Comparison of the Raman spectra of ion irradiated soot and collected extraterrestrial carbon

We use a low pressure flame to produce soot by-products as possible analogues of the carbonaceous dust present in diverse astrophysical environments, such as circumstellar shells, diffuse interstellar medium, planetary disks, as well as in our own Solar System. Several soot samples, displaying an initial chemical diversity from aromatic to aliphatic dominated material, are irradiated with 200-400 keV H⁺, He⁺, and Ar⁺⁺ ions, with fluences comprised between 10¹⁴ and 10¹⁶ ions/cm², to simulate expected radiation induced modification on extraterrestrial carbon. The evolution of the samples is monitored using Raman spectroscopy, before, during, and after irradiation. A detailed analysis of the first- and second-order Raman spectra is performed, using a fitting combination of Lorentzian and/or Gaussian-shaped bands. Upon irradiation, the samples evolve toward an amorphous carbon phase. The results suggest that the observed variations are more related to vacancy formation than ionization processes. A comparison with Raman spectra of extraterrestrial organic matter and other irradiation experiments of astrophysically relevant carbonaceous materials is presented. The results are consistent with previous experiments showing mostly amorphization of various carbonaceous materials. Irradiated soots have Raman spectra similar to those of some meteorites, IDPs, and Comet Wild 2 grains collected by the Stardust mission. Since the early-Sun expected irradiation fluxes sufficient for amorphization are compatible with accretion timescales, our results support the idea that insoluble organic matter (IOM) observed in primitive meteorites has experienced irradiation-induced amorphization prior to the accretion of the parent bodies, emphasizing the important role played by early solar nebula processing.     

Low‐energy helium ion irradiation‐induced amorphization and chemical changes in olivine: Insights for silicate dust evolution in the interstellar medium

Abstract— We present the results of irradiation experiments aimed at understanding the structural and chemical evolution of silicate grains in the interstellar medium. A series of He+ irradiation experiments have been performed on ultra‐thin olivine, (Mg,Fe)₂SiO₄, samples having a high surface/volume (S/V) ratio, comparable to the expected S/V ratio of interstellar dust. The energies and fluences of the helium ions used in this study have been chosen to simulate the irradiation of interstellar dust grains in supernovae shock waves. The samples were mainly studied using analytical transmission electron microscopy. Our results show that olivine is amorphized by low‐energy ion irradiation. Changes in composition are also observed. In particular, irradiation leads to a decrease of the atomic ratios O/Si and Mg/Si as determined by x‐ray photoelectron spectroscopy and by x‐ray energy dispersive spectroscopy. This chemical evolution is due to the differential sputtering of atoms near the surfaces. We also observe a reduction process resulting in the formation of metallic iron. The use of very thin samples emphasizes the role of surface/volume ratio and thus the importance of the particle size in the irradiation‐induced effects. These results allow us to account qualitatively for the observed properties of interstellar grains in different environments, that is, at different stages of their evolution: chemical and structural evolution in the interstellar medium, from olivine to pyroxene‐type and from crystalline to amorphous silicates, porosity of cometary grains as well as the formation of metallic inclusions in silicates.     

Production,processing and characterization techniques for cosmic dust analogues

Abstract— The laboratory analyses of cosmic dust analogues—that in the context of this paper include interstellar, circumstellar as well as cometary dust—have a critical role in the study of circumstellar and cometary dust. The morphological, structural and chemical characterization of these analogues are critical for comparisons of their infrared and ultraviolet spectra with those obtained by astronomical observations, as well as for modeling purposes. Besides, the results from these laboratory studies are important to the success of space missions to comets when testing and calibrating the payload instruments. The interpretations of returned scientific data would benefit from the comparison with data recorded by the instruments in a laboratory setting for different classes of previously characterized analogues. We produced various types of condensed samples: (1) Mg,Fe‐silicates, (olivine, pyroxene), (2) carbon‐rich dust, and (3) mixed carbon‐silicate dust. The samples were prepared using different techniques, viz. (1) laser bombardment of solid targets in an Ar and O₂ atmosphere, (2) arc discharge in an Ar and H₂ atmosphere, and (3) grinding powders of natural minerals. We simulated various post‐condensation processes, such as thermal annealing, ultraviolet irradiation, ion bombardment and exposure to atomic hydrogen. These processes produced compound samples of a wide range of physico‐chemical properties. To identify their textures, morphologies, grain compositions and crystallographic properties we used electron microscopy and far‐ultraviolet to far‐infrared (millimeter range) spectroscopy.     

