Noble gases in ureilites released by crushing

Abstract— Noble gases in two ureilites, Kenna and Allan Hills (ALH) 78019, were measured with two extraction methods: mechanical crushing in a vacuum and heating. Large amounts of noble gases were released by crushing, up to 26.5% of ¹³²Xe from ALH 78019 relative to the bulk concentration. Isotopic ratios of the crush‐released Ne of ALH 78019 resemble those of the trapped Ne components determined for some ureilites or terrestrial atmosphere, while the crush‐released He and Ne from Kenna are mostly cosmogenic. The crush‐released Xe of ALH 78019 and Kenna is similar in isotopic composition to Q gas, which indicates that the crush‐released noble gases are indigenous and not caused by contamination from terrestrial atmosphere. In contrast to the similarities in isotopic composition with the bulk samples, light elements in the crush‐released noble gases are depleted relative to Xe and distinct from those of each bulk sample. This depletion is prominent especially in the ²⁰Ne/¹³²Xe ratio of ALH 78019 and the ³⁶Ar/¹³²Xe ratio of Kenna. The values of measured ³He/²¹Ne for the gases released by crushing are significantly higher than those for heating‐released gases. This suggests that host phases of the crush‐released gases might be carbonaceous because cosmogenic Ne is produced mainly from elements with a mass number larger than Ne. Based on our optical microscopic observation, tabular‐foliated graphite is the major carbon mineral in ALH 78019, while Kenna contains abundant polycrystalline graphite aggregates and diamonds along with minor foliated graphite. There are many inclusions at the edge and within the interior of olivine grains that are reduced by carbonaceous material. Gaps can be seen at the boundary between carbonaceous material and silicates. Considering these petrologic and noble gas features, we infer that possible host phases of crush‐released noble gases are graphite, inclusions in reduction rims, and gaps between carbonaceous materials and silicates. The elemental ratios of noble gases released by crushing can be explained by fractionation, assuming that the starting noble gas composition is the same as that of amorphous carbon in ALH 78019. The crush‐released noble gases are the minor part of trapped noble gases in ureilites but could be an important clue to the thermal history of the ureilite parent body. Further investigation is needed to identify the host phases of the crush‐released noble gases.     

Carbon,Nitrogen, and Noble Gases in the Diamond Fractions of the Novo Urei Ureilite

We measured the contents and isotopic compositions for C, N, and noble gases in the diamond fractions separated in a heavy liquid ( = 2.9 g/cm³) from a sample enriched with diamond from the Novo Urei ureilite. The results show that the concentrations of nitrogen and noble gases in the diamond fraction isolated from the supernatant (the fraction is named DNU-1) are more than a factor of 1.5 higher than those in the diamond fraction from the residue (DNU-2). This difference is probably caused by smaller sizes of grains and (or) clusters of smaller grains as well as by larger defectiveness of the crystal lattice of the diamond in the DNU-1 fraction as compared to DNU-2. Both fractions are similar in the isotopic composition of C and N and in the ratios of trapped chemical elements. The results obtained and the published data concerning C, N, and noble gases in different fractions of other ureilites allow us to conclude the following. (1) The ureilite diamond was most likely formed from graphite and the fine-grained crystalline (or semiamorphous) carbonaceous phase as a result of shock transformation in the parent bodies. (2) The negative result in the search for the isotopically light component of nitrogen (¹⁵N is about –100) in the Antarctic unshocked ureilite ALH 78019 (Rai et al., 2002), which introduced serious difficulties for explaining the origin of the ureilite diamond in the parent bodies during the impact, is most likely caused by the absorption of atmospheric nitrogen by the carbonaceous material in the processes of terrestrial weathering. (3) The source of light nitrogen (¹⁵N –100) in the ureilite diamond was probably the presolar diamond in the initial carbonaceous material of the ureilite parent bodies, because the impurity elements, including nitrogen (¹⁵N < –350), in this diamond could be trapped in the magmatic processes by the carbonaceous material, which became a precursor of the ureilite diamond in the shock event.     

