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.     

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.     

Structure,composition, and location of organic matter in the enstatite chondrite Sahara 97096 (EH3)

Abstract– The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine‐grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar δ¹⁵N and δ¹³C; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium‐heterogeneity and having mean H‐ and N‐isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer‐sized areas highly enriched in ¹⁵N (δ¹⁵N up to 1600‰). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.     

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.     

Coordinated mineralogical and isotopic analyses of a cosmic symplectite discovered in a comet 81P/Wild 2 sample

We have discovered in a Stardust mission terminal particle a unique mineralogical assemblage of symplectically intergrown pentlandite ((Fe,Ni)₉S₈) and nanocrystalline maghemite (γ‐Fe₂O₃). Mineralogically similar cosmic symplectites (COS) have only been found in the primitive carbonaceous chondrite Acfer 094 and are believed to have formed by aqueous alteration. The O and S isotopic compositions of the Wild 2 COS are indistinguishable from terrestrial values. The metal and sulfide precursors were thus oxidized by an isotopically equilibrated aqueous reservoir either inside the snow line, in the Wild 2 comet, or in a larger Kuiper Belt object. Close association of the Stardust COS with a Kool mineral assemblage (kosmochloric Ca‐rich pyroxene, FeO‐rich olivine, and albite) that likely originated in the solar nebula suggests the COS precursors also had a nebular origin and were transported from the inner solar system to the comet‐forming region after they were altered.     

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 molecular and isotopic study of the macromolecular organic matter of the ungrouped C2 WIS 91600 and its relationship to Tagish Lake and PCA 91008

Abstract– Insight into the chemical history of an ungrouped type 2 carbonaceous chondrite meteorite, Wisconsin Range (WIS) 91600, is gained through molecular analyses of insoluble organic matter (IOM) using solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy, X‐ray absorption near edge structure spectroscopy (XANES), and pyrolysis‐gas chromatography coupled with mass spectrometry (pyr‐GC/MS), and our previous bulk elemental and isotopic data. The IOM from WIS 91600 exhibits similarities in its abundance and bulk δ¹⁵N value with IOM from another ungrouped carbonaceous chondrite Tagish Lake, while it exhibits H/C, δ¹³C, and δD values that are more similar to IOM from the heated CM, Pecora Escarpment (PCA) 91008. The ¹³C NMR spectra of IOM of WIS 91600 and Tagish Lake are similar, except for a greater abundance of CH_xO species in the latter and sharper carbonyl absorption in the former. Unusual cross‐polarization (CP) dynamics is observed for WIS 91600 that indicate the presence of two physically distinct organic domains, in which the degrees of aromatic condensation are distinctly different. The presence of two different organic domains in WIS 91600 is consistent with its brecciated nature. The formation of more condensed aromatics is the likely result of short duration thermal excursions during impacts. The fact that both WIS 91600 and PCA 91008 were subjected to short duration heating that is distinct from the thermal history of type 3 chondrites is confirmed by Carbon‐XANES. Finally, after being briefly heated (400 °C for 10 s), the pyrolysis behavior of Tagish Lake IOM is similar to that of WIS 91600 and PCA 91008. We conclude that WIS 91600 experienced very moderate, short duration heating at low temperatures (<500 °C) after an episode of aqueous alteration under conditions that were similar to those experienced by Tagish Lake.     

Iron oxides in comet 81P/Wild 2

Abstract– We have used synchrotron Fe‐XANES, XRS, microRaman, and SEM‐TEM analyses of Stardust track 41 slice and track 121 terminal area slices to identify Fe oxide (magnetite‐hematite and amorphous oxide), Fe‐Ti oxide, and V‐rich chromite (Fe‐Cr‐V‐Ti‐Mn oxide) grains ranging in size from 200 nm to ～10 μm. They co‐exist with relict FeNi metal. Both Fe‐XANES and microRaman analyses suggest that the FeNi metal and magnetite (Fe₂O₃FeO) also contain some hematite (Fe₂O₃). The FeNi has been partially oxidized (probably during capture), but on the basis of our experimental work with a light‐gas gun and microRaman analyses, we believe that some of the magnetite‐hematite mixtures may have originated on Wild 2. The terminal samples from track 121 also contain traces of sulfide and Mg‐rich silicate minerals. Our results show an unequilibrated mixture of reduced and oxidized Fe‐bearing minerals in the Wild 2 samples in an analogous way to mineral assemblages seen in carbonaceous chondrites and interplanetary dust particles. The samples contain some evidence for terrestrial contamination, for example, occasional Zn‐bearing grains and amorphous Fe oxide in track 121 for which evidence of a cometary origin is lacking.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.     

