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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.

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.

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.

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 ...

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.

Hydrogen (H) is considered to be one of the candidates for light elements in the Earth’s core, but the amount and timing of delivery have been unknown. We investigated the effects of sulfur (S), another candidate element in the core, on deuteration of iron (Fe) in iron–silicate–water system up to 6–12 GPa, ~ 1200 K using in situ neutron diffraction measurements. The sample initially contained saturated water (D2O) as Mg(OD)2 in the ideal composition (Fe–MgSiO3–D2O) of the primitive Earth. In the existence of water and sulfur, phase transitions of Fe, dehydration of Mg(OD)2, and formation of iron sulfide (FeS) and silicates occurred with increasing temperature. The deuterium (D) solubility (x) in iron deuterides (FeDx) increased with temperature and pressure, resulting in a maximum of x = 0.33(4) for the hydrous sample without S at 11.2 GPa and 1067 K. FeS was hardly deuterated until Fe deuteration had completed. The lower D concentrations in the S-containing system do not exceed the miscibility gap (x

Nitrogen is a crucial volatile element in the early Earth’s evolution and the origin of life. Despite its importance, nitrogen’s behavior in the Earth's interior remains poorly understood. Compared to other volatile elements, nitrogen is depleted in the Earth’s atmosphere (the so-called “missing nitrogen”), calling for a hidden deep reservoir. To investigate nitrogen’s behavior in the deep Earth including how the reservoir formed, high-pressure and high-temperature experiments were conducted at 28 GPa and 1,400–1,700 °C. To reproduce the conditions in the lower mantle, the redox was controlled using a Fe–FeO buffer. We observed that depending on the temperature conditions, stishovite can incorporate up to 90–404 ppm nitrogen, experimentally demonstrating that stishovite has the highest nitrogen solubility among the deep mantle minerals. Stishovite is the main mineral component of subducted nitrogen-rich sedimentary rocks and eroded continental crust that are eventually transported down to the lower mantle. Our results suggest that nitrogen could have been continuously transported into the lower mantle via subduction, ever since plate tectonics began.

The upper oceanic crust is mainly composed of basaltic lava that constitutes one of the largest habitable zones on Earth. However, the nature of deep microbial life in oceanic crust remains poorly understood, especially where old cold basaltic rock interacts with seawater beneath sediment. Here we show that microbial cells are densely concentrated in Fe-rich smectite on fracture surfaces and veins in 33.5- and 104-million-year-old (Ma) subseafloor basaltic rock. The Fe-rich smectite is locally enriched in organic carbon. Nanoscale solid characterizations reveal the organic carbon to be microbial cells within the Fe-rich smectite, with cell densities locally exceeding 1010 cells/cm3. Dominance of heterotrophic bacteria indicated by analyses of DNA sequences and lipids supports the importance of organic matter as carbon and energy sources in subseafloor basalt. Given the prominence of basaltic lava on Earth and Mars, microbial life could be habitable where subsurface basaltic rocks interact with liquid water., Yohey Suzuki, Seiya Yamashita et al. discover the presence of bacterial cells in the iron-rich smectite on aged subseafloor basaltic rock using nanoscale solid characterizations. Analysis of their lipid profiles and DNA sequences reveals the dominance of heterotrophic bacteria, suggesting the presence of organic matter resources in the subsea basalt.

An crystal-growth technique for single crystal x-ray structure analysis of high-pressure forms of hydrogen-bonded crystals is proposed. We used alcohol mixture (methanol: ethanol = 4:1 in volumetric ratio), which is a widely used pressure transmitting medium, inhibiting the nucleation and growth of unwanted crystals. In this paper, two kinds of single crystals which have not been obtained using a conventional experimental technique were obtained using this technique: ice VI at 1.99 GPa and MgCl2·7H2O at 2.50 GPa at room temperature. Here we first report the crystal structure of MgCl2·7H2O. This technique simultaneously meets the requirement of hydrostaticity for high-pressure experiments and has feasibility for further in-situ measurements.

More than 20 crystalline and amorphous phases have been reported for ice so far. This extraordinary polymorphism of ice arises from the geometric flexibility of hydrogen bonds and hydrogen ordering, and makes ice a unique presence with its universality in the wide fields of material and earth and planetary science. A prominent unsolved question concerning the diversity is whether a hydrogen-disordered phase of ice transforms into only one hydrogen-ordered phase, as inferred from the current phase diagram of ice, although its possible hydrogen configurations have close energies. Recent experiments on a high-pressure hydrogen-disordered phase, ice VI, revealed an unknown hydrogen-ordered form ($\beta$-XV) besides the known ordered phase, ice XV, which would be a counterexample of the question. However, due to lack of experimental evidence, it has not been clarified whether $\beta$-XV is a distinct crystalline phase. Herein we report a second hydrogen-ordered phase for ice VI, ice XIX, unambiguously demonstrated by neutron diffraction measurements. The phase boundary between ice VI and ice XIX shows that ice VI contracts upon the hydrogen ordering, which thermodynamically stabilizes ice XIX in higher-pressure region than ice XV because of its smaller volume than ice XV. The pressure-driven phase competition between hydrogen-ordered phases, also theoretically suggested in other ice polymorphs, can induce hydrogen ordering of ice in different manners. Thus, this study demonstrates a hitherto undiscovered polymorphism of ice.

