Model of molecular structure of the insoluble organic matter isolated from Murchison meteorite

Abstract– The molecular structure of the insoluble organic matter (IOM) from Murchison meteorite has been investigated by our group for several years using a large set of analytical methods including various spectroscopies (Fourier transform infrared spectroscopy, nuclear magnetic resonance, electron paramagnetic resonance, X‐ray absorption near‐edge spectroscopy), high resolution electron microscopy, and thermal (pyrolyses in the presence or not of tetramethylammonium hydroxide) and chemical (RuO₄ oxidation) degradations. Taken together, these techniques provided a wealth of qualitative and quantitative information, from which we derived 11 elemental and molecular parameters on the same IOM residue. In addition to the basic elemental composition, these parameters describe the distribution of the different types of carbon, nitrogen, and sulfur atoms as well as the size of the polyaromatic units. For this molecular structure, we therefore propose a model which fits with these 11 molecular quantitative parameters. Several cosmochemical implications are derived from this structure. Based on the fact that aromatic moieties are highly substituted and aliphatic chains highly branched, it can be anticipated that the synthesis of this IOM occurred through successive additions of single carbon units in the gas‐phase ending by a spontaneous cyclization for chain length ≥7 C. As a whole, these observations favor an organosynthesis in the solar T‐Tauri disk.     

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.     

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.     

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.     

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.     

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.     

Molecular study of insoluble organic matter in Kainsaz CO3 carbonaceous chondrite: Comparison with CI and CM IOM

Abstract— Kainsaz CO3 insoluble organic matter (IOM) was studied using Curie point pyrolysis, electronic paramagnetic resonance (EPR), and high‐resolution transmission electron microscopy (HRTEM) to determine the effect of thermal metamorphism on molecular chondritic fingerprints. Pyrolysis released a very low amount of products that consist of one‐ and two‐ring aromatic units with methyl, dimethyl, and ethyl substituents. Moreover, Kainsaz IOM contains two orders of magnitude fewer radicals than Orgueil, Murchison, and Tagish Lake IOM. In addition, no diradicaloids were found in Kainsaz, although they are thought to constitute a specific signature for weakly organized extraterrestrial organic compounds in contrast to terrestrial ones. HRTEM reveals a very heterogeneous structure, with microporous disordered carbon, mesoporous graphitic carbons and graphite. Graphitization likely occurs and explains the differences between Kainsaz and CI or CM IOM. Heating stress experienced by Kainsaz IOM, on the parent body and/or prior its accretion, is likely responsible for the differences in molecular and structural organizations compared with those of CI and CM IOM.     

Selective release of D and 13C from insoluble organic matter of the Murchison meteorite by impact shock

Abstract— We performed shock‐recovery experiments on insoluble organic matter (IOM) purified from the Murchison meteorite, and determined the abundances and isotope ratios of hydrogen and carbon in the shocked IOM sample. We also performed shock experiments on type III kerogen and compared the results of these experiments with the experimental results regarding IOM. The shock selectively released D and ¹³C from the IOM, while it preferably released H and ¹²C from the kerogen. The release of these elements from IOM cannot be explained in terms of the isotope effect, whereas their release from kerogen can be explained by this effect. The selective release of heavier isotopes from IOM would be due to its structure, in which D and ¹³C‐enriched parts are present as an inhomogeneity and are weakly attached to the main network. Shock gave rise to a high release of D even at a lower degree of dehydrogenation compared with the stepwise heating of IOM. This effective release of D is probably an inherent result of shock, in which a dynamic high‐pressure and high‐temperature condition prevails. Thus, shock would effectively control the hydrogen isotope behavior of extraterrestrial organic matter during the evolution of the solar nebula.     

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.     

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.     

