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Mossbauer effect and ionic character of iron atoms in orgueil and cold Bokkeveld meteorites
The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. Ithas been extensively studied, and despite its extensive degree of aqueous alteration andsome documented instances of contamination, several indigenous organic compoundsincluding amino acids, carboxylic acids, and nucleobases have been detected in its carbon-rich matrix. We recently developed a novel gas chromatographic method for theenantiomeric and compound-specific isotopic analyses of meteoritic aliphatic monoamines inextracts and have now applied this method to investigate the monoamine content inOrgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to332 nmol g1of meteorite and compared this amine content in Orgueil with that of theCM2 Murchison meteorite, which experienced less parent-body aqueous alteration.Methylamine is four times more abundant in Orgueil than in Murchison. As with otherspecies, the amine content in Orgueil extracts shows less structural diversity than that inMurchison extracts. We measured the compound-specific stable carbon isotopic ratios(d13C) for 5 of the 12 monoamines detected in Orgueil and found a range ofd13C valuesfrom–20 to+59&. Thesed13C values fall into the range of other meteoritic organiccompounds, although they are13C-depleted relative to their counterparts extracted from theMurchison meteorite. In addition, we measured the enantiomeric composition for the chiralmonoamines (R)- and (S)-sec-butylamine in Orgueil, and found it was racemic withinexperimental error, in contrast with theL-enantiomeric excess found for its amino acidstructural analog isovaline. The racemic nature ofsec-butylamine in Orgueil wascomparable to that previously observed in Murchison, and to other CM2 and CR2carbonaceous 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 toplace some constraints on the effects of aqueous alteration observed over the monoamineconcentrations in Orgueil and Murchison, and to evaluate the primordial syntheticrelationships between meteoritic monoamines and amino acids.
The I-Xe system was studied in a ferromagnetic sample separated from the Orgueil CI carbonaceous chondrite with a hand-held magnet and in two magnetite samples, one chemically separated before and the other one after neutron irradiation. This work was done in order to investigate the effects of chemical separation by LiCl and NaOH on the I-Xe system in magnetite. Our test demonstrated that the chemical separation of magnetite before irradiation using either LiCl or NaOH, or both, does not contaminate the sample with iodine and thus cannot lead to erroneous I-Xe ages due to introduction of uncor-related128*Xe. The I-Xe ages of two Orgueil magnetite samples are mutually consistent within experimental uncertainties and, when normalized to an absolute time scale with the reevaluated Shallowater aubrite standard, place the onset of aqueous alteration on the CI parent body at 4564.3 ± 0.3 Ma, 2.9 ± 0.3 Ma after formation of the CV Ca-AI-rich inclusions (CAIs). The I-Xe age ofthe ferromagnetic Orgueil separate is 3.4 Ma younger, corresponding to a closure of the I-Xe system at 4560.9 ± 0.2 Ma. These and previously published I-Xe data for Orgueil (Hohenberg et al., 2000) indicate that aqueous alteration on the CI parent body lasted for at least 5 Ma. Although the two magnetite samples gave indistinguishable I-Xe ages, their temperature release profiles differed. One of the two Orgueil magnetites released less radiogenic Xe than the other, 80% of it corresponding to the low-temperature peak of the release profile, compared to only 6% in case of the second Orgueil magnetite sample. This could be due to the difference in iodine trapping efficiencies for magnetite grains of different morphologies. Alternatively, the magnetite grains with the lower radiogenic Xe concentrations may have formed at a later stage of alteration when iodine in an aqueous solution was depleted.