At ambient pressure, the hydrogen bond in materials such as ice, hydrates, and hydrous minerals that compose the Earth and icy planets generally takes an asymmetric O-H···O configuration. Pressure significantly affects this configuration, and it is predicted to become symmetric, such that the hydrogen is centered between the two oxygen atoms at high pressure. Changes of physical properties of minerals relevant to this symmetrization have been found; however, the atomic configuration around this symmetrization has remained elusive so far. Here we observed the pressure response of the hydrogen bonds in the aluminous hydrous minerals δ-AlOOH and δ-AlOOD by means of a neutron diffraction experiment. We find that the transition from P21nm to Pnnm at 9.0 GPa, accompanied by a change in the axial ratios of δ-AlOOH, corresponds to the disorder of hydrogen bond between two equivalent sites across the center of the O···O line. Symmetrization of the hydrogen bond is observed at 18.1 GPa, which is considerably higher than the disorder pressure. Moreover, there is a significant isotope effect on hydrogen bond geometry and transition pressure. This study indicates that disorder of the hydrogen bond as a precursor of symmetrization may also play an important role in determining the physical properties of minerals such as bulk modulus and seismic wave velocities in the Earth’s mantle.

The high-temperature structural properties of solid benzene were studied at 1.5–8.2 GPa up to melting or decomposition using multianvil apparatus and in situ neutron and X-ray diffraction. The crystal structure of deuterated benzene phase II (P21/c unit cell) was refined at 3.6–8.2 GPa and 473–873 K. Our data show a minor temperature effect on the change in the unit cell parameters of deuterated benzene at 7.8–8.2 GPa. At 3.6–4.0 GPa, we observed the deviation of deuterium atoms from the benzene ring plane and minor zigzag deformation of the benzene ring, enhancing with the temperature increase caused by the displacement of benzene molecules and decrease of van der Waals bond length between the π-conjuncted carbon skeleton and the deuterium atom of adjacent molecule. Deformation of benzene molecule at 723–773 K and 3.9–4.0 GPa could be related to the benzene oligomerization at the same conditions. In the pressure range of 1.5–8.2 GPa, benzene decomposition was defined between 773–923 K. Melting was identi...

We report mechanochromic color change controlled by conformational change (folded and twisted conformers) of fluorenylidene-acridanes (FAs)., We report mechanochromic color change controlled by conformational change (between folded and twisted conformers) of fluorenylidene-acridanes (FAs). FAs with four N-alkyl groups (methyl, ethyl, n-butyl and n-octyl) were synthesized via the Barton–Kellogg reaction of diazofluorene and electrophilic N-tert-butoxy carbonyl thioacridone, deprotection of the tert-butoxy carbonyl group gives fluorenylacridine, and alkylation on the nitrogen atom is done using alkyl tosylate or triflate. FAs were characterized by NMR, UV-vis absorption and photoluminescence spectroscopy, theoretical calculation, cyclic voltammetry, and powder and single-crystal X-ray analyses. The color and folded/twisted conformation of the FAs were changed by the choice of substituent on the nitrogen atom, physical state (solution or solid), and morphology (crystalline or amorphous). Grinding of N-methyl FA solids, using an agate mortar, caused the morphology to change from a crystalline to amorphous state, which induced a conformational change from the folded to the twisted conformer, and a mechanochromic color change from yellow to dark green. The reverse color change, along with a morphological and conformational change to the folded conformer, was performed by solvent vapor exposure (chloroform). The twisted and folded conformers showed ambipolar (hole/electron) and hole-only transport properties, respectively.

At high temperatures and high pressures, iron reacts with hydrogen to form hydrides. Three hydride phases are present at moderate temperature and pressure ranges below 2000 K and 20 GPa: α, γ, and e′ phases, respectively, with bcc, fcc, and double-hcp (dhcp) structures. Recent reports have described studies of phase transitions at temperatures and pressures that differ greatly from those predicted from the conventional phase diagram for the Fe–H system established in the early 2000s. We conducted in-situ X-ray diffraction experiments to investigate α/e′–γ phase boundaries at temperatures up to 900 K and pressures up to 9.1 GPa. Phase transition temperatures were determined by averaging those observed upon heating and cooling under constant pressure. The α/e′–γ phase boundaries were found at temperatures 150–300 K higher than the conventional phase boundaries. The α–γ–e′ triple point was expected to relocate accordingly.

