Carbon,nitrogen and hydrogen in Saharan chondrites: The importance of weathering

Abstract— The Sahara Desert is a region of high diurnal temperature variation and sporadic rainfall that has recently yielded over 450 meteorites. Eighteen of these Saharan samples are carbonaceous chondrites, of which we have analysed 17 for C content and isotopic composition. Ten of the 18 are paired CR chondrites, of which four have also had N and H contents and compositions determined. A primitive ordinary chondrite (L/LL3.2) found in the region has also been analysed for C, N and H contents and isotopic composition. Saharan samples contain between 21% and 45% of the light elements of their non-Saharan counterparts. Paired Saharan samples show a greater heterogeneity in both C content and isotopic composition than multiple analyses of non-Saharan samples. The cause of the observed isotopic and abundance effects is due to the hot desert weathering processes experienced by these samples. Peak temperatures of meteorites on the desert floor may be in excess of 100 °C, leading to low-temperature hydrous pyrolysis and oxidation reactions, liberating volatile organics and CO₂. This may also cause the remaining material to become partially solubilised and ultimately lost during rainfall. The low δD of the CR and ordinary chondrites can be attributed to the destruction and loss of organic material through dehydrogenation and exchange reactions on the desert surface. The increased ¹³C abundance suggests that the less tightly bound C from the macromolecular organic material is isotopically lighter than the remaining C. Carbon contents and isotopic compositions are also affected by the addition of terrestrial calcitic evaporite deposits, up to 10,000 ppm carbonate has been measured, with a δ¹³C of between 0 and ?10%₀.     

Irradiated benzene ice provides clues to meteoritic organic chemistry

Aromatic hydrocarbons account for a significant portion of the organic matter in carbonaceous chondrite meteorites, as a component of both the low molecular weight, solvent-extractable compounds and the insoluble organic macromolecular material. Previous work has suggested that the aromatic compounds in carbonaceous chondrites may have originated in the radiation-processed icy mantles of interstellar dust grains. Here we report new studies of the organic residue made from benzene irradiated at 19 K by 0.8 MeV protons. Polyphenyls with up to four rings were unambiguously identified in the residue by gas chromatography–mass spectrometry. Atmospheric pressure photoionization Fourier transform mass spectrometry was used to determine molecular composition, and accurate mass measurements suggested the presence of polyphenyls, partially hydrogenated polyphenyls, and other complex aromatic compounds. The profile of low molecular weight compounds in the residue compared well with extracts from the Murchison and Orgueil meteorites. These results are consistent with the possibility that solid phase radiation chemistry of benzene produced some of the complex aromatics found in meteorites.     

Ultraviolet irradiation of naphthalene in H2O ice: Implications for meteorites and biogenesis

Abstract— The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H₂O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high‐performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H₂O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon‐rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.     

TIBOOBURRA,A NEW AUSTRALIAN METEORITE FIND,AND OTHER CARBONACEOUS CHONDRITES OF HIGH PETROLOGIC GRADE

Tibooburra, a new meteorite find from western New South Wales, belongs to the Vigarano subgroup of the carbonaceous chondrites and, on the basis of its opaque mineralogy, appears to be oxidised. Petrological evidence suggests that, like the Allende meteorite, Tibooburra is a CV3 chondrite which has experienced greater metamorphic effects than other CV3 meteorites. Tibooburra has a bulk composition intermediate between the CO and less altered CV chondrites. This transitional nature is exhibited by several elements and is convincingly displayed by the multivariate techniques of cluster analysis and principal component analysis. Tibooburra thus resembles several other CV chondrites, such as Coolidge and Karoonda, which have been strongly metamorphosed. This group of meteorites is believed to have accreted early in the history of the Vigarano parent body and, as a result, contain greater quantities of high temperature Ca-Al-rich inclusions but less low temperature matrix and volatile phases than other CV chondrites. Furthermore, in these meteorites both the matrix and magnesium silicate phases appear to be more iron rich than those in later accreted meteorites. Subsequently, these deeper seated meteorites have undergone more pronounced thermal metamorphism than those located in shallower portions of the parent body.     