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.     

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.     

Petrology,mineralogy, and oxygen isotope compositions of aluminum‐rich chondrules from CV3 chondrites

Bulk major element composition, petrography, mineralogy, and oxygen isotope compositions of twenty Al‐rich chondrules (ARCs) from five CV3 chondrites (Northwest Africa [NWA] 989, NWA 2086, NWA 2140, NWA 2697, NWA 3118) and the Ningqiang carbonaceous chondrite were studied and compared with those of ferromagnesian chondrules and refractory inclusions. Most ARCs are marginally Al‐richer than ferromagnesian chondrules with bulk Al₂O₃ of 10–15 wt%. ARCs are texturally similar to ferromagnesian chondrules, composed primarily of olivine, pyroxene, plagioclase, spinel, Al‐rich glass, and metallic phases. Minerals in ARCs have intermediate compositions. Low‐Ca pyroxene (Fs_0.6–8.8Wo_0.7–9.3) has much higher Al₂O₃ and TiO₂ contents (up to 12.5 and 2.3 wt%, respectively) than that in ferromagnesian chondrules. High‐Ca pyroxene (Fs_0.3–2.0Wo_33–54) contains less Al₂O₃ and TiO₂ than that in Ca,Al‐rich inclusions (CAIs). Plagioclase (An_77–99Ab_1–23) is much more sodic than that in CAIs. Spinel is enriched in moderately volatile element Cr (up to 6.7 wt%) compared to that in CAIs. Al‐rich enstatite coexists with anorthite and spinel in a glass‐free chondrule, implying that the formation of Al‐enstatite was not due to kinetic reasons but is likely due to the high Al₂O₃/CaO ratio (7.4) of the bulk chondrule. Three ARCs contain relict CAIs. Oxygen isotope compositions of ARCs are also intermediate between those of ferromagnesian chondrules and CAIs. They vary from ?39.4‰ to 13.9‰ in δ¹⁸O and yield a best fit line (slope = 0.88) close to the carbonaceous chondrite anhydrous mineral (CCAM) line. Chondrules with 5–10 wt% bulk Al₂O₃ have a slightly more narrow range in δ¹⁸O (?32.5 to 5.9‰) along the CCAM line. Except for the ARCs with relict phases, however, most ARCs have oxygen isotope compositions (>?20‰ in δ¹⁸O) similar to those of typical ferromagnesian chondrules. ARCs are genetically related to both ferromagnesian chondrules and CAIs, but the relationship between ARCs and ferromagnesian chondrules is closer. Most ARCs were formed during flash heating and rapid cooling processes like normal chondrules, only from chemically evolved precursors. ARCs extremely enriched in Al and those with relict phases could have had a hybrid origin (Krot et al. 2002) which incorporated refractory inclusions as part of the precursors in addition to ferromagnesian materials. The occurrence of melilite in ARCs indicates that melilite‐rich CAIs might be present in the precursor materials of ARCs. The absence of melilite in most ARCs is possibly due to high‐temperature interactions between a chondrule melt and the solar nebula.     

