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The density of the Earth’s core is several percent lower than that of iron-nickel alloy under conditions of pressure and temperature equivalent to the Earth’s core. Hydrogen is one of the most promising constituents accounting for the density deficit, but hydrogen occupation sites and density decrease of iron-nickel alloy caused by hydrogenation have never been investigated. In this study, the phase relation and crystal structure of Fe0.9Ni0.1Hx(Dx) at high pressures and temperatures up to 12 GPa and 1000 K were clarified by in situ X-ray diffraction and neutron diffraction measurements. Under the P-T conditions of the present study, no deuterium atoms occupied tetragonal (T) sites of face-centered cubic (fcc) Fe0.9Ni0.1Dx, although the T-site occupation was previously reported for fcc FeHx(Dx). The deuterium-induced volume expansion per deuterium vD was determined to be 2.45(4) and 3.31(6) Å3 for fcc and hcp Fe0.9Ni0.1Dx, respectively. These vD values are significantly larger than the corresponding values for FeDx. The vD value for fcc Fe0.9Ni0.1Dx slightly increases with increasing temperature. This study suggests that only 10% of nickel in iron drastically changes the behaviors of hydrogen in metal. Assuming that vD is constant regardless of pressure, the maximum hydrogen content in the Earth’s inner core is estimated to be one to two times the amount of hydrogen in the oceans.

A new hydrate form of potassium chloride, KCl·H2O, is identified for the first time by in situ single-crystal X-ray diffraction under high pressure. It has a monoclinic structure with lattice parameters of a = 5.687 (7), b = 6.3969 (3), c = 8.447 (3) Å and β = 107.08 (8)° at 2.23 (4) GPa and 295 K. The structure of this hydrate has K—Cl alignments similar to the B1 phase of anhydrous KCl, while water molecules intercalate among the ionic species. The coordination structures of the K and Cl atoms can be regarded as the intermediate states between the B1 and B2 phases of KCl. This finding provides a perspective on the structural interpretation of multicomponent materials and an additional candidate for bound water in salt–water systems under high pressure, such as inside of icy bodies.

The Earth’s iron-rich core contains light elements. Studying the interaction of multiple light elements with iron and silicates during core–mantle segregation process in early Earth evolution has become important. In-situ X-ray diffraction and imaging observations of the iron–silicate–water–sulfur system at 5–10 GPa, up to approximately 1900°C, were used to elucidate sequential reactions: phase transformation and hydrogenation of iron, and formation of iron sulfide and silicates. The newly constructed X-ray imaging system achieved spatial resolution of approx. 10 μm for this study to show iron blob formation and motion. Sulfur distorted the iron blob shape and affected blob growth during heating by reducing the interfacial energy between molten iron and silicates. Light elements in the molten iron and the remaining silicate grains affected core–mantle segregation in the primitive Earth as temperatures increased. Carbon and silicon were incorporated into liquid Fe during later processes at higher temperatures.

地球の核の主要成分であるFeには軽金属が固溶していると考えられている。本研究ではそのモデル物質としてFe0.95Si0.05合金の水素化物について、水素吸蔵サイトと水素誘起格子体積膨張量を中性子その場観察により評価した。14.7 GPaでの測定とリートベルト解析の結果、水素は八面体サイトのみを占有し、水素誘起体積膨張量は2.33Å^3と算出された。SiがFeに加わることによって水素誘起体積膨張量はほとんど変化しないことが明らかになった。密度一定の条件では水素とSiの量は反相関の関係にあると結論づけた。

International audience; Ice polymorphs show extraordinary structural diversity depending on pressure and temperature. The behavior of hydrogen-bond disorder not only is a key ingredient for their structural diversity but also controls their physical properties. However, it has been a challenge to determine the details of the disordered structure in ice polymorphs under pressure, because of the limited observable reciprocal space and inaccuracies related to high-pressure techniques. Here, we present an elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K, from both single-crystal and powder neutron-diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these findings are related to proton dynamics, which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