Matrix isolation spectroscopy study of iron reactivity towards PAHs

The hypothesis of organometallic chemistry between polycyclic aromatic hydrocarbons (PAHs) and metals in the interstellar medium (ISM) has been recently proposed to contribute both to the unidentified interstellar infrared (UIR) emission and to the depletion of transition metals in the ISM. Since temperature and pressure conditions of the ISM can be easily simulated by matrix isolation techniques, we have undertaken the preparation of such species through cocondensation reactions of metal atoms (iron) with some PAHs (pyrene, coronene) in low temperature argon and dinitrogen matrices. The identification of species is achieved by means of FTIR and UV-visible spectroscopies. First results show that a weak reactivity occurs between neutral species at lOK: π-complexes, hydrogen-bonded compounds, and one hydride species have been observed.     

A chemical sequence of macromolecular organic matter in the CM chondrites

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

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.     

Terrestrial microfossils in Antarctic ordinary chondrites

Abstract— Microfossils have been separated and identified in four high metamorphic grade chondrites from Allan Hills and Queen Alexandra Range, Antarctica. Diatoms and opal phytoliths representing both marine and terrestrial flora were recognized among the dust removed from cracks in all meteorites studied. It is likely that contamination of Antarctic meteorites with such biogenic material is ubiquitous. Standard clean room procedures to avoid laboratory introduction of microfossils into the meteorites were followed, and the genera and species identified so far are characteristic of marine, freshwater, and continental environments. The most probable mechanism for introduction of the microfossils into the meteorites is eolian transport to and on the polar ice cap. It is likely that wind-driven systems may sample atmospherically transported material from large portions of the southern hemisphere. Entrainment of terrestrial microfossils is probably a typical interaction of meteorites with the Antarctic environment and must be recognized and accounted for in any attempt to use Antarctic meteorites as sources of extraterrestrial life forms. Organic molecules derived from microfossils are likely to be pervasive throughout any crack network present in a meteorite at all scales from millimeter to submicron. Cracks are a ubiquitous consequence of weathering in and on the Antarctic ice and the probability that crack surfaces contain terrestrial organic materials is high.     

40Ar‐39Ar age of Northwest Africa 091: More evidence for a link between L chondrites and fossil meteorites

Abstract— Most ⁴⁰Ar‐³⁹Ar ages of L chondrites record an event at approximately 500 Ma, indicating a large collisional impact at that time. However, there is a spread in ages from 400 to 600 Ma in these meteorites that is greater than the analytical uncertainty. Identification of, and correction for, trapped Ar in a few L chondrites has given an age of 470 ± 6 Ma. This age coincides with Ordivician fossil meteorites that fell to Earth at 467 ± 2 Ma. As these fossil meteorites were originally L chondrites, the apparent conclusion is that a large impact sent a flood of L chondrite material to Earth, while material that remained on the L chondrite parent body was strongly heated and reset. We have reduced ⁴⁰Ar‐³⁹Ar data for Northwest Africa 091 using various techniques that appear in the literature, including identification and subtraction of trapped Ar. These techniques give a range of ages from 455 to 520 Ma, and show the importance of making accurate corrections. By using the most straightforward technique to identify and remove a trapped Ar component (which is neither terrestrial nor primordial), an ⁴⁰Ar‐³⁹Ar age of 475 ± 6 Ma is found for Northwest Africa 091, showing a temporal link to fossil meteorites. In addition, high temperature releases of Northwest Africa 091 contain evidence for a second trapped component, and subtraction of this component indicates a possible second collisional impact at approximately 800 Ma. This earlier age coincides with ⁴⁰Ar‐³⁹Ar ages of some H and L chondrites, and lunar samples.     

Molecular and isotopic indicators of alteration in CR chondrites

Abstract— The CR group of carbonaceous chondrites may represent some of the most primitive extraterrestrial materials available for analysis. However, in contrast to other chondrite groups, the CR organic fraction is poorly characterized. The carbonaceous chondrite literature shows that relatively anhydrous thermal processing results in a condensed, poorly alkylated, O‐poor macromolecular material, while for aqueous processing the converse is true. Such characteristics can be used to discern the alteration histories of the carbonaceous chondrites. We have performed bulk elemental and isotopic analysis and flash pyrolysis on four CR chondrites (Renazzo, Al Rais, Elephant Moraine [EET] 87770, and Yamato [Y‐] 790112) to determine the nature of their organic component. Renazzo, Al Rais, and Y‐790112 release qualitatively similar pyrolysis products, although there are some variations. Al Rais' macromolecular structure contains substantially higher relative abundances of alkylated and oxidized species and relatively lighter δ¹⁵N, suggesting that it has endured more extensive aqueous processing than the other CR chondrites. Renazzo appears relatively unprocessed, with a low degree of alkylation, a lack of detectable nitrogen‐bearing components, and low methylnaphthalene ratio. EET 87770's low abundance of alkylated species suggests its macromolecular structure may be relatively condensed, with condensation potentially assisted by a period of mild thermal alteration.     

