The stability and compressibility of MgAl2O4 high-pressure polymorphs

High-pressure and high-temperature experiments using a laser-heated diamond anvil cell (LHDAC) and synchrotron X-ray diffraction have revealed a phase transition in MgAl₂O₄. CaTi₂O₄-type MgAl₂O₄ was found to be stable at pressures between 45 and at least 117 GPa. The transition pressure of CaTi₂O₄-type phase in MgAl₂O₄ is much lower than that in the natural N-type mid-oceanic ridge basalt composition. The Birch–Murnaghan equation of state for CaTi₂O₄-type MgAl₂O₄ was determined from the experimental unit cell parameters with K ₀=219(±6) GPa, K ₀′=4(constrained value), and V ₀=238.9(±9) ų. The observed compressibility was in agreement with the theoretical compressibility calculated in a previous study. ε-MgAl₂O₄ was observed at pressures between 40 and 45 GPa, which has not been reported in natural rock compositions. The gradient (dP/dT slope) of the transition from the ε-type to CaTi₂O₄-type MgAl₂O₄ had a positive value. These results should resolve the dispute regarding the stable high-pressure phase of MgAl₂O₄, which has been reported in earlier studies using both the multi-anvil press and the diamond anvil cell.     

Evaluation of various satellite sensors for waterline extraction in a coral reef environment: Majuro Atoll, Marshall Islands

The ability of five satellite sensor bands (IKONOS band 4, Terra ASTER bands 3 and 4, and Landsat ETM+ bands 4 and 5) was examined to extract the waterline at coral reef coasts (Majuro Atoll, Marshall Islands) using different wavelength regions (near infrared [NIR] and shortwave infrared [SWIR]) and different spatial resolutions (4, 15, and 30 m). After performing georeferencing and normalization of the images, density slicing was used to extract the waterline. Comparisons of extracted waterline positions with ground-level data for eight transects and global positioning system (GPS) tracks of the island shorelines showed that NIR bands were superior to SWIR bands because of the characteristics of the coral reef coasts, including a lack of foam and suspended sediments (which can affect the NIR wavelength region, if present) and the presence of remnant water on reef flats during low tide (which can affect the SWIR wavelength region). A linear relationship was found between the estimation errors of waterline positions and the spatial resolutions of the NIR sensors. Analysis on estimation errors and image costs showed that Terra ASTER band 3 was the most cost-effective sensor for extracting waterlines with reasonable accuracy. The results serve as general guidelines for using satellite-derived data to estimate intertidal topography and detect and monitor shorelines in coral reef environments.     

Estimation of methane emission from whole waste landfill site using correlation between flux and ground temperature

A methodology to estimate a methane emission in a waste landfill site was developed. The methane flux at a waste landfill site in summer, autumn, and winter was within the following ranges: from −1.3×10⁻² to 16, from −6.4×10⁻² to 7.5, and from −1.6×10⁻³ to 1.5×10⁻² g-CH₄ m⁻² h⁻¹, respectively. In those seasons, the mean methane emission rate and coefficient of variation were 1.1 g-CH₄ m⁻² h⁻¹ ±290%, 0.57 g-CH₄ m⁻² h⁻¹ ±347%, and 5.4×10⁻² g-CH₄ m⁻² h⁻¹ ±370%, respectively. These results simultaneously showed that fluctuations of methane emission from the landfill surface were both of spatial and temporal variability. In each season, an exponential relationship was observed between the methane flux density and the ground temperature. Total methane emissions were estimated to be 5.7×10⁻², 7.1×10⁻³, and 1.7×10⁻³ g-CH₄ m⁻² h⁻¹ in the summer, autumn, and winter surveys, respectively, using a temperature surrogated-kriging method. The results of this study would improve upon the labor-intensive closed-chamber method, and could be a more practical way to estimate methane emissions from waste landfills.     

