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.     

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.     

Analysis of ordinary chondrites using powder X‐ray diffraction: 2. Applications to ordinary chondrite parent‐body processes

Abstract– We evaluate the chemical and physical conditions of metamorphism in ordinary chondrite parent bodies using X‐ray diffraction (XRD)‐measured modal mineral abundances and geochemical analyses of 48 type 4–6 ordinary chondrites. Several observations indicate that oxidation may have occurred during progressive metamorphism of equilibrated chondrites, including systematic changes with petrologic type in XRD‐derived olivine and low‐Ca pyroxene abundances, increasing ratios of MgO/(MgO+FeO) in olivine and pyroxene, mean Ni/Fe and Co/Fe ratios in bulk metal with increasing metamorphic grade, and linear Fe addition trends in molar Fe/Mn and Fe/Mg plots. An aqueous fluid, likely incorporated as hydrous silicates and distributed homogeneously throughout the parent body, was responsible for oxidation. Based on mass balance calculations, a minimum of 0.3–0.4 wt% H₂O reacted with metal to produce oxidized Fe. Prior to oxidation the parent body underwent a period of reduction, as evidenced by the unequilibrated chondrites. Unlike olivine and pyroxene, average plagioclase abundances do not show any systematic changes with increasing petrologic type. Based on this observation and a comparison of modal and normative plagioclase abundances, we suggest that plagioclase completely crystallized from glass by type 4 temperature conditions in the H and L chondrites and by type 5 in the LL chondrites. Because the validity of using the plagioclase thermometer to determine peak temperatures rests on the assumption that plagioclase continued to crystallize through type 6 conditions, we suggest that temperatures calculated using pyroxene goethermometry provide more accurate estimates of the peak temperatures reached in ordinary chondrite parent bodies.     

Fe‐Ni metal in primitive chondrites: Indicators of classification and metamorphic conditions for ordinary and CO chondrites

Abstract— We report the results of our petrological and mineralogical study of Fe‐Ni metal in type 3 ordinary and CO chondrites, and the ungrouped carbonaceous chondrite Acfer 094. Fe‐Ni metal in ordinary and CO chondrites occurs in chondrule interiors, on chondrule surfaces, and as isolated grains in the matrix. Isolated Ni‐rich metal in chondrites of petrologic type lower than type 3.10 is enriched in Co relative to the kamacite in chondrules. However, Ni‐rich metal in type 3.15–3.9 chondrites always contains less Co than does kamacite. Fe‐Ni metal grains in chondrules in Semarkona typically show plessitic intergrowths consisting of submicrometer kamacite and Ni‐rich regions. Metal in other type 3 chondrites is composed of fine‐ to coarse‐grained aggregates of kamacite and Ni‐rich metal, resulting from metamorphism in the parent body. We found that the number density of Ni‐rich grains in metal (number of Ni‐rich grains per unit area of metal) in chondrules systematically decreases with increasing petrologic type. Thus, Fe‐Ni metal is a highly sensitive recorder of metamorphism in ordinary and carbonaceous chondrites, and can be used to distinguish petrologic type and identify the least thermally metamorphosed chondrites. Among the known ordinary and CO chondrites, Semarkona is the most primitive. The range of metamorphic temperatures were similar for type 3 ordinary and CO chondrites, despite them having different parent bodies. Most Fe‐Ni metal in Acfer 094 is martensite, and it preserves primary features. The degree of metamorphism is lower in Acfer 094, a true type 3.00 chondrite, than in Semarkona, which should be reclassified as type 3.01.     

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.     

High resolution TEM of chondritic carbonaceous matter: Metamorphic evolution and heterogeneity