In-situ high-pressure synchrotron X-ray diffraction (XRD) and Fourier transform infrared absorption spectroscopy (FTIR) measurements have been conducted up to ~20 ​GPa at room temperature using diamond anvil cells (DAC), to investigate compressibility and spectroscopic properties of magnesium hydroxyfluoride, Mg(OH)F (Pnma, Z ​= ​4). Without any phase transition being observed, the pressure-volume correlation is fitted by the second-order Birch-Murnaghan equation of state, yielding K0 ​= ​80 (±2) GPa, K 0 ′ ​= ​4.0 (fixed), and V0 ​= ​145.2 (±0.3) A3. In accordance with other isostructural compounds crystallizing in the diaspore-type structure, higher contraction occurs along the c axis of Mg(OH)F. Positive pressure dependence of the O–H stretching mode frequencies initially observed at 3537 (1.56 ​cm−1/GPa), 3641 (0.67 ​cm−1/GPa), and 3680 ​cm−1 (2.85 ​cm−1/GPa) at ambient pressure indicates that the O–H ⋯ F hydrogen bond does not strengthen under compression.

Mesosiderites are a group of stony-iron meteorites, which are thought to be the result of mixing of silicates with Fe-Ni metal. In this study, we combined textural observations with geochemical and chronological studies of two zircon grains found in the Estherville mesosiderite. One of the zircons (Zrc1) occurs with pyroxene, plagioclase, troilite, and silica, and the other (Zrc2) is located at a boundary between Fe-Ni metal and a silicate part mainly composed of pyroxene and plagioclase. The textural observations demonstrate that Zrc1 is relatively homogenous, whereas Zrc2 is composed of at least two chemically distinct domains. Trace element analyses of Zrc2 resolve large concentration gradients within this single grain with variations that are an order of magnitude for rare earth elements (REE) and two orders of magnitude for U and Th. The lowest trace element concentration in Zrc2 is more than an order of magnitude lower than those of lunar and eucritic zircons. However, it is similar to those of Zrc1 and a zircon from the Vaca Muerta mesosiderite. The calculated REE composition of the melt in equilibrium with Zrc2 shows that Zrc2 and perhaps also Zrc1 did not crystallize from a melt that was produced by fractional crystallization of the primary magmatic mineral assemblages. The zircons with low REE, U, and Th concentrations can be interpreted to have formed in a residual melt after incorporation of large amounts of REE, U, and Th into secondary phosphate minerals, which formed during the metal-silicate mixing event. The large concentration gradients observed in Zrc2 suggest significant heterogeneities in the melt from which the zircon crystallized. Alternatively, either mixing or diffusion between a relict zircon and a newly formed zircon could explain the observed concentration gradients. However, the REE patterns of Zrc2 cannot be explained by mixing or diffusion between the two distinct generations of zircons. These considerations suggest that Zrc1 and Zrc2 formed during a high-temperature reheating event, which is probably related to the metal-silicate mixing event. The weighted average 207 Pb- 206 Pb age obtained by SIMS from both zircons is 4521 ± 26 Ma (2σ). This age is younger than that of a primary magmatic zircon from Vaca Muerta (4563 ± 15 Ma) and probably corresponds to the timing of the metal-silicate mixing event or a later impact event.

We investigated the relation between Sr# [= 100 Sr/(Sr + Ca) in mol] of calcites and their Raman spectra for Sr-doped calcite samples with Sr# of 0–13.2. We selected 3 major Raman peaks observed at 150–155 cm−1 (peak A), 274–282 cm−1 (peak B), and 710–712.5 cm−1 (peak C). With increasing Sr#, the peaks shifted monotonously to lower wavenumbers. We obtained a linear expression for peak B as Sr# = −1.734 ΔνB + 76.93, where ΔνB is a separation between peak B and a neon emission line of 237.07 cm−1 in Raman shift. The present spectroscopic analysis can ascertain Sr# of calcite with precision of ±1.26 in the range of Sr# of 0–13.2.

Pressure-induced phase transitions of vaterite, a metastable phase of CaCO3, were observed from Raman spectra and X-ray diffraction patterns at high pressure using diamond anvil cells at room temperature. Pressure dependence of Raman peaks assignable to the symmetric stretching vibration modes of carbonate ion indicated the phase transitions of vaterite. At 4.3 GPa, vaterite (vaterite I) transformed to a high-pressure form of vaterite (vaterite II). With increasing pressure, a part of vaterite II gradually transformed to calcite III, and the remainder of vaterite II transformed to another new phase (vaterite III). The phase transition from vaterite II to calcite III was irreversible, and calcite III back-transformed to calcite I during decompression. Moreover, at the pressures higher than 13.1 GPa, several diffraction spots were observed on an imaging plate, indicating another phase transition from vaterite III to a phase having coarse grains (vaterite IV). Our results indicate that vaterite undergoes more complex phase transitions at high pressure than other polymorphs of calcium carbonate, calcite, and aragonite. These phase transitions of vaterite will open a window to understanding phase transitions of metastable minerals at high pressure. Copyright © 2017 John Wiley & Sons, Ltd.