Effect of incorporation of iron and aluminum on the thermoelastic properties of magnesium silicate perovskite

In situ X-ray diffraction measurements of Fe- and Al-bearing MgSiO₃-rich perovskite (FeAl-Pv), which was synthesized from a natural orthopyroxene, were performed at pressures of 19–32 GPa and temperatures of 300–1,500 K using a combination of a Kawai-type apparatus with eight sintered-diamond anvils and synchrotron radiation. Two runs were performed using a high-pressure cell with two sample chambers, and both MgSiO₃ perovskite (Mg-Pv) and FeAl-Pv were synthesized simultaneously in the same cell. Thus we were able to measure specific volumes (V/V ₀) of Mg-Pv and FeAl-Pv at the same P−T conditions. At all the measurement conditions, values of the specific volume of FeAl-Pv are consistent with those of Mg-Pv within 2 Standard Deviation, strongly suggesting that effect of incorporation of iron and aluminum on the thermoelastic properties of magnesium silicate perovskite is undetectable in this composition, pressure, and temperature range. Two additional runs were performed using a high-pressure cell that has one sample chamber and unit-cell volumes of FeAl-Pv were measured at pressures and temperatures up to 32 GPa and 1,500 K, respectively. All the unit-cell volume data of FeAl-Pv perovskite were fitted to the high temperature Birch–Murnaghan equation of state and a complete set of thermoelastic parameters of this perovskite was determined with an assumption of K′ _300,0 = 4. The determined parameters are K _300,0 = 243(3) GPa, (∂K _T,0/∂T) _P = −0.030(8) GPa/K, a ₀ = 2.78(18) × 10⁻⁵ K⁻¹, and b ₀ = 0.88(28) × 10⁻⁸ K⁻², where a ₀ and b ₀ are the coefficients of the following expression describing the zero-pressure thermal expansion: α _T,0 = a ₀ + b ₀ T. The equation-of-state parameters of FeAl-Pv are in good agreement with those of MgSiO₃ perovskite at the conditions corresponding to the uppermost part of the lower mantle.     

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because ³⁴S/³²S ratios of vent fluid H₂S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ³³S (≡δ³³S-0.515 δ³⁴S) values of up to 0.04‰ even if δ³⁴S values are identical. Detection of such small Δ³³S differences is technically feasible by using the SF₆ dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H₂S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ³³S values ranging from −0.002 to 0.033 and δ³⁴S from −0.5‰ to 5.3‰. The combined δ³⁴S and Δ³³S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ³⁴S but also in Δ³³S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ³³S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that ³³S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.     

Determination of the second critical end point in silicate-H2O systems using high-pressure and high-temperature X-ray radiography

To determine the second critical end point in silicate-H₂O systems, a new method for the direct observations of immiscible fluids has been developed using a synchrotron X-ray radiography technique. High-pressure and high-temperature experiments were carried out with a Kawai-type, double-stage, multi-anvil high-pressure apparatus (SPEED-1500) installed at BL04B1, SPring-8, Japan. The Sr-plagioclase (SrAl₂Si₂O₈)-H₂O system was used as an illustrative example. A new sample container composed of a metal (Pt) tube with a pair of lids, made of single crystal diamonds, was used under pressures between 3.0 and 4.3 GPa, and temperatures up to ∼1600°C. The sample in the container could be directly observed through the diamond lids with X-ray radiography. At around 980 to 1060°C and pressures between 3.0 and 4.0 GPa, light gray spherical bubbles moving upward through the dark gray matrix were observed. The light gray spheres that absorb less X-rays represent an aqueous fluid, whereas the dark gray matrix represents a silicate melt. These two immiscible phases (aqueous fluid and silicate melt) were observed up to 4.0 GPa. At 4.3 GPa, no bubbles were observed. These observations suggest that the second critical end point in the Sr-plagioclase-H₂O system occurs at around 4.2 ± 0.2 GPa and 1020 ± 50°C. Our new technique can be applied to the direct observations of various systems with two coexisting fluids under deep mantle conditions.     

