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.     

Nanodiamonds and silicate minerals in ordinary chondrites as determined by micro‐Raman spectroscopy

We present here the Raman spectroscopic study of silicate and carbonaceous minerals in three ordinary chondrites with the aim to improve our understanding the impact process including the peak metamorphic pressures present in carbon‐bearing ordinary chondites. The characteristic Raman vibrational peaks of olivines, pyroxenes, and plagioclase have been determined on three ordinary chondrites from India, Dergaon (H5), Mahadevpur (H4/5), and Kamargaon (L6). The Raman spectra of these meteorite samples show the presence of nanodiamonds at 1334–1345 cm^?1 and 1591–1619 cm^?1. The full‐width at half maximum (FWHM) of Raman peaks for Mahadevpur and Dergaon reflect the nature of shock metamorphism in these meteorites. The frequency shift in Raman spectra might be because of shock effects during the formation of the diamond/graphite grains.     

Raman spectroscopy of olivine in dunite experimentally shocked to pressures between 5 and 59 GPa

Abstract— Previous Raman investigations on experimentally shocked ingle‐crystal olivine indicated that the olivine Raman bands seemingly shift to a higher wave number with increasing shock pressure. If this effect could be confirmed, Raman analysis of natural shock‐metamorphosed minerals could potentially provide an important shock barometric tool. We carried out a Raman spectroscopic study on olivine in a series of natural dunite samples experimentally shocked to pressures between 5 and 59 GPa. In addition, we analyzed olivine grains in a sample of the Cold Bokkeveld C1 meteorite. We studied samples of several dunites with olivine of 90.64–92.00 mole% Fo to determine Raman effects in the region from 200 to 900 cm^?1. Several olivine grains per sample/shock pressure stage were analyzed. Raman analysis, however, showed little or no shift with increasing shock pressure. The shifts to higher or lower frequencies observed were not specific for a given pressure stage, with some grains within a sample showing more shift than others. This finding is unrelated to the crystallographic orientation of analyzed grains and cannot be related systematically to the different degrees of optically determined shock metamorphism of the analyzed grains. We identified an increase in full width at half maximum (FWHM) for the 824 cm^?1 band with increased shock pressure in the shocked Åheim samples above 45 GPa and, to a lesser extent, for the 856 cm^?1 band. Evaluation of band broadening of olivine in the Cold Bokkeveld meteorite showed FWHM values that were much greater (9–20 cm^?1) than those of olivine in the shocked dunite samples (7–12 cm^?1). We concluded that these differences in FWHM are due to differences in chemical composition between the meteoritic and the experimentally shocked olivine. Therefore, using Raman spectroscopy to detect small shifts in wave numbers to higher frequencies with increased shock pressure does not yield consistent effects for polycrystalline dunite. An extra band at 650 cm^?1 was identified in the Raman spectra of the unshocked Mooihoek dunite and the Åheim dunite samples shocked to 5, 29.3, and 59 GPa, as well as another at 696 cm^?1 in all the spectra of the 59 GPa Åheim sample. The cause of these extra bands is not known. Comparison of these results with Raman spectra of olivine from the Cold Bokkeveld C1 meteorite did not allow us to determine shock pressures for the meteoritic olivine.     

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.     

Igneous petrology of the new ureilites Nova 001 and Nullarbor 010

Abstract— The Nova 001 [= Nuevo Mercurio (b)] and Nullarbor 010 meteorites are ureilites, both of which contain euhedral graphite crystals. The bulk of the meteorites are olivine (Fo₇₉) and pyroxenes (Wo₉En₇₃Fs₁₈, Wo₃En₇₇Fs₂₀), with a few percent graphite and minor amounts of troilite, Ni-Fe metal, and possibly diamond. The rims of olivine grains are reduced (to Fo₉₁) and contain abundant blebs of Fe metal. Silicate mineral grains are equant, anhedral, up to 2 mm across, and lack obvious preferred orientations. Euhedral graphite crystals (to 1 mm x 0.3 mm) are present at silicate grain boundaries, along boundaries and protruding into the silicates, and entirely within silicate mineral grains. Graphite euhedra are also present as radiating clusters and groups of parallel plates grains embedded in olivine; no other ureilite has comparable graphite textures. Minute lumps within graphite grains are possibly diamond, inferred to be a result of shock. Other shock effects are limited to undulatory extinction and fracturing. Both ureilites have been weathered significantly. Considering their similar mineralogies, identical mineral compositions, and identical unusual textures, Nova 001 and Nullarbor 010 are probably paired. Based on olivine compositions, Nova 001 and Nullarbor 010 are in Group 1 (FeO-rich) of Berkley et al. (1980). Silicate mineral compositions are consistent with those of other known ureilites. The presence of euhedral graphite crystals within the silicate minerals is consistent with an igneous origin, and suggests that large proportions of silicate magma were present locally and crystallized in situ.     