Abstract– The insoluble carbonaceous matter from 12 chondrites (CI, CM, CO, CV, EH, and UOC), was characterized by high resolution transmission electron microscopy (HRTEM). Besides ubiquitous nanoglobules, the insoluble organic matter from petrologic type 1 and 2 chondrites and Semarkona (LL 3.0) is composed of a highly disordered polyaromatic component. No structural differences were observed between these IOMs, in agreement with the limited thermal metamorphism they all experienced. In chondrites of petrologic type >3.0, the evolution of the IOM is controlled by the extent of thermal metamorphism. The polyaromatic layers, shorter than 1 nm in petrologic type ≤3.0 chondrites, grow up to sizes between 5 and 10 nm in petrologic type >3.6 chondrites, contributing to the increase of the degree of structural order. In addition, we find rare, but ubiquitous onion‐like carbons, which may be the product of nanodiamond graphitization. The insoluble carbonaceous matter of the enstatite chondrite Sahara 97096 (EH 3) is different from the other meteorites studied here. It is more heterogeneous and displays a high abundance of graphitized particles. This may be the result of a mixture between (1) the disordered carbon located in the matrix, and (2) catalytic graphitized phases associated with metal, potentially originating from partial melting events. The structural and nanostructural evolution are similar in all IOMs. This suggests that the structure of the accreted precursors and the parent body conditions of their secondary thermal modifications (temperature, duration, and pressure) were similar. The limited degree of organization of the most metamorphosed IOMs compared with terrestrial rocks submitted to similar temperature suggests that the conditions are not favorable to graphitization processes, due to the chemical nature of the precursor or the lack of confinement pressure.     

A Raman spectroscopic study of organic matter in interplanetary dust particles and meteorites using multiple wavelength laser excitation

Raman spectroscopy was used to investigate insoluble organic matter (IOM) from a range of chondritic meteorites, and a suite of interplanetary dust particles (IDPs). Three monochromatic excitation wavelengths (473 nm, 514 nm, 632 nm) were applied sequentially to assess variations in meteorite and IDP Raman peak parameters (carbon D and G bands) as a function of excitation wavelength (i.e., dispersion). Greatest dispersion occurs in CVs > OCs > CMs > CRs with type 3 chondrites compared at different excitation wavelengths displaying conformable relationships, in contrast to type 2 chondrites. These findings indicate homogeneity in the structural nature of type 3 chondrite IOM, while organic matter (OM) in type 2 chondrites appears to be inherently more heterogeneous. If type 2 and type 3 chondrite IOM shares a common source, then thermal metamorphism may have a homogenizing effect on the originally more heterogeneous OM. IDP Raman G bands fall on an extension of the trend displayed by chondrite IOM, with all IDPs having Raman parameters indicative of very disordered carbon, with almost no overlap with IOM. The dispersion effect displayed by IDPs is most similar to CMs for the G band, but intermediate between CMs and CRs for the D band. The existence of some overlapping Raman features in the IDPs and IOM indicates that their OM may share a common origin, but the IDPs preserve more pristine OM that may have been further disordered by ion irradiation. H, C, and N isotopic data for the IDPs reveal that the disordered carbon in IDPs corresponds with higher δ¹⁵N and lower δ¹³C.     

Comparison of the Raman spectra of ion irradiated soot and collected extraterrestrial carbon

We use a low pressure flame to produce soot by-products as possible analogues of the carbonaceous dust present in diverse astrophysical environments, such as circumstellar shells, diffuse interstellar medium, planetary disks, as well as in our own Solar System. Several soot samples, displaying an initial chemical diversity from aromatic to aliphatic dominated material, are irradiated with 200-400 keV H⁺, He⁺, and Ar⁺⁺ ions, with fluences comprised between 10¹⁴ and 10¹⁶ ions/cm², to simulate expected radiation induced modification on extraterrestrial carbon. The evolution of the samples is monitored using Raman spectroscopy, before, during, and after irradiation. A detailed analysis of the first- and second-order Raman spectra is performed, using a fitting combination of Lorentzian and/or Gaussian-shaped bands. Upon irradiation, the samples evolve toward an amorphous carbon phase. The results suggest that the observed variations are more related to vacancy formation than ionization processes. A comparison with Raman spectra of extraterrestrial organic matter and other irradiation experiments of astrophysically relevant carbonaceous materials is presented. The results are consistent with previous experiments showing mostly amorphization of various carbonaceous materials. Irradiated soots have Raman spectra similar to those of some meteorites, IDPs, and Comet Wild 2 grains collected by the Stardust mission. Since the early-Sun expected irradiation fluxes sufficient for amorphization are compatible with accretion timescales, our results support the idea that insoluble organic matter (IOM) observed in primitive meteorites has experienced irradiation-induced amorphization prior to the accretion of the parent bodies, emphasizing the important role played by early solar nebula processing.     

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.     