Oligomerization of alanine was observed by pressurizing its solid-free aqueous solution. Co-occurring solidifications of alanine and H2O as immiscible phases at high pressure were found to be crucial for concentrating the solute, alanine. The pressure-induced freeze concentration also enhances the pressure-induced oligomerization.

Neutron diffraction experiments of ice VII at pressures up to 6.2 GPa and 10.2 kV/mm were conducted to investigate the potential ferroelectrically ordered structure of ice VII induced by a high electric field. To accomplish this, we developed a high-pressure cell assembly to allow for powder neutron diffraction to be conducted under both high-pressure and high-electric field conditions. However, the subsequent observed diffraction patterns taken in situ at these conditions do not show sufficient evidence of the proposed ferroelectrically ordered structure of ice VII. We estimate the degree of the hydrogen ordering in ice VII under the applied conditions from high-pressure $P\ensuremath{-}E$ loop measurements, and discuss the future possibilities of detecting the ferroelectrically ordered structure.

We report cloudy micro- and nano-inclusions in a superdeep diamond from Sao-Luiz, Brazil which contains inclusions of ferropericlase (Mg, Fe)O and former bridgmanite (Mg, Fe)SiO3 and ringwoodite (Mg, Fe)2SiO4. Field emission-SEM and TEM observations showed that the cloudy inclusions were composed of euhedral micro-inclusions with grain sizes ranging from tens nanometers to submicrometers. Infrared absorption spectra of the cloudy inclusions showed that water, carbonate, and silicates were not major components of these micro- and nano-inclusions and suggested that the main constituent of the inclusions was infrared-inactive. Some inclusions were suggested to contain material with lower atomic numbers than that of carbon. Mineral phase of nano- and micro-inclusions is unclear at present. Microbeam X-ray fluorescence analysis clarified that the micro-inclusions contained transition metals (Cr, Mn, Fe, Co, Ni, Cu, Zn) possibly as metallic or sulfide phases. The cloudy inclusions provide an important information on the growth environment of superdeep diamonds in the transition zone or the lower mantle.

The stability and pressure-induced chemical reactions of naphthalene were investigated at room temperature at pressures up to 23 GPa. In-situ X-ray diffraction (XRD) measurements indicated that naphthalene retained its crystal structure up to ∼20 GPa, whereas a solid amorphous phase was observed in the recovered samples. Based on microanalysis of the recovered samples using Gas Chromatograph Mass Spectrometer (GC/MS), naphthalene dimer and trimer isomers were observed at pressures exceeding 15 GPa. The dimers were classified as products of simple dimerization, naphthylation, and condensation, similar to the case of the pressure-induced dimerization of benzene, indicating a similar dimerization mechanism for naphthalene.

Charcoal is widely used for radiocarbon dating in archaeological and paleoenvironmental studies. Reliable 14C dating requires appropriate chemical treatment to remove postdeposition contamination from the charcoal samples. This study assesses two pretreatments: acid-base-acid (ABA) and acid-base-oxidation with stepped combustion (ABOx-SC). In addition to 14C, the effects of the treatments on the chemical structure and composition of charcoal were studied using Fourier transform infrared spectroscopy (FTIR) and C/H/O elemental analysis. Samples of pine wood charred in the laboratory at 270, 300, 400, 500, and 600°C, and environmental samples of charred pine wood from pyroclastic flow deposits in southern Kyushu, Japan, were tested. The laboratory-charred samples showed that NaOH treatment removed highly hydrophilic organic components derived from endogenous and exogenous organic materials in the samples and that oxidation treatment caused the oxidative degradation of molecules in samples starting from its edges. The ABA-treated environmental charcoal yielded younger 14C dates than the ABOx-treated samples, probably owing to the effects of remaining organic contaminants bound to the edges of the aromatic molecular structures produced by the original pyrolysis. Meanwhile, it was found that ABA-SC treatment can reduce contaminants as effectively as ABOx-SC treatment. This implies that the stepped combustion (SC), not the chemical oxidation, is the key to reduce contaminant residue left after ABA and ABOx treatments. The results in this study indicate that the investigation of the structural and compositional changes of charcoal during its pretreatment is useful for assessment of the reliability of the 14C ages.

Calcite is a ubiquitous mineral in nature. Heavy alkaline-earth elements with large ionic radii such as Sr2+ and Ba2+ are highly incompatible to calcite. Our previous study clarified that incompatible Sr2+ ions can be structurally incorporated into calcite through crystallization from amorphous calcium carbonate (ACC). In this study, we synthesized Sr-doped calcite with Sr/(Sr + Ca) up to 30.7 &plusmn, 0.6 mol% and Ba-doped calcite with Ba/(Ba + Ca) up to 68.6 &plusmn, 1.8 mol%. The obtained Ba-doped calcite samples with Ba concentration higher than Ca can be interpreted as Ca-containing barium carbonates with the calcite structure which have not existed so far because barium carbonate takes the aragonite structure. X-ray diffraction (XRD) patterns of the Sr-doped and Ba-doped calcite samples obtained at room temperature showed that reflection 113 gradually weakened with increasing Sr/(Sr + Ca) or Ba/(Ba + Ca) ratios. The reflection 113 disappeared at Ba/(Ba + Ca) higher than 26.8 &plusmn, 1.6 mol%. Extinction of reflection 113 was reported for pure calcite at temperatures higher than 1240 K, which was attributed to the rotational (dynamic) disorder of CO32&minus, in calcite. Our Molecular Dynamics (MD) simulation on Ba-doped calcite clarified that the CO32&minus, ions in Ba-doped calcites are in the static disorder at room temperature. The CO32&minus, ions are notable tilted and displaced from the equilibrium position of pure calcite.