Mineralogical evidence for the origin of diamond in ureilites

Abstract— The x‐ray powder diffraction patterns of 50–100 μm C‐rich grains from five ureilitic meteorites—Kenna, Allan Hills (ALH) 78019, Yamato (Y)‐82100, Y‐791538, and ALH 77257—were obtained by using a Gandolfi camera. The results reveal that the basal spacing of part of the graphite coexisting with diamond is slightly smaller compared to the normal spacing. Compressed graphite is experimentally known to occur at the initial stage of the direct transformation from graphite to diamond structures at high pressures and temperatures. The presence of the compressed graphite in ureilites, therefore, gives clear evidence that the diamond formed by high‐pressure conversion of graphite. The modes of occurrence of C minerals observed with reflected light through an optical microscope reveal that graphite coexisted with olivine and pyroxene during igneous or metamorphic processes and, furthermore, that part of the graphite was converted to diamond by impact. The relative x‐ray intensity of diamond to graphite increases in the following order: ALH 78019 and Y‐82100 < Y‐791538 < Kenna < ALH 77257. This correlates with the shock level that is estimated mainly on the basis of the shock features of silicates. Therefore, the relative amounts of diamond to graphite suggested by x‐ray intensities may be useful as a measure of the degree of shock.     

Carbon isotope fractionation between graphite and diamond during shock experiments

Abstract— Carbon isotopic compositions were measured for shock‐produced diamond and shocked graphite formed at peak pressures ranging from 37 to 52 GPa. The δ¹³C values of diamonds produced in a sealed container were generally lower than that of the initial graphite. The differences in the carbon isotopic composition between initial graphite and shocked graphite/diamond may reflect kinetic isotopic fractionation during the oxidation of the graphite/diamond and/or analytical artifacts possibly induced by impurities in the samples. The pressure effect on the isotopic fractionations between graphite and diamond can be estimated from the δ¹³C values of impurity‐free diamonds produced using a vented container from which gases, including oxygen, in pore spaces escaped during or after the diamond formation (e.g., 0.039 ± 0.085‰ at a peak pressure of 52 GPa). Any isotopic fractionation induced by shock conversion of graphite to diamond is too small to be detected in natural shock‐induced diamond‐graphite systems related to terrestrial impact cratering processes.     

Raman spectroscopic study of diamond and graphite in ureilites and the origin of diamonds

Abstract– We performed micro‐Raman spectroscopic analyses of the carbon vein in five ureilites: Allan Hills (ALH) A77257, Northwest Africa (NWA) 3140, Shi?r 007, Yamato 790981 (Y‐790981), and Yamato 791538 (Y‐791538). The graphite peaks showed that the graphite structure in ureilite is well developed, especially compared with the carbonaceous material in carbonaceous chondrite. The domain sizes of the graphite were 45–110 Å. We observed shifts in the diamond peak positions to higher wave numbers with a large full width at half maximum (FWHM), especially for NWA 3140. Although the FWHM of a diamond peak is not a crucial diagnostic test for a chemical vapor deposition (CVD) origin of diamond, the shift of the diamond peaks to higher wave numbers could be a strong indicator that supports the CVD origin as these shifts have only been observed in CVD diamonds. We discuss the origin of diamond from various aspects, and confirm that the CVD model is the most plausible. We conclude that all carbon material (graphite, amorphous carbon, diamond, etc.) condensed on the early condensates in the primitive solar nebula.     

