Petrography,stable isotope compositions,microRaman spectroscopy,and presolar components of Roberts Massif 04133: A reduced CV3 carbonaceous chondrite

Here, we report the mineralogy, petrography, C‐N‐O‐stable isotope compositions, degree of disorder of organic matter, and abundances of presolar components of the chondrite Roberts Massif (RBT) 04133 using a coordinated, multitechnique approach. The results of this study are inconsistent with its initial classification as a Renazzo‐like carbonaceous chondrite, and strongly support RBT 04133 being a brecciated, reduced petrologic type >3.3 Vigarano‐like carbonaceous (CV) chondrite. RBT 04133 shows no evidence for aqueous alteration. However, it is mildly thermally altered (up to approximately 440 °C); which is apparent in its whole‐rock C and N isotopic compositions, the degree of disorder of C in insoluble organic matter, low presolar grain abundances, minor element compositions of Fe,Ni metal, chromite compositions and morphologies, and the presence of unequilibrated silicates. Sulfides within type I chondrules from RBT 04133 appear to be pre‐accretionary (i.e., did not form via aqueous alteration), providing further evidence that some sulfide minerals formed prior to accretion of the CV chondrite parent body. The thin section studied contains two reduced CV3 lithologies, one of which appears to be more thermally metamorphosed, indicating that RBT 04133, like several other CV chondrites, is a breccia and thus experienced impact processing. Linear foliation of chondrules was not observed implying that RBT 04133 did not experience high velocity impacts that could lead to extensive thermal metamorphism. Presolar silicates are still present in RBT 04133, although presolar SiC grain abundances are very low, indicating that the progressive destruction or modification of presolar SiC grains begins before presolar silicate grains are completely unidentifiable.     

Zoned chondrules in Semarkona: Evidence for high‐ and low‐temperature processing

Abstract— At least 15% of the low‐FeO chondrules in Semarkona (LL3.0) have mesostases that are concentrically zoned in Na, with enrichments near the outer margins. We have studied zoned chondrules using electron microprobe methods (x‐ray mapping plus quantitative analysis), ion microprobe analysis for trace elements and hydrogen isotopes, cathodoluminescence imaging, and transmission electron microscopy in order to determine what these objects can tell us about the environment in which chondrules formed and evolved. Mesostases in these chondrules are strongly zoned in all moderately volatile elements and H (interpreted as water). Calcium is depleted in areas of volatile enrichment. Titanium and Cr generally decrease toward the chondrule surfaces, whereas Al and Si may either increase or decrease, generally in opposite directions to one another; Mn follows Na in some chondrules but not in others; Fe and Mg are unzoned. D/H ratios increase in the water‐rich areas of zoned chondrules. Mesostasis shows cathodoluminescence zoning in most zoned chondrules, with the brightest yellow color near the outside. Mesostasis in zoned chondrules appears to be glassy, with no evidence for devitrification. Systematic variations in zoning patterns among pyroxene‐ and olivine‐rich chondrules may indicate that fractionation of low‐ and high‐Ca pyroxene played some role in Ti, Cr, Mn, Si, Al, and some Ca zoning. But direct condensation of elements into hot chondrules, secondary melting of late condensates into the outer portions of chondrules, and subsolidus diffusion of elements into warm chondrules cannot account for the sub‐parallel zoning profiles of many elements, the presence of H₂O, or elemental abundance patterns. Zoning of moderately volatile elements and Ca may have been produced by hydration of chondrule glass without devitrification during aqueous alteration on the parent asteroid. This could have induced structural changes in the glass allowing rapid diffusion and exchange of elements between altered glass and surrounding matrix and rim material. Calcium was mainly lost during this process, and other nonvolatile elements may have been mobile as well. Some unzoned, low‐FeO chondrules appear to have fully altered mesostasis.     

