Noble gas study of the Saratov L4 chondrite

Abstract– We have determined the elemental abundances and the isotopic compositions of noble gases in a bulk sample and an HF/HCl residue of the Saratov (L4) chondrite using stepwise heating. The Ar, Kr, and Xe concentrations in the HF/HCl residue are two orders of magnitude higher than those in the bulk sample, while He and Ne concentrations from both are comparable. The residue contains only a portion of the trapped heavy noble gases in Saratov; 40 ± 9% for ³⁶Ar, 58 ± 12% for ⁸⁴Kr, and 48 ± 10% for ¹³²Xe, respectively. The heavy noble gas elemental pattern in the dissolved fraction is similar to that in the residue but has high release temperatures. Xenon isotopic ratios of the HF/HCl residue indicate that there is no Xe‐HL in Saratov, but Ne isotopic ratios in the HF/HCl residue lie on a straight line connecting the cosmogenic component and a composition between Ne‐Q and Ne‐HL. This implies that the Ne isotopic composition of Q has been changed by incorporating Ne‐HL (Huss et al. 1996) or by being mass fractionated during the thermal metamorphism. However, it is most likely that the Ne‐Q in Saratov is intrinsically different from this component in other meteorites. The evidence of this is a lack of correlation between the isotopic ratio of Ne‐Q and petrologic types of meteorites (Busemann et al. 2000). A neutron capture effect was observed in the Kr isotopes, and this process also affected the ¹²⁸Xe/¹³²Xe ratio. The ³He and ²¹Ne exposure ages for the bulk sample are 33 and 35 Ma, respectively.     

The effect of pyridine treatment on phase Q: Orgueil and Allende

Marrocchi et al. (2005) reported that low‐temperature fractions of heavy noble gases were largely removed upon pyridine treatment of the Orgueil CI meteorite. As pyridine is known to induce the swelling of the macromolecular network of organic matter, they concluded that the low‐temperature phase Q is macromolecular organic carbon. However, Busemann et al. (2008) showed that pyridine had no significant effect on the noble gas contents for other very primitive meteorites, such as CM and CR. Therefore, we prepared an HF–HCl residue and the pyridine‐treated residue of Orgueil, and re‐examined the results of Marrocchi et al. (2005) by analyzing all noble gases. We confirmed that heavy noble gases are surely removed by the pyridine treatment, but the degree of the loss of heavy noble gases is generally small, and is even smaller for the lighter noble gases. Furthermore, we could not observe the evidence of Xe isotopic ratios by removing only phase Q after the pyridine treatment. We further prepared the HF–HCl residue and the pyridine‐treated residue of the Allende CV3 meteorite and performed noble gas analyses. For Allende, there is no significant change in the elemental abundances after the pyridine treatment. These results suggest that only Orgueil is special, and it is likely that the gas loss of the Orgueil residue is due to the loss of some kind of organic matter that was formed and that adsorbed the fractionated Q and HL gases during the aqueous alteration within the parent body of Orgueil.     

Effects of aqueous alteration on primordial noble gases and presolar SiC in the carbonaceous chondrite Tagish Lake

Effects of aqueous alteration on primordial noble gas carriers were investigated by analyzing noble gases and determining presolar SiC abundances in insoluble organic matter (IOM) from four Tagish Lake meteorite (C2‐ung.) samples that experienced different degrees of aqueous alteration. The samples contained a mixture of primordial noble gases from phase Q and presolar nanodiamonds (HL, P3), SiC (Ne‐E[H]), and graphite (Ne‐E[L]). The second most altered sample (11i) had a ~2–3 times higher Ne‐E concentration than the other samples. The presolar SiC abundances in the samples were determined from NanoSIMS ion images and 11i had a SiC abundance twice that of the other samples. The heterogeneous distribution of SiC grains could be inherited from heterogeneous accretion or parent body alteration could have redistributed SiC grains. Closed system step etching (CSSE) was used to study noble gases in HNO₃‐susceptible phases in the most and least altered samples. All Ne‐E carried by presolar SiC grains in the most altered sample was released during CSSE, while only a fraction of the Ne‐E was released from the least altered sample. This increased susceptibility to HNO₃ likely represents a step toward degassing. Presolar graphite appears to have been partially degassed during aqueous alteration. Differences in the ⁴He/³⁶Ar and ²⁰Ne/³⁶Ar ratios in gases released during CSSE could be due to gas release from presolar nanodiamonds, with more He and Ne being released in the more aqueously altered sample. Aqueous alteration changes the properties of presolar grains so that they react similar to phase Q in the laboratory, thereby altering the perceived composition of Q.     