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.     

Martian meteorite Tissint records unique petrogenesis among the depleted shergottites

Tissint, a new unaltered piece of Martian volcanic materials, is the most silica‐poor and Mg‐Fe‐rich igneous rock among the “depleted” olivine‐phyric shergottites. Fe‐Mg zoning of olivine suggests equilibrium growth (<0.1 °C h^?1) in the range of Fo_80–56 and olivine overgrowth (Fo_55–18) through a process of rapid disequilibrium (~1.0–5.0 °C h^?1). The spatially extended (up to 600 μm) flat‐top Fe‐Mg profiles of olivine indicates that the early‐stage cooling rate of Tissint was slower than the other shergottites. The chemically metastable outer rim of olivine (55) consists of oscillatory phosphorus zoning at the impact‐induced melt domains and grew rapidly compared to the early to intermediate‐stage crystallization of the Tissint bulk. High‐Ca pyroxene to low‐Ca pyroxene and high‐Ca pyroxene to plagioclase ratios of Tissint are more comparable to the enriched basaltic and enriched olivine‐phyric shergottites. Dominance of augite over plagioclase induced augite to control the Ca‐buffer in the residual melt suppressing the plagioclase crystallization, which also caused a profound effect on the Al‐content in the late‐crystallized pyroxenes. Mineral chemical stability, phase‐assemblage saturation, and pressure–temperature path of evolution indicates that the parent magma entered the solidus and left the liquidus field at a depth of 40–80 km in the upper mantle. Petrogenesis of Tissint appears to be similar to LAR 06319, an enriched olivine‐phyric shergottite, during the early to intermediate stage of crystallization. A severe shock‐induced deformation resulted in remelting (10–15 vol%), recrystallization (most Fe‐rich phases), and exhumation of Tissint in a time scale of 1–8 yr. Tissint possesses some distinct characteristics, e.g., impact‐induced melting and deformation, forming phosphorus‐rich recrystallization rims of olivine, and shock‐induced melt domains without relative enrichment of LREEs compared to the bulk; and shared characteristics, e.g., modal composition and magmatic evolution with the enriched basaltic shergottites, evidently reflecting unique mantle source in comparison to the clan of the depleted members.     

Jiddat al Harasis 422: A ureilite with an extremely high degree of shock melting

The Jiddat al Harasis (JaH) 422 ureilite was found in the Sultanate of Oman; it is classified as a ureilitic impact melt breccia. The meteorite consists of rounded polycrystalline olivine clasts (35%), pores (8%), and microcrystalline matrix (57%). Clasts and matrix have oxygen isotopic values and chemical compositions (major and trace elements) characteristic of the ureilite group. The matrix contains olivine (Fo_83–90), low‐Ca pyroxene (En_84–92Wo_0–5), augite (En_71–56Wo_20–31), graphite, diamond, Fe‐metal, sulfides, chromite, and felsic glass. Pores are partly filled by secondary Fe‐oxihydroxide and desert alteration products. Pores are surrounded by strongly reduced silicates. Clasts consist of fine‐grained aggregates of polygonal olivine. These clasts have an approximately 250 μm wide reaction rim, in which olivine composition evolves progressively from the core composition (Fo_79–81) to the matrix composition (Fo_84–87). Veins crossing the clasts comprise pyroxene, Fe‐oxihydroxide, C‐phases, and chromite. Clasts contain Ca‐, Al‐, and Cr‐rich glass along olivine grain boundaries (<1 μm wide). We suggest that a significant portion of JaH 422, including olivine and all the pyroxenes, was molten as a result of an impact. In comparison with other impact‐melted ureilites, JaH 422 shows the highest melt portion. Based on textural and compositional considerations, clasts and matrix probably originated from the same protolith, with the clasts representing relict olivine that survived, but was recrystallized in the impact melt. During the melt stage, the high availability of FeO and elevated temperatures controlled oxygen fugacity at values high enough to stabilize olivine with Fo_～83–87 and chromite. Along pores, high Mg# compositions of silicates indicate that in a late stage or after melt crystallization FeO became less available and fO₂ conditions were controlled by C?CO + CO₂.     

