Takaya Nagai

Permanent El Nino during the Pliocene warm period not supported by coral evidence

The El Niño/Southern Oscillation (ENSO) system during the Pliocene warm period (PWP; 3–5 million years ago) may have existed in a permanent El Niño state with a sharply reduced zonal sea surface temperature (SST) gradient in the equatorial Pacific Ocean. This suggests that during the PWP, when global mean temperatures and atmospheric carbon dioxide concentrations were similar to those projected for near-term climate change, ENSO variability—and related global climate teleconnections—could have been radically different from that today. Yet, owing to a lack of observational evidence on seasonal and interannual SST variability from crucial low-latitude sites, this fundamental climate characteristic of the PWP remains controversial. Here we show that permanent El Niño conditions did not exist during the PWP. Our spectral analysis of the δ18O SST and salinity proxy, extracted from two 35-year, monthly resolved PWP Porites corals in the Philippines, reveals variability that is similar to present ENSO variation. Although our fossil corals cannot be directly compared with modern ENSO records, two lines of evidence suggest that Philippine corals are appropriate ENSO proxies. First, δ18O anomalies from a nearby live Porites coral are correlated with modern records of ENSO variability. Second, negative-δ18O events in the fossil corals closely resemble the decreases in δ18O seen in the live coral during El Niño events. Prior research advocating a permanent El Niño state may have been limited by the coarse resolution of many SST proxies, whereas our coral-based analysis identifies climate variability at the temporal scale required to resolve ENSO structure firmly.

Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: A study of isotope effect and hydrogen-bond symmetrization

Abstract The compression behaviors of δ-AlOOH and δ-AlOOD were investigated under quasi-hydrostatic conditions at pressures up to 63.5 and 34.9 GPa, respectively, using results from synchrotron X-ray diffraction experiments conducted at ambient temperature. Because of the geometric isotope effect, at ambient pressure, the a and b axes of δ-AlOOD, which define the plane in which the hydrogen bond lies, are longer than those of δ-AOOH. Under increasing pressure, the a and b axes of δ-AlOOH stiffen at 10 GPa, although the c axis shows no marked change. Identical behavior was found in δ-AlOOD, but the change in compressibility was observed at a slightly higher pressure of 12 GPa. Axial ratios a/c and b/c first decrease rapidly with increasing pressure, then begin to increase at pressures >10 GPa in δ-AlOOH and >12 GPa in δ-AlOOD. At these pressures, the pressure dependence of a/b also changes from increasing to decreasing. The unit-cell volumes of δ-AlOOH and δ-AlOOD become slightly less compressible at high pressures. Assuming K0′ = 4, the calculated bulk moduli of δ-AlOOH below and above 10 GPa are 152(2) and 219(3) GPa, respectively. Those of δ-AlOOD below and above 12 GPa are 151(1) and 207(2) GPa, respectively.

Compression mechanism of brucite: An investigation by structural refinement under pressure

Abstract Synchrotron X-ray powder diffraction study of brucite, Mg(OH)2, was carried out in a diamond anvil cell with an imaging plate detector from 0.6 to 18.0 GPa at room temperature using the angular- dispersive technique on beamline BL-18C at the Photon Factory, KEK, Japan. Using Rietveld analysis, unit-cell parameters as well as atomic positions of the O atoms in brucite have been successfully refined, taking into account the effects of preferred orientation. Variation of the c/a ratio with pressure indicates that the compression mechanism changes around 10 GPa, above which the compression behavior is isotropic. Based on the changes of the refined atomic positions of the O atoms with pressure, we conclude that the shortening of the interlayer distance controls compression below 10 GPa, whereas above this pressure compression of the oxygen sublattice is the dominant mechanism. Results of the structural refinements also suggest that the MgO6 octahedral regularity initially approaches a regular configuration with pressure, which then remains unchanged above 10 GPa.

