Raman Spectra of Shocked Minerals 1: Olivine

Abstract— The Raman spectrum of olivine contained in a chip of the Twin Sisters Peak dunite shocked to 22.2 GPa is essentially identical to the spectrum of unshocked olivine in this rock. The Raman spectra of a powder of the rock shocked to 20.1 GPa and of chips shocked to 59.5 GPa and 60.7 GPa show strong and broad low-frequency features with crests at 475 cm^?1, 556 cm^?1, and 572 cm^?1, and strong as well as broad high-frequency features near 1100 cm^?1. We conclude that these features are most likely due to the formation of “olivine glass” with a considerable degree of three-dimensional Si-O-Si linkage, having scattered domains of greatly variable grain size, internal structure, and, possibly, chemical composition. We cannot conclude with our results at hand whether olivine shocked to the highest pressures has not decomposed to very fine-grained MgO plus an SiO₂-rich glass. We also conclude from our results that the structural changes are not likely to have formed in the laser beam of the measurement.     

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.     

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.     

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.     

CO2 release due to impact devolatilization of carbonate: Results of shock experiments

A study of pure, single crystal calcite shocked to pressures from 9.0 to 60.8 GPa was conducted to address contradictory data for carbonate shock behavior. The recovered materials were analyzed optically and by transmission electron microscopy (TEM), as well as by thermogravimetry (TGA), X‐ray diffraction (XRD), and Raman‐spectroscopy. In thin section, progressive comminution of calcite is observed although grains remain birefringent to at least 60.8 GPa. TGA analysis reveals a positive correlation between percent of mass loss due to shock and increasing shock pressure (R = 0.77) and suggests that shock loading leads to the modest removal of structural volatiles in this pressure range. XRD patterns of shocked Iceland spar samples produce peaks that are qualitatively and quantitatively less intense, more diffuse, and shift to lower ^o2θ. However, the regularity observed in these shocked powder patterns suggests that structures with very uniform unit cell separations persist to shock pressures as high as 60.8 GPa. Raman spectral analyses indicate no band asymmetry and no systematic peak shifting or broadening. TEM micrographs display progressively diminishing crystallite domain sizes. Selected area electron diffraction (SAED) patterns reveal no signatures of amorphous material. These data show that essentially intact calcite is recovered at shock pressures up to 60.8 GPa with only slight mass loss (~7%). This work suggests that the amount of CO₂ gas derived from shock devolatilization of carbonate by large meteorite impacts into carbonate targets has been (substantially) overestimated.     

Investigating the shock histories of lunar meteorites Miller Range 090034, 090070, and 090075 using petrography,geochemistry, and micro‐FTIR spectroscopy

Fourier transform infrared (FTIR) spectroscopy and cathodoluminescence (CL) imaging techniques, combined with electron microprobe analyses, have been used to determine the physical state of feldspathic phases that have been subject to varying levels of shock in the grouped lunar meteorites Miller Range 090034, 090070, and 090075. Six feldspathic phases have been identified based on spectral, textural, and chemical properties. A specific infrared wavelength band ratio (1064/932 cm^?1 equivalent to 9.40/10.73 μm), chosen because it can distinguish between some of the feldspathic phases, can be used to estimate the pressure regimes experienced by these phases. In addition, FTIR spatial mapping capabilities allow for visual comparison of variably shocked phases within the samples. By comparing spectral and compositional data, the origin and shock history of this lunar meteorite group has been determined, with each of the shocked feldspathic phases being related to events in its geological evolution. As such, we highlight that FTIR spectroscopy can be easily employed to identify shocked feldspathic phases in lunar samples; estimate peak shock pressures; and when compared with chemical data, can be used to investigate their shock histories.     

