 μm. The NanoSIMS measurements have shown that the crater morphology has only a minor effect on spatial resolution and on instrumental mass fractionation. The achievable spatial resolution is always better than 200 nm, and C and O isotopic ratios can be measured with a precision of several percent at a scale of several 100 nm, which is the typical size of presolar grains. This clearly demonstrates that presolar matter, provided it survives the impact into the aluminum foil partly intact, is recognizable even if embedded in material of solar system origin. TOF‐SIMS studies are restricted to materials from the crater rim. The element ratios of the major rock‐forming elements in the Allende projectiles are well‐characterized by the TOF‐SIMS measurements, indicating that fractionation of those elements during impact can be expected to be negligible. This permits chemical information on the type of impactor material to be obtained. For any more detailed assignments to specific chondrite groups, however, information on the abundances of the light elements, especially C, is crucial. This information could not be obtained in the present study due to unavoidable contamination during impact experiments.     

Heterogeneous distributions of amino acids provide evidence of multiple sources within the Almahata Sitta parent body,asteroid 2008 TC3

Abstract– Two new fragments of the Almahata Sitta meteorite and a sample of sand from the related strewn field in the Nubian Desert, Sudan, were analyzed for two to six carbon aliphatic primary amino acids by ultrahigh performance liquid chromatography with UV‐fluorescence detection and time‐of‐flight mass spectrometry (LC‐FT/ToF‐MS). The distribution of amino acids in fragment #25, an H5 ordinary chondrite, and fragment #27, a polymict ureilite, were compared with results from the previously analyzed fragment #4, also a polymict ureilite. All three meteorite fragments contain 180–270 parts‐per‐billion (ppb) of amino acids, roughly 1000‐fold lower than the total amino acid abundance of the Murchison carbonaceous chondrite. All of the Almahata Sitta fragments analyzed have amino acid distributions that differ from the Nubian Desert sand, which primarily contains l ‐α‐amino acids. In addition, the meteorites contain several amino acids that were not detected in the sand, indicating that many of the amino acids are extraterrestrial in origin. Despite their petrological differences, meteorite fragments #25 and #27 contain similar amino acid compositions; however, the distribution of amino acids in fragment #27 was distinct from those in fragment #4, even though both are polymict ureilites from the same parent body. Unlike in CM2 and CR2/3 meteorites, there are low relative abundances of α‐amino acids in the Almahata Sitta meteorite fragments, which suggest that Strecker‐type chemistry was not a significant amino acid formation mechanism. Given the high temperatures that asteroid 2008 TC₃ appears to have experienced and lack of evidence for aqueous alteration on the asteroid, it is possible that the extraterrestrial amino acids detected in Almahata Sitta were formed by Fischer‐Tropsch/Haber‐Bosch type gas‐grain reactions at elevated temperatures.     

Amino acids in the Tagish Lake meteorite

Abstract— High‐performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated from a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P‐ or D‐type asteroids. If the Tagish Lake meteorite was indeed derived from these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.     

Effect of polychromatic X‐ray microtomography imaging on the amino acid content of the Murchison CM chondrite

X‐ray microcomputed tomography (μCT) is a useful means of characterizing cosmochemical samples such as meteorites or robotically returned samples. However, there are occasional concerns that the use of μCT may be detrimental to the organic components of a chondrite. Small organic compounds such as amino acids comprise up to ~10% of the total solvent extractable carbon in CM carbonaceous chondrites. We irradiated three samples of the Murchison CM carbonaceous chondrite under conditions akin to and harsher than those typically used during typical benchtop X‐ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed Murchison control sample occurred. After subjecting three meteorite samples to ionizing radiation dosages between ~300 Gray (Gy) and 3 kGy with bremstrahlung X‐rays, we analyzed the amino acid content of each sample. Within sampling and analytical errors, we cannot discern differences in the amino acid abundances and amino acid enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We conclude that a polychromatic X‐ray μCT experiment does not alter the abundances of amino acids to a degree greater than how well those abundances are measured with our techniques and therefore any damage to amino acids is minimal.     

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography‐fluorescence detection and time‐of‐flight mass spectrometry (UPLC‐FD/ToF‐MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two‐ to five‐carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts‐per‐billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five‐carbon (C₅) amino acids with much higher relative abundances of the γ‐ and δ‐amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α‐amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α‐aminoisobutyric acid (α‐AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l ‐isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l ‐isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.     