The insoluble carbonaceous material of CM chondrites: A possible source of discrete organic compounds under hydrothermal conditions

Abstract— We report on the molecular analyses of the water‐ and solvent‐soluble organic compounds released from the insoluble organic material (IOM) of the Murray meteorite upon treatment with weight‐equivalent amounts of water and under conditions of elevated temperature and pressure. A varied suite of compounds was identified by gas chromatography‐mass spectrometry (GC‐MS). C₃‐C₁₇ alkyl dicarboxylic acids and N‐ and O‐containing hydroaromatic and aromatic compounds were found in the water extracts. The solvent extracts contained N‐, O‐, and S‐containing aromatic compounds, a large number of their isomers and homologs, and a series of polycyclic aromatic hydrocarbons (PAHs) of up to five rings, together with noncondensed aromatic species such as substituted benzenes, biphenyl, and terphenyls as well as their substituted homologs, and hydrated PAHs. Isotopic analyses showed that residue IOMs after hydrothermal treatment had lower deuterium and ¹⁵N content than the untreated material (ΔD = ?833‰ and Δ¹⁵N = ?24.1) but did not differ from it in ¹³C composition. The effect of the hydrothermolytic release was recorded in significant differences between the NMR spectra of untreated and residue IOM. A possible relation to common precursors for the dicarboxylic acids found in the IOM and bulk extracts is discussed.     

Compositional diversity in insoluble organic matter in type 1, 2 and 3 chondrites as detected by infrared spectroscopy

Insoluble organic matter (IOM) isolated from 22 carbonaceous and ordinary chondrites spanning a wide range of groups and petrologic types were analyzed using Fourier transform infrared spectroscopy (FTIR). Based on common IR spectral features, it is observed that IOM falls into 4 molecularly distinct groups (designated here as A through D). Spectral group A includes type 1 and 2 chondrites and exhibits intense aliphatic C-H and carboxyl vibrational peaks. Spectral group B includes the least metamorphosed type 3 chondrites and Tagish Lake, and exhibits weaker aliphatic and carboxyl vibrational intensity. Spectral groups C and D include metamorphosed type ?3.1 chondrites and a heated CM chondrite. The carbonyl stretching features in spectral groups C and D differ from that in spectral groups A and B and from each other. In spectral group C, the carbonyl stretching is assigned to cyclic unsaturated lactones; in spectral group D carbonyl exists predominantly in the form of unsaturated ketone moieties. Both spectral groups C and D have a relatively narrow band structure around 1210 cm⁻¹ (assigned to aromatic skeletal modes) as compared with spectral groups A and B, which is consistent with the formation of more condensed aromatics by extensive thermal metamorphism. The differences in carbonyl structures in spectral groups C and D are not the result of different effective metamorphic temperatures, rather these differences likely result from variation in the activity of water and oxygen at different stages of parent body metamorphism. Such environmental variations must be local phenomena in the parent bodies as there is no correlation between spectral grouping and chondrite class or group.     

Questions,questions: Can the contradictions between the petrologic,isotopic, thermodynamic,and astrophysical constraints on chondrule formation be resolved?

Abstract– Here, we show that several geochemical indicators point to number densities during chondrule formation that were far higher than can be accounted for by known nebula processes. The number densities implied by compound chondrules and nonspherical chondrules are shown to be significantly higher than estimated in previous studies. At the implied chondrule number densities, if a chondrule formation region survived a formation event it would have been gravitationally bound and would have collapsed quite rapidly to form an asteroidal‐sized body. The diversity of chondrule compositions and textures in a chondrite group could have formed in a single event in subvolumes of a formation region that were chemically isolated from one another because of slow diffusion in the gas. Within these subvolumes, equilibration between chondrules with different compositions would have been fairly rapid, although small isotopic mass fractionations in elements like Fe, Si, Mg, and O may persist. This could explain the existence of the small isotopic mass fractionations in these elements that have been observed in chondrules. However, the evidence for recycling of chondrules requires that there was more than one chondrule formation event prior to formation of a parent asteroid. Finally, we argue that OC and CO chondrule Mg‐Al systematics are both consistent with single ages or narrow ranges of ages, and that the CO, and possibly the OC, ages date parent body alteration. This would resolve the conundrum of needing to preserve in a turbulent nebula physically and chemically distinct CO and OC chondrule populations for 1–2 Myr.     

