Nanophase iron carbides in fine‐grained rims in CM2 carbonaceous chondrites: Formation of organic material by Fischer–Tropsch catalysis in the solar nebula

Transmission electron microscope studies of fine‐grained rims in three CM2 carbonaceous chondrites, Y‐791198, Murchison, and ALH 81002, have revealed the presence of widespread nanoparticles with a distinctive core–shell structure, invariably associated with carbonaceous material. These nanoparticles vary in size from ~20 nm up to 50 nm in diameter and consist of a core of Fe,Ni carbide surrounded by a continuous layer of polycrystalline magnetite. These magnetite shells are 5–7 nm in thickness irrespective of the diameter of the core Fe,Ni carbide grains. A narrow layer of amorphous carbon a few nanometers in thickness is present separating the carbide core from the magnetite shell in all the nanoparticles observed. The Fe,Ni carbide phases that constitute the core are consistent with both haxonite and cohenite, based on electron diffraction data, energy dispersive X‐ray analysis, and electron energy loss spectroscopy. Z‐contrast scanning transmission electron microscopy shows that these core–shell magnetite‐carbide nanoparticles can occur as individual isolated grains, but more commonly occur in clusters of multiple particles. In addition, energy‐filtered transmission electron microscopy (EFTEM) images show that in all cases, the nanoparticles are embedded within regions of carbonaceous material or are coated with carbonaceous material. The observed nanostructures of the carbides and their association with carbonaceous material can be interpreted as being indicative of Fischer–Tropsch‐type (FTT) reactions catalyzed by nanophase Fe,Ni metal grains that were carburized during the catalysis reaction. The most likely environment for these FTT reactions appears to be the solar nebula consistent with the high thermal stability of haxonite and cohenite, compared with other carbides and the evidence of localized catalytic graphitization of the carbonaceous material. However, the possibility that such reactions occurred within the CM parent body cannot be excluded, although this scenario seems unlikely, because the kinetics of the reaction would be extremely slow at the temperatures inferred for CM asteroidal parent bodies. In addition, carbides are unlikely to be stable under the oxidizing conditions of alteration experienced by CM chondrites. Instead, it is most probable that the magnetite rims on all the carbide particles are the product of parent body oxidation of Fe,Ni carbides, but this oxidation was incomplete, because of the buildup of an impermeable layer of amorphous carbon at the interface between the magnetite and the carbide phase that arrested the reaction before it went to completion. These observations suggest that although FTT catalysis reactions may not have been the major mechanism of organic material formation within the solar nebula, they nevertheless contributed to the inventory of complex insoluble organic matter that is present in carbonaceous chondrites.     

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.     

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.     

Solar wind and other gases in the regoliths of the Pesyanoe parent object and the moon

We report new data from Pesyanoe‐90,1 (dark lithology) on the isotopic signature of solar wind (SW) Xe as recorded in this enstatite achondrite which represents a soil‐breccia of an asteroidal regolith. The low temperature (≤800°C) steps define the Pesyanoe‐S xenon component, which is isotopically consistent with SW Xe reported for the lunar regolith. This implies that the SW Xe isotopic signature was the same at two distinct solar system locations and, importantly, also at different times of solar irradiation. Further, we compare the calculated average solar wind “SW‐Xe” signature to Chass‐S Xe, the indigenous Xe observed in SNC (Mars) meteorites. Again, a close agreement between these compositions is observed, which implies that a mass‐dependent differential fractionation of Xe between SW‐Xe and Chass‐S Xe is >1.5%_o per amu. We also observe fractionated (Pesyanoe‐F) Xe and Ar components in higher temperature steps and we document a fission component due to extinct ²⁴⁴Pu. Interestingly, the Pesyanoe‐F Xe component is revealed only at the highest temperatures (>1200°C). The Pesyanoe‐F gas reveals Xe isotopic signatures that are consistent with lunar solar energetic particles (SEP) data and may indicate a distinct solar energetic particle radiation as was inferred for the moon. However, we cannot rule out fractionation processes due to parent body processes. We note that ratios ³⁶Ar/³⁸Ar≤5 are also consistent with SEP data. Calculated abundances of the fission component correlate well with radiogenic ⁴⁰Ar concentrations, revealing rather constant ²⁴⁴Pu/K ratios in Pesyanoe, and separates thereof, and indicate that both components were retained. We identify a nitrogen component (δ¹⁵N = 44%_o) of non‐solar origin with an isotopic signature distinct from indigenous N (δ¹⁵N = ?33%^o). While large excesses at ¹²⁸Xe and ¹²⁹Xe are observed in the lunar regolith samples, these excesses in Pesyanoe are small. On the other hand, significant ¹²⁶Xe isotopic excesses, comparable to relative excesses observed in lunar soils and breccias, are prominent in the intermediate temperature steps of Pesyanoe‐90,1.     