Doppler weather radar as a meteorite recovery tool

Abstract– We report the use of Doppler weather radar as a tool for locating meteorites, both at the time of a fall and from archived radar data. This asset is especially useful for meteorite recovery as it can provide information on the whereabouts of falling meteorites in “dark flight” portion of their descent where information on their flight paths cannot be discerned from more traditional meteorite location techniques such as eyewitness accounts. Weather radar data can provide information from detection in three distinct regimes: (A) direct detection of the rapidly moving, optically bright fireball by distant radars, (B) detection of falling debris to include hand‐sample sized rocks, and (C) detection of dust produced by detonation events that can occur tens of minutes and many kilometers laterally removed from the actual fireball locality. We present examples of each, as well as comparisons against man‐made debris from a re‐entering Soyuz rocket and the Stardust Sample Return Capsule. The use of Doppler weather radar as a supplement to traditional meteorite recovery methods holds the promise of improving both the speed and total number of meteorite recoveries, thereby increasing the number of freshly fallen meteorites for scientific study.     

The use of Auger spectroscopy for the in situ elemental characterization of sub‐micrometer presolar grains

Abstract— Presolar grains are small samples of stardust that can be found at low abundances in some of the most unaltered types of extraterrestrial materials. While earlier laboratory studies of stardust mainly focused on grain types that can be extracted from bulk meteorites by acid dissolution techniques, such as silicon carbide and graphite, recent analyses of presolar silicates rely on isotope imaging searches for locating these grains in situ. Since presolar silicates are generally less than a micrometer in diameter and represent at best only a few hundred ppm of their host materials (e.g., primitive meteorites or interplanetary dust particles), locating and studying these particles can be analytically challenging. Recently, we began using scanning Auger spectroscopy for the in situ elemental characterization of presolar silicate grains as a complement to NanoSIMS isotopic studies for obtaining spatially matched compositional data. Auger spectroscopy is a well‐established analytical technique for elemental characterizations in the material sciences, but has not been widely used in geological applications. We discuss the application of this technique to sub‐micrometer sized silicate grains and address practical issues such as sample preparation, measurement settings, spatial resolution, data processing, and elemental quantification.     

Microscopic search for the carrier phase Q of the trapped planetary noble gases in Allende,Leoville and Vigarano

Abstract— High‐resolution transmission electron microscopy micrographs of acid‐resistant residues of the Allende, Leoville, and Vigarano meteorites show a great variety of carbon structures: curved and frequently twisted and intertwined graphene sheets, abundant carbon black‐like particles, and hollow “sacs”. It is suggested that perhaps all of these are carriers for the planetary Q‐noble gases in these meteorites. Most of these materials are pyrocarbons that probably formed by the pyrolysis of hydrocarbons either in a gas phase, or on hot surfaces of minerals. An attempt was made to analyze for argon with particle‐induced x‐ray emission in 143 spots of grains of floating and suspended matter from freeze‐dry cycles of an Allende bulk sample in water, and floating “black balls” from sonication in water of samples from the Allende meteorite. The chemical compositions of these particles were obtained, but x‐ray signals at the wavelength of argon were obtained on only a few spots.     

