Evidence for the extraterrestrial origin of a natural quasicrystal.
ABSTRACT: We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al(63)Cu(24)Fe(13), is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl(2)), cupalite (CuAl), and ?-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl(2)O(4)), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (? 10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry (18)O/(16)O and (17)O/(16)O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.
Project description:We carried out a coordinated mineralogical and isotopic study of a Wark-Lovering (WL) rim on a Ca,Al-rich inclusion (CAI) from the reduced CV3 chondrite Vigarano. The outermost edge of the CAI mantle is mineralogically and texturally distinct compared to the underlying mantle that is composed of coarse, zoned melilite (Åk<sub>~10-60</sub>) grains. The mantle edge contains fine-grained gehlenite with hibonite and rare grossite that likely formed by rapid crystallization from a melt enriched in Ca and Al. These gehlenite and hibonite layers are surrounded by successive layers of spinel, zoned melilite (Åk<sub>~0-10</sub>), zoned diopside that grades outwards from Al,Ti-rich to Al,Ti-poor, and forsteritic olivine intergrown with diopside. These layered textures are indicative of sequential condensation of spinel, melilite, diopside, and forsterite onto hibonite. Anorthite occurs as a discontinuous layer that corrodes adjacent melilite and Al-diopside, and appears to have replaced them, probably even later than the forsterite layer formation. Based on these observations, we conclude that the WL rim formation was initiated by flash melting and extensive evaporation of the original inclusion edge, followed by subsequent gas-solid reactions under highly dynamic conditions. All the WL rim minerals are <sup>16</sup>O-rich (?<sup>17</sup>O = ~-23‰), indicating their formation in an <sup>16</sup>O-rich nebular reservoir. Our Al-Mg measurements of hibonite, spinel, and diopside from the WL rim, as well as spinel and Al,Ti-diopside in the core, define a single, well-correlated isochron with an inferred initial <sup>26</sup>Al/<sup>27</sup>Al ratio of (4.94 ± 0.12) × 10<sup>-5</sup>. This indicates that the WL rim formed shortly after the host CAI. In contrast, the lack of <sup>26</sup>Mg excesses in the WL rim anorthite suggest its later formation or later isotopic disturbance in the solar nebula, after <sup>26</sup>Al had decayed.
Project description:The occurrence of phlogopite and amphibole in mantle ultramafic rocks is widely accepted as the modal effect of metasomatism in the upper mantle. However, their simultaneous formation during metasomatic events and the related sub-solidus equilibrium with the peridotite has not been extensively studied. In this work, we discuss the geochemical conditions at which the pargasite-phlogopite assemblage becomes stable, through the investigation of two mantle xenoliths from Mount Leura (Victoria State, Australia) that bear phlogopite and the phlogopite + amphibole (pargasite) pair disseminated in a harzburgite matrix. Combining a mineralogical study and thermodynamic modelling, we predict that the P-T locus of the equilibrium reaction pargasite + forsterite = Na-phlogopite + 2 diopside + spinel, over the range 1.3-3.0 GPa/540-1500 K, yields a negative Clapeyron slope of -0.003 GPa K<sup>-1</sup> (on average). The intersection of the P-T locus of supposed equilibrium with the new mantle geotherm calculated in this work allowed us to state that the Mount Leura xenoliths achieved equilibrium at 2.3 GPa /1190 K, that represents a plausible depth of ~ 70 km. Metasomatic K-Na-OH rich fluids stabilize hydrous phases. This has been modelled by the following equilibrium equation: 2 (K,Na)-phlogopite + forsterite = 7/2 enstatite + spinel + fluid (components: Na<sub>2</sub>O,K<sub>2</sub>O,H<sub>2</sub>O). Using quantum-mechanics, semi-empirical potentials, lattice dynamics and observed thermo-elastic data, we concluded that K-Na-OH rich fluids are not effective metasomatic agents to convey alkali species across the upper mantle, as the fluids are highly reactive with the ultramafic system and favour the rapid formation of phlogopite and amphibole. In addition, oxygen fugacity estimates of the Mount Leura mantle xenoliths [Δ(FMQ) = -1.97 ± 0.35; -1.83 ± 0.36] indicate a more reducing mantle environment than what is expected from the occurrence of phlogopite and amphibole in spinel-bearing peridotites. This is accounted for by our model of full molecular dissociation of the fluid and incorporation of the O-H-K-Na species into (OH)-K-Na-bearing mineral phases (phlogopite and amphibole), that leads to a peridotite metasomatized ambient characterized by reduced oxygen fugacity.