We performed decompression experiments on sulfur-bearing hydrous rhyolite magma at a temperature of 800 °C to investigate redox evolution during magma decompression. The magma was continuously decompressed from 100 MPa to 10–50 MPa at rates of 10 and 100 MPa h–1. The evolution of the ferric to total iron ratio (Fe3+/Fetotal) during decompression was investigated using XANES, and redox evolution was determined based on a thermodynamic calculation and measured Fe3+/Fetotal. Before decompression, the sample was buffered from NNO to NNO+1, and the pre-exsolved fluid phase and sulfide crystal coexisted. Sulfide crystals were found in all decompressed samples, and Fe3+/Fetotal showed a slight decrease with decompression. It was confirmed that the sample in a gold capsule was not influenced by the change in redox conditions outside of the capsule for the timescale of the decompression experiments; thus, the decompressed sample reflected the redox evolution in magma during decompression. Our experiments indicated that magma decompression causes a slight reduction when it includes water and sulfur. This evolution is qualitatively explained by sulfur degassing and fluid-melt redox equilibria. During the fluid-melt redox equilibria, magma is reduced if the existence of a pre-exsolved fluid phase is assumed, while the model calculation shows that magma is oxidized when it contains only water or no pre-exsolved fluid phases. This is because sulfur buffers the oxidation of magma through a reaction with oxygen in the fluid phase. Therefore, we inferred that the redox condition of magma is not oxidized during explosive volcanism with a pre-exsolved fluid phase and closed-system degassing. In contrast, if magma experiences open-system degassing, it may be oxidized, resulting in the breakdown of sulfide crystals as observed in some pyroclasts and lavas.

We applied Kawai-type multi-anvil assemblies (MA6-8) for time-of-flight neutron-diffraction experiments to achieve high-pressures and high-temperatures simultaneously. To achieve sufficient signal ...

Taking into account recent publications, we provide additional comprehensive evidence that type Ib cuboctahedral diamonds and some other microcrystalline diamonds from Kamchatka volcanic rocks and alluvial placers cannot be natural and undoubtedly represent synthetic materials, which appear in the natural rocks by anthropogenic contamination. The major arguments provided in favor of the natural origin of those diamonds can be easily disproved. They include the coexistence of diamond and deltalumite from Koryaksky volcano; coexistence with super-reduced corundum and moissanite, Mn-Ni silicide inclusions, F-Cl enrichment and F/Cl ratios, and carbon and nitrogen isotopes in Tolbachik diamonds, as well as microtwinning, Mn-Ni silicides, and other inclusions in microcrystalline diamond aggregates from other Kamchatka placers. We emphasize the importance of careful comparison of unusual minerals found in nature, which include type Ib cuboctahedral diamonds and super-reduced phase assemblages resembling industrial slags, with synthetic analogs. The cavitation model proposed for the origin of Tolbachik diamonds is also unreliable since cavitation has only been shown to cause the formation of nanosized diamonds only.

We report a method to synthesize dolomite [CaMg(CO

Mechanical stimulation is well known to be important for maintaining tissue and organ homeostasis. Here, we found that hydrostatic pressure induced nuclear translocation of a forkhead box O (FOXO) transcription factor DAF-16, in C. elegans within minutes, whereas the removal of this pressure resulted in immediate export of DAF-16 to the cytoplasm. We also monitored DAF-16-dependent transcriptional changes by exposure to 1 MPa pressure for 5 min, and found significant changes in collagen and other genes in a DAF-16 dependent manner. Lifespan was markedly prolonged with exposure to cyclic pressure treatment (1 MPa once a day for 5 min from L1 larvae until death). Furthermore, age-dependent decline in locomotor activity was suppressed by the treatment. In contrast, the nuclear translocation of the yes-associated protein YAP-1 was not induced under the same pressure conditions. Thus, moderate hydrostatic pressure improves ageing progression through activation of DAF-16/FOXO in C. elegans.