Chemical and physical studies of type 3 chondrites XII: The metamorphic history of CV chondrites and their components

Abstract— The induced thermoluminescence (TL) properties of 16 CV and CV-related chondrites, four CK chondrites and Renazzo (CR2) have been measured in order to investigate their metamorphic history. The petrographic, mineralogical and bulk compositional differences among the CV chondrites indicate that the TL sensitivity of the ～130 °C TL peak is reflecting the abundance of ordered feldspar, especially in chondrule mesostasis, which in turn reflects parent-body metamorphism. The TL properties of 18 samples of homogenized Allende powder heated at a variety of times and temperatures, and cathodoluminescence mosaics of Axtell and Coolidge, showed results consistent with this conclusion. Five refractory inclusions from Allende, and separates from those inclusions, were also examined and yielded trends reflecting variations in mineralogy indicative of high peak temperatures (either metamorphic or igneous) and fairly rapid cooling. The CK chondrites are unique among metamorphosed chondrites in showing no detectable induced TL, which is consistent with literature data that suggests very unusual feldspar in these meteorites. Using TL sensitivity and several mineral systems and allowing for the differences in the oxidized and reduced subgroups, the CV and CV-related meteorites can be divided into petrologic types analogous to those of the ordinary and CO type 3 chondrites. Axtell, Kaba, Leoville, Bali, Arch and ALHA81003 are type 3.0–3.1, while ALH84018, Efremovka, Grosnaja, Allende and Vigarano are type 3.2–3.3 and Coolidge and Loongana 001 are type 3.8. Mokoia is probably a breccia with regions ranging in petrologic type from 3.0 to 3.2. Renazzo often plots at the end of the reduced and oxidized CV chondrite trends, even when those trends diverge, suggesting that in many respects it resembles the unmetamorphosed precursors of the CV chondrites. The low-petrographic types and low-TL peak temperatures of all samples, including the CV3.8 chondrites, indicates metamorphism in the stability field of low feldspar (i.e., <800 °C) and a metamorphic history similar to that of the CO chondrites but unlike that of the ordinary chondrites.     

Evaluation of terrestrial carbonaceous matter aromatization by Raman spectroscopy and its application to C chondrites

A Raman method to estimate the aromatization degree of carbonaceous matter (CM) was established, and calibrated by literature data respecting differences in acquisition procedures. The generated equations allowed a comparison of the G‐band width to vitrinite reflectance, and to additional structural organization parameter extracted from X‐ray powder diffraction. The relations between aromatization degree and peak temperatures from literature were then propagated to G‐band width parameter. The applicability of these geothermometers is demonstrated by the consistency of data obtained for carbonaceous chondrites with previous estimations. Since the CM aromatization is controlled by peak temperature and time span, it is possible to estimate the duration of chondrite’s heating events. The G‐band width relation to elemental ratio trends of organic matter in chondrites, interplanetary dust particles, glucose, and saccharose‐based semi‐coke favors synthesis by formose route. These findings provide new approaches for the future development of chemical kinetic models for organic matter of chondrites. A reliable chemical model may allow the external calibration of numerical models for accurately evaluating the peak temperatures and cooling durations of chondrites.     

Ordinary chondrite metallography: Part 2. Formation of zoned and unzoned metal particles in relatively unshocked H,L, and LL chondrites

Abstract— We studied the metallography of Fe‐Ni metal particles in 17 relatively unshocked ordinary chondrites and interpreted their microstructures using the results of P‐free, Fe‐Ni alloy cooling experiments (described in Reisener and Goldstein 2003). Two types of Fe‐Ni metal particles were observed in the chondrites: zoned taenite + kamacite particles and zoneless plessite particles, which lack systematic Ni zoning and consist of tetrataenite in a kamacite matrix. Both types of metal particles formed during metamorphism in a parent body from homogeneous, P‐poor taenite grains. The phase transformations during cooling from peak metamorphic temperatures were controlled by the presence or absence of grain boundaries in the taenite particles. Polycrystalline taenite particles transformed to zoned taenite + kamacite particles by kamacite nucleation at taenite/taenite grain boundaries during cooling. Monocrystalline taenite particles transformed to zoneless plessite particles by martensite formation and subsequent martensite decomposition to tetrataenite and kamacite during the same cooling process. The varying proportions of zoned taenite + kamacite particles and zoneless plessite particles in types 4–6 ordinary chondrites can be attributed to the conversion of polycrystalline taenite to monocrystalline taenite during metamorphism. Type 4 chondrites have no zoneless plessite particles because metamorphism was not intense enough to form monocrystalline taenite particles. Type 6 chondrites have larger and more abundant zoneless plessite particles than type 5 chondrites because intense metamorphism in type 6 chondrites generated more monocrystalline taenite particles. The distribution of zoneless plessite particles in ordinary chondrites is entirely consistent with our understanding of Fe‐Ni alloy phase transformations during cooling. The distribution cannot be explained by hot accretion‐autometamorphism, post‐metamorphic brecciation, or shock processing.     