Noble gases in chondrules and associated metal‐sulfide‐rich samples: Clues on chondrule formation and the behavior of noble gas carrier phases

Abstract— Chondrules are generally believed to have lost most or all of their trapped noble gases during their formation. We tested this assumption by measuring He, Ne, and Ar in chondrules of the carbonaceous chondrites Allende (CV3), Leoville (CV3), Renazzo (CR2), and the ordinary chondrites Semarkona (LL3.0), Bishunpur (LL3.1), and Krymka (LL3.1). Additionally, metalsulfide‐rich chondrule coatings were measured that probably formed from chondrule metal. Low primordial ²⁰Ne concentrations are present in some chondrules, while even most of them contain small amounts of primordial ³⁶Ar. Our preferred interpretation is that‐in contrast to CAIs‐the heating of the chondrule precursor during chondrule formation was not intense enough to expel primordial noble gases quantitatively. Those chondrules containing both primordial ²⁰Ne and ³⁶Ar show low presolar‐diamond‐like ³⁶Ar/²⁰Ne ratios. In contrast, the metal‐sulfide‐rich coatings generally show higher gas concentrations and Q‐like ³⁶Ar/²⁰Ne ratios. We propose that during metalsilicate fractionation in the course of chondrule formation, the Ar‐carrying phase Q became enriched in the metal‐sulfide‐rich chondrule coatings. In the silicate chondrule interior, only the most stable Ne‐carrying presolar diamonds survived the melting event leading to the low observed ³⁶Ar/²⁰Ne ratios. The chondrules studied here do not show evidence for substantial amounts of fractionated solar‐type noble gases from a strong solar wind irradiation of the chondrule precursor material as postulated by others for the chondrules of an enstatite chondrite.     

Primordial noble gases in “phase Q” in carbonaceous and ordinary chondrites studied by closed‐system stepped etching

Abstract— The HF/HCI‐resistant residues of the chondrites CM2 Cold Bokkeveld, CV3 (ox.) Grosnaja, CO3.4 Lancé, CO3.7 Isna, LL3.4 Chainpur, and H3.7 Dimmitt have been measured by closed‐system stepped etching (CSSE) in order to better characterise the noble gases in “phase Q”, a major carrier of primordial noble gases. All isotopic ratios in phase Q of the different meteorites are quite uniform, except for (²⁰Ne/²²Ne)_Q. As already suggested by precise earlier measurements (Schelhaas et al., 1990; Wieler et al., 1991, 1992), (²⁰Ne/²²Ne)_Q is the least uniform isotopic ratio of the Q noble gases. The data cluster ～10.1 for Cold Bokkeveld and Lancé and 10.7 for Chainpur, Grosnaja, and Dimmitt, respectively. No correlation of (²⁰Ne/²²Ne)_Q with the classification or the alteration history of the meteorites has been found. The Ar, Kr, and Xe isotopic ratios for all six samples are identical within their uncertainties and similar to earlier Q determinations as well as to Ar‐Xe in ureilites. Thus, an unknown process probably accounts for the alteration of the originally incorporated Ne‐Q. The noble gas elemental compositions provide evidence that Q consists of at least two carbonaceous carrier phases “Q1” and “Q2” with slightly distinct chemical properties. Ratios (Ar/Xe)_Q and (Kr/Xe)_Q reflect both thermal metamorphism and aqueous alteration. These parent‐body processes have led to larger depletions of Ar and Kr relative to Xe. In contrast, meteorites that suffered severe aqueous alteration, such as the CM chondrites, do not show depletions of He and Ne relative to Ar but rather the highest (He/Ar)_Q and (Ne/Ar)_Q ratios. This suggests that Q1 is less susceptible to aqueous alteration than Q₂. Both subphases may well have incorporated noble gases from the same reservoir, as indicated by the nearly constant, though very large, depletion of the lighter noble gases relative to solar abundances. However, the elemental ratios show that Q₁ and Q₂ must have acquired (or lost) noble gases in slightly different element proportions. Cold Bokkeveld suggests that Q₁ may be related to presolar graphite. Phases Q₁ and Q₂ might be related to the subphases that have been suggested by Gros and Anders (1977). The distribution of the ²⁰Ne/²²Ne ratios cannot be attributed to the carriers Q₁ and Q₂. The residues of Chainpur and Cold Bokkeveld contain significant amounts of Ne‐E(L), and the data confirm the suggestion of Huss (1997) that the ²²Ne‐E(L) content, and thus the presolar graphite abundances, are correlated with the metamorphic history of the meteorites.     

