Major element composition of phyllosilicates in the Orgueil carbonaceous meteorite
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The discovery in chondritic meteorites of diamond, SiC, and poorly crystallized graphite that formed around other stars demonstrated conclusively that presolar dust survived the formation of the solar system to be incorporated into meteorites. The presolar nature of these grains is shown by the highly unusual isotopic compositions of their constituent elements. To date, all recognized types of presolar grains have been carbon rich and apparently formed around carbon stars, those with C/O greater than 1. The discovery of the first oxygen-rich grain with isotopic characteristics consistent with a presolar origin is reported. Oxygen-rich grains presumably form only around stars with C/O less than 1.
The relationship between the chemical composition and the interlayer spacing (d002) of organic materials (OM's) is known for various terrestrial OM's. We improved this general trend by correlation with corresponding trend of natural solid bitumens (asphaltite-kerite-anthraxolite) up to graphite. Using the improved trend we identified bitumen analogs of carbonaceous chondrite OM's residued after HF-HCl treatment. Our laboratory experiment revealed that these analogs and, hence, structure and chemical composition of carbonaceous chondrite OM's are very sensitive to the HF-HCl treatment. So, usual extraction of OM from carbonaceous chondrites may change significantly structural and chemical composition of extracted OM.
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Establishing chemical links between meteorites and small solar system bodies, such as comets and asteroids, provides a tool for investigating the processes that occurred during the formation of the solar system. Carbonaceous meteorites are of particular interest, since they may have seeded the early Earth with a variety of prebiotic organic compounds including amino acids, purines and pyrimidines, which are thought to be necessary for the origin of life. Here we report the results of high-performance liquid chromatography (HPLC) based amino acid analyses of the acid-hydrolyzed hot water extracts from pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna and the CM meteorites Murchison and Murray. We found that the CI meteorites Orgueil and Ivuna contained high abundances of beta-alanine and glycine, while only traces of other amino acids like alanine, alpha-amino-n-butryic acid (ABA) and alpha-aminoisobutyric acid (AIB) were detected in these meteorites. Carbon isotopic measurements of beta-alanine and glycine in Orgueil by gas chromatography combustion-isotope ratio mass spectrometry clearly indicate an extraterrestrial origin of these amino acids. The amino acid composition of Orgueil and Ivuna was strikingly different from the CM chondrites Murchison and Murray. The most notable difference was the high relative abundance of B-alanine in Orgueil and Ivuna compared to Murchison and Murray. Furthermore, AIB, which is one of the most abundant amino acids found in Murchison and Murray, was present in only trace amounts in Orgueil and Ivuna. Our amino acid data strongly suggest that the CI meteorites Orgueil and Ivuna came from a different type of parent body than the CM meteorites Murchison and Murray, possibly from an extinct comet. It is generally thought that carbonaceous meteorites are fragments of larger asteroidal bodies delivered via near Earth objects (NEO). Orbital and dynamic studies suggest that both fragments of main belt asteroids and comets replenish the NEO population, therefore extinct comets may contribute up to half of all NEO's. A comparison of an amino acid analysis of a returned NEO sample to CI and CM carbonaceous chondrites would help establish a link between small solar system bodies and meteorites. Based on our amino acid measurements of CI and CM chondrites, amino acid chemistry can be included as an additional set of criteria to constrain the nature of meteorite parent bodies.
Oxygen isotopic compositions and initial Al-26/Al-27 ratios were reported for two presolar Al2O3 grains, Orgueil B and Bishunpur B39. In Orgueil B, O-17/O-16 is about twice the solar value but O-18/O-16 is normal. In B39, O-17/O-16 is approximately 7x higher than solar and O-18/O-16 is 0.6x the solar value. Spectroscopic observations of red giant stars show similar O compositions, which result when material that has experienced partial H burning is mixed into the stellar envelope by the first dredge-up. The O-17/O-16 ratios indicate that Orgueil B originated around a star of approximately 1.5 solar mass, while B39 formed around either a approximately 2 solar mass or 4-7 solar mass star. Both grains formed with Al-26/Al-27 ratios of approximately 10(exp -3). Aluminum-26 is produced in the H shell after core H burning has ceased and first dredge-up has occurred. It is spread through the envelope by the third dredge-up, which occurs in low- and intermediate-mass stars as a series of mixing events driven by thermal pulses in the He shell. In intermediate-mass stars (3-8 solar mass), Al-26 can also be brought to the surface by the second dredge-up, which occurs at the end of core He burning. We have measured Ti isotopes by ion probe in Orgueil B and Bishunpur B39, looking for evidence of He-shell nucleosynthesis. Stars of approximately 1.5 solar mass do not experience second dredge-up, so the Al-26 in Orgueil B must have been mixed outward during third dredge-up, which also supplies He-shell material to the envelope. The size of the isotopic shifts in Ti and Mg suggest that Orgueil B contains approximately 5-10x more material from the He-shell than from the H-shell. In contrast, the lack of measurable Mg and Ti anomalies in B39 imply little or no He-shell contribution. This indicates that Al-26 in B39 was supplied by second dredge-up prior to He-shell ignition and points to a parent star of 4-7 solar mass.
