Phase transition in CaSiO3 perovskite

A phase transition in pure CaSiO₃ perovskite was investigated at 27 to 72 GPa and 300 to 819 K by in-situ X-ray diffraction experiments in an externally-heated diamond-anvil cell. The results show that CaSiO₃ perovskite takes a tetragonal form at 300 K and undergoes phase transition to a cubic structure above 490–580 K in a pressure range studied here. The transition boundary is strongly temperature-dependent with a slightly positive dT / dP slope of 1.1 (± 1.3) K/GPa. It is known that the transition temperature depends on Al₂O₃ content dissolved in CaSiO₃ perovskite [Kurashina et al., Phys. Earth Planet. Inter. 145 (2004) 67–74]. The phase transition in CaSiO₃(+ 3 wt.% Al₂O₃) perovskite therefore could occur in a cold subducted mid-oceanic ridge basalt (MORB) crust at about 1200 K in the upper- to mid-lower mantle. This phase transition is possibly ferroelastic-type and may cause large seismic anomalies in a wide depth range.     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

Pb, Nd, and Sr isotopic constraints on the origin of Miocene basaltic rocks from northeast Hokkaido, Japan: Implications for opening of the Kurile back-arc basin

Late Miocene (7–9 Ma) basaltic rocks from the Monbetsu‐Kamishihoro graben in northeast Hokkaido have chemical affinities to certain back‐arc basin basalts (referred to herein as Hokkaido BABB). Pb‐, Nd‐ and Sr‐isotopic compositions of the Hokkaido BABB and arc‐type volcanic rocks (11–13 Ma and 4–4.5 Ma) from the nearby region indicate mixing between the depleted mantle and an EM II‐like enriched component (e.g. subducted pelagic sediment) in the magma generation. At a given ⁸⁷Sr/⁸⁶Sr, Hokkaido BABB have slightly lower ¹⁴³Nd/¹⁴⁴Nd and slightly less radiogenic ²⁰⁶Pb/²⁰⁴Pb compared with associated arc‐type lavas, but both these suites are difficult to distinguish solely on the basis of isotopic compositions. These isotopic data indicate that while generation of the Hokkaido BABB involves smaller amounts of the EM II‐like enriched component than do associated arc lavas, Hokkaido BABB are isotopically distinct from basalts produced at normal back‐arc basin spreading centers. Instead, northeast Hokkaido BABB are more similar to basalts erupted during the initial rifting stage of back‐arc basins. The Monbetsu‐Kamishihoro graben may have developed in association with extension that formed the Kurile Basin, suggesting that opening of the basin continued until late Miocene (7–9 Ma).     

Stabilities of NAL and Ca-ferrite-type phases on the join NaAlSiO<Subscript>4</Subscript>-MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> at high pressure

Stabilities of hexagonal new aluminous (NAL) phase and Ca-ferrite-type (CF) phase were investigated on the join NaAlSiO₄-MgAl₂O₄ in a pressure range from 23 to 58 GPa at approximately constant temperature of 1,850 K, on the basis of in situ synchrotron X-ray diffraction measurements in a laser-heated diamond-anvil cell. The results show that NAL is formed as a single phase up to 34 GPa, NAL + CF between 34 and 43 GPa, and only CF at higher pressures in 40%NaAlSiO₄-60%MgAl₂O₄ bulk composition. On the other hand, both NAL and CF coexist below 38 and 36 GPa, and only CF was obtained at higher pressures in 60%NaAlSiO₄-40%MgAl₂O₄ and 20%NaAlSiO₄-80%MgAl₂O₄ composition, respectively. These results indicate that NAL appears only up to 46 GPa at 1,850 K, and CF forms continuous solid solution at higher pressures on the join NaAlSiO₄-MgAl₂O₄. NAL has limited stability in subducted mid-oceanic ridge basalt crust in the Earth’s lower mantle and undergoes a phase transition to CF in deeper levels.     

Permian Peri‐glacial Deposits from Central Mongolia in Central Asian Orogenic Belt: A Possible Indicator of the Capitanian Cooling Event

A dropstone‐bearing, Middle Permian to Early Triassic peri‐glacial sedimentary unit was first discovered from the Khangai–Khentei Belt in Mongolia, Central Asian Orogenic Belt. The unit, Urmegtei Formation, is assumed to cover the early Carboniferous Khangai–Khentei accretionary complex, and is an upward‐fining sequence, consisting of conglomerates, sandstones, and varved sandstone and mudstone beds with granite dropstones in ascending order. The formation was cut by a felsic dike, and was deformed and metamorphosed together with the felsic dike. An undeformed porphyritic granite batholith finally cut all the deformed and metamorphosed rocks. LA‐ICP‐MS, U–Pb zircon dating has revealed the following ²⁰⁶Pb/²³⁸U weighted mean igneous ages: (i) a granite dropstone in the Urmegtei Formation is 273 ± 5 Ma (Kungurian of Early Permian); (ii) the deformed felsic dike is 247 ± 4 Ma (Olenekian of Early Triassic); and (iii) the undeformed granite batholith is 218 ± 9 Ma (Carnian of Late Triassic). From these data, the age of sedimentation of the Urmegtei Formation is constrained between the Kungurian and the Olenekian (273–247 Ma), and the age of deformation and metamorphism is constrained between the Olenekian and the Carnian (247–218 Ma). In Permian and Triassic times, the global climate was in a warming trend from the Serpukhovian (early Late Carboniferous) to the Kungurian long and severe cool mode (328–271 Ma) to the Roadian to Bajocian (Middle Jurassic) warm mode (271–168 Ma), with an interruption with the Capitanian Kamura cooling event (266–260 Ma). The dropstone‐bearing strata of the Urmegtei Formation, together with the glacier‐related deposits in the Verkhoyansk, Kolyma, and Omolon areas of northeastern Siberia (said to be of Middle to Late Permian age), must be products of the Capitanian cooling event. Although further study is needed, the dropstone‐bearing strata we found can be explained in two ways: (i) the Urmegtei Formation is an autochthonous formation indicating a short‐term expansion of land glacier to the central part of Siberia in Capitanian age; or (ii) the Urmegtei Formation was deposited in or around a limited ice‐covered continent in northeast Siberia in the Capitanian and was displaced to the present position by the Carnian.     

