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.     

Polycyclic aromatic hydrocarbons and amino acids in meteorites and ice samples from LaPaz Icefield,Antarctica

Abstract— –We have analyzed ice samples and meteorites from the LaPaz region of Antarctica to investigate the composition of polycyclic aromatic hydrocarbons (PAHs) and amino acids with the goal to understand whether or not there is a compositional relationship between the two reservoirs. Four LL5 ordinary chondrites (OCs) and one CK carbonaceous chondrite were collected as part of the 2003/2004 ANSMET season. Ice samples collected from directly underneath the meteorites were extracted. In addition, exhaust particles from the snowmobiles used during the expedition were collected to investigate possible contributions from this source. The meteorite samples, the particulate matter and solid‐state extracts of the ice samples and the exhaust filters were subjected to two‐step laser mass spectrometry (L2MS) to investigate the PAH composition. For amino acids analysis, the meteorites were extracted with water and acid hydrolyzed, and the extracts were analyzed with offline OPA/NAC derivatization combined with liquid chromatography with UV fluorescence detection and time of flight mass spectrometry (LC‐FD/ToF‐MS). PAHs in the particulate matter of the ice were found to be qualitatively similar to the meteorite samples, indicating that micron‐sized grains of the meteorite may be embedded in the ice samples. The concentration levels of dissolved PAHs in all the ice samples were found to be below the detection limit of the L2MS. The PAH composition of the snowmobile exhaust is significantly different to the one in particulate matter, making it an unlikely source of contamination for Antarctic meteorites. The amino acids glycine, β‐alanine and γ‐amino‐n‐butyric acid that were detected at concentrations of 3 to 19 parts per billion (ppb) are probably indigenous to the Antarctic meteorites. Some of the LaPaz ice samples were also found to contain amino acids at concentration levels of 1 to 33 parts per trillion (ppt), in particular α‐aminoisobutyric acid (AIB), an abundant non‐protein amino acid of extraterrestrial origin found in some carbonaceous chondrites. We hypothesize that this amino acid could have been extracted from Antarctic micrometeorites and the particulate matter of the meteorites during the concentration procedure of the ice samples.     

Characterization of insoluble organic matter in primitive meteorites by microRaman spectroscopy

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

Trends in the study of presolar dust grains from primitive meteorites

Abstract— A series of trends can be discerned in the study of presolar dust grains from primitive meteorites, and these trends might give us hints in which direction this new field of astronomy is developing. They include: (1) a focus on ever smaller components of meteorites; (2) a shift from the study of the elemental abundances in the solar system to the study of isotopic abundances; (3) a shift of emphasis from averages of the isotopic abundances as represented by the whole solar system to individual isotopic components preserved in circumstellar dust grains; (4) the preferential study of rare types of presolar dust grains; (5) the emergence of new technical capabilities for the study of individual presolar dust grains; examples include isotopic imaging and resonance ionization mass spectrometry (RIMS); and (6) a shift from a situation in which grain data confirm previously held theoretical ideas to a situation in which the experimental data impose new constraints on theoretical models of nucleosynthesis, stellar mixing and grain formation in stellar outflows. In other words, the data do not confirm but drive the theory. An example is the distribution of Si isotopic ratios in individual mainstream SiC grains for which many different theoretical explanations have been offered. There are still many unsolved problems posed by the grain data, the most difficult being the interpretation of the isotopic ratios of grains with a supernova signature (evidence for ⁴⁴Ti and excesses in ²⁸Si) in terms of theoretical models of nucleosynthesis and the mixing of supernova ejecta. Future progress is expected to come from the analysis of larger numbers of grains, the search for new types of presolar grains, the analysis of smaller grains and of more elements in a given grain, both made possible by the increase in sensitivity of ion microprobes and the extended application of RIMS, from multi-dimensional models of stellar evolution with enlarged nuclear networks, and from new measurements of nuclear cross sections.     

The composition of asteroid 2 Pallas and its relation to primitive meteorites

High resolution spectroscopic observations of asteroid 2 Pallas from 1.7-3.5 μm are reported. These data are combined with previous measurements from 0.4-1.7 μm to interpret Pallas' surface mineralogy. Evidence is found for low-Fe²⁺ hydrated silicates, opaque components, and low-Fe²⁺ anhydrous silicates. This assemblage is very similar to carbonaceous chondrite matrix material such as is found in type CI and CM meteorites, but it has been subjected to substantial aqueous alteration and there is a major extraneous anhydrous silicate component. This composition is compared to that of asteroid 1 Ceres. Although there are substantial differences in their broad band spectral reflectances, it appears that both asteroids are genetically related to known carbonaceous chondrites.     