Assessment of the interstellar processes leading to deuterium enrichment in meteoritic organics

Abstract— The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low‐temperature gas phase ion‐molecule reactions, low‐temperature gas‐grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D‐enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, O, and N in the same compounds.     

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.     

Compound‐specific carbon,nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

Abstract– Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ¹³C, and δ¹⁵N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound‐specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ¹³C and increasing δD with increasing carbon number in the α‐H, α‐NH₂ amino acids that correspond to predictions made for formation via Strecker‐cyanohydrin synthesis. We also observe light δ¹³C signatures for β‐alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight‐chain, amine‐terminal amino acids (n‐ω‐amino acids). Higher deuterium enrichments are observed in α‐methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent‐body chemistry.     

A propensity for n‐ω‐amino acids in thermally altered Antarctic meteorites

Abstract– Asteroids and their fragments have impacted the Earth for the last 4.5 Gyr. Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites ranged from 300 to 3200 parts‐per‐billion (ppb), generally much less abundant than in amino acid‐rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low‐temperature aqueously altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker–cyanohydrin synthesis, the thermally altered meteorites studied here are dominated by small, straight‐chain, amine terminal (n‐ω‐amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n‐ω‐amino acids measured in one of the CV chondrites (δ¹³C approximately ?25‰) are consistent with ¹³C‐depletions observed previously in hydrocarbons produced by Fischer‐Tropsch type reactions. The predominance of n‐ω‐amino acid isomers in thermally altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.     

Oxygen isotopic and chemical zoning of melilite crystals in a type A Ca‐Al‐rich inclusion of Efremovka CV3 chondrite

Abstract– Different oxygen isotopic reservoirs have been recognized in the early solar system. Fluffy type A Ca‐Al‐rich inclusions (CAIs) are believed to be direct condensates from a solar nebular gas, and therefore, have acquired oxygen from the solar nebula. Oxygen isotopic and chemical compositions of melilite crystals in a type A CAI from Efremovka CV3 chondrite were measured to reveal the temporal variation in oxygen isotopic composition of surrounding nebular gas during CAI formation. The CAI is constructed of two domains, each of which has a core‐mantle structure. Reversely zoned melilite crystals were observed in both domains. Melilite crystals in one domain have a homogeneous ¹⁶O‐poor composition on the carbonaceous chondrite anhydrous mineral (CCAM) line of δ¹⁸O = 5–10‰, which suggests that the domain was formed in a ¹⁶O‐poor oxygen isotope reservoir of the solar nebula. In contrast, melilite crystals in the other domain have continuous variations in oxygen isotopic composition from ¹⁶O‐rich (δ¹⁸O = ?40‰) to ¹⁶O‐poor (δ¹⁸O = 0‰) along the CCAM line. The oxygen isotopic composition tends to be more ¹⁶O‐rich toward the domain rim, which suggests that the domain was formed in a variable oxygen isotope reservoir of the solar nebula. Each domain of the type A CAI has grown in distinct oxygen isotope reservoir of the solar nebula. After the domain formation, domains were accumulated together in the solar nebula to form a type A CAI.     

