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.     

Reflectance spectroscopy of insoluble organic matter (IOM) and carbonaceous meteorites

Insoluble organic matter (IOM) is the major organic component of chondritic meteorites and may be akin to organic materials from comets and interplanetary dust particles (IDPs). Reflectance spectra of IOM in the range 0.35–25 μm are presented as a tool for interpreting organic chemistry from remote measurements of asteroids, comets, IDPs, and other planetary bodies. Absorptions in the IOM spectra were strongly related to elemental H/C (atom) ratio. The aliphatic 3.4 μm absorption in IOM spectra increased linearly in strength with increasing H/C for H/C > 0.4, but was absent at lower H/C values. When meteorite spectra from the Reflectance Experiment Laboratory (RELAB) spectral catalog (n = 85) were reanalyzed at 3.4 μm, this detection limit (H/C > 0.4) persisted. Aromatic absorption features seen in IOM spectra were not observed in the meteorite spectra due to overlapping absorptions. However, the 3.4 μm aliphatic absorption strength for the bulk meteorites was correlated with both H/C of the meteorite's IOM and bulk C (wt%). Gaussian modeling of the 3 μm region provided an additional estimate of bulk C for the meteorites, along with bulk H (wt%), which is related to phyllosilicate abundance. These relationships lay the foundation for determining organic and phyllosilicate abundances from reflectance spectra. Both the full IOM spectra and the spectral parameters discussed here will aid in the interpretation of data from asteroid missions (e.g., OSIRIS‐REx, Hayabusa2), and may be able to place unknown spectral samples within the context of the meteorite collection.     

Quantifying noble gas contamination during terrestrial alteration in Martian meteorites from Antarctica

We investigated exterior and interior subsamples from the Martian shergottite meteorites Allan Hills (ALH) A77005 and Roberts Massif (RBT) 04261 for secondary minerals, oxygen isotopes, Ar‐Ar, and noble gas signatures. Electron microprobe investigations revealed that RBT 04261 does not contain any visible alteration even in its most exterior fractures, whereas fracture fillings in ALHA77005 penetrate into the meteorite up to 300 μm, beyond which the fractures are devoid of secondary minerals. Light noble gases seem to be almost unaffected by terrestrially induced alteration in both meteorites. Thus, a shock metamorphic overprint of 30–35 GPa can be deduced from the helium measurements in RBT 04261. Oxygen isotopes also seem unaffected by terrestrially weathering and variations can easily be reconciled with the differences in modal mineralogy of the exterior and interior subsamples. The measurements on irradiated samples (Ar‐Ar) showed a clear Martian atmospheric contribution in ALHA77005, but this is less apparent in our sample of RBT 04261. Exterior and interior subsamples show slight differences in apparent ages, but the overall results are very similar between the two. In contrast, krypton and xenon are severely affected by terrestrial contamination, demonstrating the ubiquitous presence of elementally fractionated air in RBT 04261. Although seemingly contradictory, our results indicate that RBT 04261 was more affected by contamination than ALHA77005. We conclude that irrespective of on which planet the alteration occurred, exposure of Martian rocks to atmosphere (or brine) introduces noble gases with signatures elementally fractionated relative to the respective atmospheric composition into the rock, and relationships of that process with oxygen isotopes or mineralogical observations are not straightforward.     

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

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

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

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

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.     

In situ identification,pairing, and classification of meteorites from Antarctica through magnetic susceptibility measurements

Abstract— We report on the effectiveness of using magnetic measurements in the search for meteorites on the Antarctic ice sheet, which is thus far the Earth's most productive terrain. Magnetic susceptibility measurements carried out with a pocket meter (SM30) during the 2003/04 PNRA meteorite collection expedition to northern Victoria Land (Antarctica) proved to be a rapid, sensitive, non‐destructive means for the in situ identification, pairing, and classification of meteorites. In blue ice fields characterized by the presence of moraines and glacial drifts (e.g., Miller Butte, Roberts Butte, and Frontier Mountain), magnetic susceptibility measurements allowed discrimination of meteorites from abundant terrestrial stones that look like meteorites thanks to the relatively high magnetic susceptibility of the former with respect to terrestrial rocks. Comparative measurements helped identify 16 paired fragments found at Johannessen Nunataks, thereby reducing unnecessary duplication of laboratory analyses and statistical bias. Following classifications schemes developed by us in this and previous works, magnetic susceptibility measurements also helped classify stony meteorites directly in the field, thereby providing a means for selecting samples with higher research priority. A magnetic gradiometer capable of detecting perturbations in the Earth's magnetic field induced by the presence of meteorites was an efficient tool for locating meteorites buried in snow along the downwind margin of the Frontier Mountain blue ice field. Based on these results, we believe that magnetic sensors should constitute an additional payload for robotic search for meteorites on the Antarctic ice sheet and, by extension, on the surface of Mars where meteorite accumulations are predicted by theoretical works. Lastly, magnetic susceptibility data was successfully used to crosscheck the later petrographic classification of the 123 recovered meteorites, allowing the detection of misclassified or peculiar specimens.     

