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 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.     

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.     

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

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

Associations of organic matter with minerals in Tagish Lake meteorite via high spatial resolution synchrotron‐based FTIR microspectroscopy

We have investigated spatial and spectral associations between mineral species and organic matter in the Tagish Lake meteorite. Synchrotron‐based infrared microspectroscopy allowed us to spatially locate specific organic and inorganic compounds within multiple Tagish Lake grains with high spatial resolution. Generated two‐dimensional infrared maps present strong spatial association between aliphatic C‐H and OH in phyllosilicates in Tagish Lake grains. These observations indicate possible roles of phyllosilicates for the formation, evolution, and preservation of organic matter. Infared spectra of all studied Tagish Lake grains show a strong carbonate band, which also shows a weak but positive correlation with organic matter in some grains. However, intergrain correlation was not observed between carbonates and organics, which is likely due to the difference of carbonate occurrence, e.g., presence of larger grains or intergrowth of carbonates on phyllosilicates. Possible scenarios further explaining the observed associations of organics with phyllosilicates and carbonates are presented.     

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.     

Compound‐specific carbon isotope compositions of aldehydes and ketones in the Murchison meteorite

Compound‐specific carbon isotope analysis (δ¹³C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker‐cyanohydrin synthesis in the early solar system. Previous δ¹³C investigations have targeted α‐amino acid and α‐hydroxy acid Strecker products and reactant HCN; however, δ¹³C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and δ¹³C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. δ¹³C values, ranging from ?10.0‰ to +66.4‰, were more ¹³C‐depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar ¹²C/¹³C ratios. These relatively ¹³C‐depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between δ¹³C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration‐driven chemical pathways.     

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.     

Short‐lived radioactivity in the early solar system: The Super‐AGB star hypothesis

Abstract– The composition of the most primitive solar system condensates, such as calcium‐aluminum‐rich inclusions (CAIs) and micron‐sized corundum grains, show that short‐lived radionuclides (SLR), e.g., ²⁶Al, were present in the early solar system. Their abundances require a local or stellar origin, which, however, is far from being understood. We present for the first time the abundances of several SLR up to ⁶⁰Fe predicted from stars with initial mass in the range approximately 7–11 M_⊙. These stars evolve through core H, He, and C burning. After core C burning they go through a “Super”‐asymptotic giant branch (Super‐AGB) phase, with the H and He shells activated alternately, episodic thermal pulses in the He shell, a very hot temperature at the base of the convective envelope (approximately 10⁸ K), and strong stellar winds driving the H‐rich envelope into the surrounding interstellar medium. The final remnants of the evolution of Super‐AGB stars are mostly O–Ne white dwarfs. Our Super‐AGB models produce ²⁶Al/²⁷Al yield ratios approximately 0.02–0.26. These models can account for the canonical value of the ²⁶Al/²⁷Al ratio using dilutions with the solar nebula of the order of 1 part of Super‐AGB mass per several 10² to several 10³ of solar nebula mass, resulting in associated changes in the O‐isotope composition in the range Δ¹⁷O from 3 to 20‰. This is in agreement with observations of the O isotopic ratios in primitive solar system condensates, which do not carry the signature of a stellar polluter. The radionuclides ⁴¹Ca and ⁶⁰Fe are produced by neutron captures in Super‐AGB stars and their meteoritic abundances are also matched by some of our models, depending on the nuclear and stellar physics uncertainties as well as the meteoritic experimental data. We also expect and are currently investigating Super‐AGB production of SLR heavier than iron, such as ¹⁰⁷Pd.     

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact‐generated gases

Abstract— Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO², and H² below approximately 250–300°C during rapid cooling of trapped magmatic or impact‐generated gases. Depending on temperature, bulk composition, and oxidation‐reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO² ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01–0.001 together with high CO/CO² ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO² ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine‐grain magnetite, formation of a CO‐rich local gas phase, reduction of water vapor to H², reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high‐temperature quenching of CO‐, H²‐rich impact gases could have led to magnetite‐catalyzed hydrocarbon synthesis     