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.     

Results of statistical analysis of primary components concentrations in bulk chemical composition of ordinary chondrite groups

We used two different methods of statistical analysis—cluster analysis and principal component analysis—to analyze the concentrations of principal chemical components (Si, Mg, Ca, Fe, Ni) and Co in ordinary chondrites. The analysis is based predominantly on published data (metadata). In total, chemical composition data from 646 ordinary chondrites were used in the statistical analysis. The aim of this analysis was to establish whether it would be possible or not to distinguish H, L, and LL chondrites based on the concentrations of major elements and Co in their bulk chemical compositions. It was also important to determine what conclusions such an analysis could enable to draw about matter differentiation in the formation environments of primordial parent bodies of particular ordinary chondrite groups (H, L, and LL). Another aim of the statistical analysis was to determine whether the distribution of Fe and Ni (with Co admixtures) is independent of petrographic types within particular groups of chondrites. This is of crucial importance for determining the distribution of FeNi(Co) ore occurrences in potential extraterrestrial deposits on modern asteroids—the sources of ordinary chondrites. The obtained results of statistical analyses confirmed that a clear-cut distinction between particular groups of ordinary chondrites is only possible for group H, while distinguishing L chondrites from LL chondrites is not always obvious. The results of the statistical analyses relating to the question of the possible existence of several primordial parent bodies (formation environments) of each group of ordinary chondrites are consistent with the results of contemporary astronomical spectroscopy research. What is particularly interesting is obtaining indications of the existence of common formation environments of the matter of L and LL chondrites, possibly on a few primordial parent bodies. The statistical analyses indicate that there is no correlation between the concentration of principal chemical components and the petrographic type of ordinary chondrites. This proves homogenous distributions of these elements within the parent bodies of each group of ordinary chondrites. Hence, the distribution of these elements in individual present-day asteroids is also homogenous.     

Peak metamorphic temperatures in type 6 ordinary chondrites: An evaluation of pyroxene and plagioclase geothermometry

Abstract— Quantifying the peak temperatures achieved during metamorphism is critical for understanding the thermal histories of ordinary chondrite parent bodies. Various geothermometers have been used to estimate equilibration temperatures for chondrites of the highest metamorphic grade (type 6), but results are inconsistent and span hundreds of degrees. Because different geothermometers and calibration models were used with different meteorites, it is unclear whether variations in peak temperatures represent actual ranges of metamorphic conditions within type 6 chondrites or differences in model calibrations. We addressed this problem by performing twopyroxene geothermometry, using QUILF95, on the same type 6 chondrites for which peak temperatures were estimated using the plagioclase geothermometer (Nakamuta and Motomura 1999). We also calculated temperatures for published pyroxene analyses from other type 6 H, L, and LL chondrites to determine the most representative peak metamorphic temperatures for ordinary chondrites. Pyroxenes record a narrow, overlapping range of temperatures in H6 (865–926 °C), L6 (812–934 °C), and LL6 (874–945 °C) chondrites. Plagioclase temperature estimates are 96–179 °C lower than pyroxenes in the same type 6 meteorites. Plagioclase estimates may not reflect peak metamorphic temperatures because chondrule glass probably recrystallized to plagioclase prior to reaching the metamorphic peak. The average temperature for H, L, and LL chondrites (～900 °C), which agrees with previously published oxygen isotope geothermometry, is at least 50 °C lower than the peak temperatures used in current asteroid thermal evolution models. This difference may require minor adjustments to thermal model calculations.     

Distribution of aliphatic amines in CO,CV, and CK carbonaceous chondrites and relation to mineralogy and processing history