Localized shock melting in lherzolitic shergottite Northwest Africa 1950: Comparison with Allan Hills 77005

Abstract— The lherzolitic Martian meteorite Northwest Africa (NWA) 1950 consists of two distinct zones: 1) low‐Ca pyroxene poikilically enclosing cumulate olivine (Fo_70–75) and chromite, and 2) areas interstitial to the oikocrysts comprised of maskelynite, low‐ and high‐Ca pyroxene, cumulate olivine (Fo_68–71) and chromite. Shock metamorphic effects, most likely associated with ejection from the Martian subsurface by large‐scale impact, include mechanical deformation of host rock olivine and pyroxene, transformation of plagioclase to maskelynite, and localized melting (pockets and veins). These shock effects indicate that NWA 1950 experienced an equilibration shock pressure of 35–45 GPa. Large (millimeter‐size) melt pockets have crystallized magnesian olivine (Fo_78–87) and chromite, embedded in an Fe‐rich, Al‐poor basaltic to picro‐basaltic glass. Within the melt pockets strong thermal gradients (minimum 1 °C/μm) existed at the onset of crystallization, giving rise to a heterogeneous distribution of nucleation sites, resulting in gradational textures of olivine and chromite. Dendritic and skeletal olivine, crystallized in the melt pocket center, has a nucleation density (1.0 × 10³ crystals/mm²) that is two orders of magnitude lower than olivine euhedra near the melt margin (1.6 × 10⁵ crystals/mm²). Based on petrography and minor element abundances, melt pocket formation occurred by in situ melting of host rock constituents by shock, as opposed to melt injected into the lherzolitic target. Despite a common origin, NWA 1950 is shocked to a lesser extent compared to Allan Hills (ALH) 77005 (45–55 GPa). Assuming ejection in a single shock event by spallation, this places NWA 1950 near to ALH 77005, but at a shallower depth within the Martian subsurface. Extensive shock melt networks, the interconnectivity between melt pockets, and the ubiquitous presence of highly vesiculated plagioclase glass in ALH 77005 suggests that this meteorite may be transitional between discreet shock melting and bulk rock melting.     

A study of the observed shift in the peak position of olivine Raman spectra as a result of shock induced by hypervelocity impacts

Kuebler et al. (2006) identified variations in olivine Raman spectra based on the composition of individual olivine grains, leading to identification of olivine composition from Raman spectra alone. However, shock on a crystal lattice has since been shown to result in a structural change to the original material, which produces a shift in the Raman spectra of olivine grains compared with the original unshocked olivine (Foster et al. 2013). This suggests that the use of the compositional calculations from the Raman spectra, reported in Kuebler et al. (2006), may provide an incorrect compositional value for material that has experienced shock. Here, we have investigated the effect of impact speed (and hence peak shock pressure) on the shift in the Raman spectra for San Carlos olivine (Fo₉₁) impacting Al foil. Powdered San Carlos olivine (grain size 1–10 μm) was fired at a range of impact speeds from 0.6 to 6.1 km s^?1 (peak shock pressures 5–86 GPa) at Al foil to simulate capture over a wide range of peak shock pressures. A permanent change in the Raman spectra was found to be observed only for impact speeds greater than ~5 km s^?1. The process that causes the shift is most likely linked to an increase in the peak pressure produced by the impact, but only after a minimum shock pressure associated with the speed at which the effect is first observed (here 65–86 GPa). At speeds around 6 km s^?1 (peak shock pressures ~86 GPa), the shift in Raman peak positions is in a similar direction (red shift) to that observed by Foster et al. (2013) but of twice the magnitude.     