ROOSEVELT COUNTY 027: A LOW-SHOCK UREILITE WITH INTERSTITIAL SILICATES AND HIGH NOBLE GAS CONCENTRATIONS

The lightly-shocked ureilite RC027 was found in Roosevelt County, New Mexico in 1984. In terms of petrography, texture, mineral compositions, bulk chemical composition, and oxygen isotopic composition it is a typical ureilite. It contains ～75% olivine (Fo 79.4) and 25% pigeonite (mg 81.3, Wo 8.0), with intergranular graphite and (Fe, Ni) metal. It also contains less than 1% of fine-grained, interstitial silicate material, which had not previously been recognized in any ureilite. This material is an assemblage of low-Ca pyroxene (Wo 3.5–9, mg 87–93), augite (Wo 24–36, mg 90–98), glass (typically ～95% SiO₂, 4% Al₂O₃, 0.5% Na₂O), and crystalline SiO₂. This material has an igneous texture, indicating that it crystallized from an interstitial liquid. Low-Ca pyroxene compositions indicate that the interstitial liquid was not in equilibrium with core pigeonite and olivine and cannot have been either an evolved intercumulus liquid or a low-degree partial melt. It may contain a component of shock-melted olivine and pigeonite, although petrographic evidence indicates that it could not have been an in situ shock melt. One sample of RC027 has a V-shaped rare earth element pattern, typical of ureilites. Another is depleted in light rare earth elements (LREE), similar to acid-treated samples of ureilites, which suggests that LREE in ureilites are contained in an inhomogeneously-distributed phase. RC027 shows the strongest olivine preferred-orientation yet observed in a ureilite. Its fabric is characteristic of fabrics formed by tabular minerals in a fluid laminar flow regime and is unlike those formed by syntectonic recrystallization and plastic flow. The elemental and isotopic compositions of noble gases in RC027 are typical of previously analyzed ureilites. This result indicates that there is no correlation of noble gas content with degree of shock in ureilites, and thus suggests that the gases were present in the ureilite material before shock. Cosmogenic He and Ne contents indicate cosmic ray exposure ages of 1.7 and 1.9 Myr, respectively. Thus, RC027 is not paired with Kenna (a ureilite also found in Roosevelt County), which has an exposure age of ～33 Myr.     

Ureilites: A critical review

Abstract— Ureilites are coarse-grained ultramafic rocks whose petrography, mineral chemistry, lithophile element bulk chemistry, and Sm-Nd isotopic systematics suggest that they are highly fractionated igneous rocks and thus are products of common planetary differentiation processes. However, they also have primitive characteristics that are difficult to reconcile with extensive igneous processing. These include high abundances of siderophile elements, planetary-type noble gases, and the oxygen isotopic signature of unequilibrated solar system materials. The incongruity between igneous and primitive features constitutes the most important problem in understanding ureilite petrogenesis. In this review the petrographic, chemical, and isotopic characteristics of ureilites are summarized, and the petrogenetic implications of these characteristics are discussed. The most important constraints on ureilite petrogenesis are: 1) Ureilites have lost a basaltic complement; 2) Ureilites had a two-stage cooling history; 3) Ureilites are probably residues but partly crystallized from melts; 4) Ureilites are derived from a minimum of six reservoirs which were distinct in oxygen isotopic composition and did not equilibrate with one another; 5) A correlation between oxygen isotopic composition and mg ratio was established in ureilite parent material in the solar nebula; 6) If carbon-metal-silicate-CO/CO₂ equilibrium was maintained then the mg ratios of ureilites were pressure/depth-dependent; however, if the pressure was sufficiently high (> 100–200 bars) that a CO/CO₂ gas phase was not present then carbon and metal could have been at equilibrium with all ureilite mg ratios at the same pressure; 7) Ureilites either lost a low-melting temperature metal fraction or gained a refractory-rich metal component; 8) Primordial noble gases were retained in carbon in ureilites; 9) The ultramafic ureilite assemblage formed at ～4.55 Ga, but Sm-Nd and Rb-Sr isotopic systematics have been subsequently disturbed. Recently proposed models for ureilite petrogenesis are evaluated in terms of how well they satisfy these constraints; no models unequivocally satisfy all of them. Reconciling constraints 5 and 6 requires a large ureilite parent body.     

Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite

This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon‐rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2–2.3 wt% carbon; most showed the major carbon release at temperatures of 600–700 °C with peak values of δ¹³C from ?7.3 to +0.4‰, similar to literature values for unbrecciated (“monomict”) ureilites. They also contained a minor low temperature (≤500 °C) component (δ¹³C = ca ?25‰). Bulk nitrogen contents (9.4–27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600–750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release δ¹⁵N values of ?53 to ?94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen‐rich and isotopically heavier. Thus, although the parent asteroid 2008TC₃ was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release δ¹³C and δ¹⁵N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.     