The nanoscale mineralogy of Fe,Ni sulfides in pristine and metamorphosed CM and CM/CI‐like chondrites: Tapping a petrogenetic record

We have sampled sulfide grains from one pristine CM2 chondrite (Yamato [Y‐] 791198), one thermally metamorphosed CM2 chondrite (Y‐793321), and two anomalous, metamorphosed CM/CI‐like chondrites (Y‐86720 and Belgica [B‐] 7904) by the focused ion beam (FIB) technique and studied them by analytical transmission electron microscopy (TEM). Our study aims at exploring the potential of sulfide assemblages and microstructures to decipher processes and conditions of chondrite petrogenesis. Complex exsolution textures of pyrrhotite (crystallographic NC‐type with N ≈ 6), troilite, and pentlandite occur in grains of Y‐791198 and Y‐793321. Additionally, polycrystalline 4C‐pyrrhotite‐pentlandite‐magnetite aggregates occur in Y‐791198, pointing to diverse conditions of gas–solid interactions in the solar nebula. Coarser exsolution textures of Y‐793321 grains indicate higher long‐term average temperatures in the <100 °C range compared to Y‐791198 and other CM chondrites. Sulfide mineralogy of Y‐86720 and B‐7904 is dominated by aggregates of pure troilite and metal, indicating metamorphic equilibration at sulfur fugacities (fS₂) of the iron‐troilite buffer. Absence of magnetite in equilibrium with sulfide and metal in Y‐86720 indicates higher peak temperatures compared with B‐7904, in which coexistence of troilite, metal, and magnetite constrains metamorphic temperature to less than 570 °C. NC‐pyrrhotite occurs in both meteorites as nm‐wide rims on troilite grains and, together with frequent anhydrite, indicates a retrograde metamorphic stage at higher fS₂ slightly above the fayalite‐magnetite‐quartz‐pyrrhotite buffer. Fine‐grained troilite‐olivine intergrowths in both meteorites suggest the pre‐metamorphic presence of tochilinite‐serpentine interlayer phases, pointing to mineralogical CM affinity. Pseudomorphs after euhedral pyrrhotite crystals in Y‐86720 in turn suggest CI affinity as do previously published O isotopic data of both meteorites.     

Laboratory analogues to cosmic dust

A pulsed laser has been used to vaporize olivine, pyroxene, nickel-iron alloy, Al₂O₃, carbon, calcium carbonate, and silicon carbide, as well as mixtures of immiscible phases (Au–Al₂O₃ and Au-olivine) in oxidizing, reducing, and inert atmospheres. The collected condensates usually consist of strings of grains which have a median diameter of 20–30 nm, which is comparable to the calculated sizes of some interstellar and circumstellar dust grains. The silicate minerals vaporized in O₂ as well as calcium carbonate and carbon vaporized in Ar or H₂, are collected as glassy grains while the other materials produced crystalline grains. The systems of immiscible phases when vaporized produced condensates consisting of intermixed 2–50 nm grains of both components. The type of size distribution, crystal structures, and qualitiative elemental analyses of the condensates are given. Possible similarities between the mechanism of grain growth, structure, morphology, and chemistry of laboratory grains compared to interstellar and circumstellar grains, phases in meteorites and extraterrestrial dust collected in the stratosphere are examined. Applications of the experimental technique include the production of grain systems to serve as laboratory analogues for spectral studies of grain materials believed to exist in astronomical environments, and studies of the structure of grains condensed from complex gas mixtures.Paper presented at the Conference on Protostars and Planets, held at the Planetary Science Institute, University of Arizona, Tucson, Arizona, between January 3 and 7, 1978.     