Amino acid analyses of Antarctic CM2 meteorites using liquid chromatography‐time of flight‐mass spectrometry

Abstract— Amino acid analyses of the Antarctic CM2 chondrites Allan Hills (ALH) 83100 and Lewis Cliff (LEW) 90500 using liquid chromatography‐time of flight‐mass spectrometry (LC‐ToF‐MS) coupled with UV fluorescence detection revealed that these carbonaceous meteorites contain a suite of indigenous amino acids not present in Antarctic ice. Several amino acids were detected in ALH 83100, including glycine, alanine, β‐alanine, γ‐amino‐n‐butyric acid (γ‐ABA), and α‐aminoisobutyric acid (AIB) with concentrations ranging from 250 to 340 parts per billion (ppb). In contrast to ALH 83100, the CM2 meteorites LEW 90500 and Murchison had a much higher total abundance of these amino acids (440–3200 ppb). In addition, ALH 83100 was found to have lower abundances of the α‐dialkyl amino acids AIB and isovaline than LEW 90500 and Murchison. There are three possible explanations for the depleted amino acid content in ALH 83100: 1) amino acid leaching from ALH 83100 during exposure to Antarctic ice meltwater, 2) a higher degree of aqueous alteration on the ALH 83100 parent body, or 3) ALH 83100 originated on a chemically distinct parent body from the other two CM2 meteorites. The high relative abundance of ?‐amino‐n‐caproic acid (EACA) in the ALH 83100 meteorite as well as the Antarctic ice indicates that Nylon‐6 contamination from the Antarctic sample storage bags may have occurred during collection.     

Free dicarboxylic and aromatic acids in the carbonaceous chondrites Murchison and Orgueil

Abstract— We have analyzed an important fraction of the free carboxylic acids present in water extracts of the CM2 chondrite Murchison and the CI1 chondrite Orgueil using gas chromatographymass spectrometry (GC‐MS). The free nature of the carboxylic acids analyzed was ensured by employing a single‐step water extraction. Analyses revealed the presence of a structurally diverse suite of both aliphatic and aromatic acids in Murchison, while Orgueil exhibits a simpler distribution of exclusively aromatic acids. Within the Murchison aromatic acids, there are previously unreported phthalic acids, methyl phthalic acids, and hydroxybenzoic acids. In Orgueil, benzoic acid and very small amounts of methylbenzoic acids and methylhydroxybenzoic acids were detected. For the aromatic acids in both Murchison and Orgueil, most structural isomers were identified, suggesting an origin by abiotic processes. Quantitative differences are evident between acids in the two meteorites; carboxylic acids are much more abundant in Murchison than in Orgueil. The data suggest that differing levels of aqueous alteration on the meteorite parent body(ies) has produced dissimilar distributions of carboxylic acids.     

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon‐rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound‐specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g^?1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent‐body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound‐specific stable carbon isotopic ratios (δ¹³C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ¹³C values from –20 to +59‰. These δ¹³C values fall into the range of other meteoritic organic compounds, although they are ¹³C‐depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)‐ and (S)‐sec‐butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the l ‐enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec‐butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.     

Highly siderophile and chalcogen element constraints on the origin of components of the Allende and Murchison meteorites

¹⁸⁷Re‐¹⁸⁷Os systematics, abundances of highly siderophile elements (HSE: Re, PGE, and Au), chalcogen elements (Te, Se, and S), and some major and minor elements were determined in physically separated components of the Allende (CV3) and Murchison (CM2) carbonaceous chondrites. Substantial differences exist in the absolute and relative abundances of elements in the components, but the similarity of calculated and literature bulk rock abundances of HSE and chalcogens indicate that chemical complementarity exists among the components, with CI chondrite‐like ratios for many elements. Despite subsequent alteration and oxidation, the overall cosmochemical behavior of most moderately to highly siderophile elements during high‐temperature processing has been preserved in components of Allende at the sampling scale of the present study. The ¹⁸⁷Re‐¹⁸⁷Os systematics and element variations of Allende are less disturbed compared with Murchison, which reflects different degrees of oxidation and alteration of these meteorites. The HSE systematics (with the exception of Au) is controlled by two types of materials: Pd‐depleted condensates and CI chondrite‐like material. Enrichment and heterogeneous distribution of Au among the components is likely the result of hydrothermal alteration. Chalcogen elements are depleted compared with HSE in all components, presumably due to their higher volatility. Small systematic variations of S, Se, and Te in components bear the signature of fractional condensation/partial evaporation and metal–sulfide–silicate partitioning.     