MicroRaman spectroscopy of diamond and graphite in Almahata Sitta and comparison with other ureilites

This work is the first detailed study of carbon phases in the ureilite Almahata Sitta (sample #7). We present microRaman data for diamond and graphite in Almahata Sitta, seven unbrecciated ureilites, and two brecciated ureilites. Diamond in Almahata Sitta was found to be distinct from that in unbrecciated and brecciated ureilites, although diamond in unbrecciated and brecciated ureilites is indistinguishable. Almahata Sitta diamond shows a peak center range of 1318.5–1330.2 cm^?1 and a full width at half maximum (FWHM) range of 6.6–17.4 cm^?1, representing a shock pressure of at least 60 kbar. The actual peak shock pressure may be higher than this due to postshock annealing, if shock synthesis is the source of ureilite diamonds. Diamond in unbrecciated and brecciated ureilites have peak center wave numbers closer to terrestrial kimberlite diamond, but show a wider range of FWHM than Almahata Sitta. The larger peak shift observed in Almahata Sitta may indicate the presence of lonsdaleite. Alternatively, the lower values in brecciated ureilites may be evidence of an annealing step either following the initial diamond‐generating shock or as a consequence of heating during reconsolidation of the breccia. Graphite in Almahata Sitta shows a G‐band peak center range of 1569.1–1577.1 cm^?1 and a G‐band FWHM range of 24.3–41.6 cm^?1 representing a formation temperature of 990 ± 120 °C. Amorphous carbon was also found. We examine the different theories for diamond formation in ureilites, such as chemical vapor deposition and shock origin from graphite, and explore explanations for the differences between Almahata Sitta and other ureilites.     

Light dement geochemistry of the Tagish Lake CI2 chondrite: Comparison with CI1 and CM2 meteorites

Abstract— We have studied the carbon and nitrogen stable isotope geochemistry of a small pristine sample of the Tagish Lake carbonaceous chondrite by high‐resolution stepped‐combustion mass spectrometry, and compared the results with data from the Orgueil (CI1), Elephant Moraine (EET) 83334 (CM1) and Murchison (CM2) chondrites. The small chip of Tagish Lake analysed herein had a higher carbon abundance (5.81 wt%) than any other chondrite, and a nitrogen content (?1220 ppm) between that of CI1 and CM2 chondrites. Owing to the heterogeneous nature of the meteorite, the measured carbon abundance might be artificially high: the carbon inventory and whole‐rock carbon isotopic composition (δ¹³C ? +24.4%_o) of the chip was dominated by ¹³C‐enriched carbon from the decomposition of carbonates (between 1.29 and 2.69 wt%; δ¹³C ? +67%_o and δ¹⁸O ? +35%_o, in the proportions ?4:1 dolomite to calcite). In addition to carbonates, Tagish Lake contains organic carbon (?2.6 wt%, δ¹³C ? ?9%_o; 1033 ppm N, δ¹⁵N ? +77%_o), a level intermediate between CI and CM chondrites. Around 2% of the organic material is thermally labile and solvent soluble. A further ?18% of the organic species are liberated by acid hydrolysis. Tagish Lake also contains a complement of presolar grains. It has a higher nanodiamond abundance (approximately 3650–4330 ppm) than other carbonaceous chondrites, along with ?8 ppm silicon carbide. Whilst carbon and nitrogen isotope geochemistry is not diagnostic, the data are consistent with classification of Tagish Lake as a CI2 chondrite.     