Mid-infrared spectra of the shocked Murchison CM chondrite: Comparison with astronomical observations of dust in debris disks

We present laboratory mid-infrared transmission/absorption spectra obtained from matrix of the hydrated Murchison CM meteorite experimentally shocked at peak pressures of 10-49 GPa, and compare them to astronomical observations of circumstellar dust in different stages of the formation of planetary systems. The laboratory spectra of the Murchison samples exhibit characteristic changes in the infrared features. A weakly shocked sample (shocked at 10 GPa) shows almost no changes from the unshocked sample dominated by hydrous silicate (serpentine). Moderately shocked samples (21-34 GPa) have typical serpentine features gradually replaced by bands of amorphous material and olivine with increasing shock pressure. A strongly shocked sample (36 GPa) shows major changes due to decomposition of the serpentine and due to devolatilization. A shock melted sample (49 GPa) shows features of olivine recrystallized from melted material.The infrared spectra of the shocked Murchison samples show similarities to astronomical spectra of dust in various young stellar objects and debris disks. The spectra of highly shocked Murchison samples (36 and 49 GPa) are similar to those of dust in the debris disks of HD113766 and HD69830, and the transitional disk of HD100546. The moderately shocked samples (21-34 GPa) exhibit spectra similar to those of dust in the debris disks of Beta Pictoris and BD+20307, and the transitional disk of GM Aur. An average of the spectra of all Murchison samples (0-49 GPa) has a similarity to the spectrum of the older protoplanetary disk of SU Auriga. In the gas-rich transitional and protoplanetary disks, the abundances of amorphous silicates and gases have widely been considered to be a primary property. However, our study suggests that impact processing may play a significant role in generating secondary amorphous silicates and gases in those disks. Infrared spectra of the shocked Murchison samples also show similarities to the dust from comets (C/2002 V1, C/2001 RX14, 9P/Tempel 1, and Hale Bopp), suggesting that the comets also contain shocked Murchison-like material.     

Thermal infrared spectra of experimentally shocked andesine anorthosite

Andesine-rich (An_36–46) anorthosite rocks experimentally shocked to high pressures (16–57 GPa) exhibit changes in spectral features with increasing pressure in laboratory thermal infrared emission spectra (250–1400 cm^?1). These results are similar to previous studies of shocked bytownite- and albite-rich rocks, albeit with differences in absorption band centers characteristic of mineralogy and composition. Typical spectral absorptions result from Si–O antisymmetric stretch motions of the silica tetrahedral (1000–1250 cm^?1) and weaker absorptions due to Si–O–Si octahedral bending vibrations (350–700 cm^?1). Many of these features persist to higher pressures in the andesine spectra compared to similar features in measurements of shocked bytownite. This is consistent with previous thermal infrared absorption studies of shocked feldspars and likely is related to differences in density, hardness, and Al content. A transparency feature at ～832 cm^?1 observed in powdered andesine spectra also degrades with increasing pressure, intermediate between the ～828 cm^?1 and ～855 cm^?1 transparency features in spectra of powders of shocked bytownite and albitite, respectively. These data can be incorporated into thermal infrared spectral analyses of cratered planetary surfaces (or laboratory spectra of shocked samples) to help constrain the occurrence and degree of shock in plagioclase feldspars.     

Revising the shock classification of meteorites

The current shock classification scheme of meteorites assigns shock levels of S1 (unshocked) to S6 (very strongly shocked) using shock effects in rock‐forming minerals such as olivine and plagioclase. The S6 stage (55–90 GPa; 850–1750 °C) relies solely on localized effects in or near melt zones, the recrystallization of olivine, or the presence of mafic high‐pressure phases such as ringwoodite. However, high whole rock temperatures and the presence of high‐pressure phases that are unstable at those temperatures and pressures of zero GPa (e.g., ringwoodite) are two criteria that exclude each other. Each type of high‐pressure phase provides a minimum shock pressure during elevated pressure conditions to allow the formation of this phase, and a maximum temperature of the whole rock after decompression to allow the preservation of this phase. Rocks classified as S6 are characterized not by the presence but by the absence of those thermally unstable high‐pressure phases. High‐pressure phases in or attached to shock melt zones form mainly during shock pressure decline. This is because shocked rocks (<60 GPa) experience a shock wave with a broad isobaric pressure plateau only during low velocity (<4.5 km s^?1) impacts, which rarely occur on small planetary bodies; e.g., the Moon and asteroids. The mineralogy of shock melt zones provides information on the shape and temporal duration of the shock wave but no information on the general maximum shock pressure in the whole rock.     