Simulation of the Ion Modification Processes in the Silicate Dust of Protoplanetary Disks

The modification of crystalline olivine under irradiation with 1.43-MeV deuterons was studied experimentally. For the first time, the partial destruction of olivine in the surface (100–200 nm) layer was found at a current density of 5–10 A/cm². This effect is caused by ionization and desorption of Mg and Fe atoms at deuteron fluences (3–8 × 10¹⁶cm^–2) which are substantially below the amorphization threshold. It was suggested that the negative charge of the anion group SiO₄ ^4–is neutralized by the interaction with the deuterium ions and Frenkel pairs. The mechanism of sputtering of the crystalline olivine surfaces under irradiation with H, D, He, and Ar ions was studied using of the TRIM 98 program.     

Thermoluminescence of forsterite and fused quartz as a candidate for the extended red emission

Abstract— We investigated thermoluminescence of silicates that are of interest in the interstellar and circumstellar medium after irradiation by γ‐rays and fast neutrons. The silicates are forsterite, orthoenstatite, olivine, quartz, and crystalline silicon. The irradiated enstatite shows weak and broad peaks at 545 and 760 nm. In contrast, irradiated bulk and powder samples of forsterite show strong and broad peaks at 640–660 nm. Although thermoluminescence of bulk forsterite is very similar to the extended red emission (ERE) of the Red Rectangle nebula, irradiated powdered forsterite did not reveal any sharp emission features over the broad band. Further, we investigated the possibility of thermoluminescence of crystalline silicon and found that luminescence scarcely appears. It is emphasized that the prominent carrier of ERE is forsterite and fused quartz.     

Formation of feldspathic and metallic melts by shock in enstatite chondrite Reckling Peak A80259

Abstract— The enstatite chondrite reckling peak (rkp) a80259 contains feldspathic glass, kamacite, troilite, and unusual sets of parallel fine‐grained enstatite prisms that formed by rapid cooling of shock melts. Metallic Fe,Ni and troilite occur as spherical inclusions in feldspathic glass, reflecting the immiscible Fe‐Ni‐S and feldspathic melts generated during the impact. The Fe‐Ni‐S and feldspathic liquids were injected into fractures in coarse‐grained enstatite and cooled rapidly, resulting in thin (≤ 10 μm) semicontinuous to discontinuous veins and inclusion trails in host enstatite. Whole‐rock melt veins characteristic of heavily shocked ordinary chondrites are conspicuously absent. Raman spectroscopy shows that the feldspathic material is a glass. Elevated MgO and SiO₂ contents of the glass indicate that some enstatite and silica were incorporated in the feldspathic melt. Metallic Fe,Ni globules are enclosed by sulfide and exhibit Nienrichment along their margins characteristic of rapid crystallization from a Fe‐Ni‐S liquid. Metal enclosed by sulfide is higher in Si and P than metal in feldspathic glass and enstatite, possibly indicating lower O fugacities in metal/sulfide than in silicate domains. Fine‐grained, elongate enstatite prisms in troilite or feldspathic glass crystallized from local pyroxene melts that formed along precursor grain boundaries, but most of the enstatite in the target rock remained solid during the impact and occurs as deformed, coarsegrained crystals with lower CaO, Al₂O₃, and FeO than the fine‐grained enstatite. Reckling Peak A80259 represents an intermediate stage of shock melting between unmelted E chondrites and whole‐rock shock melts and melt breccias documented by previous workers. The shock petrogenesis of RKPA80259 reflects the extensive impact processing of the enstatite chondrite parent bodies relative to those of other chondrite types.     

Properties of simulated cosmic matters after gamma-ray and neutron irradiation

Interstellar and circumstellar matter is known to be strongly irradiated by cosmic radiation and several types of cosmic ray particles. The effects of irradiation on simulated interstellar and circumstellar matter such as CaCO₃, MgCO₃, SiO₂ and Al₂O₃ are investigated. Especially, thermoluminescence (TL) spectra after γ-ray and neutron irradiation are compared carefully. It is shown that the thermoluminescence after neutron irradiation appears significantly in the wavelength of blue region. On the reflectance in infrared region, the irradiation effect appears scarcely.     