Nitrogen and noble gases in micrometeorites

Abstract— Micrometeorites (MMs) currently represent the largest steady‐state mass flux of extraterrestrial matter to Earth and may have delivered a significant fraction of volatile elements and organics to the Earth's surface. Nitrogen and noble gases contents and isotopic ratios have been measured in a suite of 17 micrometeorites recovered in Antarctica (sampled in blue ice at Cap Prudhomme) and Greenland (separated from cryoconite) that have experienced variable thermal metamorphism during atmospheric entry. MMs were pyrolized using a CO₂ laser and the released gases were analyzed for nitrogen and noble gas abundances and isotopic ratios by static mass spectrometry after specific purification. Noble gases are a mixture of cosmogenic, solar, atmospheric, and possibly chondritic components, with atmospheric being predominant in severely heated MMs. δ¹⁵N values vary between ?240 ± 62‰ and +206 ± 12‰, with most values being within the range of terrestrial and chondritic signatures, given the uncertainties. Crystalline MMs present very high noble gas contents up to two orders of magnitude higher than carbonaceous chondrite concentrations. In contrast, nitrogen contents between 4 ppm and 165 ppm are much lower than those of carbonaceous chondrites, evidencing either initially low N content in MMs and/or degradation of phases hosting nitrogen during atmospheric entry heating and terrestrial weathering. Assuming that the original N content of MMs was comparable to that of carbonaceous chondrites, the contribution of nitrogen delivery by these objects to the terrestrial environment would have been probably marginal from 3.8 Gyr ago to present but could have been significant (?10%) in the Hadean, and even predominant during the latest stages of terrestrial accretion.     

In situ micro‐Raman and X‐ray diffraction study of diamonds and petrology of the new ureilite UAE 001 from the United Arab Emirates

Abstract— A new olivine‐pigeonite ureilite containing abundant diamonds and graphite was found in the United Arab Emirates. This is the first report of a meteorite in this country. The sample is heavily altered, of medium shock level, and has a total weight of 155 g. Bulk rock, olivine (Fo_79.8–81.8) and pyroxene (En_73.9–75.2, Fs_15.5–16.9, Wo_8.8–9.5) compositions are typical of ureilites. Olivine rims are reduced with Fo increasing up to Fo_96.1–96.8. Metal in these rims is completely altered to Fehydroxide during terrestrial weathering. We studied diamond and graphite using micro‐Raman and in situ synchrotron X‐ray diffraction. The main diamond Raman band (LO = TO mode at ?1332 cm^?1) is broadened when compared to well‐ordered diamond single crystals. Full widths at half maximum (FWHM) values scatter around 7 cm^?1. These values resemble FWHM values obtained from chemical vapor deposition (CVD) diamond. In situ XRD measurements show that diamonds have large grain sizes, up to >5 μm. Some of the graphite measured is compressed graphite. We explore the possibilities of CVD versus impact shock origin of diamonds and conclude that a shock origin is much more plausible. The broadening of the Raman bands might be explained by prolonged shock pressure resulting in a transitional Raman signal between experimentally shock‐produced and natural diamonds.     

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.     

Search for solar-type nitrogen in the gas-rich Pesyanoe meteorite

Abstract— We report nitrogen isotopic data obtained from a stepwise gas release of two grain-size fractions of the gas-rich meteorite Pesyanoe. Cosmic-ray-produced ¹⁵N_c may be present in all temperature steps ≥600 °C, and we correct this component using spallation ²¹Ne data. The resulting ratios reveal the presence of more than one trapped N component. Indigenous N is released above 1000 °C with an isotopic signature of δ¹⁵N = ?33‰. This is consistent with the rather uniform signatures of indigenous nitrogen in enstatite meteorites. There is no evidence for the presence of “very light” N of δ¹⁵N ? ?200‰. On the other hand, a “heavy” nitrogen component appears in the temperature range 700–800 °C, and coincides with a major release of solar-type noble gases. For a two-component mixture, the isotopic shifts in this temperature range define a lower limit δ¹⁵N_corr = ?6‰ for the second component (e.g., solar-type nitrogen). However, for the case of a solar-type component, the calculated δ¹⁵N signature depends on the adopted elemental abundances. For example, adoption of the relative abundances of ¹⁴N and noble gases in lunar ilmenite 71501 yields δ¹⁵N ? +170, which is in the range of the heavier nitrogen signatures observed on the lunar surface.     