A chemical sequence of macromolecular organic matter in the CM chondrites

Abstract— A new organic parameter is proposed to show a chemical sequence of organic matter in carbonaceous chondrites, using carbon, hydrogen, and nitrogen concentrations of solvent‐insoluble and high‐molecular weight organic matter (macromolecules) and the molecular abundance of solvent‐extractable organic compounds. The H/C atomic ratio of the macromolecule purified from nine CM chondrites including the Murchison, Sayama, and seven Antarctic meteorites varies widely from 0.11 to 0.72. During the H/C change of ?0.7 to ?0.3, the N/C atomic ratio remains at ?0.04, followed by a sharp decline from ?0.040 to ?0.017 between H/C ratios from ?0.3 to ?0.1. The H/CN/C sequence shows different degrees of organic matter thermal alteration among these chondrites in which the smaller H/C‐N/C value implies higher alteration levels on the meteorite parent body. In addition, solvent‐extractable organic compounds such as amino acids, carboxylic acids, and polycyclic aromatic hydrocarbons are abundant only in chondrites with macromolecular H/C values >?0.5. These organic compounds were extremely depleted in the chondrites with a macromolecular H/C value of <?0.5. Possibly, most solvent‐extractable organic compounds could have been lost during the thermal alteration event that caused the H/C ratio of the macromolecule to fall below 0.4.     

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.     

NanoSIMS analysis of organic carbon from the Tissint Martian meteorite: Evidence for the past existence of subsurface organic‐bearing fluids on Mars

Two petrographic settings of carbonaceous components, mainly filling open fractures and occasionally enclosed in shock‐melt veins, were found in the recently fallen Tissint Martian meteorite. The presence in shock‐melt veins and the deuterium enrichments (δD up to +1183‰) of these components clearly indicate a pristine Martian origin. The carbonaceous components are kerogen‐like, based on micro‐Raman spectra and multielemental ratios, and were probably deposited from fluids in shock‐induced fractures in the parent rock of Tissint. After precipitation of the organic matter, the rock experienced another severe shock event, producing the melt veins that encapsulated a part of the organic matter. The C isotopic compositions of the organic matter (δ¹³C = ?12.8 to ?33.1‰) are significantly lighter than Martian atmospheric CO₂ and carbonate, providing a tantalizing hint for a possible biotic process. Alternatively, the organic matter could be derived from carbonaceous chondrites, as insoluble organic matter from the latter has similar chemical and isotopic compositions. The presence of organic‐rich fluids that infiltrated rocks near the surface of Mars has significant implications for the study of Martian paleoenvironment and perhaps to search for possible ancient biological activities on Mars.     

Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

Raman spectroscopic investigation of two grains from comet 81P/Wild 2: Information that can be obtained beyond the presence of sp2‐bonded carbon

Abstract– Raman analyses were performed of individual micrometer‐sized fragments of material returned to Earth by the NASA Stardust mission to comet 81P/Wild 2. The studied fragments originated from grains (C2054,0,35,91,0 and C2092,6,80,51,0) of two different penetration tracks that occurred in two different silica aerogel collector cells. All fragments of both particles have Raman spectra characteristic of amorphous sp²‐bonded carbon that are in general agreement with the results published in previous Stardust particle studies. The present study, however, does not focus on the discussion of specific details of the D and G band parameters, but rather reports on additional information that can be obtained from returned Stardust samples via Raman spectroscopy. Most notably, the Raman spectra show that all analyzed fragments of the particles were contaminated with the capture medium (i.e., aerogel). The silica aerogel is laced with organic aliphatic and aromatic hydrocarbon impurities that resulted in strong bands in the ～ 2900 Δcm^?1 spectral range (C‐H stretching modes). Aerogel bands are also found in the 1000–1600 Δcm^?1 spectral range, where they overlap with the bands of the amorphous sp²‐bonded carbon. The peaks associated with the aerogel contamination differ between the two grains that originated from two different aerogel cells. In addition to the bands due to aerogel contamination and the always present sp²‐bonded carbon bands, fragments of particle C2092,6,80,51,0 also show Raman peaks for pyrrhotite and Fa₃₀Fo₇₀ olivine. Complete (up to 4000 Δcm^?1) raw and baseline‐corrected Raman spectra of the Stardust particles are shown and discussed in detail.     

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.     