Infrared,ultraviolet, and electron paramagnetic resonance measurements on presolar diamonds: Implications for optical features and origin

Abstract— Infrared (IR) and ultraviolet (UV) absorption spectra were obtained for diamonds from the Allende and Murchison meteorites. In addition, and for the first time, electron paramagnetic resonance spectra were measured. The IR and UV data confirm the suspicion of Russell et al. (1996) that N in presolar diamonds predominantly appears in the form of dispersed N atoms, as is the case for terrestrial type Ib diamonds. In accordance with other observations, our electron paramagnetic resonance measurements suggest a high H content in presolar diamonds. The presolar diamonds most likely originated in a H‐rich region, an environment in which nanometer‐sized diamonds may be more stable than graphite (Badziag et al., 1990). This adds to the evidence—previously based mainly on the twin microstructures of presolar diamonds (Daulton et al., 1996) and the absence of graphite with the same isotopic composition as presolar diamonds (Anders and Zinner, 1993)—for a homogeneous nucleation of presolar diamonds from a gas phase. Based on our results for detection of diamonds in space, we suggest searching for the N‐induced IR and UV absorption features of type Ib diamonds. Other characteristic diamond features that could also be used to detect diamonds in space are the (‐CH_n) IR absorption features due to H‐coated diamonds, as they are described by Allamandola et al. (1993) and the IR multiphonon absorption features of the diamond lattice. The multiphonon features are very weak (Edwards, 1985), but their intensity increases somewhat with increasing temperature (Collins and Fan, 1954), so perhaps a search for them is not totally hopeless.     

Purely physical separation of a small fraction of the Allende meteorite that is highly enriched in noble gases

Abstract— Fine material that floats during freeze-thaw disaggregation of the Allende meteorite is greatly enriched in noble gases compared to the bulk meteorite. Not only the elemental concentrations, but also most isotopic ratios of the noble gases in this fraction, strongly suggest that this material is very similar to the gas-rich carbonaceous residue isolated from the bulk meteorite by chemical treatment. The only significant difference in noble gas signature between our separated fraction and the chemical residues is that the ¹²⁹Xe/¹³²Xe ratio in the former is significantly lower than that in the latter, which suggests readsorption of ¹²⁹Xe released from the dissolved minerals during the chemical treatment. This is the first time that a gas-rich residue of a meteorite has been separated by a purely physical method alone. We also show that noble gases in phase Q and presolar diamond may be separable physically, although both are closely associated.     