New observations on high‐pressure phases in a shock melt vein in the Villalbeto de la Peña meteorite: Insights into the shock behavior of diopside

The petrology and mineralogy of shock melt veins in the L6 ordinary chondrite host of Villalbeto de la Peña, a highly shocked, L chondrite polymict breccia, have been investigated in detail using scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and electron probe microanalysis. Entrained olivine, enstatite, diopside, and plagioclase are transformed into ringwoodite, low‐Ca majorite, high‐Ca majorite, and an assemblage of jadeite‐lingunite, respectively, in several shock melt veins and pockets. We have focused on the shock behavior of diopside in a particularly large shock melt vein (10 mm long and up to 4 mm wide) in order to provide additional insights into its high‐pressure polymorphic phase transformation mechanisms. We report the first evidence of diopside undergoing shock‐induced melting, and the occurrence of natural Ca‐majorite formed by solid‐state transformation from diopside. Magnesiowüstite has also been found as veins injected into diopside in the form of nanocrystalline grains that crystallized from a melt and also occurs interstitially between majorite‐pyrope grains in the melt‐vein matrix. In addition, we have observed compositional zoning in majorite‐pyrope grains in the matrix of the shock‐melt vein, which has not been described previously in any shocked meteorite. Collectively, all these different lines of evidence are suggestive of a major shock event with high cooling rates. The minimum peak shock conditions are difficult to constrain, because of the uncertainties in applying experimentally determined high‐pressure phase equilibria to complex natural systems. However, our results suggest that conditions between 16 and 28 GPa and 2000–2200 °C were reached.     

Heating effects of the matrix of experimentally shocked Murchison CM chondrite: Comparison with micrometeorites

Abstract— Micrometeorites have been significantly altered or melted by heating, which has been mainly ascribed to aerodynamic drag during atmospheric entry. However, if a major fraction of micrometeorites are produced by impacts on porous asteroids, they may have experienced shock heating before contact with the Earth's atmosphere (Tomeoka et al. 2003). A transmission electron microscope (TEM) study of the matrix of Murchison CM chondrite experimentally shocked at pressures of 10–49 GPa shows that its mineralogy and texture change dramatically, mainly due to shock heating, with the progressive shock pressures. Tochilinite is completely decomposed to an amorphous material at 10 GPa. Fe‐Mg serpentine is partially decomposed and decreases in amount with increasing pressure from 10 to 30 GPa and is completely decomposed at 36 GPa. At 49 GPa, the matrix is extensively melted and consists mostly of aggregates of equigranular grains of Fe‐rich olivine and less abundant low‐Ca pyroxene embedded in Si‐rich glass. The mineralogy and texture of the shocked samples are similar to those of some types of micrometeorites. In particular, the samples shocked at 10 and 21 GPa are similar to the phyllosilicate (serpentine)‐rich micrometeorites, and the sample shocked at 49 GPa is similar to the olivine‐rich micrometeorites. The shock heating effects also resemble the effects of pulse‐heating experiments on the CI and CM chondrite matrices that were conducted to simulate atmospheric entry heating. We suggest that micrometeorites derived from porous asteroids are likely to go through both shock and atmospheric‐entry heating processes.     

First discovery of stishovite in an iron meteorite

Abstract— The first occurrence of stishovite in an iron meteorite, Muonionalusta (group IVA), is reported. The mineral occurs intimately mixed with amorphous silica, forming tabular grains up to ?3 mm wide, with a hexagonal outline. It was identified using X‐ray diffraction and Raman microspectroscopy. The unit‐cell parameters of stishovite are a = 4.165(3) Å and c = 2.661(6) Å, and its chemical composition is nearly pure SiO₂. Raman spectra show relatively sharp bands at 231 and 754 cm^?1 and a broad band with an asymmetric shape and a maximum around 500 cm^?1. The rare grains are found within troilite nodules together with chromite, daubreelite, and schreibersite. From their composition and morphology, and by comparisons with silica inclusions in, e.g., the Gibeon IVA iron, we conclude that these rare grains represent pseudomorphs after tridymite. The presence of stishovite in Muonionalusta is suggested to reflect shock metamorphic conditions in the IVA parent asteroid during a cosmic impact event.     