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.     

Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X‐ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe³⁺/(Fe²⁺+Fe³⁺) ratio, determined from the analysis of the pre‐edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre‐edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North American microtektites.     

The thermodynamics of dust formation: Evidence from meteorites

A substantial fraction of interstellar dust probably formed in the nebulae around protostars, a setting similar to that envisioned for meteoritic material. From studies of the mineralogy and composition of meteorites it is possible to obtain quantitative information on the conditions that prevailed in the nebula. For example, pressures in the range 10^–3 to 10^–6 atm are indicated. At these pressures the kinetics of nucleation and grain growth are favorable.The fact that the gas associated with interstellar dust has solar H/S ratios indicates that FeS, which forms at 680 K, independent of pressure, is not present in the dust. Since iron only becomes oxidized at even lower temperatures, also via pressure-independent reactions, oxidized iron is not expected in the dust. If most interstellar dust forms in nebulae and is ejected back into space, a relatively high temperature is implied, 700K. Dust formation around stars with high C/O ratios is expected to produce minerals found in the highly reduced enstatite chondrites.High-temperature fractionation processes ( 1000 K) played an important role in the nebula. Much of the Al, Ca, Ti, etc., evidently condensed and accreted into cm-sized objects, some of which are found in carbonaceous chondrites. These objects are explicable in terms of formation from a cooling neutral gas with cosmic composition. Their most important distinguishing characteristics are low volatile and low Si contents, coupled with high refractory element contents constrains formation via isothermal compression to grain temperature 1000 K.Invited contribution to the proceedings of a workshop onThermodynamics and Kinetics of Dust Formation in the Space Medium held at the Lunar and Planetary Institute, Houston, 6–8 September, 1978.     

The gentle separation of presolar SiC grains from meteorites

Abstract— This paper describes the development of a new, effective, and non‐destructive method of SiC isolation from meteorites by freeze‐thaw disaggregation, size, and density separation. This new method is important because there is evidence that current methods, which use strong acids and chemical treatments to dissolve silicates and separate out the interstellar grains, may alter the surfaces of the grains chemically and isotopically. Furthermore, any non‐refractory coating present on the grains would be destroyed. Using our new separation method, SiC grains were enriched from ?6 ppm abundance in Murchison whole rock to 0.67% abundance in the 0.4‐1.4 μm size range and 0.27% abundance in the 1.4–17 μm size range. Individual SiC grains were easily identified using electron probe microanalysis (EPMA) mapping of grains distributed thinly on gold foil; a small aliquot from these fractions has so far yielded >150 SiC grains for isotopic analysis. The method separates out SiC grains efficiently, is applicable to very small or rare samples, and avoids the harsh acid treatments that may alter possible amorphous or non‐refractory coats on the grains. The procedure also preserves the remainder of the original sample and it is hoped that it may be extended to other micron‐sized presolar grains found in meteorites such as corundum, graphite, and silicon nitride.     

The delivery of organic matter from asteroids and comets to the early surface of Mars

Carbon delivered to the Earth by interplanetary dust particles may have been an important source of pre-biotic organic matter (Anders, 1989). Interplanetary dust is shown to deliver an order-of-magnitude higher surface concentration of carbon onto Mars than onto Earth, suggesting interplanetary dust may be an important source of carbon on Mars as well.     

The delivery of organic matter from asteroids and comets to the early surface of Mars

Carbon delivered to the Earth by interplanetary dust particles may have been an important source of pre-biotic organic matter (Anders, 1989). Interplanetary dust is shown to deliver an order-of-magnitude higher surface concentration of carbon onto Mars than onto Earth, suggesting interplanetary dust may be an important source of carbon on Mars as well.     

Comparison of FT‐IR spectra of bulk and acid insoluble organic matter in chondritic meteorites: An implication for missing carbon during demineralization

Past studies of the various separable carbonaceous fractions have been unable to account for all of C in primitive chondrites. In particular, up to 20–50% of the C is lost during acid leaching of bulk samples even after the C in carbonates and soluble organic matter is accounted for. To try to better characterize the nature of this “missing C,” we have compared the bulk infrared (IR) absorption spectra of a number of primitive chondrites with those of their previously reported insoluble organic matter (IOM). The aliphatic C–H stretching bands, in particular, allow us to compare the molecular structures of bulk C with that of IOM. The spectral differences between bulk C and IOM reflect “missing C” phases that were lost during acid leaching, although we cannot completely exclude the possibility that the OM was modified after demineralization. Comparing IR spectra of bulk meteorite powder and IOM suggests that the missing C varies in its molecular structure, and that mildly thermally metamorphosed type 3 chondrites tend to be richer in an aliphatic fraction with lower CH₂/CH₃ ratios, relative to IOM, compared to aqueously altered carbonaceous chondrites (CI/CM/CR). The missing C is most likely released from acid‐labile functional groups, such as esters, acetals, and amides, during demineralization, although it cannot be ruled out that some fraction of the missing C is in small grains that are difficult to recover from suspension, or in water‐soluble compounds trapped in phyllosilicates.     