The Orgueil CII meteorite, which fell in southern France on the evening of May 14, 1864, has been one of the most extensively studied of all known carbonaceous meteorites. Field Emission Scanning Electron Microscopy (FESEM) studies of freshly fractured interior surfaces of the Orgueil meteorite have resulted in the detection of the fossilized remains of a large and diverse population of filamentous prokaryotic microorganisms. The taphonomy and the diverse modes of the preservation of these remains ,are diverse. Some of the remains exhibit carbonization of a hollow sheath and in other cases the remains are permineralized with water-soluble evaporite minerals, such as magnesium sulfate or ammonium salts. After the sample is fractured and the interior surfaces are exposed to the atmospheric moisture, some of these friable remains have been observed to exhibit significant alterations in appearance with time. Images are presented to document the changes that have been observed in some forms within the past two years. Images and EDS spectral data will also be presented to document the studies carried out on abiotic forms to search for possible nonbiological interpretations of the indigenous filamentous microstructures that have been found in the Orgueil meteorite. Images and EDS data will be presented showing the size, size range, morphology and chemical compositions of abiotic microstructures found in native crystalline and fibrous Epsomites from Poison Lake, Washington, USA and Catalayud, Zaragoza, Aragon, Spain. Many of these embedded forms are consistent in size and microstructure with cyanobacteria morphotypes. Some of the forms are exhibit known characteristics differentiation of cells, and reproductive structures of filamentous trichomic prokaryotes (bacteria and cyanobacteria) and the degraded remains of microfibrils associated with sheaths of cyanobacteria. In this paper, recently obtained comparative images and EDS data will be presented for the mineralized remains found in the Orgueil meteorite and these forms will be compared with known cyanobacteria of the family Oscillatoriaceae. Many of the indigenous filamentous microstructures found in Orgueil filaments are dramatically different from the abiotic microstructures found in the fibrous epsomites and these forms are interpreted as the molds, casts and the well preserved permineralized remains (microfossils) of filamentous prokaryotes that are embedded in and indigenous to the matrix of the Orgueil CI1 carbonaceous meteorite.
I-Xe ages of Murchison and Orgueil magnetites were reported to be the oldest [1] and interpreted as the condensation time of the solar nebula. More recent measurements, conducted on a highly magnetic separate from Orgueil (but not pure magnetite), gave much younger I-Xe ages [2]. We have since performed new studies on two pure separates of Orgueil magnetite, confirming the later closing time of the I-Xe system in this mineral phase. In the previous work of Lewis and Anders [1] special attention was paid to the purity of the analyzed material. It was shown, that the trapped Xe resided mostly in hydrated silicates and the radiogenic 129Xe in magnetite [3]. Therefore, Orgueil was finely ground and stirred with a saturated LiCl solution for 8 days at 60 C to remove the silicate-magnetite intergrowth. Although this procedure yields magnetic fractions that are at least 90% pure [1], it could potentially contaminate the magnetite with iodine and produce noncorrelated 128Xe and spurious I-Xe ages. To avoid this possibility, in our first work with Orgueil we deliberately omitted separation in LiCl solution. Instead, the meteorite was ground into a fine powder and the highly magnetic fraction was separated with a hand magnet and was confirmed to be largely magnetite [2]. The new work, reported here, was done in order to confirm our previous results and investigate the effects of the LiCl treatment on the I-Xe system in magnetite.
Infrared spectroscopy of the Orgueil C-1 chondrite and polymorphs of serpentine was performed in order to further define the mineralogy of Orgueil. Spectra of the meteorite and a synthetic serpentine (Mg3(Si2O5)(OH)4) were obtained in the regions from 1400 to 200 and from 4000 to 2500 kayers using a double beam infrared spectrometer. The spectra of Orgueil are found to be incompatible with those of the chrysotile, antigorite and lizardite polymorphs of serpentine, indicating a very low abundance of these minerals in the meteorite. It is suggested that chamosite or minerals related to chamosites may prove to be compatible with the compositional, structural and infrared properties of Orgueil.
Evaluating the molecular distribution of organic compounds in pristine extraterrestrial materials is cornerstone to understanding the abiotic synthesis of organics and allows us to better understand the molecular diversity available during the formation of our solar system and before the origins of life on Earth. In this work we identify multiple organic compounds in solvent extracts of asteroid Ryugu samples A0106 and C0107 and the Orgueil meteorite using two-dimensional gas chromatography and time-of-flight high resolution mass spectrometry (GC×GC-HRMS). Our analyses found similarities between the molecular distribution of organic compounds in Ryugu and the CI carbonaceous chondrite Orgueil. Specifically, several PAHs and organosulfides were found in Ryugu and Orgueil suggesting an interstellar and parent body origin for these compounds. We also evaluated the common relationship between Ryugu, Orgueil, and comets like Wild-2; however, until comprehensive compound-specific isotopic analyses for these organic species are undertaken, and until the effects of parent body processes and Earth’s weathering processes on meteoritic organics are better understood, their parent-daughter relationships will remain unanswered. Finally, the study of organic compounds in Ryugu samples and the curation practices for the future preservation of these unvaluable materials are also of special interest for future sample return missions, including NASA’s OSIRIS-REx asteroid sample return mission.