High-pressure responses of RbHCO3 and CsHCO3 were characterized by in situ Raman spectroscopy and X-ray and neutron diffraction observations. RbHCO3 exhibited a monoclinic (phase IV) and a triclinic (phase V) high-pressure phase at ~0.5 ​GPa and room temperature. Increasing compression induced unique behavior in a specific cell parameter (a in phase IV or c in phase V), which first increased, and then decreased at ~1 ​GPa, likely owing to the rearrangement of Rb+ and reconfiguration of the ordered (HCO3−)2 dimers. Deuterium positions in phase IV of RbDCO3 were determined. The hydrogen bonding remained moderately strong, and possibly did not affect the phase transition despite the accompanying disordering and ordering of the dimers. CsHCO3 showed no structural change up to 5 ​GPa, suggesting that its ambient phase (isostructural to phase IV of KHCO3) was already stable at high pressure. The structural stability appeared to be systematically related to the cation size.

Pressure-induced irreversible chemical reactions of naphthalene, 2,3-naphthyridine (2,3-Nap), and 1,5-naphthyridine (1,5-Nap) were observed after compression (>16–18 GPa) at room temperature. Regardless of the initial materials, amorphous products in which sp3 carbon was formed were obtained after the samples were recovered at ambient pressure. The X-ray photoelectron spectroscopy (XPS) of the product from naphthalene indicated that the carbon sp3/sp2 ratio was much lower than that of benzene nanothreads. Nitrogen remained in the amorphous products from 1,5-Nap and 2,3-Nap and bonded to both sp3 and sp2 carbons.

Stability and phase relations of coexisting enstatite and H2 fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO2 grains were found at the margin of the heating hot spot, suggesting that the SiO2 component dissolved in the H2 fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH4 and H2O molecules formed through the reaction between dissolved SiO2 and H2. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO2 components of enstatite in H2 fluid, as well as that observed in the forsterite H2 system and the quartz H2 system, implies that H2-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.

Photoluminescence (PL) spectroscopy and electron paramagnetic resonance (EPR) were used for the first time to characterize properties of superdeep diamonds from the Sao-Luis alluvial deposits (Brazil). The infrared measurements showed the low nitrogen content (>50 of 87 diamonds from this locality were nitrogen free and belonged to type IIa) and simultaneously the extremely high level of nitrogen aggregation (pure type IaB being predominant), which indicates that diamonds under study might have formed under high pressure and temperature conditions. In most cases, PL features excited at various wavelengths (313, 473, and 532 nm) were indicative of different growth and post-growth processes during which PL centers could be formed via interaction between vacancies and nitrogen atoms. The overall presence of the 490.7 nm, H3, and H4 centers in the luminescence spectra attests to strong plastic deformations in these diamonds. The neutral vacancy known as the GR1 center has probably occurred in a number of crystals due to radiation damage in the post-growth period. The 558.5 nm PL center is found to be one of the most common defects in type IIa samples which is accompanied by the EPR center with g-factor of 2.00285. The 536 and 576 nm vibronic systems totally dominated the PL spectra of superdeep diamonds, while none of “normal” diamonds from the Mir pipe (Yakutia) with similar nitrogen characteristics showed the latter three PL centers.

Plates made of diamonds from the São Luiz province (Brazil) were investigated by confocal scanning luminescence microscopy. The samples have many macroinhomogeneities (cracks and inclusions), but there is a quasi-uniform distribution of luminescence centers in the bulk. At all investigated points of the crystals, the same group of centers was observed: N3, H4, 575, and a red band with a maximum at 690–700 nm. The visible nonuniformities in the distribution of luminescence over the area of the plates are determined by relatively small fluctuations in the ratio of the intensities of individual bands in the spectra. Nitrogen centers of different degrees of aggregation (H4, N3, and 575 nm, with four, three, and one nitrogen atom, respectively) coexist in these crystals. In the same zones of the samples, the distribution of blue luminescence (N3 centers) is diffuse (uniform), but the distribution of yellow-green luminescence is characterized by layering on (111). This might be a consequence of the tangential growth of octahedron faces or a result of plastic deformation of the crystals and dislocations along (111).

