Samples of the carbonaceous asteroid Ryugu were brought to Earth by the Hayabusa2 spacecraft. We analyzed 17 Ryugu samples measuring 1 to 8 millimeters. Carbon dioxide–bearing water inclusions are present within a pyrrhotite crystal, indicating that Ryugu’s parent asteroid formed in the outer Solar System. The samples contain low abundances of materials that formed at high temperatures, such as chondrules and calcium- and aluminum-rich inclusions. The samples are rich in phyllosilicates and carbonates, which formed through aqueous alteration reactions at low temperature, high pH, and water/rock ratios of <1 (by mass). Less altered fragments contain olivine, pyroxene, amorphous silicates, calcite, and phosphide. Numerical simulations, based on the mineralogical and physical properties of the samples, indicate that Ryugu’s parent body formed ~2 million years after the beginning of Solar System formation.
3 October 2011 in Proceedings of the National Academy of Sciences
Phases of the iron–oxygen binary system are significant to most scientific disciplines, directly affecting planetary evolution, life, and technology. Iron oxides have unique electronic properties and strongly interact with the environment, particularly through redox reactions. The iron–oxygen phase diagram therefore has been among the most thoroughly investigated, yet it still holds striking findings. Here, we report the discovery of an iron oxide with formula Fe4O5, synthesized at high pressure and temperature. The previously undescribed phase, stable from 5 to at least 30 GPa, is recoverable to ambient conditions. First-principles calculations confirm that the iron oxide here described is energetically more stable than FeO + Fe3O4at pressure greater than 10 GPa. The calculated lattice constants, equation of states, and atomic coordinates are in excellent agreement with experimental data, confirming the synthesis of Fe4O5. Given the conditions of stability and its composition, Fe4O5is a plausible accessory mineral of the Earth’s upper mantle. The phase has strong ferrimagnetic character comparable to magnetite. The ability to synthesize the material at accessible conditions and recover it at ambient conditions, along with its physical properties, suggests a potential interest in Fe4O5for technological applications.
1 February 2002 in Physics and Chemistry of Minerals
In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV)=O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O 2 at low temperatures to form high-spin iron(IV)=O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O 2 , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.
Siderite (FeCO3) forms a complete solid solution with magnesite (MgCO3), the most likely candidate for a mantle carbonate. Our experiments with natural siderite reveal spin pairing of d‐orbital electrons of Fe2+ at 43 GPa, as evidenced by a sharp volume collapse of about 10%. The initially colorless crystals assume an intense green color after the transition, which progressively turns to red above 60 GPa. We present clear evidence for the instability of an intermediate spin state in siderite at ambient temperature. At the transition pressure, domains of high and low spin siderite coexist. The unit cell volume difference between magnesite and siderite is significantly decreased by the spin transition, enhancing the solubility between the two calcite‐type minerals. A siderite component in magnesite at lower mantle pressure would significantly increase its density and slightly increase the carbonate bulk modulus.