Dibenzofurans a greater global pollutant than dioxins ? : Evidence from analyses of open ocean killer whale

Three specimens of killer whales (Orcinus orca), an open ocean carnivore, were analysed for extremely toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) to understand their long-range distribution patterns. Several PCDF congeners, including the highly toxic 2,3,7,8-tetra- and 2,3,4,7,8-penta-CDFs were identified in the blubber of those specimens. The PCDF isomeric pattern in killer whale is more complex than the reported patterns in humans and birds, indicating the weaker metabolic potency of killer whales for these toxic compounds. High levels of PCBs (about 400 mg kg⁻¹) have also been detected in those specimens. The 2,3,7,8-substituted PCDF congeners identified in commercial PCBs were also found in killer whale, indicating PCBs as the possible source. Isomer-specific and trace level determinations of PCDD in killer whale, revealed no detectable quantities. The detection of comparatively high levels ( > 300 ng kg⁻¹) of PCDFs and undetection of PCDDs in open ocean killer whales suggest that PCDFs are more ubiquitous than PCDDs.     

Aeromagnetic surveys of Kuttyaro and Aso caldera regions,Japan

Detailed total-intensity aeromagnetic surveys of the Kuttyaro and Aso caldera regions, eastern Hokkaido and central Kyushu, were made during early 1964 under the auspices of the U.S.-Japan Co-operative Science Program in conjunction with a project for geophysical studies of calderas in Japan. Each caldera has a maximum diameter of about 22 km; the flights cover a 60 × 60 km rectangular area in each region. The Kuttyaro survey also encompasses the older caldera Akan, south-west of Kuttyaro, and the younger caldera Mashu to the east. All three lie within the Chīshīma (Kurile) volcanic zone. The isomagnetic contour map shows this zone as a belt of short wave-length anomaies which trends east-northeast across the region. Broad wavelength anomalies with trends intersecting the Chīshīma belt at an acute angle probably reflect structural relief on the Neogene volcanic basement concealed beneath Kuttyaro pyroclastic flows. The centre of Kuttyaro caldera coincides with the sharp southern termination of a strong basement high, whereas caldera faults and post-caldera domes have little magnetic expression. Mashu caldera is marked by a minimum in the position of the caldera lake; a symmetrical positive anomaly centering southeast of the caldera suggests either a buried older volcanic edifice or an intrusion. Akan caldera is represented by a magnetic depression encompassing a positive anomaly produced by its central post-caldera cone. The depression extends north of the geologically-deduced boundary of the caldera and may include an earlier collapse structure. Several volcanoes and lava sequences in the region produce negative anomalies due to inverse polarization. The most significant feature of the Aso isomagnetic map is a large, elongate positive anomaly that occupies the southern half of the caldera and extends about one caldera diameter to the south-west along the trend of the Median Tectonic Line of south-west Japan. Whether the anomaly represents the pre-Tertiary basement complex or a younger intrusion perhaps associated with Aso eruptive activity is uncertain. However, the causative body is abruptly truncated within the caldera by a major east-south-east structure passing through the eastern rim and coincident with the approximate locus of resurgent central vent eruptions. The structure may be a fault system that provided egress for the Aso pyroclastic flows. Superimposed on the basement anomaly are the effects of the topography of the caldera, the superficial caldera structure, and the post-caldera cones. An area of intense solfataric activity in the Kuju group of young volcanoes north of Aso has a pronounced negative anomaly. These two surveys illustrate the utility of the magnetic method for investigations of basement structure in caldera regions. They have served as a guide in interpreting reconnaissance aeromagnetic profiles flown concurrently for this project across some 14 other calderas or caldera-like structures in the Japanese islands.     

网点再现与油墨流动性及纸张表面的关系

分数维Ｄ值能够表示印刷网点与底片上网点的相似性关系，本文用分数维法定量评价了印刷网点的再现性，主要分析了网点再现与网屏线数、网点面积率、纸张表面粗度及油墨物性的关系。