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

Abstract— The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three‐ through ten‐carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of 44 of these compounds were detected with the most abundant, succinic acid, present at ?40 nmol/g meteorite. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound‐to‐compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All δD and δ¹³C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. δD values vary from, approximately, +1120%_o for succinic acid to +1530%_o for methyl glutaric acid. δ¹³C values ranged from +12.6%_o for methyl glutaric acid to +22.9%_o for glutaric acid, with adipic acid having a significantly lower value (+5.5%_o). Murchison dicarboxylic acid showed similar isotopic values: their δ5¹³C values were generally higher by an average 17% and δD values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre‐accretionary processes.     

Primordial noble gases in “phase Q” in carbonaceous and ordinary chondrites studied by closed‐system stepped etching

Abstract— The HF/HCI‐resistant residues of the chondrites CM2 Cold Bokkeveld, CV3 (ox.) Grosnaja, CO3.4 Lancé, CO3.7 Isna, LL3.4 Chainpur, and H3.7 Dimmitt have been measured by closed‐system stepped etching (CSSE) in order to better characterise the noble gases in “phase Q”, a major carrier of primordial noble gases. All isotopic ratios in phase Q of the different meteorites are quite uniform, except for (²⁰Ne/²²Ne)_Q. As already suggested by precise earlier measurements (Schelhaas et al., 1990; Wieler et al., 1991, 1992), (²⁰Ne/²²Ne)_Q is the least uniform isotopic ratio of the Q noble gases. The data cluster ～10.1 for Cold Bokkeveld and Lancé and 10.7 for Chainpur, Grosnaja, and Dimmitt, respectively. No correlation of (²⁰Ne/²²Ne)_Q with the classification or the alteration history of the meteorites has been found. The Ar, Kr, and Xe isotopic ratios for all six samples are identical within their uncertainties and similar to earlier Q determinations as well as to Ar‐Xe in ureilites. Thus, an unknown process probably accounts for the alteration of the originally incorporated Ne‐Q. The noble gas elemental compositions provide evidence that Q consists of at least two carbonaceous carrier phases “Q1” and “Q2” with slightly distinct chemical properties. Ratios (Ar/Xe)_Q and (Kr/Xe)_Q reflect both thermal metamorphism and aqueous alteration. These parent‐body processes have led to larger depletions of Ar and Kr relative to Xe. In contrast, meteorites that suffered severe aqueous alteration, such as the CM chondrites, do not show depletions of He and Ne relative to Ar but rather the highest (He/Ar)_Q and (Ne/Ar)_Q ratios. This suggests that Q1 is less susceptible to aqueous alteration than Q₂. Both subphases may well have incorporated noble gases from the same reservoir, as indicated by the nearly constant, though very large, depletion of the lighter noble gases relative to solar abundances. However, the elemental ratios show that Q₁ and Q₂ must have acquired (or lost) noble gases in slightly different element proportions. Cold Bokkeveld suggests that Q₁ may be related to presolar graphite. Phases Q₁ and Q₂ might be related to the subphases that have been suggested by Gros and Anders (1977). The distribution of the ²⁰Ne/²²Ne ratios cannot be attributed to the carriers Q₁ and Q₂. The residues of Chainpur and Cold Bokkeveld contain significant amounts of Ne‐E(L), and the data confirm the suggestion of Huss (1997) that the ²²Ne‐E(L) content, and thus the presolar graphite abundances, are correlated with the metamorphic history of the meteorites.     