A primitive dark inclusion with radiation‐damaged silicates in the Ningqiang carbonaceous chondrite

Abstract— A petrologic and TEM study of a remarkable dark inclusion (DI) in the Ningqiang CV3 chondrite reveals that it is a mixture of highly primitive solar nebula materials. The DI contains two lithologies. The first, lithology A, contains micron‐sized olivine and pyroxene grains rimmed by amorphous materials with compositions similar to the underlying crystalline grains. The second, lithology B, appears to preserve the mineralogy of lithology A before formation of the amorphous rims. Overall, the Ningqiang DI appears to record the following processes: 1) formation (condensation and Fe‐enrichment) of olivine crystals in the nebula with compositions of Fo_42–62; 2) irradiation, resulting in amorphitization of the olivine and pyroxene to varying degrees; 3) partial annealing, resulting in formation of fairly large, euhedral olivine and pyroxene grains with remnant amorphous sharply‐bounded rims; 4) in some cases, prolonged annealing, resulting in the formation of microcrystalline olivine or pyroxene rims. The latter annealing would have been a natural consequence of irradiation near the critical temperature for olivine; and 5) mixture of the above materials (lithology A) with nebular condensate high‐Ca pyroxene and olivine, which escaped nebular processing, to become lithology B. We suggest that the amorphous rims in lithology A formed in an energetic solar event such as a bi‐polar outflow or FU‐orionis flare.     

Trace elements in olivine and the petrogenesis of the intermediate,olivine‐phyric shergottite NWA 10170

Olivine‐phyric shergottites represent primitive basaltic to picritic rocks, spanning a large range of Mg# and olivine abundances. As primitive olivine‐bearing magmas are commonly representative of their mantle source on Earth, understanding the petrology and evolution of olivine‐phyric shergottites is critical in our understanding of Martian mantle compositions. We present data for the olivine‐phyric shergottite Northwest Africa (NWA) 10170 to constrain the petrology with specific implications for magma plumbing‐system dynamics. The calculated oxygen fugacity and bulk‐rock REE concentrations (based on modal abundance) are consistent with a geochemically intermediate classification for NWA 10170, and overall similarity with NWA 6234. In addition, we present trace element data using laser ablation ICP‐MS for coarse‐grained olivine cores, and compare these data with terrestrial and Martian data sets. The olivines in NWA 10170 contain cores with compositions of Fo₇₇ that evolve to rims with composition of Fo₅₈, and are characterized by cores with low Ni contents (400–600 ppm). Nickel is compatible in olivine and such low Ni content for olivine cores in NWA 10170 suggests either early‐stage fractionation and loss of olivine from the magma in a staging chamber at depth, or that Martian magmas have lower Ni than terrestrial magmas. We suggest that both are true in this case. Therefore, the magma does not represent a primary mantle melt, but rather has undergone 10–15% fractionation in a staging chamber prior to extrusion/intrusion at the surface of Mars. This further implies that careful evaluation of not only the Mg# but also the trace element concentrations of olivine needs to be conducted to evaluate pristine mantle melts versus those that have fractionated olivine (±pyroxene and oxide minerals) in staging chambers.     

Raman spectroscopic investigation of two grains from comet 81P/Wild 2: Information that can be obtained beyond the presence of sp2‐bonded carbon

Abstract– Raman analyses were performed of individual micrometer‐sized fragments of material returned to Earth by the NASA Stardust mission to comet 81P/Wild 2. The studied fragments originated from grains (C2054,0,35,91,0 and C2092,6,80,51,0) of two different penetration tracks that occurred in two different silica aerogel collector cells. All fragments of both particles have Raman spectra characteristic of amorphous sp²‐bonded carbon that are in general agreement with the results published in previous Stardust particle studies. The present study, however, does not focus on the discussion of specific details of the D and G band parameters, but rather reports on additional information that can be obtained from returned Stardust samples via Raman spectroscopy. Most notably, the Raman spectra show that all analyzed fragments of the particles were contaminated with the capture medium (i.e., aerogel). The silica aerogel is laced with organic aliphatic and aromatic hydrocarbon impurities that resulted in strong bands in the ～ 2900 Δcm^?1 spectral range (C‐H stretching modes). Aerogel bands are also found in the 1000–1600 Δcm^?1 spectral range, where they overlap with the bands of the amorphous sp²‐bonded carbon. The peaks associated with the aerogel contamination differ between the two grains that originated from two different aerogel cells. In addition to the bands due to aerogel contamination and the always present sp²‐bonded carbon bands, fragments of particle C2092,6,80,51,0 also show Raman peaks for pyrrhotite and Fa₃₀Fo₇₀ olivine. Complete (up to 4000 Δcm^?1) raw and baseline‐corrected Raman spectra of the Stardust particles are shown and discussed in detail.     