The shear modulus of neutron star matter in the free-neutron state

The lattice whose properties have been tabulated by Baymet al. (1971) is unstable against nuclear quadrupole deformation for nuclear chargeZ>Z _c, 120<Z _c<201, if the electron gas is assumed to be of uniform density. Electron screening corrections to the change in energy density with nuclear deformation are large and it is shown that their inclusion removes the instability. The expression of Fuchs (1936), given originally for monovalent metals, overestimates the shear modulus of the lattice, for largeZ, by less than a factor of two.     

The density and porosity of meteorites from the Vatican collection

Abstract— We have developed a nondestructive technique to measure the densities and porosities of large (50 g to several kilogram) meteorite samples and have begun a systematic measurement program starting with meteorites from the Vatican Observatory collection. Our technique utilizes a modified Archimedean method (40 μm glass spheres substituting for the fluid) to determine bulk density, and an unusually large He pycnometer to determine grain density. From these, the porosity is calculated. We report here our first results for 89 samples (nearly doubling the published database on porosities of meteorite hand samples), including porosities of 35 different meteorites. These include several types not previously reported: eight iron meteorites, six stony-iron meteorites, an enstatite chondrite, the CI carbonaceous chondrite Orgueil, and the shergottite-nakhlatite-chassignite (SNC) meteorite Nakhla.     

Organic matter from comet 81P/Wild 2, IDPs,and carbonaceous meteorites; similarities and differences

Abstract— During preliminary examination of 81P/Wild 2 particles collected by the NASA Stardust spacecraft, we analyzed seven, sulfur embedded and ultramicrotomed particles extracted from five different tracks. Sections were analyzed using a scanning transmission X‐ray microscope (SXTM) and carbon X‐ray absorption near edge structure (XANES) spectra were collected. We compared the carbon XANES spectra of these Wild 2 samples with a database of spectra on thirty‐four interplanetary dust particles (IDPs) and with several meteorites. Two of the particles analyzed are iron sulfides and there is evidence that an aliphatic compound associated with these particles can survive high temperatures. An iron sulfide from an IDP demonstrates the same phenomenon. Another, mostly carbon free containing particle radiation damaged, something we have not observed in any IDPs we have analyzed or any indigenous organic matter from the carbonaceous meteorites, Tagish Lake, Orgueil, Bells and Murchison. The carbonaceous material associated with this particle showed no mass loss during the initial analysis but chemically changed over a period of two months. The carbon XANES spectra of the other four particles varied more than spectra from IDPs and indigenous organic matter from meteorites. Comparison of the carbon XANES spectra from these particles with 1. the carbon XANES spectra from thirty‐four IDPs (<15 micron in size) and 2. the carbon XANES spectra from carbonaceous material from the Tagish Lake, Orgueil, Bells, and Murchison meteorites show that 81P/Wild 2 carbon XANES spectra are more similar to IDP carbon XANES spectra then to the carbon XANES spectra of meteorites.     

Astronomy from Dome A in Antarctica

Dome A in Antarctica has been demonstrated to be the best site on earth for optical, infrared, and terahertz astronomical observations by more and more evidence, such as excellent free-atmosphere seeing,extremely low perceptible water vapor, low sky background, and continuous dark time, etc. In this paper,we present a complete picture of the development of astronomy at Dome A from the very beginning, review recent progress in time-domain astronomy, demonstrate exciting results of the site testing, and address the challenges in instrumentation. Currently proposed projects are briefly discussed.     

Radiation history of fossil meteorites from Sweden

We present the results of the analysis of the data obtained by Heck et al. (2004; 2008) regarding the contents of ⁴He and ^20,21,22Ne and the exposure age of chromite grains recovered from fossil meteorites (L-chondrites) found in marine limestone—mid-Ordovician sediments—in the Thorsberg and Gullhogen quarries of southern Sweden. It has been shown that the increase of the content of noble gases in the chromite grains (by 1–2 orders of magnitude) and their exposure age with a decreasing mass of the samples (by approximately an order of magnitude) can be caused by an increase of the portion of small grains and by their poor preservation in the samples of small mass. The revealed relationships, as well as the fact that practically all fossil meteorites were found in a small area (∼6000 m²), can be explained by the following assumption: a meteorite shower, caused by a single meteorite, fell ∼470 Myr; this occurred less than 0.2 Myr after the catastrophic destruction of the L-chondrite parent body. The time of this fall corresponds to that of the formation of the oldest sedimentation stratum, containing the meteorite fragments, in the Thorsberg quarry. Meteorite fragments in the younger strata are most likely the result of the subsequent redeposition that occurred in a shallow sea, when the sediment mass was forming. In this case, to explain the distribution of fossil meteorites in the mid-Ordovician sediments in Sweden, there is no necessity to hypothesize that an intense flux of meteorites was falling onto the Earth over the course of ∼1–2 Myr about 470 million years ago.