Pressure and temperature dependence of EXAFS Debye-Waller factors in diamond-type and white-tin-type germanium

Extended X-ray absorption fine-structure (EXAFS) spectra near the Ge K-edge in diamond- and white-tin-type Ge under high temperature and high pressure were measured using a cubic-anvil-type apparatus (MAX90) with synchrotron radiation from the Photon Factory, Tsukuba, Japan. Pressure values up to 10.6 GPa were estimated on the basis of the isothermal equation of state of the diamond-type Ge within an accuracy of 0.4 GPa. Pressures for the same cell assembly were also determined by X-ray diffraction experiment using the NaCl scale. The diamond-type Ge is of great advantage to the pressure calibrant of EXAFS measurements at elevated temperature because a harmonic approximation can be applied up to 900 K. By the phase transition from diamond- to white-tin-type phases, with an increase in coordination number, Ge—Ge distances increase. A sixfold-coordinated Ge atom in the white-tin-type structure has crystallographically non-equivalent two kinds of nearest-neighbour distances [2.530 (8) A and 2.697 (8) A at 12.8 GPa]. The harmonic effective interatomic potential, V(u) = 1/2αu2, was evaluated from the contribution to the thermal vibration, where u is the deviation of the bond distance from the location of the potential minimum. The potential coefficient, α, at 0.1 MPa is essentially temperature independent and is 9.06 eV A−2. At 9 GPa the potential coefficient is 9.71 eV A−2. The effective interatomic potential is influenced not only by pressure but also by changes in coordination number. The high-pressure white-tin-type phase has a broader potential and a relatively larger mean square amplitude of vibration than the diamond-type phase.

Pressure-induced spin transition in FeCO3-siderite studied by X-ray diffraction measurements

We have collected synchrotron X-ray diffraction patterns of FeCO3-siderite after or in-situ laser heating at high pressures to 66 GPa. Diffraction peaks of FeCO3 in all diffraction patterns obtained can be indexed as a trigonal cell. However, calculated cell volumes show an abrupt decrease (about 6.5%) between 47 and 50 GPa at room temperature. This abrupt change of the cell volume on FeCO3 is possibly due to a pressure-induced spin transition of ferrous Fe (HS: high-spin → LS: low-spin). Because cell parameters obtained at high temperature and at pressures above 50 GPa suggest HS state rather than LS state, the Clapeyron slope of the HS-to-LS transition of FeCO3 should be positive.

Comparative Raman spectroscopic study on ilmenite-type MgSiO3 (akimotoite), MgGeO3, and MgTiO3 (geikielite) at high temperatures and high pressures

Abstract The Raman spectra of MgXO3-ilmenites (X = Si, Ge, Ti) were recorded up to 773 K at ambient pressure and up to 20-30 GPa at room temperature. Temperature and pressure dependence of the force constant of X-O stretching bands revealed that the expansion and compression behavior of XO6 octahedra differed in the three ilmenites. For SiO6 and GeO6 octahedra, the shorter Si-O or Ge-O bonds became more lengthened with temperature and more shortened with pressure than did the longer Si-O or Ge-O bonds. In contrast, for TiO6 octahedra, the longer Ti-O bonds became more lengthened with temperature and more shortened with pressure than did the shorter Ti-O bonds. For SiO6 and GeO6 at high temperatures and TiO6 at high pressures, the cation positions moved in the direction of the c axis and tended to approach the center of the octahedra, decreasing the distortion of XO6. For SiO6 and GeO6 at high pressures and TiO6 at high temperatures, the cations moved away from the center, increasing the distortion of XO6. One of the anharmonic correction terms on isochoric specific heat was also elucidated. The anharmonic effects were related to the elastic Debye temperature of the three ilmenites.

Pressure-induced phase transformation of kalicinite (KHCO3) at 2.8 GPa and local structural changes around hydrogen atoms

Abstract The pressure-induced structural phase transition in kalicinite, KHCO3, has been studied by neutron powder diffraction, and infrared (IR) and Raman spectroscopy at high pressure and room temperature. The neutron diffraction study of deuterated kalicinite (KDCO3) revealed that for the one site for hydrogen (deuterium) found in the low-pressure phase, the O-D···O angle decreases from 176 to 161° and the distance between donor and acceptor O atoms of the O-D···O group decreases from 2.66 to 2.59 Å in the pressure range from 0 to 2.5 GPa. The crystal structure of the high-pressure polymorph was not determined. Infrared spectra were obtained at pressures up to 6.3 GPa using a diamond anvil cell. At ambient pressure, the O-H stretching, O-H···O in-plane bending, and O-H···O out-of-plane bending modes occur at 2620, 1405, and 988 cm-1, respectively. The frequency of the O-H stretch mode was nearly constant in the pressure range from 0 to 2.8 GPa, while that of O-H···O in-plane bending and out-of-plane modes increased with increasing pressure up to 2.8 GPa and remained constant above the phase transition pressure. The Raman spectra showed a clear phase transition at 2.8 GPa. The three Raman modes observed are assigned to internal vibrational modes of HCO3- and this suggests that the surrounding environment did change dramatically at the phase transition. These results suggest that the phase transition in kalicinite is triggered by the distortion of C-O-H bond at high pressure.