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.     

Shock experiments with the H6 chondrite Kernouvé: Pressure calibration of microscopic shock effects

Abstract— Shock‐recovery experiments were carried out on samples of the H6 chondrite Kernouvé at shock pressures of 10, 15, 20, 25, 30, 35, 45, and 60 GPa and preheating temperatures of 293 K (low‐temperature experiments) and 920 K (high‐temperature experiments). Using a calculated equation of state of Kernouvé, pressure‐pulse durations of 0.3 to 1.2 μs were estimated. The shocked samples were investigated by optical microscopy to calibrate the various shock effects in olivine, orthopyroxene, oligoclase, and troilite. The following pressure calibration is proposed for silicates: (1) undulatory extinction of olivine <GPa; (2) weak mosaicism of olivine from 10–15 GPa to 20–25 GPa; (3) onset of strong mosaicism of olivine at 20–25 GPa; (4) transformation of oligoclase to diaplectic glass completed at 25–30 GPa (low‐temperature experiments) and at 20–25 GPa (high‐temperature experiments); (5) onset of weak mosaicism in orthopyroxene at 30–35 GPa (low‐temperature experiments) and at 25–30 GPa (high‐temperature experiments); and (6) recrystallization or melting of olivine starting at 45–60 GPa (low‐temperature experiments) and at 35–45 GPa (high‐temperature experiments), and completed above 45–60 GPa in the high‐temperature experiments. Troilite displays distinct differences between the samples shocked at low and high temperatures. In the low‐temperature experiments, the following effects can be observed in troilite: (1) undulatory extinction up to 25 GPa, (2) twinning up to 45 GPa, (3) partial recrystallization from 30 to 60 GPa, and (4) complete recrystallization >35 GPa; whereas in the high‐temperature experiments, troilite shows (1) complete recrystallization from 10 up to 45 GPa and (2) melting and crystallization above 45 GPa. Localized shock‐induced melting is observed in samples shocked to pressures >15 GPa in the high‐temperature experiments and >30 GPa for the low‐temperature experiments in the form of FeNi metal and troilite melt injections and intergrowths and as pockets and veins of whole‐rock melt. Obviously, the onset and abundance of shock‐induced localized melting strongly depends on the initial temperature of the sample.     

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.     

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.     

Scanning electron microscopy,cathodoluminescence, and Raman spectroscopy of experimentally shock‐metamorphosed quartzite

Abstract— We studied unshocked and experimentally (at 12, 25, and 28 GPa, with 25, 100, 450, and 750°C pre‐shock temperatures) shock‐metamorphosed Hospital Hill quartzite from South Africa using cathodoluminescence (CL) images and spectroscopy and Raman spectroscopy to document systematic pressure or temperature‐related effects that could be used in shock barometry. In general, CL images of all samples show CL‐bright luminescent patchy areas and bands in otherwise nonluminescent quartz, as well as CL‐dark irregular fractures. Fluid inclusions appear dominant in CL images of the 25 GPa sample shocked at 750°C and of the 28 GPa sample shocked at 450°C. Only the optical image of our 28 GPa sample shocked at 25°C exhibits distinct planar deformation features (PDFs). Cathodoluminescence spectra of unshocked and experimentally shocked samples show broad bands in the near‐ultraviolet range and the visible light range at all shock stages, indicating the presence of defect centers on, e.g., SiO₄ groups. No systematic change in the appearance of the CL images was obvious, but the CL spectra do show changes between the shock stages. The Raman spectra are characteristic for quartz in the unshocked and 12 GPa samples. In the 25 and 28 GPa samples, broad bands indicate the presence of glassy SiO₂, while high‐pressure polymorphs are not detected. Apparently, some of the CL and Raman spectral properties can be used in shock barometry.     