Mass-dependent fractionation of Mg, Si, and Fe isotopes in five stony cosmic spherules

We have measured with an electron microprobe the Mg, Al, Si, Ca, Ti, Mn, and Fe contents of five strongly heated stony cosmic spherules (sCS) from the South Pole water well. We have also measured the isotopic compositions of Si, and when possible of Mg and of Fe in these objects by ion microprobe. Except for iron, the measured elemental compositions are chondritic within a factor of 2. In four samples, the ratio of ⁵⁷Fe/⁵⁶Fe exceeds the terrestrial value by 3.5‰ to 48‰. Mass-dependent fractionation of the isotopes of Si ranges from ∼2 to ∼8 ‰/AMU in three samples. Mg is clearly fractionated in only one sample, for which δ²⁵Mg = ∼8 ‰. The extent of mass-dependent fractionation of the isotopes and, by implication, of evaporative loss generally follows a trend Mg < Si < Fe. The trend is similar to that found in laboratory heating experiments of charges with solar composition. Although the observed isotopic inhomogeneities within some samples call into question the strict validity of the Rayleigh equation for the sCS, its approximate application to our new and to previously published results for Mg suggests that evaporative losses of greater than 40 wt.% occur rarely from sCS, and that the precursor grains of the sCS had a CM-carbonaceous-chondrite-like complement of Mg, Si, Ca, and Al. Low Fe contents relative to CM abundances could reflect an unusual precursor composition, or, more probably, losses by processes that did not fractionate isotopes, i.e., ejection of immiscible FeS and FeNi beads from the melt or rapid, complete separation and decomposition of FeS at the surface.     

NMR studies of chemical structural variation of insoluble organic matter from different carbonaceous chondrite groups

Solid-state ¹H and ¹³C Nuclear Magnetic Resonance (NMR) spectroscopic experiments have been performed on isolated meteoritic Insoluble Organic Matter (IOM) spanning four different carbonaceous chondrite meteorite groups; a CR2 (EET92042), a CI1 (Orgueil), a CM2 (Murchison), and the unique C2 meteorite, Tagish Lake. These solid state NMR experiments reveal considerable variation in bulk organic composition across the different meteorite group’s IOM. The fraction of aromatic carbon increases as CR2 < CI1 < CM2 < Tagish Lake. The increases in aromatic carbon are offset by reductions in aliphatic (sp³) carbon moieties, e.g., “CH_x,” and “CH_x(O,N).” Oxidized sp² bonded carbon, e.g., carboxyls and ketones grouped as “CO,” are largely conservative across these meteorite groups. Single pulse (SP) ¹³C magic angle spinning (MAS) NMR experiments reveal the presence of nanodiamonds with an apparent concentration ranking in the IOM of CR2 < CI1 < CM2 < Tagish Lake. A pair of independent NMR experiments reveals that, on average, the aromatic moieties in the IOM of all four meteoritic IOM fractions are highly substituted. Fast spinning SP ¹H MAS NMR spectral data combined with other NMR experimental data reveal that the average hydrogen content of sp³ bonded carbon functional groups is low, requiring a high degree of aliphatic chain branching in each IOM fraction. The variation in chemistry across the meteorite groups is consistent with alteration by low temperature chemical oxidation. It is concluded that such chemistry principally affected the aliphatic moieties whereas the aromatic moieties and nanodiamonds may have been largely unaffected.     

Organics preserved in anhydrous interplanetary dust particles: Pristine or not?