Spallation recoil and age of presolar grains in meteorites

Abstract— We have determined the recoil losses from silicon carbide (SiC) grain‐size fractions of spallation Ne produced by irradiation with 1.6 GeV protons. During the irradiation, the SiC grains were dispersed in paraffin wax in order to avoid reimplantation into neighboring grains. Analysis for spallogenic ²¹Ne of grain‐size separates in the size range 0.3 to 6 μm and comparison with the ²²Na activity of the SiC + paraffin mixture indicates an effective recoil range of 2–3 μm with no apparent effect from acid treatments, which are routinely used in the isolation of meteoritic SiC grains. Our results indicate that the majority of presolar SiC grains in primitive meteorites, which are micrometer‐sized, will have lost essentially all spallogenic Ne produced by cosmic‐ray interaction in the interstellar medium. This argues against the validity of previously published presolar ages of Murchison SiC (～10 to ～130 Ma, increasing with grain size; Lewis et al., 1994), where recoil losses had been based on calculated recoil energies. It is argued that the observed variations in meteoritic SiC grain‐size fractions of ²¹Ne/²²Ne ratios are more likely due to the effects of nucleosynthesis in the He‐burning shell of the parent AGB stars which imposes new boundary conditions on nuclear parameters and stellar models. It is suggested that spallation‐Xe produced on the abundant Ba and REE in presolar SiC, rather than spallogenic Ne, may be a promising approach to the presolar age problem. There is a hint in the currently available Xe data (Lewis et al., 1994) that the large (>1 μm) grains may be younger than the smaller (<1 μm) grains. The retention of spallogenic ²¹Ne produced by the bombardment of SiC grains of different grain sizes with 1.6 GeV protons, avoiding reimplantation into neighboring grains by dispersing the SiC grains in paraffin wax, has been derived from a comparison of mass spectrometrically determined ²¹Ne, retained in the grains, with the ²²Na activity of the grains‐plus‐paraffin mixture. Compared to estimates of retention used in previous attempts to determine presolar ages for SiC (Tang and Anders, 1988b; Lewis et al., 1990, 1994), the results indicate significantly lower values. They do, however, agree with retention as expected from previous measurements of recoil ranges in similar systems (Nyquist et al., 1973; Steinberg and Winsberg, 1974). The prime reason for the discrepancy must lie in the energy of the recoiling nuclei entering in the calculation of retention by Tang and Anders (1988b), which is based on considerations by Ray and Völk (1983). Based on the results, it appears questionable that spallation contributes significantly to the observed variations of ²¹Ne/²²Ne ratios among various SiC grain‐size separates (Lewis et al., 1994). We rather suggest that the variations, just as it has been observed for Kr and Ba already (Lewis et al., 1994; Prombo et al., 1993), have a nucleosynthetic origin. Confirmation needs input of improved nuclear data and stellar models into new network calculations of the nucleosynthesis in AGB stars of elements in the Ne region. Finally we argue that, to determine presolar system irradiation effects, spallation Xe is more favorable than is Ne, primarily because of smaller recoil losses for Xe. Although preliminary estimates hint at the possibility that the larger (>1 μm) grains are younger than the smaller (<1 μm) ones, the major uncertainty for a quantitative evaluation lies in the exact composition of the Xe‐N component thought to originate from the envelope of the SiC grains' parent stars.     

MgAl2O4 spinels from Allende and NWA 763 carbonaceous chondrites: Structural refinement,cooling history,and trace element contents

MgAl₂O₄ spinels from Allende and NWA 763 carbonaceous chondrites were studied by X‐ray single crystal diffraction, SEM, electron microprobe, LA‐ICP‐MS, and Raman spectroscopy. Those from Allende are almost pure, but, in one case, we found a strong FeO_tot zonation. Spinels from NWA 763 show Mg‐Fe²⁺ substitutions. Almost pure MgAl₂O₄ spinels from both meteorites underwent slow cooling and reached their intracrystalline closure temperature (T_c) in the range 460–520 °C. The NWA 763 spinel with higher FeO content shows a T_c of about 720 °C. X‐ray single crystal diffraction and Raman spectroscopy suggest a slow cooling and an ordered structure with trivalent cations in M site and divalent in T site. Among the trace elements, Ti and Co are enriched with respect to the terrestrial analogs, while Mn, Ni, and Sn show intermediate values between different terrestrial occurrences. Vanadium cannot be used as a tracer of extraterrestrial origin as for Cr‐spinels, because its content is similar in extraterrestrial and terrestrial spinels. In the zoned crystal from Allende, Co show a strong zonation similar to that of FeO.     