Confirmation of a meteoritic component in impact‐melt rocks of the Chesapeake Bay impact structure,Virginia, USA—Evidence from osmium isotopic and PGE systematics

Abstract— The osmium isotope ratios and platinum‐group element (PGE) concentrations of impact‐melt rocks in the Chesapeake Bay impact structure were determined. The impact‐melt rocks come from the cored part of a lower‐crater section of suevitic crystalline‐clast breccia in an 823 m scientific test hole over the central uplift at Cape Charles, Virginia. The ¹⁸⁷Os/¹⁸⁸Os ratios of impact‐melt rocks range from 0.151 to 0.518. The rhenium and platinum‐group element (PGE) concentrations of these rocks are 30–270x higher than concentrations in basement gneiss, and together with the osmium isotopes indicate a substantial meteoritic component in some impact‐melt rocks. Because the PGE abundances in the impact‐melt rocks are dominated by the target materials, interelemental ratios of the impact‐melt rocks are highly variable and nonchondritic. The chemical nature of the projectile for the Chesapeake Bay impact structure cannot be constrained at this time. Model mixing calculations between chondritic and crustal components suggest that most impact‐melt rocks include a bulk meteoritic component of 0.01–0.1% by mass. Several impact‐melt rocks with lowest initial ¹⁸⁷Os/¹⁸⁸Os ratios and the highest osmium concentrations could have been produced by additions of 0.1%–0.2% of a meteoritic component. In these samples, as much as 70% of the total Os may be of meteoritic origin. At the calculated proportions of a meteoritic component (0.01–0.1% by mass), no mixtures of the investigated target rocks and sediments can reproduce the observed PGE abundances of the impact‐melt rocks, suggesting that other PGE enrichment processes operated along with the meteoritic contamination. Possible explanations are 1) participation of unsampled target materials with high PGE abundances in the impact‐melt rocks, and 2) variable fractionations of PGE during syn‐ to post‐impact events.     

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.     

“Sweating meteorites”—Water‐soluble salts and temperature variation in ordinary chondrites and soil from the hot desert of Oman

The common appearance of hygroscopic brine (“sweating”) on ordinary chondrites (OCs) from Oman during storage under room conditions initiated a study on the role of water‐soluble salts on the weathering of OCs. Analyses of leachates from OCs and soils, combined with petrography of alteration features and a 11‐month record of in situ meteorite and soil temperatures, are used to evaluate the role of salts in OC weathering. Main soluble ions in soils are Ca²⁺, SO₄^2?, HCO₃^?, Na⁺, and Cl^?, while OC leachates are dominated by Mg²⁺ (from meteoritic olivine), Ca²⁺ (from soil), Cl^? (from soil), SO₄^2? (from meteoritic troilite and soil), and iron (meteoritic). “Sweating meteorites” mainly contain Mg²⁺ and Cl^?. The median Na/Cl mass ratio of leachates changes from 0.65 in soils to 0.07 in meteorites, indicating the precipitation of a Na‐rich phase or loss of an efflorescent Na‐salt. The total concentrations of water‐soluble ions in bulk OCs ranges from 600 to 9000 μg g^?1 (median 2500 μg g^?1) as compared to 187–14140 μg g^?1 in soils (median 1148 μg g^?1). Soil salts dissolved by rain water are soaked up by meteorites by capillary forces. Daily heating (up to 66.3 °C) and cooling of the meteorites cause a pumping effect, resulting in a strong concentration of soluble ions in meteorites over time. The concentrations of water‐soluble ions in meteorites, which are complex mixtures of ions from the soil and from oxidation and hydrolysis of meteoritic material, depend on the degree of weathering and are highest at W3. Input of soil contaminants generally dominates over the ions mobilized from meteorites. Silicate hydrolysis preferentially affects olivine and is enhanced by sulfide oxidation, producing local acidic conditions as evidenced by jarosite. Plagioclase weathering is negligible. After completion of troilite oxidation, the rate of chemical weathering slows down with continuing Ca‐sulfate contamination.     

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon‐rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound‐specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g^?1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent‐body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound‐specific stable carbon isotopic ratios (δ¹³C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ¹³C values from –20 to +59‰. These δ¹³C values fall into the range of other meteoritic organic compounds, although they are ¹³C‐depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)‐ and (S)‐sec‐butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the l ‐enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec‐butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.