Forsterite‐rich accretionary rims around calcium‐aluminum‐rich inclusions from the reduced CV3 chondrite Efremovka

Abstract— It was suggested that multilayered accretionary rims composed of ferrous olivine, andradite, wollastonite, salite‐hedenbergitic pyroxenes, nepheline, and Ni‐rich sulfides around Allende calcium‐aluminum‐rich inclusions (CAIs) are aggregates of gas‐solid condensates which reflect significant fluctuations in physico‐chemical conditions in the slowly cooling solar nebula and grain/gas separation processes. In order to test this model, we studied the mineralogy of accretionary rims around one type A CAI (E104) and one type B CAI (E48) from the reduced CV3 chondrite Efremovka, which is less altered than Allende. In contrast to the Allende accretionary rims, those in Efremovka consist of coarse‐grained (20–40 μm), anhedral forsterite (Fa_1–8), Fe, Ni‐metal nodules, amoeboid olivine aggregates (AOAs) and fine‐grained CAIs composed of Al‐diopside, anorthite, and spinel, ± forsterite. Although the fine‐grained CAIs, AOAs and host CAIs are virtually unaltered, a hibonite‐spinel‐perovskite CAI in the E48 accretionary rim experienced extensive alteration, which resulted in the formation of Fe‐rich, Zn‐bearing spinel, and a Ca, Al, Si‐hydrous mineral. Forsterites in the accretionary rims typically show an aggregational nature and consist of small olivine grains with numerous pores and tiny inclusions of Al‐rich minerals. No evidence for the replacement of forsterite by enstatite was found; no chondrule fragments were identified in the accretionary rims. We infer that accretionary rims in Efremovka are more primitive than those in Allende and formed by aggregation of high‐temperature condensates around host CAIs in the CAI‐forming regions. The rimmed CAIs were removed from these regions prior to condensation of enstatite and alkalies. The absence of andradite, wollastonite, and hedenbergite from the Efremovka rims may indicate that these rims sampled different nebular regions than the Allende rims. Alternatively, the Ca, Fe‐rich silicates rimming Allende CAIs may have resulted from late‐stage metasomatic alteration, under oxidizing conditions, of original Efremovka‐like accretionary rims. The observed differences in O‐isotope composition between forsterite and Ca, Fe‐rich minerals in the Allende accretionary rims (Hiyagon, 1998) suggest that the oxidizing fluid had an ¹⁶O‐poor oxygen isotopic composition.     

Space weathering of silicates simulated by successive laser irradiation: In situ reflectance measurements of Fo90, Fo99+, and SiO2

Pulsed‐laser irradiation causes the visible‐near‐infrared spectral slope of olivine (Fo₉₀ and Fo₉₉₊) and SiO₂ to increase (redden), while the olivine samples darken and the SiO₂ samples brighten slightly. XPS analysis shows that irradiation of Fo₉₀ produces metallic Fe. Analytical SEM and TEM measurements confirm that reddening in the Fo₉₀ olivine samples correlates with the production of “nanophase” metallic Fe (npFe⁰) grains, 20–50 nm in size. The reddening observed in the SiO₂ sample is consistent with the formation of SiO or other SiO_x species that absorb in the visible. The weak spectral brightening induced by laser irradiation of SiO₂ is consistent with a change in surface topography of the sample. The darkening observed in the olivine samples is likely caused by the formation of larger npFe⁰ particles, such as the 100–400 nm diameter npFe⁰ identified during our TEM analysis of Fo₉₀ samples. The Fo₉₀ reflectance spectra are qualitatively similar to those in previous experiments suggesting that in all cases formation of npFe⁰ is causing the spectral alteration. Finally, we find that the accumulation of successive laser pulses cause continued sample darkening in the Vis‐NIR, which suggests that repeated surface impacts are an efficient way to darken airless body surfaces.     