Project description:In chloroethene-contaminated sites undergoing in situ bioremediation, groundwater acidification is a frequent problem in the source zone, and buffering strategies have to be implemented to maintain the pH in the neutral range. An alternative to conventional soluble buffers is silicate mineral particles as a long-term source of alkalinity. In previous studies, the buffering potentials of these minerals have been evaluated based on abiotic dissolution tests and geochemical modeling. In the present study, the buffering potentials of four silicate minerals (andradite, diopside, fayalite, and forsterite) were tested in batch cultures amended with tetrachloroethene (PCE) and inoculated with different organohalide-respiring consortia. Another objective of this study was to determine the influence of pH on the different steps of PCE dechlorination. The consortia showed significant differences in sensitivities toward acidic pH for the different dechlorination steps. Molecular analysis indicated that Dehalococcoides spp. that were present in all consortia were the most pH-sensitive organohalide-respiring guild members compared to Sulfurospirillum spp. and Dehalobacter spp. In batch cultures with silicate mineral particles as pH-buffering agents, all four minerals tested were able to maintain the pH in the appropriate range for reductive dechlorination of chloroethenes. However, complete dechlorination to ethene was observed only with forsterite, diopside, and fayalite. Dissolution of andradite increased the redox potential and did not allow dechlorination. With forsterite, diopside, and fayalite, dechlorination to ethene was observed but at much lower rates for the last two dechlorination steps than with the positive control. This indicated an inhibition effect of silicate minerals and/or their dissolution products on reductive dechlorination of cis-dichloroethene and vinyl chloride. Hence, despite the proven pH-buffering potential of silicate minerals, compatibility with the bacterial community involved in in situ bioremediation has to be carefully evaluated prior to their use for pH control at a specific site.
Project description:The major problem in arsenic (As(III)) removal using adsorbents is that the method is time-consuming and inefficient owing to the fact that most of the adsorbents are more effective for As(V). Herein, we report a new discovery regarding the significant simultaneous oxidation and sequestration of As(III) by a heterogeneous catalytic process of copper aluminate (CuAl<sub>2</sub>O<sub>4</sub>) coupled with peroxymonosulfate (PMS). Oxidation and adsorption promote each other. With the help of the active radicals, the As(III) removal efficiency can be increased from 59.4 to 99.2% in the presence of low concentrations of PMS (50 ?M) and CuAl<sub>2</sub>O<sub>4</sub> (300 mg/L) in solution. CuAl<sub>2</sub>O<sub>4</sub>/PMS can work effectively in a wide pH range (3.0-9.0). Other substances, such as nitrate, sulfate, chloride, carbonate, and humic acid, exert an insignificant effect on As(III) removal. Based on X-ray photoelectron spectroscopy (XPS) analysis, the exposed reductive copper active sites might drive the redox reaction of Cu(II)/Cu(I), which plays a key role in the decomposition of PMS and the oxidation of As(III). The exhausted CuAl<sub>2</sub>O<sub>4</sub> could be refreshed for cycling runs with insignificant capacity loss by the combined regeneration strategy because of the stable spinel structure. According to all results, the CuAl<sub>2</sub>O<sub>4</sub>/PMS with favorable oxidation ability and stability could be employed as a promising candidate in real As(III)-contaminated groundwater treatment.
Project description:Icosahedral quasicrystals (i-phases) in the Al-Cu-Fe system are of great interest because of their perfect quasicrystalline structure and natural occurrences in the Khatyrka meteorite. The natural quasicrystal of composition Al62Cu31Fe7, referred to as i-phase II, is unique because it deviates significantly from the stability field of i-phase and has not been synthesized in a laboratory setting to date. Synthetic i-phases formed in shock-recovery experiments present a novel strategy for exploring the stability of new quasicrystal compositions and prove the impact origin of natural quasicrystals. In this study, an Al-Cu-W graded density impactor (GDI, originally manufactured as a ramp-generating impactor but here used as a target) disk was shocked to sample a full range of Al/Cu starting ratios in an Fe-bearing 304 stainless-steel target chamber. In a strongly deformed region of the recovered sample, reactions between the GDI and the steel produced an assemblage of co-existing Al61.5Cu30.3Fe6.8Cr1.4 i-phase II + stolperite (?, AlCu) + khatyrkite (?, Al2Cu), an exact match to the natural i-phase II assemblage in the meteorite. In a second experiment, the continuous interface between the GDI and steel formed another more Fe-rich quinary i-phase (Al68.6Fe14.5Cu11.2Cr4Ni1.8), together with stolperite and hollisterite (?, Al13Fe4), which is the expected assemblage at phase equilibrium. This study is the first laboratory reproduction of i-phase II with its natural assemblage. It suggests that the field of thermodynamically stable icosahedrite (Al63Cu24Fe13) could separate into two disconnected fields under shock pressure above 20?GPa, leading to the co-existence of Fe-rich and Fe-poor i-phases like the case in Khatyrka. In light of this, shock-recovery experiments do indeed offer an efficient method of constraining the impact conditions recorded by quasicrystal-bearing meteorite, and exploring formation conditions and mechanisms leading to quasicrystals.
Project description:Glyphosate, which has been widely reported to be a toxic pollutant, is often present at trace amounts in the environment. In this study, a novel copper-aluminum metal hydroxide doped graphene nanoprobe (labeled as CuAl-LDH/Gr NC) was first developed to construct a non-enzymatic electrochemical sensor for detection trace glyphosate. The characterization results showed that the synthesized CuAl-LDH had a high-crystallinity flowered structure, abundant metallic bands and an intercalated functional group. After mixed with Gr, the nanocomposites provided a larger surface area and better conductivity. The as-prepared CuAl-LDH/Gr NC dramatically improved the enrichment capability for glyphosate to realize the stripping voltammetry detection. The logarithmic linear detection range of the sensor was found to be 2.96 × 10-9-1.18 × 10-6 mol L-1 with the detection limit of 1 × 10-9 mol L-1 with excellent repeatability, good stability and anti-interference ability. Further, the sensor achieved satisfactory recovery rates in spiked surface water, ranging from 97.64% to 108.08%, demonstrating great accuracy and practicality.