Magnesium dichloride decahydrate (MgCl2·10H2O) and its deuterated counterpart (MgCl2·10D2O) are identified for the first time byin-situpowder synchrotron X-ray and spallation neutron diffraction. These substances are crystallized from a previously unidentified nanocrystalline compound, which originates from an amorphous state at low temperature. A combination of a recently developed autoindexing procedure and the charge-flipping method reveals that the crystal structure of MgCl2·10H2O consists of an ABCABC... sequence of Mg(H2O)6octahedra. The Cl−anions and remaining water molecules unconnected to the Mg2+cations bind the octahedra, similar to other water-rich magnesium dichloride hydrates. The D positions in MgCl2·10D2O, determined by the difference Fourier methods using the neutron powder diffraction patterns at 2.5 GPa, show the features such as bifurcated hydrogen bonds and tetrahedrally coordinated O atoms, which were not found in other forms of magnesium chloride hydrates.

Pressure-induced oligomerization was found from high-pressure experiments at 25 °C on alanine powder soaked in its saturated aqueous solution. The oligomerization to alanylalanine occurred at 5 GPa. The maximum yields of alanylalanine and trialanine were, respectively, 1.1 × 10(-3) and 1.3 × 10(-4) at 11 GPa.

Doping large amounts of a incompatible element into calcite, a polymorph of CaCO3, was achieved by pressurizing amorphous calcium carbonate (ACC) containing a dopant. Strontium-doped ACC samples were prepared from supersaturated solutions. ACC was transformed to calcite at 0.8 GPa and 25 °C. The lattice volume of calcite obtained by pressurizing ACC increased monotonically up to 372.5 A3 (1.3% increase from a Sr-free sample) with increasing Sr content in ACC up to 0.15 in Sr/(Sr + Ca). For comparison, the lattice volumes of calcite samples precipitated from supersaturated CaCO3 solution containing Sr were obtained, but the lattice volume of calcite precipitated from supersaturated solutions showed no noteworthy increase. Results of this study indicate that pressure-induced crystallization is an efficient pathway to dope incompatible elements into crystals.

In situ neutron diffraction measurements combined with the pulsed neutron source at the Japan Proton Accelerator Research Complex (J-PARC) were conducted on high-pressure polymorphs of deuterated portlandite (Ca(OD) 2 ) using a Paris–Edinburgh cell and a multi-anvil press. The atomic positions including hydrogen for the unquenchable high-pressure phase at room temperature (phase II′) were first clarified. The bent hydrogen bonds under high pressure were consistent with results from Raman spectroscopy. The structure of the high-pressure and high-temperature phase (Phase II) was concordant with that observed previously by another group for a recovered sample. The observations elucidate the phase transition mechanism among the polymorphs, which involves the sliding of CaO polyhedral layers, position modulations of Ca atoms, and recombination of Ca–O bonds accompanied by the reorientation of hydrogen to form more stable hydrogen bonds.

Species dissolved in H 2 fluid were investigated in a SiO 2 –H 2 system. Raman and infrared (IR) spectra were measured at high pressure and room temperature after heating experiments were conducted at two pressure and temperature conditions: 2.0 GPa, 1700 K and 3.0 GPa, 1500 K. With the dissolution of quartz, a SiH vibration mode assignable to SiH 4 was detected from Raman spectra of the fluid phase. Furthermore, an OH vibration mode was observed at 3260 cm −1 from the IR spectra at 3.0 GPa. With decreasing pressure, the OH vibration frequencies observed between 3.0 and 2.1 GPa correspond to that of ice VII, and those observed at 1.4 and 1.1 GPa correspond to that of ice VI. These results indicate that the chemical reaction between dissolved SiO 2 components and H 2 fluid caused the formation of H 2 O and SiH 4 , which was contrastive to that observed in SiO 2 –H 2 O fluid. Results imply that a part of H 2 is oxidized to form H 2 O when SiO 2 components of mantle minerals dissolve in H 2 fluid, even in an iron-free system.

Diamonds from Juina province, Brazil, and some others localities reveal the existence of a deep, Ca-rich carbonate-silicate source different from ultramafic and eclogite compositions. In this study, we describe the first observation of merwinite (Ca 2.85 Mg 0.96 Fe 0.11 Si 2.04 O 8 ) in a diamond; it occurs as an inclusion in the central growth domain of a diamond from the Sao Luiz river alluvial deposits (Juina, Brazil). In addition, the diamond contains inclusions of walstromite-structured CaSiO 3 in the core and (Mg 0.86 Fe 0.14 ) 2 SiO 4 olivine in the rim. According to available experimental data, under mantle conditions, merwinite can only be formed in a specific Ca-rich and Mg- and Si-depleted enviroment that differs from any known mantle lithology (peridotitic or eclogitic). We suggest that such chemical conditions can occur during the interaction of subduction-derived calcium carbonatite melt with peridotitic mantle. The partial reduction of the melt could cause the simultaneous crystallization of Ca-rich silicates (CaSiO 3 and merwinite) and diamond at an early stage, and (Mg 0.86 Fe 0.14 ) 2 SiO 4 olivine and diamond at a later stage, after the Ca-Mg exchange between carbonatite melt and peridotite has ceased. This scenario is supported by the presence of calcite microinclusions within merwinite.