Metamorphism of four desert ureilites and luminescence spectroscopy of defects in ureilitic diamonds

Four ureilites subjected to impact metamorphism in a pressure range of ~15–100 GPa were investigated for mineralogical and petrological features and optical luminescence of their diamonds with the aim to understand how properties of ureilitic diamonds are correlated with shock and thermal histories of the host meteorite. Petrological data show that all the investigated ureilites experienced multistage metamorphic histories. Some of them were shocked at least twice or/and underwent high‐temperature thermal metamorphism and fluid metasomatism in the parent body interior. Photoluminescence spectra of individual diamond grains reveal the presence of neutral and negatively charged nitrogen‐vacancy (NV⁰ and NV^?, respectively) and H3 (two nitrogens and a vacancy) defects, indicating relatively high nitrogen contents of the diamonds and some degree of thermal annealing of the grains. The diamond grain size and morphology, a texture of graphite‐diamond aggregates, and spectroscopic properties of the diamond phase vary widely both within an individual meteorite and between the ureilites. Shock‐driven transformation of sp2‐C into diamond provides the most natural explanation of the observed spectroscopic diversity of the diamond grains if one takes into account strong dependence of the PT parameters and efficiency of the transformation on structure of the carbonaceous precursor.     

Carbon,nitrogen, argon and helium study of impact diamonds from Ebeliakh alluvial deposits and Popigai crater

Abstract— Nineteen diamond aggregate specimens (1–2 mm in size) from impactites of Popigai crater and five diamond samples (5–7 mm in size) from Ebeliakh river placers were studied. Our investigations indicate that samples from Ebeliakh were formed in an impact event with the exception of one specimen (Y7). The carbon isotopic composition of diamonds from Popigai varies within the previously reported limits (δ¹³C, ?8 to ?22%); whereas, diamonds from Ebeliakh placers show heavier values of δ¹³C (?7 to ?10%). All the specimens studied contain very low amounts of N, mostly <20 ppm, but a few contained up to 60 ppm. For specimens, where the quantity of N allowed reliable analysis, δ¹⁵N values were found to be in the range of ?3.9 to +11.9%. On the basis of combined Ar and N study, it was concluded that impact diamonds studied here can be a mixture of at least two types of gas carriers (e.g., different diamond components). A possible explanation would be involvement of a carbon vapour deposition (CVD) process or diamond growth in the impact melt in addition to the direct graphite-diamond shock transformation. The δ¹³C distributions and different N/³⁶Ar correlations have indicated a difference between impact diamonds from Ebeliakh and diamonds extracted from Popigai crater. This could be explained by the existence of different diamond populations formed during the Popigai impact event. On the other hand, Ebeliakh diamonds could have resulted from a separate impact event to Popigai and an alternative crater is yet to be found.     

Nitrogen in diamond‐free ureilite Allan Hills 78019: Clues to the origin of diamond in ureilites

Abstract— Nitrogen and noble gases were measured in a bulk sample and in acid‐resistant carbon‐rich residues of the ureilite Allan Hills (ALH) 78019 which has experienced low shock and is free of diamond. A small amount of amorphous carbon combusting at ≤500 °C carries most of the noble gases, while the major carbon phase consisting of large crystals of graphite combusts at ≥800 °C, and is almost noble‐gas free. Nitrogen on the other hand is present in both amorphous carbon and graphite, with different δ¹⁵N signatures of ?21%_o and +19%_o, respectively, distinctly different from the very light nitrogen (about ?100%_o) of ureilite diamond. Amorphous carbon in ALH 78019 behaves similar to phase Q of chondrites with respect to noble gas release pattern, behavior towards oxidizing acids as well as nitrogen isotopic composition. In situ conversion of amorphous carbon or graphite to diamond through shock would require an isotopic fractionation of 8 to 12% for nitrogen favoring the light isotope, an unlikely proposition, posing a severe problem for the widely accepted shock origin of ureilite diamond.     