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.     

Shock-implanted noble gases II: Additional experimental studies and recognition in naturally shocked terrestrial materials

Abstract— Several experimentally and naturally shocked silicate samples were analyzed for noble gas contents to further characterize the phenomenon by which ambient gases can be strongly implanted into silicates by shock and to evaluate the possible importance of this process in capturing planetary atmospheres in naturally shocked samples. Gas implantation efficiency is apparently mineral independent, as mono-mineralic powders of oligoclase, labradorite, and diopside and a powdered basalt shocked to 20 GPa show similar efficiencies. The retentivity of shock-implanted gas during stepwise heating in the laboratory is defined in terms of two parameters: activation energy for diffusion as determined from Arrhenius plots, and the extraction temperature at which 50% of the gas is released, both of which correlate with shock pressure. These gas diffusion parameters are essentially identical for radiogenic ⁴⁰Ar and shock-implanted ⁴⁰Ar in oligoclase and labradorite shocked to 20 GPa, suggesting that the two ⁴⁰Ar components occupy analogous lattice sites. Our experiments indicate that gas implantation occurs through an increasing production of microcracks/defects in the lattice with increasing shock pressure. The ease of diffusive loss of implanted gas is controlled by the degree of annealing of these microcracks/defects. Identification of a shock-implanted component requires relatively large concentrations of implanted gas which is strongly retained (i.e., moderate activation energy) in order to separate implanted gas from surface adsorbed gases. Literature data on shocked terrestrial samples indicate only weak evidence for shock-implanted gases, with an upper limit for ⁴⁰Ar of ～ 10^?6 cm³STP/g. New analyses of shocked samples from the Wabar Crater indicate the presence of shock-implanted Ar, having concentrations (～ 10^?4 cm³STP/g) and activation energies for diffusive loss which are essentially that expected from experimental studies. Lack of sufficient target porosity or the presence of ground water may explain the sparse evidence for shock-implanted gas at other terrestrial craters. Although Wabar Crater may represent an unusually favorable environment on Earth for shock-implanting gases, surfaces of other planetary bodies, such as Mars, may frequently provide such environments. Analyses of returned samples from old Martian terraines may document temporal changes in earlier atmospheric composition.     

Mineralogical study of brown olivine in Northwest Africa 1950 shergottite and implications for the formation mechanism of iron nanoparticles

Martian meteorites, in particular shergottites, contain darkened olivine (so‐called “brown olivine”) whose color is induced by iron nanoparticles formed in olivine during a shock event. The formation process and conditions of brown olivine have been discussed in the Northwest Africa 2737 (NWA 2737) chassignite. However, formation conditions of brown olivine in NWA 2737 cannot be applied to shergottites because NWA 2737 has a different shock history from that of shergottites. Therefore, this study observed brown olivine in the NWA 1950 shergottite and discusses the general formation process and conditions of brown olivine in shergottites. Our observation of NWA 1950 revealed that olivine is heterogeneously darkened between and within grains different from brown olivine in NWA 2737. XANES analysis showed that brown olivine contains small amounts of Fe³⁺ and TEM/STEM observation revealed that there is no SiO‐rich phase around iron metal nanoparticles. These observations indicate that iron nanoparticles were formed by a disproportionation reaction of olivine (3Fe²⁺_olivine → Fe⁰_metal + 2Fe³⁺_olivine + V_olivine, where V_olivine means a vacancy in olivine). Some parts of brown olivine show lamellar textures in SEM observation and Raman peaks in addition to those expected for olivine, implying that brown olivine experienced a phase transition (to e.g., ringwoodite). In order to induce heterogeneous darkening, heterogeneous high temperature of about 1500–1700 K and shock duration of at least ~90 ms are required. This heterogeneous high temperature resulted in high postshock temperature (>900 K) inducing back‐transformation of most high‐pressure phases. Therefore, in spite of lack of high‐pressure phases, NWA 1950 (= Martian meteorites with brown olivine) experienced higher pressure and temperature compared to other highly shocked meteorite groups.