Compression of Na0.4Mg0.6Al1.6Si0.4O4 NAL and Ca-ferrite-type phases

Compression behaviors of two Al-rich phases in the lower mantle, hexagonal new aluminum-rich (NAL) phase and its high-pressure polymorph Ca-ferrite-type (CF) phase, were examined for identical Na_0.4Mg_0.6Al_1.6Si_0.4O₄ (40?% NaAlSiO₄–60?% MgAl₂O₄) composition. The volumes of the NAL and CF phases were obtained at room temperature up to 31 and 134?GPa, respectively, by a combination of laser-annealed diamond-anvil cell techniques and synchrotron X-ray diffraction measurements. Fitting of the third-order Birch–Murnaghan equation of state to such pressure–volume data yields bulk modulus K ₀?=?199(6) GPa at 1?bar and its pressure derivative K ₀′?=?5.0(6) for the NAL phase and K ₀?=?169(5) GPa and K ₀′?=?6.3(3) for the CF phase. These results indicate that the bulk modulus increases from 397 to 407 GPa across the phase transition from the NAL to CF phase at 43 GPa, where the NAL phase completely transforms into the CF phase on Na_0.4Mg_0.6Al_1.6Si_0.4O₄. Density also increases by 2.1?% across the phase transition.     

High-temperature compression experiments of CaSiO3 perovskite to lowermost mantle conditions and its thermal equation of state

In order to examine pressure–volume–temperature (P–V–T) relations for CaSiO₃ perovskite (Ca-perovskite), high-temperature compression experiments with in situ X-ray diffraction were performed in a laser-heated diamond anvil cell (DAC) to 127 GPa and 2,300 K. We also employed an external heating system in the DAC in order to obtain P–V data at a moderate temperature of 700 K up to 113 GPa, which is the reference temperature for constructing an equation of state. The P–V data at 700 K were fitted to the second-order Birch–Murnaghan equation of state, yielding K _700,1bar = 207 ± 4 GPa and V _700,1bar = 46.5 ± 0.1 Å³. Thermal pressure terms were evaluated in the framework of the Mie–Grüneisen–Debye model, yielding γ _700,1bar = 2.7 ± 0.3, q _700,1bar = 1.2 ± 0.8, and θ _700,1bar = 1,300 ± 500 K. A thermodynamic thermal pressure model was also employed, yielding α_700,1bar = 5.7 ± 0.5 × 10^?5/K and (?K/?T) _V  = ?0.010 ± 0.004 GPa/K. Computed densities along a lower mantle geotherm demonstrate that Ca-perovskite is denser than the surrounding lower mantle, suggesting that Ca-perovskite-rich rocks do not rise up through the lower mantle. One of such rocks might be a residue of partial melting of subducted mid-oceanic ridge basalt (MORB) at the base of the mantle. Since the partial melt is FeO-rich and therefore denser than the mantle, all the components of subducted MORB may not return to shallow levels.     

Possible variation in methane flux caused by gas hydrate formation on the northeastern continental slope off Sakhalin Island, Russia

The Sakhalin Slope Gas Hydrate Project (SSGH) is an international collaborative effort by scientists from Japan, Korea, and Russia to investigate natural gas hydrates (GHs) that have accumulated on the continental slope off Sakhalin Island, Okhotsk Sea. From 2009 to 2011, field operations of the SSGH-09, -10, and -11 projects were conducted. GH-bearing and -free sediment cores were retrieved using steel hydro- and gravity corers. The concentrations of sulfate ions in sediment pore waters were measured to investigate sulfate concentration–depth profiles. Seventeen cores showed linear depth profiles of sulfate concentrations. In contrast, eight cores and two cores showed concave-up and -down profiles plausibly explained by sudden increase and decrease in methane flux from below, respectively, presumably caused by the formation of gas hydrate adjacent to the core sampling sites.     

Subaqueous geothermal activity revealed by lacustrine sediments of the acidic Nakadake crater lake, Aso Volcano, Japan

Lacustrine sediments were sampled from the inaccessible acidic (pH = 0.43) Nakadake crater lake of Aso Volcano, Japan by a simple method. The sediments contain an extremely high content (74 wt.%) of sulfur, which exits as elemental sulfur, gypsum and anhydrite. The abundant elemental sulfur is likely formed by the reaction of SO₂ and H₂S gases and by the SO₂ disproportionation reaction in magmatic hydrothermal system below the crater lake. Based on the sulfur content of sediments and measurements of elevation change of the crater bottom, the sulfur accumulation rate at the Nakadake crater lake was calculated as 250 tonne/day, which is comparable with the SO₂ emission rate (200–600 tonne/day) from the Nakadake crater. The sediments include a small amount (9%) of clear glass shards that are apparently not altered in spite of the high reactivity of hyperacid lake water. This finding suggests that the clear glass shards are fragments of recently emitted magmas from fumaroles on the bottom of the crater lake and the magma emissions continuously occur even in quiescent periods.