Water freezes below 0 °C at ambient pressure ordinarily to ice Ih, with hexagonal stacking sequence. Under certain conditions, ice with a cubic stacking sequence can also be formed, but ideal ice Ic without stacking-disorder has never been formed until recently. Here we demonstrate a route to obtain ice Ic without stacking-disorder by degassing hydrogen from the high-pressure form of hydrogen hydrate, C2, which has a host framework isostructural with ice Ic. The stacking-disorder free ice Ic is formed from C2 via an intermediate amorphous or nano-crystalline form under decompression, unlike the direct transformations occurring in ice XVI from neon hydrate, or ice XVII from hydrogen hydrate. The obtained ice Ic shows remarkable thermal stability, until the phase transition to ice Ih at 250 K, originating from the lack of dislocations. This discovery of ideal ice Ic will promote understanding of the role of stacking-disorder on the physical properties of ice as a counter end-member of ice Ih., Metastable cubic ice has been identified in several conditions relevant to geo and astrochemistry, but was always characterized by stacking disorder. Here the authors synthesize a hydrogen hydrate and degas hydrogen, obtaining pure non-defected cubic ice, observed by X-ray and neutron diffraction.

In the paper by Yamashita et al. [Acta Cryst. (2022), C78, 749–754], an incorrect phrase is updated.

Ferropericlase (Mg,Fe)O is the second most abundant mineral in Earth's lower mantle and a common inclusion found in subcratonic diamonds. Pyrolitic mantle has Mg# (100 × Mg/(Mg+Fe)) ~89. However, ferropericlase inclusions in diamonds show a broad range of Mg# between 12 and 93. Here we use Synchrotron Mössbauer Source (SMS) spectroscopy and single-crystal X-ray diffraction to determine the iron oxidation state and structure of two magnesiowüstite and three ferropericlase inclusions in diamonds from São Luiz, Brazil. Inclusion Mg#s vary between 16.1 and 84.5. Ferropericlase inclusions contain no ferric iron within the detection limit of SMS, while both magnesiowüstite inclusions show the presence of monocrystalline magnesioferrite ((Mg,Fe)Fe

Esterification reaction between phosphoric acid and methanol proceeded markedly at 6 GPa and 25 °C. The yields of monomethyl phosphate and dimethyl phosphate were 17.0% and 0.3%, respectively. The ...

International audience; A high-pressure cell for in-situ single-crystal neutron diffraction was developed. The cell uses nano-polycrystalline diamond anvils in a tubular load frame made of bulk metallic glass which is highly transparent to neutrons and does not produce Bragg reflections. Diffraction peaks from a sample can be measured from almost any direction and the simple geometry of the cell allows accurate attenuation corrections. We demonstrate the operation of the cell by ambient-pressure experiment using a single-crystal of NaCl on the D9 diffractometer at the Institute-Laue-Langevin. A high-pressure experiment was also carried out on a single crystal of ice VII at 2.35 GPa showing the potential to detect weak diffraction spots. The correct integration of weak reflections together with the simple attenuation correction will help to carry out precise structure analysis and address new scientific problems using neutron diffraction.

Detection and monitoring of SO2 is important because it is a representative toxic gas in the atmospheric environment that is emitted from industrial and natural processes. Localized surface plasmon resonance (LSPR) sensing is a promising method to develop a robust and low-cost sensor for gaseous species. However, with conventional LSPR sensing, inorganic gases including SO2 are not detectable at the ppm level. In this study, we developed Au-nanopatterned chips coated with porous silica, which enabled detection of SO2 gas at ppm levels using the LSPR sensing system. The Au nanopattern was optimized using a finite-difference time-domain simulation and fabricated on quartz substrates using electron beam lithography. The Au-nanopatterned chips were coated with porous silica by the sol-gel method, which enables detection of 20 ppm of SO2. The sensitivity of the porous-silica-coated chip was four times higher than that of the uncoated chip. Modification of the porous silica layer with 3-aminopropyltrimethoxysilane (APTMS) using chemical vapor deposition further enhanced the sensitivity to SO2 gas, which was 13 times higher than that of the unmodified porous-silica-coated chip. Depth profiles by X-ray photoelectron spectroscopy indicated that APTMS was uniformly introduced into the porous silica layer. This study demonstrates that porous silica coatings on Au-nanopatterned chips and their additional modification with functional groups are potentially important to develop a low-cost and sensitive sensor for inorganic gases such as SO2.

