Kinetics of organic matter degradation in the Murchison meteorite for the evaluation of parent‐body temperature history

Abstract– To evaluate kinetic parameters for thermal degradation of organic matter, in situ heating experiments of insoluble organic matter (IOM) and bulk of Murchison (CM2) meteorite were conducted under Fourier transform infrared micro‐spectroscopy combined with a heating stage. Decreases of aliphatic C–H band area under Ar flow were well fitted with Ginstling‐Brounshtein three‐dimensional diffusion model, and the rate constants for decreases of aliphatic C–H were determined. Activation energies E_a and frequency factors A obtained from these rate constants at different temperatures using the Arrhenius equation were E_a = 109 ± 3 kJ mol^?1 and A = 8.7 × 10⁴ s^?1 for IOM, and E_a = 61 ± 6 kJ mol^?1 and A = 3.8 s^?1 for bulk, respectively. Activation energy values of aliphatic C–H decrease are larger for IOM than bulk. Hence, the mineral assemblage of the Murchison meteorite might have catalytic effects for the organic matter degradation. Using obtained kinetic expressions, the time scale for metamorphism can be estimated for a given temperature with aliphatic C–H band area, or the temperature of metamorphism can be estimated for a given time scale. For example, using the obtained kinetic parameters of IOM, aliphatic C–H is lost approximately within 200 years at 100 °C and 100 Myr at 0 °C. Assuming alteration period of 7.5 Myr, alteration temperatures could be calculated to be <15 ± 12 °C. Aliphatic C–H decrease profiles in a parent body can be estimated using time–temperature history model. The kinetic expression obtained by the infrared spectral band of aliphatic C–H could be used as an alternative method to evaluate thermal processes of organic matter in carbonaceous chondrites.     

Elemental,isotopic, and structural changes in Tagish Lake insoluble organic matter produced by parent body processes

Here, we present the results of a multitechnique study of the bulk properties of insoluble organic material (IOM) from the Tagish Lake meteorite, including four lithologies that have undergone different degrees of aqueous alteration. The IOM C contents of all four lithologies are very uniform and comprise about half the bulk C and N contents of the lithologies. However, the bulk IOM elemental and isotopic compositions vary significantly. In particular, there is a correlated decrease in bulk IOM H/C ratios and δD values with increasing degree of alteration—the IOM in the least altered lithology is intermediate between CM and CR IOM, while that in the more altered lithologies resembles the very aromatic IOM in mildly metamorphosed CV and CO chondrites, and heated CMs. Nuclear magnetic resonance (NMR) spectroscopy, C X‐ray absorption near‐edge (XANES), and Fourier transform infrared (FTIR) spectroscopy confirm and quantitate this transformation from CR‐like, relatively aliphatic IOM functional group chemistry to a highly aromatic one. The transformation is almost certainly thermally driven, and probably occurred under hydrothermal conditions. The lack of a paramagnetic shift in ¹³C NMR spectra and 1s‐σ* exciton in the C‐XANES spectra, both typically seen in metamorphosed chondrites, shows that the temperatures were lower and/or the timescales were shorter than experienced by even the least metamorphosed type 3 chondrites. Two endmember models were considered to quantitatively account for the changes in IOM functional group chemistry, but the one in which the transformations involved quantitative conversion of aliphatic material to aromatic material was the more successful. It seems likely that similar processes were involved in producing the diversity of IOM compositions and functional group chemistries among CR, CM, and CI chondrites. If correct, CRs experienced the lowest temperatures, while CM and CI chondrites experienced similar more elevated temperatures. This ordering is inconsistent with alteration temperatures based on mineralogy and O isotopes.     

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.     

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.     

Infrared imaging spectroscopy with micron resolution of Sutter's Mill meteorite grains

Synchrotron‐based Fourier transform infrared spectroscopy and Raman spectroscopy are applied with submicrometer spatial resolution to multiple grains of Sutter's Mill meteorite, a regolith breccia with CM1 and CM2 lithologies. The Raman and infrared active functional groups reveal the nature and distribution of organic and mineral components and confirm that SM12 reached higher metamorphism temperatures than SM2. The spatial distributions of carbonates and organic matter are negatively correlated. The spatial distributions of aliphatic organic matter and OH relative to the distributions of silicates in SM2 differ from those in SM12, supporting a hypothesis that the parent body of Sutter's Mill is a combination of multiple bodies with different origins. The high aliphatic CH₂/CH₃ ratios determined from band intensities for SM2 and SM12 grains are similar to those of IDPs and less altered carbonaceous chondrites, and they are significantly higher than those in other CM chondrites and diffuse ISM objects.     