The role of Fischer‐Tropsch catalysis in solar nebula chemistry

Abstract— Fischer‐Tropsch catalysis, the iron/nickel catalyzed conversion of CO and H₂ to hydrocarbons, would have been the only thermally‐driven pathway available in the solar nebula to convert CO into other forms of carbon. A major issue in meteoritics is to determine the origin of meteoritic organics: are they mainly formed from CO in the solar nebula via a process such as Fischer‐Tropsch, or are they derived from interstellar organics? In order to determine the role that Fischer‐Tropsch catalysis may have played in the organic chemical evolution of the solar nebula, we have developed a kinetic model for this process. Our model results agree well with experimental data from several existing laboratory studies. In contrast, empirical rate equations, which have been derived from experimental rate data for a limited temperature (T) and pressure (P) range, are inconsistent with experimental rate data for higher T and lower P. We have applied our model to pressure and temperature profiles for the solar nebula, during the epoch in which meteorite parent bodies condensed and agglomerated. We find that, under nebular conditions, the conversion rate of CO to CH₄ does not simply increase with temperature as the empirically‐derived equations suggest. Instead, our model results show that this process would have been most efficient in a fairly narrow region that coincides with the present position of the asteroid belt. Our results support the hypothesis that Fischer‐Tropsch catalysis may have played a role in solar nebula chemistry by converting CO into less volatile materials that can be much more readily processed in the nebula and in parent bodies.     

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.     

Titanium isotopic compositions of well‐characterized silicon carbide grains from Orgueil (CI): Implications for s‐process nucleosynthesis

Abstract— We have measured the titanium isotopic compositions of 23 silicon carbide grains from the Orgueil (CI) carbonaceous chondrites for which isotopic compositions of silicon, carbon, and nitrogen and aluminum‐magnesium systematics had been measured previously. Using the 16 most‐precise measurements, we estimate the relative contributions of stellar nucleosynthesis during the asymptotic giant branch (AGB) phase and the initial compositions of the parent stars to the compositions of the grains. To do this, we compare our data to the results of several published stellar models that employ different values for some important parameters. Our analysis confirms that s‐process synthesis during the AGB phase only slightly modified the titanium compositions in the envelopes of the stars where mainstream silicon carbide grains formed, as it did for silicon. Our analysis suggests that the parent stars of the >1 μm silicon carbide grains that we measured were generally somewhat more massive than the Sun (2–3 M_⊙) and had metallicities similar to or slightly higher than solar. Here we differ slightly from results of previous studies, which indicated masses at the lower end of the range 1.5–3 M_⊙ and metallicities near solar. We also conclude that models using a standard ¹³C pocket, which produces a good match for the main component of s‐process elements in the solar system, overestimate the contribution of the ¹³C pocket to s‐process nucleosynthesis of titanium found in silicon carbide grains. Although previous studies have suggested that the solar system has a significantly different titanium isotopic composition than the parent stars of silicon carbide grains, we find no compelling evidence that the Sun falls off of the array defined by those stars. We also conclude that the Sun does lie on the low‐metallicity end of the silicon and titanium arrays defined by mainstream silicon carbide grains.     

Application Of Organic Geochemistry To Detect Signatures Of Organic Matter In The Haughton Impact Structure

Abstract— Organic geochemistry applied to samples of bedrock and surface sediment from the Haughton impact structure detects a range of signatures representing the impact event and the transfer of organic matter from the crater bedrock to its erosion products. The bedrock dolomite contains hydrocarbon‐bearing fluid inclusions which were incorporated before the impact event. Comparison of biomarker data from the hydrocarbons in samples inside and outside of the crater show the thermal signature of an impact. The occurrence of hydrocarbon inclusions in hydrothermal mineral samples shows that organic matter was mobilized and migrated in the immediate aftermath of the impact. The hydrocarbon signature was then transferred from bedrock to the crater‐fill lacustrine deposits and present‐day sediments in the crater, including wind‐blown detritus in snow/ice. Separate signatures are detected from modern microbial life in crater rock and sediment samples. Signatures in Haughton crater samples are readily detectable because they include hydrocarbons generated by the burial of organic matter. This type of organic matter is not expected in crater samples on other planets, but the Haughton data show that, using very high resolution detection of organic compounds, any signature of primitive life in the crater rocks could be transferred to surface detritus and so extend the sampling medium.     