The Kr and H2O adsorption properties of Orgueil were studied. Dehydration by stepwise calcination produced a tenfold change in its B.E.T. surface area, which increased to 120 and then fell to 40 square meters per gram. Water exchangeability was measured by water regain from lab air between calcination cycles. Dehydration at room temperature showed that Orgueil contained 6 per cent by weight of water adsorbed on free surfaces. These results are consistent with an identification of Orgueil as montmorillonite, although chemical data conflict with this. High D/H ratios in CI carbonaceous chondrites may result from D enrichment in OH- groups during equilibration of dispersed phyllosilicate dust with preplanetary nebula gas at temperatures much less than 0 C.
This paper presents the results of petrographic, SEM, and TEM studies of the matrix minerals in Orgueil. It was found that the matrix consists mainly of Fe-bearing Mg-rich serpentine and saponite, and a poorly crystallized Fe-rich ferrihydrite containing small and varying amounts of S and Ni. The serpentine and saponite, which occur in roughly equal molar proportions, are coherently intergrown and occur mainly in fine phyllosilicates in intimate association with the ferrihydrite. Coarse phylosilicates occur in clusters relatively free of ferrihydrite. The matrix mineralogy of the Orgueil chondrite suggests that Orgueil experienced considerably different alteration conditions than did the CM chondrites.
In 1971, Rossignol-Strick and Barghoorn provided images and a description of a number of spherical hollow microstructures showing well-defined walls in acid macerated extract of the Orgueil CI carbonaceous meteorite. Other forms such as membranes and spiral shaped structures were also reported. The carbon-rich (kerogen) hollow spheres were found to be in a narrowly constrained distribution of sizes (mainly 7 to 10 microns in diameter). Electron microprobe analysis revealed that these spheres contained Carbon, possibly P, N, and K. It was established that these forms could not be attributed to pollen or other recent terrestrial contaminants. It was concluded that they most probably represented organic coatings on globules of glass, olivine or magnetite in the meteorite. However, recent studies of the Orgueil meteorite have been carried out at the NASA/Marshall Space Flight Center with the S-4000 Hitachi Field Emission Scanning Electron Microscope (FESEM). These investigations have revealed the presence of numerous carbon encrusted spherical magnetite platelets and spherical and ovoidal bodies of elemental iron in-situ in freshly fractured interior surfaces of the meteorite. Their size range is also very narrowly constrained (typically approximately 6 to 12 microns) in diameter. High resolution images reveal that these bodies are also encrusted with a thin carbonaceous sheath and are surrounded by short nanofibrils that are shown to be composed of high purity iron by EDAX elemental analysis. We present Secondary and Backscatter Electron FESEM images and associated EDAX elemental analyses and 2D X-ray maps of these forms as we re-examine the hollow spheres of Orgueil and attempt to determine if they are representatives of the same population of indigenous microstructures.
In the last 100 years, the global population has more than quadrupled to over seven billion people. At the same time, the demand for food and standard of living has been increasing which has amplified the global water use by nearly eight times from approximately 500 to 4000 cu km per yr from 1900 to 2010. With the increasing concern to sustain the growing population on Earth it is necessary to seek other approaches to ensure that our planet will have resources for generations to come. In recent years, the advancement of space travel and technology has allowed the idea of mining asteroids with resources closer to becoming a reality. During the duration of the internship at NASA Kennedy Space Center, several geotechnical tests were conducted on BP-1 lunar simulant and asteroid simulant Orgueil. The tests that were conducted on BP-1 was to practice utilizing the equipment that will be used on the asteroid simulant and the data from those tests will be omitted from report. Understanding the soil mechanics of asteroid simulant Orgueil will help provide basis for future technological advances and prepare scientists for the conditions they may encounter when mining asteroids becomes reality in the distant future. Distinct tests were conducted to determine grain size distribution, unconsolidated density, and maximum density. Once the basic properties are known, the asteroid simulant will be altered to different levels of compaction using a vibrator table to see how compaction affects the density. After different intervals of vibration compaction, a miniature vane shear test will be conducted. Laboratory vane shear testing is a reliable tool to investigate strength anisotropy in the vertical and horizontal directions of a very soft to stiff saturated fine-grained clayey soil. This test will provide us with a rapid determination of the shear strength on the undisturbed compacted regolith. The results of these tests will shed light on how much torque is necessary to drill through the surface of an asteroid. Most of the known asteroids are believed to be left over material during the formation of the solar system that never accreted to form planets. Asteroids can be found in several groups such as Trojan Asteroids, Near Earth Asteroids (NEAs) and the main asteroid belt. The Trojan Asteroids orbit the 4th and 5th Lagrange points of major planets in the Solar System while the NEA's have orbits that are close to and sometimes intersect with Earths orbit and the Main Asteroid Belt which is found between the orbit of Mars and Jupiter. Gravitational perturbations can alter the orbit of asteroids in the Main Asteroid Belt causing them to move closer to earth causing them to become in the NEA class.