Project description:Thermochemical heterogeneities detected today in the Earth's mantle could arise from ongoing partial melting in different mantle regions. A major open question, however, is the level of chemical stratification inherited from an early magma-ocean (MO) solidification. Here we show that the MO crystallized homogeneously in the deep mantle, but with chemical fractionation at depths around 1000?km and in the upper mantle. Our arguments are based on accurate measurements of the viscosity of melts with forsterite, enstatite and diopside compositions up to ~30?GPa and more than 3000?K at synchrotron X-ray facilities. Fractional solidification would induce the formation of a bridgmanite-enriched layer at ~1000?km depth. This layer may have resisted to mantle mixing by convection and cause the reported viscosity peak and anomalous dynamic impedance. On the other hand, fractional solidification in the upper mantle would have favored the formation of the first crust.
Project description:Diopside is a common natural pyroxene that is rarely found in a pure state, since magnesium is often partially substituted by iron, and other elements (sodium and aluminum) are often present. This pyroxene, along with feldspars and olivines, is common in concrete. As the prospective license renewal of light water reactors to 80 years of operation has raised concerns on the effects of radiation in the concrete biological shield surrounding the reactors, mineral nanoparticles can be valuable to perform amorphization studies to inform predictive models of mechanical properties of irradiated concrete. The synthesis of diopside nanoparticles was achieved in this study using a reverse-micelle sol-gel method employing TEOS, calcium chloride and Mg(MeO)2 in a methanol/toluene solution. Tert-butylamine and water were used as hydrolysis agents, and dodecylamine as a surfactant. The resulting amorphous precursor was centrifuged to remove organics and fired at 800?°C. Additional reaction with hydrogen peroxide was used to remove amine remnants. TEM and SEM examinations revealed a product comprised of 50-100?nm diameter nanoparticles. XRD indicated phase pure diopside and BET indicated a surface area of 63.5?m2/g before peroxide treatment, which at a bulk density of 3.4 g/cm3 is equivalent to particles with diameter of 28?nm.
Project description:Dissimilar Al 3003 and Cu tubular components were successfully brazed without interface cracking using ZrO? nanomaterials reinforced with Al-19Cu-11Si-2Sn filler. The filler was initially cast using an induction furnace and processed into ring form for brazing. Al-19Cu-11Si-2Sn filler with coarse CuAl? and Si phases (43 and 20 ?m) were refined to 8 and 4 ?m, respectively, after the addition of 0.1 wt. % ZrO? and shows significant improvement in the mechanical properties. ZrO? nanomaterials' induced diffusion controlled growth mechanism is found be the responsible for the refinement of CuAl? intermetallic and Si particles. The wettability of Al-19Cu-11Si-2Sn-0.1ZrO? increased to 78.17% on Cu side and 93.19% on the Al side compared from 74.8% and 89.9%, respectively. Increase in the yield strength, ultimate tensile strength, and percentage elongation were noted for the brazed joints. Microstructure of induction brazed joint with 40 kW for 6 seconds using Al-19Cu-11Si-2Sn-0.1ZrO? filler shows thin interfacial CuAl? intermetallic compound along the copper side and inter-diffusion region along the aluminum side and their respective mechanism is discussed. The tensile strength of the joints increased with increasing the nanomaterials addition and shows a base metal fracture. Analysis of fractured samples shows the effectiveness of ZrO? reinforced filler in crack propagation through the filler.
Project description:Equilibrium omphacite-garnet-bearing mafic rocks have been classified as eclogites, either pristine or retrogressed, that were formed at great depths in the lithosphere. Here we report a unique natural example of eclogite resembling assemblage in disequilibrium formed through fluid-induced metasomatic reactions under the amphibolite to granulite facies. Primarily, the amphibolized protolith experienced a garnet-amphibolite facies metamorphism at?~?500-700 °C and?~?0.8-1 GPa. Subsequently, CO<sub>2</sub> fluid induced fracturing and dissolution-reprecipitation reactions occurred at peak metamorphic conditions of?~?700 °C and?~?1 GPa. Occasional omphacite-albite assemblage, which gradually replace diopside-oligoclase symplectite adjacent to albite veins along fractures, indicates fluid-induced coupled dissolution-reprecipitation disequilibrium reactions. Here the albite-omphacite assemblage is in local equilibrium at least on 1 mm length scale, during cooling, below?~?600 ºC and?~?1 GPa, within the amphibolite facies conditions. The results from this study clearly suggest that disequilibrium garnet-omphacite assemblage in mafic rocks could be formed by crustal reworking processes below granulite facies conditions, and their textural equilibrium is an important criterion while defining eclogite facies.