Abundance and isotopic composition of noble gases in metal and graphite of the Bohumilitz IAB iron meteorite

Abstract— Abundances and isotopic compositions of noble gases in metal and graphite of the Bohumilitz IAB iron meteorite were measured. The abundance ratios of spallogenic components in metal reveal a ³He deficiency which is due to the diffusive loss of parent isotopes, that is, tritium (Tilles, 1963; Schultz, 1967). The diffusive loss likely has been induced by thermal heating by the Sun during cosmic‐ray exposure (～160 Ma; Lavielle et al, 1999). Thermal process such as impact‐induced partial loss may have affected the isotopic composition of spallogenic Ne. The ¹²⁹Xe/¹³¹Xe ratio of cosmogenic components in the metal indicates an enhanced production of epi‐thermal neutrons. The abundance ratios of spallogenic components in the graphite reveal that it contained small amounts of metal and silicates. The isotopic composition of heavy noble gases in graphite itself was obtained from graphite treated with HF/HCl. The isotopic composition of the etched graphite shows that it contains two types of primordial Xe (i.e., Q‐Xe and El Taco Xe). The isotopic heterogeneity preserved in the Bohumilitz graphite indicates that the Bohumilitz graphite did not experience any high‐temperature event and, consequently, must have been emplaced into the metal at subsolidus temperatures. This situation is incompatible with an igneous model as well as the impact melting models for the IAB‐IIICD iron meteorites as proposed by Choi et al. (1995) and Wasson et al (1980).     

Noble gases in presolar diamonds I: Three distinct components and their implications for diamond origins

Abstract— High-purity separates of presolar diamond were prepared from 14 primitive chondrites from 7 compositional groups. Their noble gases were measured using stepped pyrolysis. Three distinct noble gas components are present in diamonds, HL, P3, and P6, each of which is found to consist of five noble gases. P3 , released between 200 °C and 900 °C, has a “planetary” elemental abundance pattern and roughly “normal” isotopic ratios. HL , consisting of isotopically anomalous Xe-HL and Kr-H, Ar with high ³⁸Ar/³⁶Ar, and most of the gas making up Ne-A2 and He-A, is released between 1100 °C and 1600 °C. HL has “planetary” elemental ratios, except that it has much more He and Ne than other known “planetary” components. HL gases are carried in the bulk diamonds, not in some trace phase. P6 has a slightly higher median release temperature than HL and is not cleanly separated from HL by stepped pyrolysis. Our data suggest that P6 has roughly “normal” isotopic compositions and “planetary” elemental ratios. Both P3 and P6 seem to be isotopically distinct from P1, the dominant “planetary” noble-gas component in primitive chondrites. Release characteristics suggest that HL and P6 are sited in different carriers within the diamond fractions, while P3 may be sited near the surfaces of the diamonds. We find no evidence of separability of Xe-H and Xe-L or other isotopic variations in the HL component. However, because ～10¹⁰ diamonds are required to measure a Xe composition, a lack of isotopic variability does not constrain diamonds to come from a single source. In fact, the high abundance of diamonds in primitive chondrites and the presence of at least three distinct noble-gas components strongly suggest that diamonds originated in many sources. Relative abundances of noble-gas components in diamonds correlate with degree of thermal processing (see companion paper), indicating that all meteorites sampled essentially the same mixture of diamonds. That mixture was probably inherited from the Sun's parent molecular cloud.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.     

Noble gases in oxidized residue prepared from the Saratov L4 chondrite and Raman spectroscopic study of residues to characterize phase Q

We analyzed noble gases in an oxidized residue prepared from a HF‐HCl residue of the Saratov L4 chondrite. The Ar, Kr, and Xe concentrations in the oxidized residue are two orders of magnitude lower than those in the HF‐HCl residue, and they are close to concentrations in the bulk. The He and Ne concentrations are similar in the three samples. The Ne isotopic ratios are almost purely cosmogenic, indicating absence of presolar diamonds (the carrier of the HL component). Thus, Saratov contains phase Q without presolar diamond. A study of the Raman spectroscopic parameters for the HF‐HCl residue and the oxidized residue shows large changes due to oxidation. The directions of these changes are the same as observed in Allende, except oxidation increased the I_D/I_G (intensity ratio of the D band to the G band) in Saratov but decreased in Allende. This difference may be attributed to the different crystalline stages of carbon in both meteorites. The shifts in the Raman parameters to a discrete and/or more expanded region suggest that (1) oxidation changes the crystalline condition of graphitic carbon, (2) phase Q is not a dissolved site, and (3) the release of Q‐gas is simply related to the rearrangement of the carbon structure during oxidation.