The problems of separation of contaminant from indigenous amino-acids in meteorites can be largely overcome by applying gas chromatographic techniques for the separation of D,L enantiomers of amino-acids as their diastereomeric derivatives and the identification of these compounds by gas chromatographic retention times and mass spectral fragmentation patterns. Two samples of Orgueil meteorite were examined. The results show that there are amino-acids indigenous to the Orgueil meteorite in addition to those present as contaminants.
Results are reported for analysis of polymeric organic material contained in powder from the Orgueil chondrite, using a stepwise high-vacuum pyrolysis-gas chromatography-mass spectrometry technique. Pyrolysis products obtained include a series of alkanes and alkenes to C8, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, benzothiophene, acetonitrile, acrylonitrile, benzonitrile, acetone, and phenol. Most of these products are shown to be similar both qualitatively and quantitatively to those previously obtained from solvent-extracted Allende powder, indicating a basically aromatic and heteroaromatic polymer matrix with short aliphatic bridges or side chains. The production of acrylonitrile, acetonitrile, and benzonitrile (common breakdown products of amino acids) from the insoluble organic material is taken to suggest that amino acids exist in an insoluble form, perhaps as peptides, in the meteorite's polymeric component. Similarities between the structure of the Orgueil polymeric material and terrestrial kerogen are discussed which raise the possibility that both might have been produced in part by similar reactions.
Sympathetic variations in nickel and sulfur abundances, on a scale of micrometers, in Orgueil phyllosilicates apparently reproduce similar correlations among matrices of different carbonaceous chondrites. In Orgueil this effect probably results from aqueous alteration of a Ni-Si-bearing phase on the parent body.
In the reported investigation, the approach employed by Jeffery and Anders (1970) and Eberhardt (1974), who used colloidal suspensions in separating minerals of the Orgueil carbonaceous chondrite (C1), was extended to an application involving the enrichment of a planetary noble gas carrier in several C1 and C2 meteorites. The thermal release pattern of Orgueil 'carbon' is considered, taking into account elemental effects, a comparison of noble gas release from 'carbon' separates and bulk meteorite samples, isotopic effects, and a comparison with Murray 'carbon'. An evaluation is conducted of the noble gas components in carbonaceous chondrites. The origin of primordial noble gases in carbonaceous chondrites is also discussed, giving attention to the origin of solar gases, the role of 'carbon' as the novel vehicle for planetary gases, and plausible astrophysical sites for the production of anomalous krypton and xenon.
Studies of individual presolar SiC grains have shown that most are enriched in Si-29, Si-30, and C-13, and depleted in N-15, compared to solar-system abundances and that many have large excesses of Mg-26, most plausibly from in situ decay of Al-26. Stone et al., observed that Si from a family of platy SiC grains define a linear array on a 3-isotope plot that does not pass through normal solar-system Si. In contrast, Si-isotope data from over 100 3-4 micron SiC grains from Murchison from an elongate ellipse enclosing the Stone et al. linear array but also including 'normal' solar-system Si. To investigate whether this difference in Si isotopes indicates different populations of SiC in the two meteorites and to improve the characterization of Orgueil SiC, we used the PANURGE ion microprobe to measure Si, C, N, and Mg isotopes and Al and Na concentrations in a suite of 2-5 micron SiC grains from a new sample of Orgueil.
A reexamination of a piece of the Orgueil meteorite revealed that its amino acid composition is strikingly different to two other carbonaceous chondrites, suggesting different parent bodies. A cometary origin for Orgueil would be one possibility.
Amino acid analyses using HPLC of pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna have found that beta-alanine, glycine, and gamma-amino-n-butyric acid (ABA) are the most abundant amino acids in these two meteorites, with concentrations ranging from approx. 600 to 2,000 parts per billion (ppb). Other alpha-amino acids such as alanine, alpha-ABA, alpha-aminoisobutyric acid (AIB), and isovaline are present only in trace amounts (less than 200 ppb). Carbon isotopic measurements of beta-alanine and glycine and the presence of racemic (D/L 1) alanine and beta-ABA in Orgueil suggest that these amino acids are extraterrestrial in origin. In comparison to the CM carbonaceous chondrites Murchison and Murray, the amino acid composition of the CIs is strikingly distinct, suggesting that these meteorites came from a different type of parent body, possibly an extinct comet, than did the CM carbonaceous chondrites.