碳质球粒陨石有机物红外光谱研究

碳质球粒陨石是太阳系中最原始的物质之一.通过对碳质球粒陨石的光谱分析,可以建立其与母体小行星之间的联系,有助于探测小行星表面物质成分、研究太阳系早期的演化历史.研究了6个CM2型碳质球粒陨石和11个煤炭样品(碳质球粒陨石所含有机质的地球类比物)可见-远红外谱段反射光谱特征,并分析了它们与有机组分的关系.结果表明,对于不...     

Characterization of insoluble organic matter in primitive meteorites by microRaman spectroscopy

Abstract— We have analyzed the chemically and isotopically well‐characterized insoluble organic matter (IOM) extracted from 51 unequilibrated chondrites (8 CR, 9 CM, 1 CI, 3 ungrouped C, 9 CO, 9 CV, 10 ordinary, 1 CB and 1 E chondrites) using confocal imaging Raman spectroscopy. The average Raman properties of the IOM, as parameterized by the peak characteristics of the so‐called D and G bands, which originate from aromatic C rings, show systematic trends that are correlated with meteorite (sub‐) classification and IOM chemical compositions. Processes that affect the Raman and chemical properties of the IOM, such as thermal metamorphism experienced on the parent bodies, terrestrial weathering and amorphization due to irradiation in space, have been identified. We established separate sequences of metamorphism for ordinary, CO, oxidized, and reduced CV chondrites. Several spectra from the most primitive chondrites reveal the presence of organic matter that has been amorphized. This amorphization, usually the result of sputtering processes or UV or particle irradiation, could have occurred during the formation of the organic material in interstellar or protoplanetary ices or, less likely, on the surface of the parent bodies or during the transport of the meteorites to Earth. D band widths and peak metamorphic temperatures are strongly correlated, allowing for a straightforward estimation of these temperatures.     

Reflectance spectroscopy of insoluble organic matter (IOM) and carbonaceous meteorites

Insoluble organic matter (IOM) is the major organic component of chondritic meteorites and may be akin to organic materials from comets and interplanetary dust particles (IDPs). Reflectance spectra of IOM in the range 0.35–25 μm are presented as a tool for interpreting organic chemistry from remote measurements of asteroids, comets, IDPs, and other planetary bodies. Absorptions in the IOM spectra were strongly related to elemental H/C (atom) ratio. The aliphatic 3.4 μm absorption in IOM spectra increased linearly in strength with increasing H/C for H/C > 0.4, but was absent at lower H/C values. When meteorite spectra from the Reflectance Experiment Laboratory (RELAB) spectral catalog (n = 85) were reanalyzed at 3.4 μm, this detection limit (H/C > 0.4) persisted. Aromatic absorption features seen in IOM spectra were not observed in the meteorite spectra due to overlapping absorptions. However, the 3.4 μm aliphatic absorption strength for the bulk meteorites was correlated with both H/C of the meteorite's IOM and bulk C (wt%). Gaussian modeling of the 3 μm region provided an additional estimate of bulk C for the meteorites, along with bulk H (wt%), which is related to phyllosilicate abundance. These relationships lay the foundation for determining organic and phyllosilicate abundances from reflectance spectra. Both the full IOM spectra and the spectral parameters discussed here will aid in the interpretation of data from asteroid missions (e.g., OSIRIS‐REx, Hayabusa2), and may be able to place unknown spectral samples within the context of the meteorite collection.     

Solid‐state 13C NMR characterization of insoluble organic matter from Antarctic CM2 chondrites: Evaluation of the meteoritic alteration level

Abstract— Chemical structures of the insoluble organic matter (IOM) from the Antarctic CM2 chondrites (Yamato [Y‐] 791198, 793321; Belgica [B‐] 7904; Asuka [A‐] 881280, 881334) and the Murchison meteorite were analyzed by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Different types of carbons were characterized, such as aliphatic carbon (Ali‐C), aliphatic carbon linked to hetero atom (Hetero‐Ali‐C), aromatic carbon (Aro‐C), carboxyls (COOR), and carbonyls (C=O). The spectra of the IOM from Murchison and Y‐791198 showed two major peaks: Ali‐C and Aro‐C, while the spectra from the other meteorites showed only one major peak of Aro‐C. Carbon distribution was determined both by manual integration and deconvolution. For most IOM, the Aro‐C was the most abundant (49.8–67.8%) of all carbon types. When the ratios of Ali‐C to Aro‐C (Ali/Aro) were plotted with the atomic hydrogen to carbon ratio (H/C), a correlation was observed. If we use the H/C as a parameter for the thermal alteration event on the meteorite parent body, this result shows a different extent of thermal alteration. In addition, IOM with a lower Ali/Aro showed a lower ratio of Ali‐C to COOR plus C=O (Ali / (COOR + C=O)). This result suggests that the ratio of CO moieties to aliphatic carbon in IOM might reflect chemical oxidation that was involved in hydrothermal alteration.     