Expected characteristics of cometary meteorites

Abstract— Recent developments in our understanding of comets provide insights into the topic of cometary meteorites. These developments include the identification of comet-asteroid transition objects (such as 4015 Wilson-Harrington and 3200 Phaethon), information on the composition of cometary solids, and new ideas on the collisional history of Jupiter-family comets. In this work, we revisit this question, and we conclude that comets do indeed yield macroscopic meteorites, which either have not been found or have not been recognized. We also consider the expected characteristics of cometary meteorites, with an emphasis on those that may help identify and differentiate them from other types of meteorites. If cometary meteorites have preserved the main characteristics of cometary dust, the mineralogy would be dominated by highly unequilibrated anhydrous silicates, and the chemistry would be nearly chondritic but with a high abundance of C and N. On the other hand, if an unknown process produced extensive aqueous alteration in the material that formed cometary meteorites, they would resemble (or could even be) CI carbonaceous chondrites. We do not expect cometary meteorites to have chondrules. So far, no single meteorite looks unequivocally cometary. However, we have identified xenoliths in ordinary chondrite regolith breccias that meet most of our criteria for a cometary origin and deserve further study.     

Hydrocarbons on Saturn's satellites Iapetus and Phoebe

Material of low geometric albedo (pV?0.1) is found on many objects in the outer Solar System, but its distribution in the saturnian satellite system is of special interest because of its juxtaposition with high-albedo ice. In the absence of clear, diagnostic spectral features, the composition of this low-albedo (or “dark”) material is generally inferred to be carbon-rich, but the form(s) of the carbon is unknown. Near-infrared spectra of the low-albedo hemisphere of Saturn's satellite Iapetus were obtained with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft at the fly-by of that satellite of 31 December 2004, yielding a maximum spatial resolution on the satellite's surface of ∼65 km. The spectral region 3-3.6 μm reveals a broad absorption band, centered at 3.29 μm, and concentrated in a region comprising about 15% of the low-albedo surface area. This is identified as the CH stretching mode vibration in polycyclic aromatic hydrocarbon (PAH) molecules. Two weaker bands attributed to CH₂ stretching modes in aliphatic hydrocarbons are found in association with the aromatic band. The bands most likely arise from aromatic and aliphatic units in complex macromolecular carbonaceous material with a kerogen- or coal-like structure, similar to that in carbonaceous meteorites. VIMS spectra of Phoebe, encountered by Cassini on 11 June 2004, also show the aromatic hydrocarbon band, although somewhat weaker than on Iapetus. The origin of the PAH molecular material on these two satellites is unknown, but PAHs are found in carbonaceous meteorites, cometary dust particles, circumstellar dust, and interstellar dust.     

Partial amorphization of experimentally shocked plagioclase: A spectroscopic study

Shock amorphization of plagioclase, from partial to complete, has been used to evaluate the degree of shock in meteorites. Important information on the shock amplitude can be derived from the measurement of the refractive index in plagioclase, either from mineral separates or in petrographic thin sections. However, this technique is time‐consuming, and associated sample preparations are considered destructive and are not always possible for precious and rare meteorite samples. In addition, plagioclase amorphization is commonly inhomogeneous at the sample scale and a statistically meaningful number of grains must be considered. Here, we apply several nondestructive spectroscopic techniques, such as Raman spectroscopy, photoluminescence, and cathodoluminescence, to plagioclase experimentally shocked at 28 GPa, and thus in the transition regime between crystalline plagioclase and fully amorphous material. Most of the plagioclase was transformed into diaplectic glass at 28 GPa, yet some grains exhibit heterogeneously distributed crystalline domains. This confirms that intrinsic and extrinsic factors lead to local variations in the intensity of the shock pressure within individual plagioclase crystals of homogeneous composition. The amorphization of plagioclase can qualitatively (and potentially also quantitatively) be investigated by spectroscopic techniques, highlighting such local variations in the shock efficiency.     

Compositional and lithological diversity among brecciated lunar meteorites of intermediate iron concentration

Abstract— We present new compositional data for 30 lunar stones representing about 19 meteorites. Most have iron concentrations intermediate to those of the numerous feldspathic lunar meteorites (3–7% FeO) and the basaltic lunar meteorites (17–23% FeO). All but one are polymict breccias. Some, as implied by their intermediate composition, are mainly mixtures of brecciated anorthosite and mare basalt, with low concentrations of incompatible elements such as Sm (1–3 μg/g). These breccias likely originate from points on the Moon where mare basalt has mixed with material of the FHT (Feldspathic Highlands Terrane). Others, however, are not anorthosite‐basalt mixtures. Three (17–75 μ/g Sm) consist mainly of nonmare mafic material from the nearside PKT (Procellarum KREEP Terrane) and a few are ternary mixtures of material from the FHT, PKT, and maria. Some contain mafic, nonmare lithologies like anorthositic norites, norites, gabbronorites, and troctolite. These breccias are largely unlike breccias of the Apollo collection in that they are poor in Sm as well as highly feldspathic anorthosite such as that common at the Apollo 16 site. Several have high Th/Sm compared to Apollo breccias. Dhofar 961, which is olivine gabbronoritic and moderately rich in Sm, has lower Eu/Sm than Apollo samples of similar Sm concentration. This difference indicates that the carrier of rare earth elements is not KREEP, as known from the Apollo missions. On the basis of our present knowledge from remote sensing, among lunar meteorites Dhofar 961 is the one most likely to have originated from South Pole‐Aitken basin on the lunar far side.     