Primordial heavy noble gases in the pristine Paris carbonaceous chondrite

The Paris carbonaceous chondrite represents the most pristine carbonaceous chondrite, providing a unique opportunity to investigate the composition of early solar system materials prior to the onset of significant aqueous alteration. A dual origin (namely from the inner and outer solar system) has been demonstrated for water in the Paris meteorite parent body (Piani et al. 2018 ). Here, we aim to evaluate the contribution of outer solar system (cometary‐like) water ice to the inner solar system water ice using Xe isotopes. We report Ar, Kr, and high‐precision Xe isotopic measurements within bulk CM 2.9 and CM 2.7 fragments, as well as Ne, Ar, Kr, and Xe isotope compositions of the insoluble organic matter (IOM). Noble gas signatures are similar to chondritic phase Q with no evidence for a cometary‐like Xe component. Small excesses in the heavy Xe isotopes relative to phase Q within bulk samples are attributed to contributions from presolar materials. CM 2.7 fragments have lower Ar/Xe relative to more pristine CM 2.9 fragments, with no systematic difference in Xe contents. We conclude that Kr and Xe were little affected by aqueous alteration, in agreement with (1) minor degrees of alteration and (2) no significant differences in the chemical signature of organic matter in CM 2.7 and CM 2.9 areas (Vinogradoff et al. 2017 ). Xenon contents in the IOM are larger than previously published data of Xe in chondritic IOM, in line with the Xe component in Paris being pristine and preserved from Xe loss during aqueous alteration/thermal metamorphism.     

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.     

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.     

Diamond xenolith and matrix organic matter in the Sutter's Mill meteorite measured by C‐XANES

The Sutter's Mill (SM) meteorite fell in El Dorado County, California, on April 22, 2012. This meteorite is a regolith breccia composed of CM chondrite material and at least one xenolithic phase: oldhamite. The meteorite studied here, SM2 (subsample 5), was one of three meteorites collected before it rained extensively on the debris site, thus preserving the original asteroid regolith mineralogy. Two relatively large (10 μm sized) possible diamond grains were observed in SM2‐5 surrounded by fine‐grained matrix. In the present work, we analyzed a focused ion beam (FIB) milled thin section that transected a region containing these two potential diamond grains as well as the surrounding fine‐grained matrix employing carbon and nitrogen X‐ray absorption near‐edge structure (C‐XANES and N‐XANES) spectroscopy using a scanning transmission X‐ray microscope (STXM) (Beamline 5.3.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory). The STXM analysis revealed that the matrix of SM2‐5 contains C‐rich grains, possibly organic nanoglobules. A single carbonate grain was also detected. The C‐XANES spectrum of the matrix is similar to that of insoluble organic matter (IOM) found in other CM chondrites. However, no significant nitrogen‐bearing functional groups were observed with N‐XANES. One of the possible diamond grains contains a Ca‐bearing inclusion that is not carbonate. C‐XANES features of the diamond‐edges suggest that the diamond might have formed by the CVD process, or in a high‐temperature and ‐pressure environment in the interior of a much larger parent body.     

Diradicaloids in the insoluble organic matter from the Tagish Lake meteorite: Comparison with the Orgueil and Murchison meteorites

Abstract— The radicals in the insoluble organic matter (IOM) from the Tagish Lake meteorite were studied by electron paramagnetic resonance and compared to those existing in the Orgueil and Murchison meteorites. As in the Orgueil and Murchison meteorites, the radicals in the Tagish Lake meteorite are heterogeneously distributed and comprise a substantial amount (?42%) of species with a thermally accessible triplet state and with the same singlet‐triplet gap, ΔE ?0.1 eV, as in the Orgueil and Murchison meteorites. These species were identified as diradicaloid moieties. The existence of similar diradicaloid moieties in three different carbonaceous chondrites but not in terrestrial IOM strongly suggests that these moieties could be “fingerprints” of the extraterrestrial origin of meteoritic IOM and markers of its synthetic pathway before its inclusion into a parent body.     

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.     

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.     

Carbonaceous materials in the acid residue from the Orgueil carbonaceous chondrite meteorite

Abstract— Insoluble organic matter (IOM) dominates the HF/HCl residue of the Orgueil (CI) carbonaceous chondrite meteorite. The IOM is composed primarily of two C‐rich particle types. The first has a fluffy texture similar to crumpled tissue paper, and the second type occurs as solid or hollow nanospheres. High‐resolution transmission electron microscope (HRTEM) images of the fluffy material show it is poorly ordered, with small, irregularly shaped regions having fringes with 0.34–0.38 nm spacings and locally 0.21 nm cross‐fringes. Nanodiamonds occur in the fluffy material. The rounded C‐rich particles are common in the residue and their HRTEM images show neither fringes nor nanodiamonds. Both types of carbonaceous materials have a high aromatic component, as revealed by electron energy‐loss spectroscopy (EELS), with up to 10 at% substitution by S, N, and O. The average compositions of the fluffy material and nanospheres are C₁₀₀S_1.9N_3.7O_4.9 and C₁₀₀S_2.4N_5.0O_3.9, respectively. The structural and chemical heterogeneity of the carbonaceous materials may represent material from multiple sources.     

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.     

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.