Molecular distribution, 13C‐isotope,and enantiomeric compositions of carbonaceous chondrite monocarboxylic acids

The water‐soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound‐specific δ¹³C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot‐water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The δ¹³C isotopic values of MCAs ranged from ?52 to +27‰, and aside from an inverse relationship between δ¹³C value and carbon straight‐chain length for C₃–C₆ MCAs in Murchison, the ¹³C‐isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2‐methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.     

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.     

Correlated microanalysis of cometary organic grains returned by Stardust

Abstract– Carbonaceous matter in Stardust samples returned from comet 81P/Wild 2 is observed to contain a wide variety of organic functional chemistry. However, some of this chemical variety may be due to contamination or alteration during particle capture in aerogel. We investigated six carbonaceous Stardust samples that had been previously analyzed and six new samples from Stardust Track 80 using correlated transmission electron microscopy (TEM), X‐ray absorption near‐edge structure spectroscopy (XANES), and secondary ion mass spectroscopy (SIMS). TEM revealed that samples from Track 35 containing abundant aliphatic XANES signatures were predominantly composed of cometary organic matter infilling densified silica aerogel. Aliphatic organic matter from Track 16 was also observed to be soluble in the epoxy embedding medium. The nitrogen‐rich samples in this study (from Track 22 and Track 80) both contained metal oxide nanoparticles, and are likely contaminants. Only two types of cometary organic matter appear to be relatively unaltered during particle capture. These are (1) polyaromatic carbonyl‐containing organic matter, similar to that observed in insoluble organic matter (IOM) from primitive meteorites, interplanetary dust particles (IDPs), and in other carbonaceous Stardust samples, and (2) highly aromatic refractory organic matter, which primarily constitutes nanoglobule‐like features. Anomalous isotopic compositions in some of these samples also confirm their cometary heritage. There also appears to be a significant labile aliphatic component of Wild 2 organic matter, but this material could not be clearly distinguished from carbonaceous contaminants known to be present in the Stardust aerogel collector.     

Thermal metamorphism of CI and CM carbonaceous chondrites: An internal heating model

Abstract— Infrared diffuse reflectance spectra were measured for several thermally metamorphosed carbonaceous chondrites with CI-CM affinities which were recently found from Antarctica. Compared with other CI or CM carbonaceous chondrites, these Antarctic carbonaceous chondrites show weaker absorption bands near 3 μm due to hydrous minerals, and weaker absorption bands near 6.9 μm due to carbonates, interpreted as thermal metamorphic features. These absorption bands also disappear in the spectra of samples of the Murchison (CM) carbonaceous chondrite heated above 500 °C, implying that the metamorphic temperatures of the Antarctic carbonaceous chondrites considered here were higher than about 500 °C. Model calculations were performed to study thermal metamorphism of carbonaceous chondrites in a parent body internally heated by the decay of the extinct nuclide ²⁶Al. The maximum temperature of the interior of a body more than 20 km in radius is 500–700 °C for the bulk Al contents of CI and CM carbonaceous chondrites, assuming a ratio of ²⁶Al/²⁷Al = 5 × 10^?6 which has been previously proposed for an ordinary-chondrite parent body. The metamorphic temperatures experienced by the Antarctic carbonaceous chondrites considered here may be attainable by an internally heated body with an ²⁶Al/²⁷Al ratio similar to that inferred for an ordinary-chondrite parent body.     

Synchrotron‐based infrared microspectroscopy as a useful tool to study hydration states of meteorite constituents

Abstract— We present the results of the infrared (IR) microscopic study of the anomalous carbonaceous chondrites Dhofar (Dho) 225 and Dhofar 735 in comparison to typical CM2 chondrites Cold Bokkeveld, Murray, and Mighei. The Fourier transform infrared (FTIR) 2.5–14 μm reflectance measurements were performed on conventional polished sections using an infrared microscope with a synchrotron radiation source. We demonstrate that the synchrotron‐based IR microspectroscopy is a useful, nondestructive tool for studying hydration states of meteorite constituents in situ. Our results show that the matrices of Dho 225 and Dho 735 are dehydrated compared to the matrices of typical CM2 chondrites. The spectra of the Dho 225 and Dho 735 matrices lack the 2.7–2.8 μm absorption feature present in the spectra of Cold Bokkeveld, Murray, and Mighei. Spectral signatures caused by Si‐O vibrations in fine‐grained, Fe‐rich olivines dominate the 10 μm spectral region in the spectra of Dho 225 and Dho 735 matrices, while the spectra of normal CM2 chondrites are dominated by spectral signatures due to Si‐O vibrations in phyllosilicates. We did not detect any hydrated phases in the spectra of Dho 225 and Dho 735 polished sections. In addition, the near‐infrared reflectance spectra of Dho 225 and Dho 735 bulk powders show spectral similarities to the Antarctic metamorphosed carbonaceous chondrites. We confirm the results of previous mineralogical, chemical, and isotopic studies indicating that the two meteorites from Oman are the first non‐Antarctic metamorphosed carbonaceous chondrites.     