Concentration and variability of the AIB amino acid in polar micrometeorites: Implications for the exogenous delivery of amino acids to the primitive Earth

Abstract— Micrometeorites (MMs) are extraterrestrial particles ranging in size from 25 μm to 2 mm that survive atmospheric entry and are collected on the Earth's surface. They represent the largest mass flux (MF) of extraterrestrial material (30,000 ± 20,000 t/yr) to the present‐day Earth. Studies of large collections of MMs suggest that about 20% have not been heated to high temperatures and that they contain organic carbon. Since non‐protein amino acids have been found in some carbonaceous meteorites, they might also be found in unmelted MMs. However, previous searches for amino acids in MMs were inconclusive. We combined a new extraction method for amino acids with a highly sensitive analytical method to detect and quantitate amino acids in MMs collected at the South Pole. We found the non‐protein amino acid α‐amino isobutyric acid (AIB) in one of our samples. The non‐detection of this amino acid in the other samples analyzed suggests that there are amino acid‐containing and amino acid‐free MMs, with ?14% of the MMs containing AIB. Since the MF of MMs is much higher than that of carbonaceous chondrites (CMs), amino acids in these small particles would represent an important source of exogenous delivery of organic molecules. Therefore, the results are discussed on the basis of their implications for astrobiology.     

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.     

An experimental study of the formation of cubanite (CuFe2S3) in primitive meteorites

The low‐temperature form of CuFe₂S₃, cubanite, has been identified in the CI chondrite and NASA Stardust mission collections. The presence of this mineral constrains the maximum temperature to 210 °C since the time of its formation. However, until now, the conditions under which cubanite forms were less well constrained. In order to refine the history of the time‐varying, low‐temperature fluids which existed on the CI‐chondrite parent body and Comet 81P/Wild 2 (Wild 2), we synthesized cubanite. The experimental synthesis of this mineral was achieved, for the first time, under low‐temperature aqueous conditions relevant to the CI‐chondrite parent body. Using a variant of in situ hydrothermal recrystallization, cubanite formed in aqueous experiments starting with temperatures of 150 and 200 °C, pH approximately 9, and oxygen fugacities corresponding to the iron‐magnetite buffer. The composition and structure of the cubanite were determined using electron microprobe and transmission electron microscopy techniques, respectively. The combined compositional, crystallographic, and experimental data allow us to place limits on the conditions under which the formation of cubanite is feasible, which in turn constrains the nature of the fluid phase on the CI‐chondrite parent body and Wild 2 when cubanite was forming.     

FTIR 2–16 micron spectroscopy of micron‐sized olivines from primitive meteorites

Abstract— Infrared spectra of mineral grains from primitive meteorites could be useful for comparison with astronomical infrared spectra since some of their grains might be similar to those formed in the planet‐forming disks around young stars or in the envelopes surrounding late‐type stars. To assess the usefulness of meteorite spectra, olivine grains separated from primitive meteorites have been analyzed using FTIR microscope techniques in the 2–16 μm wavelength range. The sub‐micron sizes of the grains made a complex preparation process necessary. Five characteristic bands were measured near 11.9, 11.2, 10.4, 10.1, and 10.0 μm. The results of 59 analyses allow the calculation of band positions for meteoritic olivines as a function of their iron and magnesium contents. Comparison of the meteoritic results with astronomical data for comets and dust around young and old stars, which exhibit bands similar to the strongest infrared bands observed in the grains (at 11.2 μm), show that the spectral resolution of the astronomical observations is too low to ascertain the exact iron and magnesium (Mg: Fe) ratio of the dust in the 8–13 μm wavelength range.     

Amino acids in Antarctic CM1 meteorites and their relationship to other carbonaceous chondrites

Abstract— CM2 carbonaceous chondrites are the most primitive material present in the solar system, and some of their subtypes, the CM and CI chondrites, contain up to 2 wt% of organic carbon. The CM2 carbonaceous chondrites contain a wide variety of complex amino acids, while the CI1 meteorites Orgueil and Ivuna display a much simpler composition, with only glycine and β‐alanine present in significant abundances. CM1 carbonaceous chondrites show a higher degree of aqueous alteration than CM2 types and therefore provide an important link between the CM2 and CI1 carbonaceous chondrites. Relative amino acid concentrations have been shown to be indicative for parent body processes with respect to the formation of this class of compounds. In order to understand the relationship of the amino acid composition between these three types of meteorites, we have analyzed for the first time three Antarctic CM1 chondrites, Meteorite Hills (MET) 01070, Allan Hills (ALH) 88045, and LaPaz Icefield (LAP) 02277, using gas chromatography‐mass spectrometry (GC‐MS) and high performance liquid chromatography‐fluorescence detection (HPLC‐FD). The concentrations of the eight most abundant amino acids in these meteorites were compared to those of the CM2s Murchison, Murray, Mighei, Lewis Cliff (LEW) 90500, ALH 83100, as well as the CI1s Orgueil and Ivuna. The total amino acid concentration in CM1 carbonaceous chondrites was found to be much lower than the average of the CM2s. Relative amino acid abundances were compared in order to identify synthetic relationships between the amino acid compositions in these meteorite classes. Our data support the hypothesis that amino acids in CM‐ and CI‐type meteorites were synthesized under different physical and chemical conditions and may best be explained with differences in the abundances of precursor compounds in the source regions of their parent bodies in combination with the decomposition of amino acids during extended aqueous alteration.     