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.     

A clast of Bali‐like oxidized CV material in the reduced CV chondrite breccia Vigarano

Abstract— The CV (Vigarano‐type) chondrites are a petrologically diverse group of meteorites that are divided into the reduced and the Bali‐like and Allende‐like oxidized subgroups largely based on secondary mineralogy (Weisberg et al., 1997; Krot et al., 1998b). Some chondrules and calcium‐aluminum‐rich inclusions (CAIs) in the reduced CV chondrite Vigarano show alteration features similar to those in Allende: metal is oxidized to magnetite; low‐Ca pyroxene, forsterite, and magnetite are rimmed and veined by ferrous olivine (Fs_40–50); and plagioclase mesostases and melilite are replaced by nepheline and sodalite (Sylvester et al., 1993; Kimura and Ikeda, 1996, 1997, 1998). Our petrographic observations indicate that Vigarano also contains individual chondrules, chondrule fragments, and lithic clasts of the Bali‐like oxidized CV materials. The largest lithic clast (about 1 times 2 cm in size) is composed of opaque matrix, type‐I chondrules (400–2000 μm in apparent diameter) surrounded by coarse‐grained and fine‐grained rims, and rare CAIs. The matrix‐chondrule ratio is about 1.1. Opaque nodules in chondrules in the clast consist of Cr‐poor and Cr‐rich magnetite, Ni‐ and Co‐rich metal, Ni‐poor and Ni‐rich sulfide; low‐Ni metal nodules occur only inside chondrule phenocrysts. Chromium‐poor magnetite is preferentially replaced by fayalite. Chondrule mesostases are replaced by phyllosilicates; low‐Ca pyroxene and olivine phenocrysts appear to be unaltered. Matrix in the clast consists of very fine‐grained (<1 μm) ferrous olivine, anhedral fayalite grains (Fa_80–100), rounded objects of porous Ca‐Fe‐rich pyroxenes (Fs_10–50Wo₅₀), Ni‐poor sulfide, Ni‐ and Co‐rich metal, and phyllosilicates; magnetite is rare. On the basis of the presence of the Bali‐like lithified chondritic clast—in addition to individual chondrules and CAIs of both Bali‐like and Allende‐like materials—in the reduced CV chondrite Vigarano, we infer that (1) all three types of materials were mixed during regolith gardening on the CV asteroidal body, and (2) the reduced and oxidized CV materials may have originated from a single, heterogeneously altered asteroid.     

Reaction of Q to thermal metamorphism in parent bodies: Experimental simulation

Planetary noble gases in chondrites are concentrated in an unidentified carrier phase, called “Q.” Phase Q oxidized at relatively low temperature in pure oxygen is a very minor part of insoluble organic matter (IOM), but has not been separated in a pure form. High‐pressure (HP) experiments have been used to test the effects of thermal metamorphism on IOM from the Orgueil (CI1) meteorite, at conditions up to 10 GPa and 700 °C. The effect of the treatment on carbon structural order was characterized by Raman spectroscopy of the carbon D and G bands. The Raman results show that the IOM becomes progressively more graphite‐like with increasing intensity and duration of the HP treatment. The carbon structural transformations are accompanied by an increase in the release temperatures for IOM carbon and ³⁶Ar during stepped combustion (the former to a greater extent than the latter for the most HP treated sample) when compared with the original untreated Orgueil (CI1) sample. The ³⁶Ar/C ratio also appears to vary in response to HP treatment. Since ³⁶Ar is a part of Q, its release temperature corresponds to that for Q oxidation. Thus, the structural transformations of Q and IOM upon HP treatment are not equal. These results correspond to observations of thermal metamorphism in the meteorite parent bodies, in particular those of type 4 enstatite chondrites, e.g., Indarch (EH4), where graphitized IOM oxidized at significantly higher temperatures than Q (Verchovsky et al. 2002 ). Our findings imply that Q is less graphitized than most of the macromolecular carbonaceous material present during parent body metamorphism and is thus a carbonaceous phase distinct from other meteoritic IOM.     