Raman spectroscopy of cubic boron nitride under high temperature and pressure conditions: A new optical pressure marker

The pressure dependence of Raman peaks of cubic boron nitride (cBN) is determined at 100, 200 and 300 °C using pressure scales of ruby and gold. At pressures lower than 6 GPa, the pressure dependences of cBN Raman determined with the ruby pressure scale for transverse-optical (TO) and longitudinal-optical modes are 3.45±0.02 and 3.36±0.02 cm−1/GPa at 100 °C and 3.43±0.02 and 3.44±0.07 cm−1/GPa at 300 °C, respectively. These values are consistent with those in a previous study conducted at room temperature using the ruby pressure scale. Synchrotron x-ray diffraction experiments using a gold pressure marker also yield 3.45±0.03 cm−1/GPa for TO mode at 200 °C in a range of pressure up to 32 GPa. Under the present pressure and temperature conditions, the pressure dependence of Raman peaks of cBN seems to be independent of the temperature conditions. cBN can be used as an optical pressure marker under high temperature conditions.

High-pressure phase relation of MnSiO3 up to 85 GPa: Existence of MnSiO3 perovskite

Abstract The high-pressure phase relation of MnSiO3 was examined up to 85 GPa and 2600 K using a laserheated diamond-anvil cell combined with synchrotron radiation. MnSiO3 garnet decomposes into a mixture of MnO with a rock-salt structure (B1) + SiO2 stishovite at pressures higher than ~20 GPa and temperatures higher than ~1200 K. However, MnO (B1) + SiO2 stishovite further transforms to a perovskite structure with increasing pressure. The phase boundary between these structures is positive in the pressure-temperature diagram. The triple point of garnet, MnO + SiO2 and perovskite in the pressure-temperature diagram is ~20 GPa and 1200 K. MnSiO3 perovskite is orthorhombic, and consistent with space group Pbnm, both at high pressure and high temperature and at high pressure and room temperature, but becomes amorphous during decompression. The refined cell parameters of MnSiO3 perovskite at 85 GPa and 2600 K are a = 4.616(2) Å, b = 4.653(2) Å, c = 6.574(3) Å, and V = 141.2(2) Å3. The a/b ratio increases (approaches 1) with pressure and temperature, while the √2a/c ratio remains nearly constant (<1). This indicates that the orthorhombic distortion decreases and the structure tends toward a tetragonal perovskite with increasing pressure and temperature.

Structure change of Mn2O3 under high pressure and pressure-induced transition

Abstract Bixbyite (Mn,Fe)2O3 has a C-type rare-earth oxide structure with space group of Ia-3 and different from corundum structure R-3c. Single-crystal structure analyses and powder diffraction experiments were carried out using synchrotron radiation under high pressures up to 41.21 GPa. Lattice constants and bond distances were elucidated as a function of pressure. Single crystal structure analyses under high pressures up to 9.64 GPa have been executed using DAC. There are two octahedral Mn3+ sites: M1 (-3) and M2 (-2.). M1O6 and M2O6 octahedral volumes and void space of vacant sites show different compression curves. M1O6 octahedron is less compressive than M2O6 octahedron. The former is a little deformed from an ideal octahedron with m-3m of MnO6 but the latter is a largely distorted octahedron. The quadratic elongation is applied in order to comprehend the polyhedral distortion and finite homogeneous strain. Both octahedra do not show a noticeable Jahn-Teller distortion induced from Mn3+. Six bond lengths of M1O6 are equivalent but the octahedron more elongates along the direction of -3 axis with increasing pressure and is more deformed from the regular octahedron. The M2O6 octahedron has two long bond distances among six bonds, which are most compressive. The octahedral deformations seem to reduce the Jahn-Teller effect due to the compression. The bulk modulus: Ko = 169.1(4.9) GPa and Ko′ = 7.35(0.99), was observed from the volume change with pressure. Pressure-induced phase transition was confirmed at about 21 GPa with a large hysteresis. The transition is reversible and non-quenchable. Powder indexing of the high-pressure phase was carried out using diffraction pattern taken at 35.06 GPa. It has a monoclinic symmetry and is not a corundum, Rh2O3(II) or perovskite structure.