Pressure-induced crystallization from amorphous calcium carbonate (ACC) was observed with X-ray diffraction at room temperature. Time-resolved diffraction patterns revealed that calcite and vaterit...

This report describes a newly observed phenomenon: pressure-induced crystallization from amorphous calcium carbonate (ACC). Synthetic ACC samples were pressurized up to 800 MPa at room temperature. Then crystallization of vaterite and calcite was observed from X-ray diffraction patterns. The crystallization pressure depends on the H2O contents of ACCs. The ACC samples with high-H2O content (21 wt %), middle-H2O content (17 wt %), and low-H2O content (10 wt %) underwent crystallization at pressures higher than 240 MPa, 400 MPa, and 640 MPa, respectively. These results indicate that H2O in the ACC serves an important role in the crystallization process and that we should treat ACC carefully in preparation for analyses such as infrared spectroscopy to obtain the intrinsic information related to amorphous materials.

Effects of L-Aspartic acid (L-Asp) on step retreat kinetics in the dissolution of calcite were investigated. The step retreat velocities under surface-controlled kinetics were determined from in-situ atomic force microscopic observations using an improved flow-through system. Comparison of the present results with those obtained under a mixed kinetics condition revealed that the addition of L-Asp promotes the transport process in the calcite dissolution through acid–base and/or complex forming reactions in the diffusion boundary layer. Additionally, promotion of the acute and obtuse step retreats by the L-Asp additive was observed under surface-controlled kinetics. This report is the first to clarify that L-Asp promotes surface processes in the dissolution of calcite.

Congruent evaporation of a crystalline material in vacuum is an extreme reaction in that backward reactions and transport processes in the reactant can be neglected. The evaporation is strongly governed by surface processes and intrinsic nature of the substance. A thorough knowledge of the atomistic evaporation mechanism is fundamental for better understanding reaction kinetics between gas and condensed materials in general. We have conducted a series of evaporation experiments of forsterite in vacuum for crystallographically oriented surfaces at 1500 to 1810 °C. The (100), (010), and (001) surfaces developed their own morphology characterized by evaporation pits and grooves originated from dislocation outcrops. Nominal overall evaporation rate (average retreat rate of a surface) shows significant anisotropy with the maximum difference by a factor of five below 1740 °C. The overall evaporation rates for individual surfaces are fitted with respective Arrhenius relationships, giving the highest activation energy for (100), intermediate for (001), and the lowest for (010). The anisotropy decreases to within 50% at ~1800 °C, which is caused by enhancement of evaporation from (010) owing to preferential evaporation around dislocation outcrops. “Intrinsic evaporation rates” estimated by subtracting contributions of initial roughness and the preferential evaporation around dislocations from the nominal overall evaporation rates show substantial anisotropy even at ~1800 °C. The “intrinsic evaporation rate” for (010) is adequately fitted by an Arrhenius relationship over the examined temperature range giving a single activation energy of 655 kJ/mol. The prevalence of steps with submicrometer to nanometer-scale height shows that forsterite evaporates mostly by layer-by-layer mechanism. The only exception is the (001) surface above ~1650 °C, on which such steps are absent except for surface-parallel minor facets which are rapidly diminishing with time. The (001) surface is inferred to evaporate by direct detachment mechanism at high temperatures. The change of evaporation mechanisms for (001) at around 1650 °C corresponds to a rough-smooth transition kinetically induced by an atomistic evaporation process.

Copyright © 2012 by The Geochemical Society of Japan. phenomenon presenting important implications for environmental problems (Wittbrodt and Palmer, 1996, 1997; Kožuh et al., 2000). Reduction-oxidation studies of Cr in soils have mainly targeted estimation of the reduction kinetics and stability constants (complexation capacities), or have addressed the presence of Cr(VI) (Fukushima et al., 1995; Wittbrodt and Palmer, 1995, 1996, 1997; Nakayasu et al., 1999; Kožuh et al., 2000). Information about the detailed chemical structure of Cr in nature is also necessary for complete understanding of toxicity and stability. However, determining a chemical state of Cr during or after a reaction process of Cr(VI) and soils is challenging because the soil system is too complex for speciation studies of Cr. Analysis using X-ray absorption fine structure (XAFS) spectroscopy is effective for determination of a valence state and a chemical form of metals in heterogeneous materials because it yields information with elemental selectivity obtained through Speciation study of Cr(VI/III) reacting with humic substances and determination of local structure of Cr binding humic substances using XAFS spectroscopy

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H2 molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.