A high-pressure phase of magnesium chloride hexahydrate (MgCl2·6H2O-II) and its deuterated counterpart (MgCl2·6D2O-II) have been identified for the first time byin-situsingle-crystal X-ray and powder neutron diffraction. The crystal structure was analyzed by the Rietveld method for the neutron diffraction pattern based on the initial structure determined by single-crystal X-ray diffraction. This high-pressure phase has a similar framework to that in the known ambient-pressure phase, but exhibits some structural changes with symmetry reduction caused by a subtle modification in the hydrogen-bond network around the Mg(H2O)6octahedra. These structural features reflect the strain in the high-pressure phases of MgCl2hydrates.

The enigmatic appearance of cuboctahedral diamonds in ophiolitic and arc volcanic rocks with morphology and infrared characteristics similar to synthetic diamonds that were grown from metal solvent requires a critical reappraisal. We have studied 15 diamond crystals and fragments from Tolbachik volcano lava flows, using Fourier transform infrared spectrometry (FTIR), transmission electron microscopy (TEM), synchrotron X-ray fluorescence (SRXRF) and laser ablation inductively coupled plasma mass-spectrometry (LA-ICP-MS). FTIR spectra of Tolbachik diamonds correspond to typical type Ib patterns of synthetic diamonds. In TEM films prepared using focused ion beam technique, we find Mn-Ni and Mn-Si inclusions in Tolbachik diamonds. SRXRF spectra indicate the presence of Fe-Ni and Fe-Ni-Mn inclusions with Cr, Ti, Cu, and Zn impurities. LA-ICP-MS data show variable but significantly elevated concentrations of Mn, Fe, Ni, and Cu reaching up to 70 ppm. These transition metal concentration levels are comparable with those determined by LA-ICP-MS for similar diamonds from Tibetan ophiolites. Mn-Ni (+Fe) solvent was widely used to produce industrial synthetic diamonds in the former USSR and Russia with very similar proportions of these metals. Hence, it appears highly probable that the cuboctahedral diamonds recovered from Kamchatka arc volcanic rocks represent contamination and are likely derived from drilling tools or other hard instruments. Kinetic data on diamond dissolution in basaltic magma or in fluid phase demonstrate that diamond does not form under the pressures and temperature conditions prevalent within the magmatic system beneath the modern-day Klyuchevskoy group of arc volcanoes. We also considered reference data for inclusions in ophiolitic diamonds and compared them with the composition of solvent used in industrial diamond synthesis in China. The similar inclusion chemistry close to Ni70Mn25Co5 for ophiolitic and synthetic Chinese diamonds scrutinized here suggests that most diamonds recovered from Tibetan and other ophiolites are not natural but instead have a synthetic origin. In order to mitigate further dubious reports of diamonds from unconventional tectonic settings and source rocks, we propose a set of discrimination criteria to better distinguish natural cuboctahedral diamonds from those produced synthetically in industrial environments and found as contaminants in mantle- and crust-derived rocks.

The specific features of the mineralogy of SiO 2 inclusions in sublithospheric diamonds are described in this study. Such diamonds are characterized by a complex growth history with stages of growth and dissolution and postgrowth processes of deformation and crushing. The nitrogen content in all studied crystals does not exceed 71 ppm and nitrogen is detected only as B-defects. The carbon isotope composition of diamonds varies widely from -26.5 to -6.7 ‰ of δ 13 С. SiO 2 inclusions associate with omphacitic clinopyroxenes, majoritic garnets, CaSiO 3 , jeffbenite and ferropericlase. All SiO 2 inclusions are coesite, which is often accompanied by micro-blocks of kyanite. These phases are suggested to represent the product of the retrograde transformation of the primary Al-stishovite. Significant internal stresses in the inclusions and deformations around them can be evidence of thise phase transformation. The heavier oxygen isotope composition of SiO 2 inclusions in sublithospheric diamonds (up to 12.9 δ 18 O) indicates the crustal origin of their protoliths. The observed anti-correlation of δ 18 O of SiO 2 inclusions and δ 13 C of their host diamonds reflects the processes of interaction of slab-derived melts with reduced mantle rocks at depths above 270 km.