Reclassification of four aubrites as enstatite chondrite impact melts: Potential geochemical analogs for Mercury

We present petrologic and isotopic data on Northwest Africa (NWA) 4799, NWA 7809, NWA 7214, and NWA 11071 meteorites, which were previously classified as aubrites. These four meteorites contain between 31 and 56 vol% of equigranular, nearly endmember enstatite, Fe,Ni metal, plagioclase, terrestrial alteration products, and sulfides, such as troilite, niningerite, daubréelite, oldhamite, and caswellsilverite. The equigranular texture of the enstatite and the presence of the metal surrounding enstatite indicate that these rocks were not formed through igneous processes like the aubrites, but rather by impact processes. In addition, the presence of pre‐terrestrially weathered metal (7.1–14 vol%), undifferentiated modal abundances compared to enstatite chondrites, presence of graphite, absence of diopside and forsterite, low Ti in troilite, and high Si in Fe,Ni metals suggest that these rocks formed through impact melting on chondritic and not aubritic parent bodies. Formation of these meteorites on a parent body with similar properties to the EHa enstatite chondrite parent body is suggested by their mineralogy. These parent bodies have undergone impact events from at least 4.5 Ga (NWA 11071) until at least 4.2 Ga (NWA 4799) according to ³⁹Ar‐⁴⁰Ar ages, indicating that this region of the solar system was heavily bombarded early in its history. By comparing NWA enstatite chondrite impact melts to Mercury, we infer that they represent imperfect petrological analogs to this planet given their high metal abundances, but they could represent important geochemical analogs for the behavior and geochemical affinities of elements on Mercury. Furthermore, the enstatite chondrite impact melts represent an important petrological analog for understanding high‐temperature processes and impact processes on Mercury, due to their similar mineralogies, Fe‐metal‐rich and FeO‐poor silicate abundances, and low oxygen fugacity.     

Raman spectroscopic properties and Raman identification of CaS‐MgS‐MnS‐FeS‐Cr2FeS4 sulfides in meteorites and reduced sulfur‐rich systems

Raman spectra were acquired on a series of natural and synthetic sulfide minerals, commonly found in enstatite meteorites: oldhamite (CaS), niningerite or keilite ((Mg,Fe)S), alabandite (MnS), troilite (FeS), and daubreelite (Cr₂FeS₄). Natural samples come from three enstatite chondrites, three aubrites, and one anomalous ungrouped enstatite meteorite. Synthetic samples range from pure endmembers (CaS, FeS, MgS) to complex solid solutions (Fe, Mg, Ca)S. The main Raman peaks are localized at 225, 285, 360, and 470 cm^?1 for the Mg‐rich sulfides; at 185, 205, and 285 cm^?1 for the Ca‐rich sulfides; at 250, 370, and 580 cm^?1 for the Mn‐rich sulfides; at 255, 290, and 365 cm^?1 for the Cr‐rich sulfides; and at 290 and 335 cm^?1 for troilite with, occasionally, an extra peak at 240 cm^?1. A peak at 160 cm^?1 is present in all Raman spectra and cannot be used to discriminate between the different sulfide compositions. According to group theory, none of the cubic monosulfides oldhamite, niningerite, or alabandite should present first‐order Raman spectra because of their ideal rocksalt structure. The occurrence of broad Raman peaks is tentatively explained by local breaking of symmetry rules. Measurements compare well with the infrared frequencies calculated from first‐principles calculations. Raman spectra arise from activation of certain vibrational modes due to clustering in the solid solutions or to coupling with electronic transitions in semiconductor sulfides.     

Dust metamorphosis in the galaxy

Summary Cosmic dust grains play an important role for the thermal, dynamical, and chemical structure of the interstellar medium. This is especially true for the star formation process and the late stages of stellar evolution. Dust grains determine the spectral appearance of protostars, very young stellar objects with disk-like structures as well as of evolved stars with circumstellar envelopes.In this review, we will demonstrate that solid particles in interstellar space are both agent and subject of galactic evolution. We will especially discuss the different dust populations in circumstellar envelopes, the diffuse interstellar medium, and the molecular clouds with strong emphasis on the evolutionary aspects and the metamorphosis of these populations.     

Mass Loss and Circumstellar Dust Shells at T Tauri Stars

The mass loss of T Tauri stars leads to the production of dust in circumstellar space. The total amount of lost mass (and therefore of produced dust) is observed to be positiv correlated with the intensity of the H and Call emission lines of the objects. This fact is used in the present paper to explain quantitatively another correlation, namely the observation, that the interstellar extinction which is found by star counts in the wider surroundings of a T Tauri star is roughly proportional to the intensity of its Hα emission. By this, the outflow of circumstellar matter into the interstellar space seems to be observable directly.     