Heavily metamorphosed clasts from the CV chondrite breccias Mokoia and Yamato‐86009

Abstract– Metamorphosed clasts in the CV carbonaceous chondrite breccias Mokoia and Yamato‐86009 (Y‐86009) are coarse‐grained, granular, polymineralic rocks composed of Ca‐bearing (up to 0.6 wt% CaO) ferroan olivine (Fa_34–39), ferroan Al‐diopside (Fs_9–13Wo_47–50, approximately 2–7 wt% Al₂O₃), plagioclase (An_37–84Ab_63–17), Cr‐spinel (Cr/(Cr + Al) = 0.19–0.45, Fe/(Fe + Mg) = 0.60–0.79), nepheline, pyrrhotite, pentlandite, Ca‐phosphate, and rare grains of Ni‐rich taenite; low‐Ca pyroxene is absent. Most clasts have triple junctions between silicate grains, indicative of prolonged thermal annealing. Based on the olivine‐spinel and pyroxene thermometry, the estimated metamorphic temperature recorded by the clasts is approximately 1100 K. Few clasts experienced thermal metamorphism to a lower degree and preserved chondrule‐like textures. The Mokoia and Y‐86009 clasts are mineralogically unique and different from metamorphosed chondrites of known groups (H, L, LL, R, EH, EL, CO, CK) and primitive achondrites (acapulcoites, brachinites, lodranites). On a three‐isotope oxygen diagram, compositions of olivine in the clasts plot along carbonaceous chondrite anhydrous mineral line and the Allende mass‐fractionation line, and overlap with those of the CV chondrule olivines; the Δ¹⁷O values of the clasts range from about ?4.3‰ to ?3.0‰. We suggest that the clasts represent fragments of the CV‐like material that experienced metasomatic alteration, high‐temperature metamorphism, and possibly melting in the interior of the CV parent asteroid. The lack of low‐Ca pyroxene in the clasts could be due to its replacement by ferroan olivine during iron‐alkali metasomatic alteration or by high‐Ca ferroan pyroxene during melting under oxidizing conditions.     

Gas/solid carbon branching ratios in surface‐mediated reactions and the incorporation of carbonaceous material into planetesimals

We report the ratio of the initial carbon available as CO that forms gas‐phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface‐mediated reactions in an excess of hydrogen and in the presence of N₂. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO₂, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume “filamentous” structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain–grain sticking during low‐velocity collisions.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Unusual forms of magnetite in the Orgueil carbonaceous chondrite

Abstract— The Orgueil CI carbonaceous chondrite contains magnetite (Fe₃O₄) that displays a rich and seemingly unique variety of morphologies. While many have already been described, recent images provide far greater definition and, thus, provide more unambiguous identification of trapezohedral crystals and possibly also trisoctahedral forms. Although it is an extremely abundant terrestrial mineral and commonly occurs in well-developed crystals, neither of these forms have been recognized previously from magnetite. The barrel-shaped arrays of magnetite discs (“plaquettes”) are also unique. It appears as if the circumstances for the formation of these unusual crystals were somehow exceptional. Their morphologies and association with sulfates and carbonates suggest an aqueous origin.     

A strongly hydrated microclast in the Rumuruti chondrite NWA 6828: Implications for the distribution of hydrous material in the solar system

Hydrous carbonaceous microclasts are by far the most abundant foreign fragments in stony meteorites and mostly resemble CI1‐, CM2‐, or CR2‐like material. Their occurrence is of great importance for understanding the distribution and migration of water‐bearing volatile‐rich matter in the solar system. This paper reports the first finding of a strongly hydrated microclast in a Rumuruti chondrite. The R3‐6 chondrite Northwest Africa 6828 contains a 420 × 325 μm sized angular foreign fragment exhibiting sharp boundaries to the surrounding R‐type matrix. The clast is dominantly composed of magnetite, pyrrhotite, rare Ca‐carbonate, and very rare Mg‐rich olivine set in an abundant fine‐grained phyllosilicate‐rich matrix. Phyllosilicates are serpentine and saponite. One region of the clast is dominated by forsteritic olivine (Fa_<2) supported by a network of interstitial Ca‐carbonate. The clast is crosscut by Ca‐carbonate‐filled veins and lacks any chondrules, calcium‐aluminum‐rich inclusions, or their respective pseudomorphs. The hydrous clast contains also a single grain of the very rare phosphide andreyivanovite. Comparison with CI1, CM2, and CR2 chondrites as well as with the ungrouped C2 chondrite Tagish Lake shows no positive match with any of these types of meteorites. The clast may, thus, either represent a fragment of an unsampled lithology of the hydrous carbonaceous chondrite parent asteroids or constitute a sample from an as yet unknown parent body, maybe even a comet. Rumuruti chondrites are a unique group of highly oxidized meteorites that probably accreted at a heliocentric distance >1 AU between the formation regions of ordinary and carbonaceous chondrites. The occurrence of a hydrous microclast in an R chondrite attests to the presence of such material also in this region at least at some point in time and documents the wide distribution of water‐bearing (possibly zodiacal cloud) material in the solar system.     