Recently a number of reports claimed enigmatic appearance of high-pressure and super-reduced minerals in ophiolitic chromitite and peridotite. Diamond, moissanite, various metal alloys, and native metals, carbides and nitrides were found in mineral separates from bulk rock probes of chromitite and peridotite from Tibet, Polar Ural and other localities. Similar findings of super-reduced phases were reported for pyroclastic rocks and alluvial deposits of Mt. Carmel in Israel. We performed the study of microinclusions in corundum grains from abrasive materials produced industrially in an electric arc furnace and found that they are very similar to microinclusions in corundum grains from natural samples. The key similar phases are Ti3+4Al2(Zr,Ti4+)4O11 carmeltazite, Ti2O3 tistarite, TiN1-x, TiC1-x, Fe Si and Fe-Si-Ti alloys, hibonite, grossite, anorthite, and residual feldspatic glass. Although some differences between abrasive corundum and corundum from Tibet and Mt. Carmel are obvious, the morphology of melt pockets and amount of mineralogical similarities is more than critical to suggest that they can be of the same origin. The additional possible source of corundum grains with super-reduced inclusions is various Al-bearing slags after aluminothermic reactions during steelmaking. Moreover, taking into account the spectacular similarity of diamonds from ophiolite with synthetic diamonds, we claim for a thorough reconsideration of ultrahigh-pressure and super-reduced phases in natural rocks and argue that we need to find criteria for discrimination between natural and artificial samples. One of the strongest criteria would be textural and structural features that clearly demonstrate the indigenous character of the host minerals.

The paper describes mineralogical characteristics of SiO2 inclusions in sublithospheric diamonds, which typically have complicated growth histories showing alternating episodes of growth, dissolution, and postgrowth deformation and crushing processes. Nitrogen contents in all of the crystals do not exceed 71 ppm, and nitrogen is detected exclusively as B-defects. The carbon isotope composition of the diamonds varies from δ13С = –26.5 to –6.7‰. The SiO2 inclusions occur in association with omphacitic clinopyroxenes, majoritic garnets, CaSiO3, jeffbenite, and ferropericlase. All SiO2 inclusions are coesite, which is often associated with micro-blocks of kyanite in the same inclusions. It was suggested that these phases have been produced by the retrograde dissolution of primary Al-stishovite, which is also evidenced by the significant internal stresses in the inclusions and by deformations around them. The oxygen isotope composition of SiO2 inclusions in sublithospheric diamonds (δ18O up to 12.9‰) indicates a crustal origin of the protoliths. The negative correlation between the δ18O of the SiO2 inclusions and the δ13C of their host diamonds reflects interaction processes between slab-derived melts and reduced mantle rocks at depths greater than 270 km.

Basalt weathering in oceanic crust controls long-term elemental cycling on Earth. It is unknown whether basalt weathering tends to continue in unsedimented oceanic crust with formation ages of >10–20 million years (Ma), when fluid circulation is restricted by the formation of secondary minerals in fractures/veins. We investigated basalt weathering in 13.5-, 33.5- and 104-Ma oceanic crust below the South Pacific Gyre by combining bulk and in-situ clay mineral characterisations. Here we show the formation of iron-rich smectite at the rims of fractures/veins in 33.5-Ma and 104-Ma core samples from depths as great as 121 metres below the seafloor. In contrast, iron-rich smectite formation was not observed in three 13.5-Ma core samples, which suggests that iron-rich smectite formation may be affected by the dilution of aqueous silica supplied from basalt dissolution by actively circulating fluid. As iron-rich smectite from the 33.5-Ma and 104-Ma core samples was more enriched in Mg and K than that typically found at hydrothermal mounds, iron-rich smectite formation appears to result from basalt weathering rather than hydrothermal alteration. Our results suggest that unsedimented basaltic basement is permeable and reactive to host microbial life in aged oceanic crust on Earth and possibly in the deep subsurface on Mars.

Here we present trace element compositions of synthetic diamonds, which show spectacular similarity with the compositions of metallic inclusions in type Ib cuboctahedral diamonds in ophiolitic chro...

The microtexture of graphite exposed on the polished surface was studied using confocal laser scanning microscopy, laser Raman spectroscopy, and focused ion beam–transmission electron microscopy (FIB–TEM) to elucidate the effect on surface condition and crystallinity of graphite by polishing process. The polished surface of the graphite was divided into a flat part with no irregularities and a grooved band with a width of