The effect of oxygen as a light element in metallic liquids on partitioning behavior

Oxygen has been considered a potentially important light element in metallic liquids during a range of planetary processes, yet the influence of O in a metallic melt on element partitioning behavior is largely unknown. To investigate the effect of O in such systems, we conducted experiments in the Fe‐S‐O system, doped with 25 trace elements, which produced two immiscible metallic liquids. Our results indicate that the presence of O in the metallic liquid produces a distinctive chemical signature for W and Ga in particular. Tungsten shows an affinity for O in the metallic liquid and partitions more strongly into the metallic melt in the presence of O. The partitioning of Ga is relatively constant despite the presence of O, which is in contrast to the majority of the other siderophile elements in the study. Our experiments from 1400 to 1600 °C show no significant effect from temperature on the partitioning behavior of any trace elements over this limited temperature range. This distinctive chemical signature due to the presence of O in the metallic liquid has potential implications for modeling core formation, evaluating isotopic signatures produced by core crystallization, and interpreting chemical assemblages observed in meteorites.     

Pristine stratospheric collection of interplanetary dust on an oil‐free polyurethane foam substrate

We performed chemical, mineralogical, and isotopic studies of the first interplanetary dust particles (IDPs) collected in the stratosphere without the use of silicone oil. The collection substrate, polyurethane foam, effectively traps impacting particles, but the lack of an embedding medium results in significant particle fragmentation. Two dust particles found on the collector exhibit the typical compositional and mineralogical properties of chondritic porous interplanetary dust particles (CP‐IDPs). Hydrogen and nitrogen isotopic imaging revealed isotopic anomalies of typical magnitude and spatial variability observed in previous CP‐IDP studies. Oxygen isotopic imaging shows that individual mineral grains and glass with embedded metal and sulfide (GEMS) grains are dominated by solar system materials. No systematic differences are observed in element abundance patterns of GEMS grains from the dry collection versus silicone oil‐collected IDPs. This initial study establishes the validity of a new IDP collection substrate that avoids the use of silicone oil as a collection medium, removing the need for this problematic contaminant and the organic solvents necessary to remove it. Additional silicone oil‐free collections of this type are needed to determine more accurate bulk element abundances of IDPs and to examine the indigenous soluble organic components of IDPs.     

A review of volatile compounds in tektites,and carbon content and isotopic composition of moldavite glass

Abstract– Tektites, natural silica‐rich glasses produced during impact events, commonly contain bubbles. The paper reviews published data on pressure and composition of a gas phase contained in the tektite bubbles and data on other volatile compounds which can be released from tektites by either high‐temperature melting or by crushing or milling under vacuum. Gas extraction from tektites using high‐temperature melting generally produced higher gas yield and different gas composition than the low‐temperature extraction using crushing or milling under vacuum. The high‐temperature extraction obviously releases volatiles not only from the bubbles, but also volatile compounds contained directly in the glass. Moreover, the gas composition can be modified by reactions between the released gases and the glass melt. Published data indicate that besides CO₂ and/or CO in the bubbles, another carbon reservoir is present directly in the tektite glass. To clarify the problem of carbon content and carbon isotopic composition of the tektite glass, three samples from the Central European tektite strewn field—moldavites—were analyzed. The samples contained only 35–41 ppm C with δ¹³C values in the range from ?28.5 to ?29.9‰ VPDB. This indicates that terrestrial organic matter was a dominant carbon source during moldavite formation.     

Clay mineral‐organic matter relationships in the early solar system

Abstract— As the solar system formed, it inherited and perpetuated a rich organic chemistry, the molecular products of which are preserved in ancient extraterrestrial objects such as carbonaceous chondrites. These organic‐rich meteorites provide a valuable and tangible record of the chemical steps taken towards the origin of life in the early solar system. Chondritic organic matter is present in the inorganic meteorite matrix which, in the CM and CI chondrites, contains evidence of alteration by liquid water on the parent asteroid. An unanswered and fundamental question is to what extent did the organic matter and inorganic products of aqueous alteration interact or display interdependence? We have used an organic labelling technique to reveal that the meteoritic organic matter is strongly associated with clay minerals. This association suggests that clay minerals may have had an important trapping and possibly catalytic role in chemical evolution in the early solar system prior to the origin of life on the early Earth.     

Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.     

The isotopic composition and fluence of solar‐wind nitrogen in a genesis B/C array collector

Abstract– We have measured the isotopic composition and fluence of solar‐wind nitrogen in a diamond‐like‐carbon collector from the Genesis B/C array. The B and C collector arrays on the Genesis spacecraft passively collected bulk solar wind for the entire collection period, and there is no need to correct data for instrumental fractionation during collection, unlike data from the Genesis “Concentrator.” This work validates isotopic measurements from the concentrator by Marty et al. (2010, 2011) ; nitrogen in the solar wind is depleted in ¹⁵N relative to nitrogen in the Earth’s atmosphere. Specifically, our array data yield values for ¹⁵N/¹⁴N of (2.17 ± 0.37) × 10^?3 and (2.12 ± 0.34) × 10^?3, depending on data‐reduction technique. This result contradicts preliminary results reported for previous measurements on B/C array materials by Pepin et al. (2009) , so the discrepancy between Marty et al. (2010, 2011) and Pepin et al. (2009) was not due to fractionation of solar wind by the concentrator. Our measured value of ¹⁵N/¹⁴N in the solar wind shows that the Sun, and by extension the solar nebula, lie at the low‐¹⁵N/¹⁴N end of the range of nitrogen isotopic compositions observed in the solar system. A global process (or combination of processes) must have operated in interstellar space and/or during the earliest stages of solar system formation to increase the ¹⁵N/¹⁴N ratio of the solar system solids. We also report a preliminary Genesis solar‐wind nitrogen fluence of (2.57 ± 0.42) × 10¹² cm^?2. This value is higher than that derived by backside profiling of a Genesis silicon collector ( Heber et al. 2011a ).     

Mineralogy and oxygen isotope systematics of magnetite grains and a magnetite‐dolomite assemblage in hydrated fine‐grained Antarctic micrometeorites

We report the mineralogy and texture of magnetite grains, a magnetite‐dolomite assemblage, and the adjacent mineral phases in five hydrated fine‐grained Antarctic micrometeorites (H‐FgMMs). Additionally, we measured the oxygen isotopic composition of magnetite grains and a magnetite‐dolomite assemblage in these samples. Our mineralogical study shows that the secondary phases identified in H‐FgMMs have similar textures and chemical compositions to those described previously in other primitive solar system materials, such as carbonaceous chondrites. However, the oxygen isotopic compositions of magnetite in H‐FgMMs span a range of ?¹⁷O values from +1.3‰ to +4.2‰, which is intermediate between magnetites measured in carbonaceous and ordinary chondrites (CCs and OCs). The δ¹⁸O values of magnetites in one H‐FgMM have a ~27‰ mass‐dependent spread in a single 100 × 200 μm particle, indicating that there was a localized control of the fluid composition, probably due to a low water‐to‐rock mass ratio. The ?¹⁷O values of magnetite indicate that H‐FgMMs sampled a different aqueous fluid than ordinary and carbonaceous chondrites, implying that the source of H‐FgMMs is probably distinct from the asteroidal source of CCs and OCs. Additionally, we analyzed the oxygen isotopic composition of a magnetite‐dolomite assemblage in one of the H‐FgMMs (sample 03‐36‐46) to investigate the temperature at which these minerals coprecipitated. We have used the oxygen isotope fractionation between the coexisting magnetite and dolomite to infer a precipitation temperature between 160 and 280 °C for this sample. This alteration temperature is ~100–200 °C warmer than that determined from a calcite‐magnetite assemblage from the CR2 chondrite Al Rais, but similar to the estimated temperature of aqueous alteration for unequilibrated OCs, CIs, and CMs. This suggests that the sample 03‐36‐46 could come from a parent body that was large enough to attain temperatures as high as the OCs, CIs, and CMs, which implies an asteroidal origin for this particular H‐FgMM.