Thallium in meteorites

Abstract— Thallium has been quantified in 50 iron meteorites and 6 chondrites using a combination of solvent extraction and graphite furnace atomic absorption spectrometry. The accuracy of the data was checked by analysis of two iron meteorites by laser-excited ICP mass spectrometry. The Tl abundance values for irons appear to be the first recorded and show that the Tl content allows for taxonomic separation of several groups on Tl vs. Ni abundance plots. The Tl content of irons is inversely correlated with abundances of platinum group metals such as Ir, Pt, and Rh and, in this respect, behaves like Pd and As that favour sulphur-rich phases in meteorites. Analysis of carbonaceous chondrites showed a 30-fold enrichment of Tl compared with ordinary chondrites.     

Molecular and chiral analyses of some protein amino acid derivatives in the Murchison and Murray meteorites

Abstract— The varied organic suite extracted from the Murchison meteorite contains several amino acids that are common to the biosphere. Some of these have been found to be non‐racemic, but the indigenous nature of their L‐enantiomeric excesses has been subject to debate in view of possible terrestrial contamination. We have investigated two amino acids of common terrestrial and meteoritic occurrence, alanine and glutamic acid, and assessed their indigenous enantiomeric ratios in the Murchison and Murray meteorites through the ratios of some of their derivatives. Analyzed were N‐acetyl alanine, α‐imino propioacetic acid, N‐acetyl glutamic acid and pyroglutamic acid. Both alanine derivatives were found to be racemic, while those of glutamic acid showed L‐enantiomeric excesses varying from 16% to 47.2% for pyroglutamic acid, and from 8.6% to 41% for N‐acetyl glutamic acid. The δ¹³C was determined for the two enantiomers of Murchison pyroglutamic acid both before and after acid hydrolysis to glutamic acid. The values of +27.7%0 (D‐pyro), +10.0%0 (L‐pyro), +32.2%0 (D‐glu) and +14.6%0 (L‐glu) were obtained. The racemic nature of alanine derivatives strongly suggests that alanine itself, as indigenous to the meteorite, is racemic. The explanation of the L‐enantiomeric excesses found for glutamic acid derivatives is less direct; however, the variability of the enantiomeric ratios for these compounds and the distinctly lower δ¹³C values determined for pyroglutamic L‐enantiomer point to a terrestrial contamination, possibly dating to the time of fall.     

Chlorine abundances in meteorites

Abstract— We used the nuclear reaction ³⁷Cl (n,γ) ³⁸Ar, achieved during neutron irradiation for dating meteorites by the ³⁹Ar‐⁴⁰Ar technique, to calculate the elemental Cl concentration of 132 samples of 94 different meteorites (mostly finds) representing several different classes. determined k and ca concentrations are also reported. Total [Cl] varies considerably, both among meteorites of the same class and among different meteorite classes. The range in [Cl] is approximately 15–177 ppm for ordinary chondrites; approximately 24–650 ppm for enstatite chondrites; approximately 4–177 ppm for eucrites; approximately 7–128 ppm for mesosiderites; approximately 35–268 ppm for acapulcoites and lodranites; and approximately 12–507 ppm for winonaites and iron silicates. As expected, most differentiated meteorites have lower [Cl] compared to chondrites and iron silicates. Analyses of 11 interior samples (～0.1 g each) of a large L6 chondrite varied over 68–129 ppm, which is a measure of the homogeneity of Cl distribution. By evaluating Ar release during stepwise sample degassing, we separated the Cl into low‐temperature and high‐temperature components, the former of which may consist of terrestrial contamination. Most samples show low‐temperature Cl concentrations of <40 ppm, but for several samples terrestrial Cl contamination constitutes significant fractions of the total Cl. Among most differentiated meteorites, finds show considerably greater low‐temperature [Cl] compared to falls.     