Noble gas studies in CAIs from CV3 chondrites: No evidence for primordial noble gases

Abstract— Calcium‐aluminum‐rich inclusions (CAIs) were among the first solids in the solar system and were, similar to chondrules, created at very high temperatures. While in chondrules, trapped noble gases have recently been detected, the presence of trapped gases in CAIs is unclear but could have important implications for CAI formation and for early solar system evolution in general. To reassess this question, He, Ne, and Ar isotopes were measured in small, carefully separated and, thus, uncontaminated samples of CAIs from the CV3 chondrites Allende, Axtell, and Efremovka. The ²⁰Ne/²²Ne ratios of all CAIs studied here are <0.9, indicating the absence of trapped Ne as, e.g., Ne‐HL, Ne‐Q, or solar wind Ne. The ²¹Ne/²²Ne ratios range from 0.86 to 0.72, with fine‐grained, more altered CAIs usually showing lower values than coarse‐grained, less altered CAIs. This is attributed to variable amounts of cosmogenic Ne produced from Na‐rich alteration phases rather than to the presence of Ne‐G or Ne‐R (essentially pure ²²Ne) in the samples. Our interpretation is supported by model calculations of the isotopic composition of cosmogenic Ne in minerals common in CAIs. The ³⁶Ar/³⁸Ar ratios are between 0.7 and 4.8, with fine‐grained CAIs within one meteorite showing higher ratios than the coarse‐grained ones. This agrees with higher concentrations of cosmogenic ³⁶Ar produced by neutron capture on ³⁵Cl with subsequent β^?‐decay in finer‐grained, more altered, and thus, more Cl‐rich CAIs than in coarser‐grained, less altered ones. Although our data do not strictly contradict the presence of small amounts of Ne‐G, Ne‐R, or trapped Ar in the CAIs, our noble gas signatures are most simply explained by cosmogenic production, mainly from Na‐, Ca‐, and Cl‐rich minerals.     

Search for extinct aluminum‐26 and titanium‐44 in nanodiamonds from the Allende CV3 and Murchison CM2 meteorites

Abstract– We report Mg‐Al and Ca‐Ti isotopic data for meteoritic nanodiamonds separated from the Allende CV3 and Murchison CM2 meteorites. The goal of this study was to search for excesses in ²⁶Mg and ⁴⁴Ca, which can be attributed to the in situ decay of radioactive and now extinct ²⁶Al and ⁴⁴Ti, respectively. Previous work on presolar SiC and graphite had shown that ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios in presolar grains can be used to discriminate between different types of stellar sources. Aluminum and Ti concentrations are low in the meteoritic nanodiamonds of this study. Murchison nanodiamonds have higher Al and Ti concentrations than the Allende nanodiamonds. This can be attributed to contamination and the presence of presolar SiC in the Murchison nanodiamond samples. ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca ratios are close to normal in Allende nanodiamonds with upper limits on the initial ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios of approximately 1 × 10^?3. These ratios are factors of 10–1000 and, respectively, 1–1000 lower than those of presolar SiC and graphite grains from supernovae. The ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti data for nanodiamonds are compatible with an asymptotic giant branch star or solar system origin, but not with a supernova origin of a major fraction of meteoritic nanodiamonds. The latter possibility cannot be excluded, though, as the diamond separates may contain significant amounts of contaminating Al and Ti, which would lower the inferred ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios considerably.     