The analysis of water‐soluble organic compounds in meteorites provides valuable insights into the prebiotic synthesis of organic matter and the processes that occurred during the formation of the solar system. We investigated the concentration of aliphatic monoamines present in hot acid water extracts of the unaltered Antarctic carbonaceous chondrites, Dominion Range (DOM) 08006 (CO3) and Miller Range (MIL) 05013 (CO3), and the thermally altered meteorites, Allende (CV3), LAP 02206 (CV3), GRA 06101 (CV3), Allan Hills (ALH) 85002 (CK4), and EET 92002 (CK5). We have also reviewed and assessed the petrologic characteristics of the meteorites studied here to evaluate the effects of asteroidal processing on the abundance and molecular distributions of monoamines. The CO3, CV3, CK4, and CK5 meteorites studied here contain total concentrations of amines ranging from 1.2 to 4.0 nmol g^?1 of meteorite; these amounts are 1–3 orders of magnitude below those observed in carbonaceous chondrites from the CI, CM, and CR groups. The low‐amine abundances for CV and CK chondrites may be related to their extensive degree of thermal metamorphism and/or to their low original amine content. Although the CO3 meteorites, DOM 08006 and MIL 05013, do not show signs of thermal and aqueous alteration, their monoamine contents are comparable to those observed in moderately/extensively thermally altered CV3, CK4, and CK5 carbonaceous chondrites. The low content of monoamines in pristine CO carbonaceous chondrites suggests that the initial amounts, and not asteroidal processes, play a dominant role in the content of monoamines in carbonaceous chondrites. The primary monoamines, methylamine, ethylamine, and n‐propylamine constitute the most abundant amines in the CO3, CV3, CK4, and CK5 meteorites studied here. Contrary to the predominance of n‐ω‐amino acid isomers in CO3 and thermally altered meteorites, there appears to be no preference for the larger n‐amines.     

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.     

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.     

Magnetic classification of stony meteorites: 2. Non‐ordinary chondrites

Abstract— A database of magnetic susceptibility (χ) measurements on different non‐ordinary chondrites (C, E, R, and ungrouped) populations is presented and compared to our previous similar work on ordinary chondrites. It provides an exhaustive study of the amount of iron‐nickel magnetic phases (essentially metal and magnetite) in these meteorites. In contrast with all the other classes, CM and CV show a wide range of magnetic mineral content, with a two orders of magnitude variation of χ. Whether this is due to primary parent body differences, metamorphism or alteration, remains unclear. C3–4 and C2 yield similar χ values to the ones shown by CK and CM, respectively. By order of increasing χ, the classes with well‐grouped χ are: R << CO < CK ≈ CI < Kak < CR < E ≈ CH < CB. Based on magnetism, EH and EL classes have indistinguishable metal content. Outliers that we suggest may need to have their classifications reconsidered are Acfer 202 (CO), Elephant Moraine (EET) 96026 (C4–5), Meteorite Hills (MET) 01149, and Northwest Africa (NWA) 521 (CK), Asuka (A)‐88198, LaPaz Icefield (LAP) 031156, and Sahara 98248 (R). χ values can also be used to define affinities of ungrouped chondrites, and propose pairing, particularly in the case of CM and CV meteorites.     

Ar‐Ar ages and thermal histories of enstatite meteorites

Abstract– Compared with ordinary chondrites, there is a relative paucity of chronological and other data to define the early thermal histories of enstatite parent bodies. In this study, we report ³⁹Ar‐⁴⁰Ar dating results for five EL chondrites: Khairpur, Pillistfer, Hvittis, Blithfield, and Forrest; five EH chondrites: Parsa, Saint Marks, Indarch, Bethune, and Reckling Peak 80259; three igneous‐textured enstatite meteorites that represent impact melts on enstatite chondrite parent bodies: Zaklodzie, Queen Alexandra Range 97348, and Queen Alexandra Range 97289; and three aubrites, Norton County, Bishopville, and Cumberland Falls Several Ar‐Ar age spectra show unusual ³⁹Ar recoil effects, possibly the result of some of the K residing in unusual sulfide minerals, such as djerfisherite and rodderite, and other age spectra show ⁴⁰Ar diffusion loss. Few additional Ar‐Ar ages for enstatite meteorites are available in the literature. When all available Ar‐Ar data on enstatite meteorites are considered, preferred ages of nine chondrites and one aubrite show a range of 4.50–4.54 Ga, whereas five other meteorites show only lower age limits over 4.35–4.46 Ga. Ar‐Ar ages of several enstatite chondrites are as old or older as the oldest Ar‐Ar ages of ordinary chondrites, which suggests that enstatite chondrites may have derived from somewhat smaller parent bodies, or were metamorphosed to lower temperatures compared to other chondrite types. Many enstatite meteorites are brecciated and/or shocked, and some of the younger Ar‐Ar ages may record these impact events. Although impact heating of ordinary chondrites within the last 1 Ga is relatively common for ordinary chondrites, only Bethune gives any significant evidence for such a young event.