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 review of the chondrite–achondrite transition,and a metamorphic facies series for equilibrated primitive stony meteorites

Here, the petrological features of numerous primitive achondrites and highly equilibrated chondrites are evaluated to review and expand upon our knowledge of the chondrite–achondrite transition, and primitive achondrites in general. A thermodynamic model for the initial silicate melting temperature and progressive melting for nearly the entire known range of oxidation states is provided, which can be expressed as T_m = 0.035Fa²?3.51Fa + 1109 (in °C, where Fa is the proportion of fayalite in olivine). This model is then used to frame a discussion of textural and mineralogical evolution of stony meteorites with increasing temperature. We suggest that the metamorphic petrology of these meteorites should be based on diffusive equilibration among the silicate minerals, and as such, the chondrite–achondrite transition should be defined by the initial point of silicate melting, not by metal–troilite melting. Evidence of silicate melting is preserved by a distinctive texture of interconnected interstitial plagioclase ± pyroxene networks among rounded olivine and/or pyroxene (depending on ?O₂), which pseudomorph the former silicate melt network. Indirectly, the presence of exsolution lamellae in augite in slowly cooled achondrites also implies that silicate melting occurred because of the high temperatures required, and because silicate melt enhances diffusion. A metamorphic facies series is defined: the Plagioclase Facies is equivalent to petrologic types 5 and 6, the Sub‐calcic Augite Facies is bounded at lower temperatures by the initiation of silicate melting and at higher temperatures by the appearance of pigeonite, which marks the transition to the Pigeonite Facies.     

NWA 1152 and Sahara 00182: New primitive carbonaceous chondrites with affinities to the CR and CV groups

Abstract— We have investigated the mineralogy, petrography, bulk chemistry, and light element isotope composition of the ungrouped chondrites North West Africa (NWA) 1152 and Sahara 00182. NWA 1152 contains predominantly type 1 porphyritic olivine (PO) and porphyritic olivinepyroxene (POP) chondrules. Chondrule silicates are magnesium‐rich (Fo_{98.8 ± 1.2}, n = 36; Fs_{2.3 ± 2.1} Wo_{1.2 ± 0.3}, n = 23). Matrix comprises ?40 vol% of the sample and is composed of a micron sized silicate groundmass with larger silicate, sulfide, magnetite, and Fe‐Ni metal (Ni ?50 wt%) grains. Phyllosilicates were not observed in the matrix. Refractory inclusions are rare (0.3 vol%) and are spinel pyroxene aggregates or amoeboid olivine aggregates; melilite is absent from the refractory inclusions. Sahara 00182 contains predominantly type 1 PO chondrules, POP chondrules are less common. Most chondrules contain blebs of, and are often rimmed with, Fe‐Ni metal and sulfide. Chondrule phenocrysts are magnesium‐rich (Fo_{92.2 ± 0.6}, n = 129; Fs_{4.4 ± 1.8} Wo_{1.3 ± 1.1}, n = 16). Matrix comprises ?30 vol% of the meteorite and is predominantly sub‐micron silicates, with rare larger silicate gains. Matrix Fe‐Ni metal (mean Ni = 5.8 wt%) and sulfide grains are up to mm scale. No phyllosilicates were observed in the matrix. Refractory inclusions are rare (1.1 vol%) and melilite is absent. The oxygen isotope composition of NWA 1152 falls within the range of the CV chondrites with δ¹⁷O = ?3.43%0 δ¹⁸O = 0.70%0 and is similar to Sahara 00182, δ¹⁷O = ?3.89%0, δ¹⁸O = ?0.19%0 (Grossman and Zipfel 2001). Based on mineralogical and petrographic characteristics, we suggest NWA 1152 and Sahara 00182 show many similarities with the CR chondrites, however, oxygen isotopes suggest affinity with the CVs. Thus, neither sample can be assigned to any of the currently known carbonaceous chondrite groups based on traditionally recognized characteristics. Both samples demonstrate the complexity of inter‐ and intra‐group relationships of the carbonaceous chondrites. Whatever their classification, N WA 1152 and Sahara 00182 represent a source of relatively pristine solar system material.     

Analysis and survival of amino acids in Martian regolith analogs

Abstract— We have investigated the native amino acid composition of two analogs of Martian soil, JSC Mars‐1 and Salten Skov. A Mars simulation chamber has been built and used to expose samples of these analogs to temperature and lighting conditions similar to those found at low latitudes on the Martian surface. The effects of the simulated conditions have been examined using high‐performance liquid chromatography (HPLC). Exposure to energetic ultraviolet (UV) light in vacuum appears to cause a modest increase in the concentration of certain amino acids within the materials, which is interpreted as resulting from the degradation of microorganisms. The influence of low temperatures shows that the accretion of condensed water on the soils leads to the destruction of amino acids, supporting the idea that reactive chemical processes involving H₂O are at work within the Martian soil. We discuss the influence of UV radiation, low temperatures, and gaseous CO₂ on the intrinsic amino acid composition of Martian soil analogs and describe, with the help of a simple model, how these studies fit within the framework of life detection on Mars and the practical tasks of choosing and using Martian regolith analogs in planetary research.