Origins of meteoritic nanodiamonds investigated by coordinated atom‐probe tomography and transmission electron microscopy studies

To constrain the origins of meteoritic nanodiamonds, the abundance ratios of stable C isotopes in acid residues from the carbonaceous chondritic meteorite Allende CV3 were measured using coordinated atom‐probe tomography (APT) and transmission electron microscopy (TEM). We combined our data with previously published APT data. A statistical analysis of this combined data set suggests an upper bound of 1 in 10² on the subpopulation that could have a large isotopic enrichment in ¹³C relative to ¹²C, consistent with the possible detection by secondary ion mass spectrometry of a similar enrichment in a 1 in 10⁵ fraction, abundant enough to account for the Xe‐HL anomalous isotopic component carried by the acid residues. Supernovae are believed to be the source of Xe‐HL, leading to the mystery of why all other supernova minerals do not carry Xe‐HL. The lack of Xe‐HL in low‐density disordered supernova graphite suggests that the isotopically anomalous component is the nanodiamonds, but the disordered C in the residue is not ruled out. We discuss possible origins of the disordered C and implications of our results for proposed formation scenarios for nanodiamonds. At least 99% of the meteoritic acid residue exhibits no unambiguous evidence of presolar formation, although production with solar isotope ratios in asymptotic giant branch stars is not ruled out. Comparison of TEM and APT results indicates that a minority of the APT reconstructions may preferentially sample disordered C rather than nanodiamonds. If this is the case, a presolar origin for a larger fraction of the nanodiamonds remains possible.     

Formation of orange hibonite,as inferred from some Allende inclusions

Abstract— We studied three fluffy Type A refractory inclusions from Allende that contain orange hibonite. The melilite in the present samples is very Al‐rich, averaging Åk₆, Åk₁₄, and Åk₁₂ in the three samples studied. Hibonite in two inclusions, unlike that in Murchison, has low rare earth element abundances of <10 × CI; in the other inclusion, the hibonite, melilite and perovskite have Group II‐like patterns. The hibonite and melilite in all three inclusions studied have excess ²⁶Mg consistent with (²⁶Al/²⁷Al)_I = 5 × 10^?5. Much of the hibonite and some of the spinel in these inclusions is corroded. These phases are found enclosed in melilite, but based on bulk compositions and phase equilibria, hibonite should not be an early‐crystallizing phase in these inclusions. We conclude that the hibonite and probably some of the spinel is relic. Reversely zoned melilite, rounded spinel and isotopically heavy Mg in the inclusions probably reflect reheating events that involved melting and evaporation. Alteration of the gehlenitic melilite gave rise to some rare phases, including corundum and nearly pure CaTs pyroxene. Studies have shown that blue hibonite contains Ti³⁺ while orange hibonite does not (Ihinger and Stolper, 1986; Beckett et al., 1988). Orange hibonite formed either under oxidizing conditions (such as at oxygen fugacities at least seven orders of magnitude greater than that of a solar gas at 1700 K), or under conditions reducing enough (e.g., solar) that it contained Ti³⁺, which was later oxidized in situ. Although V and Ce oxides are volatile at the temperature and range of oxygen fugacities at which orange hibonite is known to be stable, we find that (a) the hibonite is V‐rich (～1 wt% V₂O₃) and (b) there are no negative Ce anomalies in Allende hibonite. This indicates that the hibonite did not form by condensation under oxidizing conditions. In addition, there are slight excesses of Ti + Si cations relative to Mg + Fe cations (up to 0.1 of 0.8 cations per 19 oxygen anions), probably reflecting the original presence of Ti³⁺. The results of this study strongly support the suggestion (Ihinger and Stolper, 1986) that Allende hibonite originally formed under reducing conditions and was later oxidized. Oxygen fugacities within ～2–3 orders of magnitude of that of a solar gas are implied; otherwise, strong Ce and V depletions would be observed.     