Cloudy circumstellar dust shells around young variable stars

A number of variable stars of the Orion population has been identified with IRAS point sources by us. This finding supports the conclusion that the prominent Algol-like minima in the lightcurves of these stars originate from obscurations by dust clouds in a circumstellar shell. The discussion of the existingUBVR data leads to the remarkable conclusion that the extinction properties of the grain populations contained in individual dust clouds moving in one and the same circumstellar shell are quite different.From the multicolour photometric data of the different Algol-like minima we derived individual values of the reddening parameterR = A _v /E(B - V). It covers a remarkable wide range of values from that one typical of the interstellar extinction law up to 7. In the case of SV Cep one of the grain populations produces a virtually neutral extinction. The large values ofR speak in favour of larger than normal (interstellar) dust grains, which may have grown by coagulation processes. The cloudy circumstellar dust shell provides a natural explanation for the observed infrared excess. The properties derived from the optical light variations are fully compatible with the properties deduced from the infrared radiation. The irregularity of the light variations indicates that many clouds are involved and may sometimes superimpose themselves.Paper presented at the Conference onPlanetary Systems: Formation, Evolution, and Detection held 7–10 December, 1992 at CalTech, Pasadena, California, U.S.A.     

“Sweating meteorites”—Water‐soluble salts and temperature variation in ordinary chondrites and soil from the hot desert of Oman

The common appearance of hygroscopic brine (“sweating”) on ordinary chondrites (OCs) from Oman during storage under room conditions initiated a study on the role of water‐soluble salts on the weathering of OCs. Analyses of leachates from OCs and soils, combined with petrography of alteration features and a 11‐month record of in situ meteorite and soil temperatures, are used to evaluate the role of salts in OC weathering. Main soluble ions in soils are Ca²⁺, SO₄^2?, HCO₃^?, Na⁺, and Cl^?, while OC leachates are dominated by Mg²⁺ (from meteoritic olivine), Ca²⁺ (from soil), Cl^? (from soil), SO₄^2? (from meteoritic troilite and soil), and iron (meteoritic). “Sweating meteorites” mainly contain Mg²⁺ and Cl^?. The median Na/Cl mass ratio of leachates changes from 0.65 in soils to 0.07 in meteorites, indicating the precipitation of a Na‐rich phase or loss of an efflorescent Na‐salt. The total concentrations of water‐soluble ions in bulk OCs ranges from 600 to 9000 μg g^?1 (median 2500 μg g^?1) as compared to 187–14140 μg g^?1 in soils (median 1148 μg g^?1). Soil salts dissolved by rain water are soaked up by meteorites by capillary forces. Daily heating (up to 66.3 °C) and cooling of the meteorites cause a pumping effect, resulting in a strong concentration of soluble ions in meteorites over time. The concentrations of water‐soluble ions in meteorites, which are complex mixtures of ions from the soil and from oxidation and hydrolysis of meteoritic material, depend on the degree of weathering and are highest at W3. Input of soil contaminants generally dominates over the ions mobilized from meteorites. Silicate hydrolysis preferentially affects olivine and is enhanced by sulfide oxidation, producing local acidic conditions as evidenced by jarosite. Plagioclase weathering is negligible. After completion of troilite oxidation, the rate of chemical weathering slows down with continuing Ca‐sulfate contamination.     

Rumanová H5 chondrite,Slovaki

Abstract— An H5 chondrite was found near the village of Rumanová, Slovakia. dominant minerals of the meteorite are enstatite, olivine, kamacite, taenite and troilite. The minor minerals are oligoclase, augite, pigeonite, accessory chromite, whitlockite and chlorapatite. The composition of olivine (Fa_19.0) and low-Ca orthopyroxene (Fs_17.0), and the density and chemical composition of the meteorite correspond to those of an H chondrite. Normal zoning of Ni in metal grains and parallel planar fractures in olivine suggest weak shock metamorphism of stage S3. Due to moderate oxidation of metal, iron hydroxides were formed corresponding to weathering stage W2.     