Modal mineralogy of carbonaceous chondrites by X‐ray diffraction and Mössbauer spectroscopy

Abstract— Carbonaceous chondrites are among the most analyzed geological materials on Earth. However, despite this attention, and unlike most terrestrial rocks, little is known on the abundance of individual phases within them. Here, we show how a combination of several novel X‐ray diffraction (XRD) techniques (including a high‐brightness X‐ray MicroSource®), and Mössbauer spectroscopy, allows a complete modal mineralogy to be ascertained from even the most highly unequilibrated, fine‐grained chondrites for all minerals of abundance >1 wt%. Knowledge of the modal mineralogy of a sample also allows us to calculate grain density. We analyzed Allende, Murchison, Tagish Lake, and Orgueil. Based on our modal data, the grain density estimates for Allende, Murchison, and Orgueil are close to literature values. In the case of Tagish Lake, there is no published grain density, although a bulk density measurement does exist. Taking our estimate of grain density, and the measured bulk density, we calculate an exceptionally high porosity of 41% for this meteorite, similar to some chondritic IDPs and in line with a porosity calculated from an entry model for the Tagish Lake fireball. Although it is an oxidized CV, magnetite is present in Allende at a level of <0.5 wt% or <0.3 vol%, a result that is substantiated by several other instrumental studies. This may be an oxidized meteorite, but that oxidation is not manifested in abundant magnetite. In addition, we note appreciable fayalitic olivine in Orgueil, detected by both XRD and Mössbauer. We employed MicroSource® XRD to look at heterogeneity in mineral abundance in Orgueil and found substantial variation, with phyllosilicates varying inversely with olivine. The data suggest that Orgueil was initially composed primarily of anhydrous materials, which have been partially, but not completely, altered. Although the data are preliminary, comparison between our XRD modal assessment, bulk chemistry, grain density, and Mössbauer data, suggests that our estimates of mineral abundance are robust. The advent of MicroSource® XRD allows similar modal data to be acquired from samples as small as a few hundred micrograms.     

Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

TOF‐SIMS analysis of Allende projectiles shot into silica aerogel

Abstract— Powdered Allende projectiles were fired into silica aerogel at 6.1 km/sec in order to evaluate particle retrieval and analysis techniques for samples from the Stardust mission. Since particles may disintegrate and ablate along the penetration paths in a high‐porosity aerogel, TOF‐SIMS analysis may be a suitable method to determine the distribution of such materials along the tracks as well as potential compositional modifications. Therefore, two ?350 μm‐sized tracks, residing at the surface of a keystone specimen that was flattened between two silicon chips, were analyzed. TOF‐SIMS allows for a detailed study of the chemical composition of particles that survived the impact mostly intact and of fine‐grained material from disintegrated projectiles. In the investigated keystone, material from light gas gun debris dominated. Besides the two tracks, a continuous, 40‐μm‐thick surface layer of implanted material—probably gun residue—was found. One of the two analyzed tracks is compositionally distinct from this surface layer and is likely to contain residual material of an Allende projectile. The analyses clearly demonstrate that tracks, resulting from impactors in the 5–10 μm size range, can be successfully analyzed with TOF‐SIMS.     

Petrographic comparison of refractory inclusions from different chemical groups of chondrites

Abstract— Twenty‐four refractory inclusions (40–230 μm, with average of 86 ± 40 μm) were found by X‐ray mapping of 18 ordinary chondrites. All inclusions are heavily altered, consisting of finegrained feldspathoids, spinel, and Ca‐pyroxene with minor ilmenite. The presence of feldspathoids and lack of melilite are due to alteration that took place under oxidizing conditions as indicated by FeO‐ZnO‐rich spinel and ilmenite. The pre‐altered mineral assemblages are dominated by two types: one rich in melilite, referred to as type A‐like, and the other rich in spinel, referred to as spinelpyroxene inclusions. This study and previous data show similar type and size distributions of refractory inclusions in ordinary and enstatite chondrites. A survey of refractory inclusions was also conducted on Allende and Murchison in order to make unbiased comparison with their counterparts in other chondrites. The predominant inclusions are type A and spinel‐pyroxene, with average sizes of 170 ± 130 μm (except for two mm‐sized inclusions) in Allende and 150 ± 100 μm in Murchison. The relatively larger sizes are partially due to common conglomerating of smaller nodules in both chondrites. The survey reveals closely similar type and size distributions of refractory inclusions in various chondrites, consistent with our previous data of other carbonaceous chondrites. The petrographic observations suggest that refractory inclusions in various groups of chondrites had primarily formed under similar processes and conditions, and were transported to different chondrite‐accreting regions. Heterogeneous abundance and distinct alteration assemblages of refractory inclusions from various chondrites could be contributed to transporting processes and secondary reactions under different conditions.