The dominant sulfide in CI carbonaceous chondrites is an Fe-deficient pyrrhotite containing about 1% Ni, Alais, Ivuna, and Orgueil also contain minor cubanite, CuFe2S3, and Alais minor pentlandite, (Fe,Ni)9S8. All pyrrhotites contain 39.4 + or - 0.1% S; Ni contents range from 0.7 to 1.3%. The phase diagrams reveal no temperature at which the observed pentlandite-pyrrhotite assemblage is at equilibrium. Similarly, the pyrrhotite composition alone are inconsistent with equilibrium formation from a gas of solar composition. In Xe from high-purity submilligram Orgueil pyrrhotite separates, the ratios Xe-129/Xe-132 are not significantly larger than those in trapped meteoritic Xe. The lack of positive evidence for extinct I-129 in pyrrhotite does not permit any inferences regarding cooling rates in the early solar nebula. It is concluded that sulfides in CI chondrites cannot be nebular condensates formed under equilibrium conditions. Argon isotopic abundances reveal the presence of significant spallation and trapped gas components in Orgueil pyrrhotite. The Orgueil exposure age is calculated to be at least about 10 m.y.
Antarctic micrometeorites (AMM's) have similarities (but also differences) with primitive meteorites, such as unequilibrated mineral assemblages. To further assess such similarities, we have measured the carbon content of micrometeorites and meteorites (Orgueil and Murchison), as determined in a random selection of micrometer-size crushed grain, with an analytical transmission electron microscope. Such analyses yield the C/O atomic ratio, the major and minor elements contents, and the textural features of the grains on a scale of approx. equal to 100 nanometers. An important proportion of micrometeorites from both the 100-400 micron and the 50-100 micron size fractions contains much more carbon than CI chondrite Orgueil. The average C-content of all micrometeorites in these two size fractions amount to approximately 1.8 x CI, and approximately 0.8 x CI, respectively (CI refers to the bulk C-content of Orgueil, of about 3.5 percent by weight). Carbon is usually not homogeneously distributed in the micrometeorite but is concentrated in C-rich grains. So far, most of these grains are amorphous, and seem to be associated with an oxidized Fe-rich phase (possibly a variety of 'dirty' magnetite). About 5 percent of them have the composition of 'COPS', a phase additionally enriched in O, P, and S.
Investigations have been carried out on freshly broken, internal surfaces of the Murchison, Efremovka and Orgueil carbonaceous chondrites using Scanning Electron Microscopes (SEM) in Russia and the Environmental Scanning Electron Microscope (ESEM) in the United States. These independent studies on different samples of the meteorites have resulted in the detection of numerous spherical and ellipsoidal bodies (some with spikes) similar to the forms of uncertain biogenicity that were designated "organized elements" by prior researchers. We have also encountered numerous complex biomorphic microstructures in these carbonaceous chondrites. Many of these complex bodies exhibit diverse characteristics reminiscent of microfossils of cyanobacteria such as we have investigated in ancient phosphorites and high carbon rocks (e.g. oil shales). Energy Dispersive Spectroscopy (EDS) analysis and 2D elemental maps shows enhanced carbon content in the bodies superimposed upon the elemental distributions characteristic of the chondritic matrix. The size, distribution, composition, and indications of cell walls, reproductive and life cycle developmental stages of these bodies are strongly suggestive of biology' These bodies appear to be mineralized and embedded within the meteorite matrix, and can not be attributed to recent surface contamination effects. Consequently, we have interpreted these in-situ microstructures to represent the lithified remains of prokaryotes and filamentous cyanobacteria. We also detected in Orgueil microstructures morphologically similar to fibrous kerite crystals. We present images of many biomorphic microstructures and possible microfossils found in the Murchison, Efremovka, and Orgueil chondrites and compare these forms with known microfossils from the Cambrian phosphate-rich rocks (phosphorites) of Khubsugul, Northern Mongolia.