Petrogenesis of the Northwest Africa 4898 high‐Al mare basalt

Northwest Africa (NWA) 4898 is the only low‐Ti, high‐Al basaltic lunar meteorite yet recognized. It predominantly consists of pyroxene (53.8 vol%) and plagioclase (38.6 vol%). Pyroxene has a wide range of compositions (En_12–62Fs_25–62Wo_11–36), which display a continuous trend from Mg‐rich cores toward Ca‐rich mantles and then to Fe‐rich rims. Plagioclase has relatively restricted compositions (An_87–96Or_0–1Ab_4–13), and was transformed to maskelynite. The REE zoning of all silicate minerals was not significantly modified by shock metamorphism and weathering. Relatively large (up to 1 mm) olivine phenocrysts have homogenous inner parts with Fo ~74 and sharply decrease to 64 within the thin out rims (~30 μm in width). Four types of inclusions with a variety of textures and modal mineralogy were identified in olivine phenocrysts. The contrasting morphologies of these inclusions and the chemical zoning of olivine phenocrysts suggest NWA 4898 underwent at least two stages of crystallization. The aluminous chromite in NWA 4898 reveals that its high alumina character was inherited from the parental magma, rather than by fractional crystallization. The mineral chemistry and major element compositions of NWA 4898 are different from those of 12038 and Luna 16 basalts, but resemble those of Apollo 14 high‐Al basalts. However, the trace element compositions demonstrate that NWA 4898 and Apollo 14 high‐Al basalts could not have been derived from the same mantle source. REE compositions of its parental magma indicate that NWA 4898 probably originated from a unique depleted mantle source that has not been sampled yet. Unlike Apollo 14 high‐Al basalts, which assimilated KREEPy materials during their formation, NWA 4898 could have formed by closed‐system fractional crystallization.     

Complexly zoned chromium‐aluminum spinel found in situ in the Allende meteorite

Abstract— In addition to the Mg‐, Al‐, ¹⁶O‐rich spinels that are known to occur in refractory inclusions, the Murchison meteorite contains Cr‐rich, ¹⁶O‐poor spinels, most of whose sources are unknown because they are rarely found in situ. Here we report the in situ occurrence in Allende of Cr‐rich spinels, found in 13 chondrules and 4 “olivine‐rich objects”. The Allende spinels exhibit major and minor element contents, isotopic compositions, and zoning of Cr₂O₃ contents like those of the Cr‐spinels from Murchison. Some chondrules contain patchy‐zoned spinel (Simon et al., 1994), which suggests that such grains did not form by sintering but perhaps by formation of overgrowths on relic grains. Unlike the olivine‐rich objects, phases in all three chondrules that were analyzed by ion microprobe have uniform, near‐normal O‐isotopic compositions. One olivine‐rich object, ALSP1, has a huge (1 mm) fragment of chevron‐zoned spinel. This spinel has near‐normal O‐isotopic compositions that are quite distinct from those of adjacent forsteritic olivine, which are relatively ¹⁶O‐rich and plot on the calcium‐aluminum‐inclusion (CAI) line, like some isolated forsterite grains found in Allende. The spinel and olivine in this object are therefore not genetically related to each other. Another olivine‐rich object, ALSP11A, contains a rectangular, 150 ×s 100 μm, homogeneous spinel grain with 50 wt% Cr₂O₃ and 23 wt% FeO in a vuggy aggregate of finer‐grained (5–90 μm), FeO‐rich (Fo_47–55) olivine. The magnesian core of one olivine grain has a somewhat ¹⁶O‐rich isotopic composition like that of the large spinel, whereas the FeO‐rich olivine is relatively ¹⁶O‐poor. The composition of the spinel in ALSP11A plots on the CAI line, the first Cr‐rich spinel found to do so. Chevron‐zoned spinel has not been observed in chondrules, and it is unlikely that either ALSP1 or ALSP11A were ever molten. Calculations show that a spinel with the composition of that in ALSP1 can condense at 1780 K at a P^tot of 10^?3 atm and a dust/gas ratio of 100 relative to solar. The Cr‐rich spinel in ALSP11A could condense at ～1420 K, but this would require a dust/gas enrichment of 1000 relative to solar. The data presented here confirm that, as in Murchison, the coarse Cr‐rich spinels in Allende are relatively ¹⁶O‐depleted and are isotopically distinct from the ¹⁶O‐enriched MgAl₂O₄ from CAIs. Sample ALSP11A may represent a third population, one that is Cr‐rich and plots on the CAI line. That the O‐isotopic composition of ALSP1 is like those of Cr‐rich spinels from chondrules indicates that O‐isotopic compositions cannot be used to distinguish whether grains from such unequilibrated objects are condensates or are fragments from a previous generation of chondrules.