星周尘埃壳层的消光值

本文首次提出了从观测得到的具有星周尘埃壳层的恒星的能谱分布求取星周尘埃云的消光,并由此可通过改正星周消光改正后的星际消光法求得恒星距离的方法。     

Mineralogy of meteorite groups

Abstract— Approximately 275 mineral species have been identified in meteorites, reflecting diverse redox environments, and, in some cases, unusual nebular formation conditions. Anhydrous ordinary, carbonaceous and R chondrites contain major olivine, pyroxene and plagioclase; major opaque phases include metallic Fe-Ni, troilite and chromite. Primitive achondrites are mineralogically similar. The highly reduced enstatite chondrites and achondrites contain major enstatite, plagioclase, free silica and kamacite as well as nitrides, a silicide and Ca-, Mg-, Mn-, Na-, Cr-, K- and Ti-rich sulfides. Aqueously altered carbonaceous chondrites contain major amounts of hydrous phyllosilicates, complex organic compounds, magnetite, various sulfates and sulfides, and carbonates. In addition to kamacite and taenite, iron meteorites contain carbides, elemental C, nitrides, phosphates, phosphides, chromite and sulfides. Silicate inclusions in IAB/IIICD and IIE iron meteorites consist of mafic silicates, plagioclase and various sulfides, oxides and phosphates. Eucrites, howardites and diogenites have basaltic to orthopyroxenitic compositions and consist of major pyroxene and calcic plagioclase and several accessory oxides. Ureilites are made up mainly of calcic, chromian olivine and low-Ca clinopyroxene embedded in a carbonaceous matrix; accessory phases include the C polymorphs graphite, diamond, lonsdaleite and chaoite as well as metallic Fe-Ni, troilite and halides. Angrites are achondrites rich in fassaitic pyroxene (i.e., Al-Ti diopside); minor olivine with included magnesian kirschsteinite is also present. Martian meteorites comprise basalts, lherzolites, a dunite and an orthopyroxenite. Major phases include various pyroxenes and olivine; minor to accessory phases include various sulfides, magnetite, chromite and Ca-phosphates. Lunar meteorites comprise mare basalts with major augite and calcic plagioclase and anorthositic breccias with major calcic plagioclase. Several meteoritic phases were formed by shock metamorphism. Martensite (α₂-Fe,Ni) has a distorted body-centered-cubic structure and formed by a shear transformation from taenite during shock reheating and rapid cooling. The C polymorphs diamond, lonsdaleite and chaoite formed by shock from graphite. Suessite formed in the North Haig ureilite by reduction of Fe and Si (possibly from olivine) via reaction with carbonaceous matrix material. Ringwoodite, the spinel form of (Mg,Fe)₂SiO₄, and majorite, a polymorph of (Mg,Fe)SiO₃ with the garnet structure, formed inside shock veins in highly shocked ordinary chondrites. Secondary minerals in meteorite finds that formed during terrestrial weathering include oxides and hydroxides formed directly from metallic Fe-Ni by oxidation, phosphates formed by the alteration of schreibersite, and sulfates formed by alteration of troilite.     

Spectral alteration of the Meteorite Epinal (H5) induced by heavy ion irradiation: a simulation of space weathering effects on near-Earth asteroids

We present results obtained for Epinal (H5), an ordinary chondrite meteorite, irradiated with 60 keV Ar⁺⁺ ions, simulating solar wind heavy particle irradiation. Bidirectional reflectance spectra (0.3-2.67 μm) measured after irradiating Epinal samples with different ion fluences exhibit a progressive reddening that is similar to the spread of spectra observed for S-type near-Earth asteroids. The timescales for inducing the same effects in space as those obtained in laboratory are estimated to be ¹⁰⁴-¹⁰⁶ yr. These results suggest irradiation by heavy ions may be a very efficient weathering process in near-Earth space.     

Absorption bands and extinction in small interstellar particles

The production of discrete line and broad-band extinction by small interstellar oxide and silicate particles is discussed quantitatively. Restrictions on particle size and refractive index that are required to produce ‘pure’ absorption features are reviewed. The relationship between optical depth in interstellar extinction and absorption coefficients for bulk materials is used to reach some general conclusions concerning the diffuse interstellar features, VUV extinction and the composition of interstellar dust. It is noted that charge transfer bands of ions such as Fe³⁺ may be detectable in the VUV spectrum of dust. Several effects that lead to the enhancement of oscillator strength by 10³–10⁴ in small particles are discussed.