We performed heating experiments of the Orgueil CI chondrite in vacuum conditions at fO2 around I/W to evaluate systematic changes in mineralogy, water contents, and visible to infrared spectral features. Our goal is to interpret the spectra of Ryugu, the target C asteroid of the Hayabusa2 mission, because Ryugu shows spectral features similar to partially dehydrated carbonaceous chondrites. However heated carbonaceous chondrites can be easily contaminated by terrestrial water, which makes it almost impossible for laboratory data to be compared with spectra of asteroids directly. Therefore, our heated samples were analyzed without exposure to the air after experimental heating to minimize the effects of terrestrial water. The depth of the 2.7-µm absorption band and the water content of the heated Orgueil form a positive correlation trend which follows the results of experimental heating of CM and Tagish Lake meteorites using our experimental procedures. It is found that 500-°C heated Orgueil sample shows the best spectral match with Ryugu in terms of the low reflectance (~2%) at visible wavelengths and a weak absorption (~10%) at around 2.72 µm owing to survival of Mg-rich phyllosilicates. We suggest that Ryugu might have experienced heating and dehydration at a temperature around 500 °C, after aqueous alteration, and presently contains a small quantity of hydrated minerals equivalent to 1-2 wt.% of water at the surface.
The Hayabusa 2 spacecraft brought back to Earth grains of the carbonaceous asteroid Ryugu. Such grains represent the pristine state of CI chondritic materials and have been preserved from exposure to Earth’s atmosphere. Here, we show evidence of the presence of organics trapped within the interlayer space of smectite layers in Ryugu grains. No such organics are found in the Orgueil CI meteorite. We put forward that the organics within the interlayer space of smectite in Orgueil CI meteorite were lost during their oxidation on Earth. Also, we propose that the presence of organics within the interlayers space of smectite might be responsible for the possible NH infrared signature observed in Ryugu particles and potentially to a few large C-type asteroids including Ceres
Samples of all five of the known Cl chondrites have been analyzed thermomagnetically. The only magnetic phase found in four of the chondrites (Alais, Ivuna, Orgueil, Tonk) was magnetite containing less than 6% nickel. The Revelstoke Cl chondrite contains essentially Ni-free Fe3O4 as the predominant phase; however, a small amount of a thermally unstable iron compound (presumably FeS) is additionally present. Estimates of the weight percentage of magnetite, based on saturation moments, are: Alais, 5.3 plus or minus 0.4%; Ivuna, 12.2 plus or minus 0.9%; Orgueil, 11.9 plus or minus 0.8%; Revelstoke, 7.2 plus or minus 0.5%; and Tonk, 9.4 plus or minus 0.6%.
Noting that the iron sulfide in the Orgueil carbonaceous meteorite is an Fe-deficient monosulfide (pyrrhotite), it is suggested that such mineral chemistry is inconsistent with equilibrium condensation of the solar nebula and that the course of condensation may have been modified by kinetic effects. The effect of Ni on the reaction between Fe and S to produce FeS is examined, and possible reasons are considered for the fact that the cited meteorite differs in both crystal structure and Ni content from the predictions of equilibrium condensation. It is proposed that sulfide formation in the solar nebula may have been inhibited by sluggish diffusion, so that sulfur began to react with previously condensed troilite to form pyrrhotite. On this basis, observations of the Orgueil sulfides are shown to suggest that the course of solar-system condensation was modified by kinetic effects below about 700 K and that equilibrium may not have been achieved.
The concentrations of zirconium and hafnium have been determined in the Orgueil, Murchison, Allende, Bruderheim, and Alais meteorites by radiochemical neutron activation analysis. The mean Zr/Hf weight ratio in the first four of these meteorites is 31.3 (plus or minus 2.2), indicating no major fractionation of Zr from Hf. Alais contains anomalously high amounts of many refractory lithophile elements, including Zr and Hf. Orgueil contains 3.1 ppm Zr and 0.11 ppm Hf, corresponding to 9.0 and 0.16 atoms, respectively, relative to 1 million Si atoms.
Rb-Sr whole rock analyses have been performed on 2 CI and 3 CM chondrites. Four of these stones (Ivuna, Orgueil, Cold Bokkeveld and Erakot) were previously studied in this laboratory and were shown to be discordant from a 4.6 Gyr isochron. The fifth, Murchison, was not previously studied. The new data support the discordance of the first four stones, and indicate that Murchison is also discordant. Studies of Sr isotope ratios in unspiked Orgueil show that the discordance is not due to inhomogeneities in the Sr-84/Sr-86 ratio caused by incomplete mixing of nucleosynthesis products. In order to gauge the effects of weathering, two leaching experiments were performed on fresh, interior samples of Murchison; one for a period of 1.5 hr and the other for 117 hr. The results indicate that the relative solubility of nonradiogenic Sr is approximately twice that of Rb and radiogenic Sr is more soluble than the nonradiogenic Sr.