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

Evaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.     

Evaporation of nebular fines during chondrule formation

Studies of matrix in primitive chondrites provide our only detailed information about the fine fraction (diameter <2 μm) of solids in the solar nebula. A minor fraction of the fines, the presolar grains, offers information about the kinds of materials present in the molecular cloud that spawned the Solar System. Although some researchers have argued that chondritic matrix is relatively unaltered presolar matter, meteoritic chondrules bear witness to multiple high-temperature events each of which would have evaporated those fines that were inside the high-temperature fluid. Because heat is mainly transferred into the interior of chondrules by conduction, the surface temperatures of chondrules were probably at or above 2000 K. In contrast, the evaporation of mafic silicates in a canonical solar nebula occurs at around 1300 K and FeO-rich, amorphous, fine matrix evaporates at still lower temperatures, perhaps near 1200 K. Thus, during chondrule formation, the temperature of the placental bath was probably >700 K higher than the evaporation temperatures of nebular fines. The scale of chondrule forming events is not known. The currently popular shock models have typical scales of about ¹⁰⁵ km. The scale of nebular lightning is less well defined, but is certainly much smaller, perhaps in the range 1 to 1000 m. In both cases the temperature pulses were long enough to evaporate submicrometer nebular fines. This interpretation disagrees with common views that meteoritic matrix is largely presolar in character and CI-chondrite-like in composition. It is inevitable that presolar grains (both those recognized by their anomalous isotopic compositions and those having solar-like compositions) that were within the hot fluid would also have evaporated. Chondrule formation appears to have continued down to the temperatures at which planetesimals formed, possibly around 250 K. At temperatures >600 K, the main form of C is gaseous CO. Although the conversion of CO to CH₄ at lower temperatures is kinetically inhibited, radiation associated with chondrule formation would have accelerated the conversion. There is now evidence that an appreciable fraction of the nanodiamonds previously held to be presolar were actually formed in the solar nebula. Industrial condensation of diamonds from mixtures of CH₄ and H₂ implies that high nebular CH₄/CO ratios favored nanodiamond formation. A large fraction of chondritic insoluble organic matter may have formed in related processes. At low nebular temperatures appreciable water should have been incorporated into the smoke that condensed following dust (and some chondrule) evaporation. If chondrule formation continued down to temperatures as low as 250 K this process could account for the water concentration observed in primitive chondrites such as LL3.0 and CO3.0 chondrites. Higher H₂O contents in CM and CI chondrites may reflect asteroidal redistribution. In some chondrite groups (e.g., CR) the Mg/Si ratio of matrix material is appreciably (30%) lower than that of chondrules but the bulk Mg/Si ratio is roughly similar to the CI or solar ratio. This has been interpreted as a kind of closed-system behavior sometimes called “complementarity.” This leads to the conclusion that nebular fines were efficiently agglomerated. Its importance, however is obscured by the observation that bulk Mg/Si ratios in ordinary and enstatite chondrites are much lower than those in carbonaceous chondrites, and thus that complementarity did not hold throughout the solar nebula.     

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.     

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.     

Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

Prebiotic carbon in clays from Orgueil and Ivuna (CI), and Tagish Lake (C2 ungrouped) meteorites

Abstract— Transmission electron microscopic (TEM) and electron energy‐loss spectroscopic (EELS) study of the Ivuna and Orgueil (CI), and Tagish Lake (C2 ungrouped) carbonaceous chondrite meteorites shows two types of C‐clay assemblages. The first is coarser‐grained (to 1 μm) clay flakes that show an intense O K edge from the silicate together with a prominent C K edge, but without discrete C particles. Nitrogen is common in some clay flakes. Individual Orgueil and Tagish Lake meteorite clay flakes contain up to 6 and 8 at% C, respectively. The C K‐edge spectra from the clays show fine structure revealing aromatic, aliphatic, carboxylic, and carbonate C. The EELS data shows that this C is intercalated with the clay flakes. The second C‐clay association occurs as poorly crystalline to amorphous material occurring as nanometer aggregates of C, clay, and Fe‐O‐rich material. Some aggregates are dominated by carbonaceous particles that are structurally and chemically similar to the acid insoluble organic matter. The C K‐edge shape from this C resembles that of amorphous C, but lacking the distinct peaks corresponding to aliphatic, carboxylic, and carbonate C groups. Nanodiamonds are locally abundant in some carbonaceous particles. The abundance of C in the clays suggest that molecular speciation in the carbonaceous chondrites is partly determined by the effects of aqueous processing on the meteorite parent bodies, and that clays played an important role. This intricate C‐clay association lends credence to the proposal that minerals were important in the prebiotic chemical evolution of the early solar system.