The chondritic‐porous subset of interplanetary dust particles (CP‐IDPs) are thought to have a cometary origin. Since the CP‐IDPs are anhydrous and unaltered by aqueous processes that are common to chondritic organic matter (OM), they represent the most pristine material of the solar system. However, the study of IDP OM might be hindered by their further alteration by flash heating during atmospheric entry, and we have limited understanding on how short‐term heating influences their organic content. In order to investigate this problem, five CP‐IDPs were studied for their OM contents, distributions, and isotopic compositions at the submicro‐ to nanoscale levels. The OM contained in the IDPs in this study spans the spectrum from primitive OM to that which has been significantly processed by heat. Similarities in the Raman D bands of the meteoritic and IDP OMs indicate that the overall gain in the sizes of crystalline domains in response to heating is similar. However, the Raman Γ_G values of the OM in all of the five IDPs clearly deviate from those of chondritic OM that had been processed during a prolonged episode of parent body heating. Such disparity suggests that the nonaromatic contents of the OM are different. Short duration heating further increases the H/C ratio and reduces the δ¹³C and δD values of the IDP OM. Our findings suggest that IDP OM contains a significant proportion of disordered C with low H content, such as sp² olefinic C=C, sp³ C–C, and/or carbonyl contents as bridging material.     

Comparison of FT‐IR spectra of bulk and acid insoluble organic matter in chondritic meteorites: An implication for missing carbon during demineralization

Past studies of the various separable carbonaceous fractions have been unable to account for all of C in primitive chondrites. In particular, up to 20–50% of the C is lost during acid leaching of bulk samples even after the C in carbonates and soluble organic matter is accounted for. To try to better characterize the nature of this “missing C,” we have compared the bulk infrared (IR) absorption spectra of a number of primitive chondrites with those of their previously reported insoluble organic matter (IOM). The aliphatic C–H stretching bands, in particular, allow us to compare the molecular structures of bulk C with that of IOM. The spectral differences between bulk C and IOM reflect “missing C” phases that were lost during acid leaching, although we cannot completely exclude the possibility that the OM was modified after demineralization. Comparing IR spectra of bulk meteorite powder and IOM suggests that the missing C varies in its molecular structure, and that mildly thermally metamorphosed type 3 chondrites tend to be richer in an aliphatic fraction with lower CH₂/CH₃ ratios, relative to IOM, compared to aqueously altered carbonaceous chondrites (CI/CM/CR). The missing C is most likely released from acid‐labile functional groups, such as esters, acetals, and amides, during demineralization, although it cannot be ruled out that some fraction of the missing C is in small grains that are difficult to recover from suspension, or in water‐soluble compounds trapped in phyllosilicates.     

Isotopic and chemical variation of organic nanoglobules in primitive meteorites

Organic nanoglobules are microscopic spherical carbon‐rich objects present in chondritic meteorites and other astromaterials. We performed a survey of the morphology, organic functional chemistry, and isotopic composition of 184 nanoglobules in insoluble organic matter (IOM) residues from seven primitive carbonaceous chondrites. Hollow and solid nanoglobules occur in each IOM residue, as well as globules with unusual shapes and structures. Most nanoglobules have an organic functional chemistry similar to, but slightly more carboxyl‐rich than, the surrounding IOM, while a subset of nanoglobules have a distinct, highly aromatic functionality. The range of nanoglobule N isotopic compositions was similar to that of nonglobular ¹⁵N‐rich hotspots in each IOM residue, but nanoglobules account for only about one third of the total ¹⁵N‐rich hotspots in each sample. Furthermore, many nanoglobules in each residue contained no ¹⁵N enrichment above that of bulk IOM. No morphological indicators were found to robustly distinguish the highly aromatic nanoglobules from those that have a more IOM‐like functional chemistry, or to distinguish ¹⁵N‐rich nanoglobules from those that are isotopically normal. The relative abundance of aromatic nanoglobules was lower, and nanoglobule diameters were greater, in more altered meteorites, suggesting the creation/modification of IOM‐like nanoglobules during parent‐body processing. However, ¹⁵N‐rich nanoglobules, including many with highly aromatic functional chemistry, likely reflect preaccretionary isotopic fractionation in cold molecular cloud or protostellar environments. These data indicate that no single formation mechanism can explain all of the observed characteristics of nanoglobules, and their properties are likely a result of multiple processes occurring in a variety of environments.