The pressure responses of portlandite and the isotope effect on the phase transition were investigated at room temperature from single-crystal Raman and IR spectra and from powder X-ray diffraction using diamond anvil cells under quasi-hydrostatic conditions in a helium pressure-transmitting medium. Phase transformation and subsequent peak broadening (partial amorphization) observed from the Raman and IR spectra of Ca(OH)2 occurred at lower pressures than those of Ca(OD)2. In contrast, no isotope effect was found on the volume and axial compressions observed from powder X-ray diffraction patterns. X-ray diffraction lines attributable to the high-pressure phase remained up to 28.5 GPa, suggesting no total amorphization in a helium pressure medium within the examined pressure region. These results suggest that the H–D isotope effect is engendered in the local environment surrounding H(D) atoms. Moreover, the ratio of sample-to-methanol–ethanol pressure medium (i.e., packing density) in the sample chamber had a significant effect on the increase in the half widths of the diffraction lines, even at pressures below the hydrostatic limit of the pressure medium.

The relationship between Mg# [ = 100 Mg/(Mg + Fe) in mol] and the Raman shift was analyzed precisely for olivine [(Mg, Fe)2SiO4] samples with Mg# between 100 and 62.8. Two prominent peaks at 826–820 cm−1 (peak 1) and 858–849 cm−1 (peak 2) and three subordinate peaks at 883–881 cm−1 (peak 3), 920–914 cm−1 (peak 4), and 967–951 cm−1 (peak 5) were observed to shift monotonously to lower wavenumbers with decreasing Mg#. The ΔMg#( = Mg#ref − Mg#) versus Δν(= νref − ν) can be linearly regressed for each peak as ΔMg# = A Δν, where ν is a peak wavenumber of olivine with Mg# ranging from 100 to 62.8, and νref is that of olivine with a reference value of Mg#, namely, Mg#ref. We set Mg#ref as 100 (i.e.pure forsterite Mg2SiO4) whereas A is a regression parameter (5.789, 4.294, 12.34, 6.348, and 2.09, respectively,for peaks 1, 2, 3, 4, and 5). This equation enables us to avoid small inter-laboratory differences of wavenumber calibration. The equation for peak 2 yields estimations of Mg# in geologically satisfactory precision, ± 1 Mg# (1σ) in the Mg# range of 100–62.8. Copyright © 2011 John Wiley & Sons, Ltd.

We conducted powder neutron diffraction for δ-AlOOH samples with and without Mg and Si ions under ambient conditions in order to investigate the long-standing problem of the symmetry of this phase. The observed reflection conditions clearly show that the space group of pure δ-AlOOH is P21 nm with ordered hydrogen bonds, whereas that of δ-(Al0.86Mg0.07Si0.07)OOH is Pnnm or Pnn2 with disordered hydrogen bonds. It is more likely that the space group of δ-(Al0.86Mg0.07Si0.07)OOH is Pnnm, because cation or hydrogen ordering that breaks the mirror plane perpendicular to c axis in the Pnnm structure would not occur. The previously reported inconsistency for the space group of this phase was caused by the substitution of Mg and Si ions to Al site, i.e., the disordered cations with different valences may fluctuate hydrogen positions, and the disordered hydrogen causes the symmetry change.

This study reports the first application of dynamic light scattering to observations of crystal growth of calcium carbonate from a supersaturated solution. Crystal size distributions around the cri...

To elucidate processes of Cr(VI) reduction by humic acids in soils, humic acids reacting with Cr(VI) were characterized using IR and X-ray absorption near edge structure (XANES) spectroscopy. It is expected that oxidation of humic acid by Cr(VI) gives rise to the formation of aldehyde, ketone, and carboxyl species. However, no significant increase of IR-bands assignable to these functional groups has been reported. Instead, IR absorption spectra of humic acid oxidized by Cr(VI) show similar features to those of humic acid reacting with Cr(III). Consequently, the types and proportions of functional groups of HA substances did not differ significantly among experimental conditions. The IR spectra of humic acid reacting with Cr(III) and Cr(VI) show increased intensity of IR bands at 3400 cm, 1608 cm, and 1384 cm, with decreased intensity of peaks at 1707 cm and 1236–1250 cm. Those changes suggest the existence of bonding structures of two kinds: hydrated Cr forming an outer-sphere complex with humic acid, and Cr forming an inner-sphere complex with the carboxylate ligand of humic acid. The Cr-K edge XANES spectra of humic acid reacting with Cr(VI) suggest that Cr(III), reduced from Cr(VI), binds with humic acid. No systematic difference of XANES spectra was found with increased amounts of Cr(VI) in experimental solutions. These features are consistent with IR absorption spectra. The fractions of two kinds of binding forms suggested by IR spectra were determined from linear combination fitting using XANES spectra of reference compounds: 50% hydrated Cr(III) adsorbed onto HA electrostatically and the remainder of Cr(III) binding to carboxylic acid of HA. However, with increasing pH of experimental solutions, some Cr precipitates as Cr(OH)3•nH2O in the solid phase. The pH level or Cr concentration must be reduced to prevent production of a Cr(OH)3•nH2O precipitate.