METEORITES AND THERMOLUMINESCENCE

The TL techniques that have been developed successfully for archaeological and dosimetric applications cannot be unambiguously applied to meteorites because of the possibility that most or all of the meteorite TL is in dynamic equilibrium — its rate of thermal decay balancing its rate of build-up. In this situation, space irradiation temperature and, thereby, orbital information for the most recent eras (10⁵-10⁶ years), can be determined. In only a few instances (e.g. meteorites with very low exposure ages) will the possibility exist that equilibrium may not have been reached, but even here it has to be shown that the exposure event had removed previously existing TL before normal TL dating techniques can be employed. There is some evidence to suggest that the TL sensitivity builds up with time. This raises the possibility of dating major shock and/or reheating events, if it can be shown that such events destroyed the TL sensitivity.     

The preservation state of organic matter in meteorites from Antarctica

Abstract— The recovery of large numbers of meteorites from Antarctica has dramatically increased the amount of extraterrestrial material available for laboratory studies of solar system origin and evolution. Yet, the great age of Antarctic meteorites raises the concern that significant amounts of terrestrial weathering has corrupted their pre‐terrestrial record. Organic matter found in carbonaceous chondrites is one of the components most susceptible to alteration by terrestrial processes. To assess the effects of Antarctic weathering on both non‐Antarctic and Antarctic chondritic organic matter, a number of CM chondrites have been analyzed. Mössbauer spectroscopy has been used to ascertain pre‐terrestrial and terrestrial oxidation levels, while pyrolysis‐gas chromatography‐mass spectrometry was used to determine the constitution of any organic matter present. Increased oxidation levels for iron bearing minerals within the non‐Antarctic chondrites are likely to be a response to increased amounts of parent body aqueous alteration. Parent body processing also appears to remove ether bonds from organic material and alkyl side chains from its constituent units. The iron in Antarctic chondrites is generally more oxidized than that in their non‐Antarctic counterparts, reflecting terrestrial weathering. Antarctic weathering of chondritic organic matter appears to proceed in a similar way to parent body aqueous alteration and simply enhances the organic responses observed in the non‐Antarctic data set. Degradation of the record of preterrestrial processes in Antarctic chondrites should be taken into account when interpreting data from these meteorites.     

Physical properties of Martian meteorites: Porosity and density measurements

Abstract— Martian meteorites are fragments of the Martian crust. These samples represent igneous rocks, much like basalt. As such, many laboratory techniques designed for the study of Earth materials have been applied to these meteorites. Despite numerous studies of Martian meteorites, little data exists on their basic structural characteristics, such as porosity or density, information that is important in interpreting their origin, shock modification, and cosmic ray exposure history. Analysis of these meteorites provides both insight into the various lithologies present as well as the impact history of the planet's surface. We present new data relating to the physical characteristics of twelve Martian meteorites. Porosity was determined via a combination of scanning electron microscope (SEM) imagery/image analysis and helium pycnometry, coupled with a modified Archimedean method for bulk density measurements. Our results show a range in porosity and density values and that porosity tends to increase toward the edge of the sample. Preliminary interpretation of the data demonstrates good agreement between porosity measured at 100× and 300× magnification for the shergottite group, while others exhibit more variability. In comparison with the limited existing data for Martian meteorites we find fairly good agreement, although our porosity values typically lie at the low end of published values. Surprisingly, despite the increased data set, there is little by way of correlation between either porosity or density with parameters such as shock effect or terrestrial residency. Further data collection on additional meteorite samples is required before more definitive statements can be made concerning the validity of these observations.