A REFRACTORY GLASS CHONDRULE IN THE VIGARANO CHONDRITE

Vigarano, a type 3 carbonaceous chondrite, contains a chondrule composed of highly refractory Ca and Al rich glass with minor spinel. The chondrule formed from material similar to the Ca, Al, Ti-rich aggregates that are common in Vigarano and other type 3 chondrites and formation of these refractory aggregates must predate formation of some Vigarano chondrules. Experiments with synthetic analogues and a comparison with studies in the system CaO-MgO-Al₂O₃-SiO₂ indicate a temperature for formation of the chondrule at or above 1700 °C followed by very rapid cooling.     

Spatial distribution of organic matter in the Bells CM2 chondrite using near‐field infrared microspectroscopy

Abstract– Distributions of organic functional groups as well as inorganic features were analyzed in the Bells (CM2) carbonaceous chondrite using near‐field infrared (NFIR) spectroscopy. NFIR spectroscopy has recently been developed to enable infrared spectral mapping beyond the optical diffraction limit of conventional Fourier transform infrared microspectroscopy. NFIR spectral mapping of the Bells 300 nm thick sections on Al plates for 7.5 × 7.5 μm² areas showed some C‐H‐rich areas which were considered to represent the organic‐rich areas. Heterogeneous distributions of organic matter as well as those of inorganic phases such as silicates (Si‐O) were observed with 1 μm spatial resolution. The NFIR mappings of aliphatic C‐H (2960 and 2930 cm^?1) and structural OH (3650 cm^?1) confirm that organic matter is associated with phyllosilicates as previously suggested. The NFIR mapping method can provide 1 μm spatial distribution of organic functional groups and their association with minerals. High local sensitivity of NFIR enables us to find organic‐rich areas and to characterize them by their aliphatic CH₂/CH₃ ratios. The aliphatic CH₂/CH₃ ratio of Bells is slightly higher than Murchison, similar to Orgueil, and lower than literature values of IDPs and cometary dust particles.     

Total internal partition sums to support planetary remote sensing

Total internal partition sums are determined from 65 to 3010 K for ¹³C¹⁸O₂, ¹³C¹⁸O¹⁷O, ¹²CH₃D, ¹³CH₃D, H¹²C¹²CD, ¹³C¹²CH₆, ¹²CH₃⁷⁹Br, ¹²CH₃⁸¹Br, ¹²CF₄, H¹²C¹²C¹²C¹²CH, H¹²C¹²C¹²C¹⁴N, H¹²C¹²C¹³C¹⁴N, H¹²C¹³C¹²C¹⁴N, H¹³C¹²C¹²C¹⁴N, H¹²C¹²C¹²C¹⁵N, D¹²C¹²C¹²C¹⁴N, ¹⁴N¹²C¹²C¹⁴N, ¹⁵N¹²C¹²C¹⁵N, ¹²C³²S, ¹²C³³S, ¹²C³⁴S, ¹³C³²S, H₂, HD, ³²S¹⁶O, ³²S¹⁸O, ³⁴S¹⁶O, ¹²C₃H₄, ¹²CH₃, ¹²C³²S₂, ³²S¹²C³⁴S, ¹³C³²S₂, and ³²S¹²C³³S. These calculations complete the partition sum data needed for additional isotopologues in HITRAN2008 and also extend the partition sums to molecules of astrophysical interest. These data, at 25 K steps, are incorporated into a FORTRAN code (TIPS_2011.for) that can be used to rapidly generate the data at any temperature in the range 70-3000 K.