Carbon,Oxygen, Silicon,Sulphur, Calcium,and Iron Determinations in Twenty-four Dark Clasts and One Dark Inclusion of the Allende Meteorite by 12C(d,p)13C Nuclear Reaction and PIXE

Abstract— A study of carbon contents of millimeter-sized dark clasts and of one dark inclusion of the Allende meteorite with the ¹³C(d,P₀)¹³C method has been undertaken. The results show that C in dark Allende areas varies, perhaps in a “clustered” fashion, from near 0.3%, which is essentially the bulk C-content of the meteorite, to at least 2.1% in the dark rim of a dark inclusion. At least one cluster has now been identified with C-contents in the range 0.4%-0.5%. Raman spectra of C in the dark inclusion ADIR 4E1-fu and in matrix have also been determined. These are identical. Our results are consistent with a comparatively low temperature origin of essentially all elemental carbon in Allende.     

Ionized nitrogen mono‐hydride bands are identified in the presolar and carbonado diamond spectra

Abstract– None of the well‐established nitrogen‐related IR absorption bands, common in synthetic and terrestrial diamonds, have been identified in the presolar diamond spectra. In the carbonado diamond spectra, only the single nitrogen impurity (C center) is identified and the assignments of the rest of the nitrogen‐related bands are still debated. It is speculated that the unidentified bands in the nitrogen absorption region are not induced by nitrogen, but rather by nitrogen‐hydrides because in the interstellar environment, nitrogen reacts with hydrogen and forms NH⁺; NH; NH₂; NH_3. Among these hydrides, the electronic configuration of NH⁺ is the closest to carbon. Thus, this ionized nitrogen‐mono‐hydride is the best candidate to substitute carbon in the diamond structure. The bands of the substitutional NH⁺ defect are deduced by redshifting the irradiation‐induced N⁺ bands due to the mass of the additional hydrogen. The six bands of the NH⁺ defects are identified in both the presolar and the carbonado diamond spectra. The new assignments identify all of the nitrogen‐related bands in the spectra, indicating that presolar and carbonado diamonds contain only single nitrogen impurities.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.     

He and Ne in individual chromite grains from the regolith breccia Ghubara (L5): Exploring the history of the L chondrite parent body regolith

We analyzed He and Ne in chromite grains from the regolith breccia Ghubara (L5), to compare it with He and Ne in sediment‐dispersed extraterrestrial chromite (SEC) grains from mid‐Ordovician sediments. These SEC grains arrived on Earth as micrometeorites in the aftermath of the L chondrite parent body (LCPB) breakup event, 470 Ma ago. A significant fraction of them show prolonged exposure to galactic cosmic rays for up to several 10 Ma. The majority of the cosmogenic noble gases in these grains were probably acquired in the regolith of the LCPB (Meier et al. 2010 ). Ghubara, an L chondritic regolith breccia with an Ar‐Ar shock age of 470 Ma, is a sample of that regolith. We find cosmic‐ray exposure ages of up to several 10 Ma in some Ghubara chromite grains, confirming for the first time that individual chromite grains with such high exposure ages indeed existed in the LCPB regolith, and that the >10 Ma cosmic‐ray exposure ages found in recent micrometeorites are thus not necessarily indicative of an origin in the Kuiper Belt. Some Ghubara chromite grains show much lower concentrations of cosmogenic He and Ne, indicating that the 4π (last‐stage) exposure age of the Ghubara meteoroid lasted only 4–6 Ma. This exposure age is considerably shorter than the 15–20 Ma suggested before from bulk analyses, indicating that bulk samples have seen regolith pre‐exposure as well. The shorter last‐stage exposure age probably links Ghubara to a small peak of ⁴⁰Ar‐poor L5 chondrites of the same exposure age. Furthermore, and quite unexpectedly, we find a Ne component similar to presolar Ne‐HL in the chromite grains, perhaps indicating that some presolar Ne can be preserved even in meteorites of petrologic type 5.