High-pressure and high-temperature stability of chlorite and 23-Å phase in the natural chlorite and synthetic MASH system

A series of experiments was conducted on the decomposition of natural and chemically mixed chlorites to examine the stable hydrous phases in the MgO–FeO–Al₂O₃–SiO₂–H₂O (MFASH) system under 5–12 GPa and 700–1100 °C. The upper pressure and temperature limits of the stability region of chlorite are consistent with those observed in previous studies. The hydrous aluminum bearing pyroxene (phase HAPY) and Mg-sursassite (Sur) were observed just above the temperature stability region of chlorite (Chl); clinohumite (cHm) was observed coexisting with phase HAPY at 6 GPa and 800 °C and coexisting with the 23-Å phase at 7 GPa and 800 °C, which may suggest the transportation of water through Chl → (HAPY → cHm) → 23-Å phase along a relatively warm slab. The 23-Å phase has a wider stability region in the pure MASH system (up to 12 GPa and 1100 °C) than it does in the MFASH system (7–10 GPa, up to 1000 °C). The stability of the 23-Å phase beyond the chlorite breakdown pressure indicates that it may play an important role in transporting water into the deep Earth and even into the mantle transition zone.     

Study on the Historical Distribution of Metals in Aquatic Sediments

In this study, the historical distribution of metals, phosphorous, and sulfur at four different depths in the sediments of different lakes formed in the course of an urban river (in Londrina, Parana State, Brazil) were determined. The transport of metals along the course of the river was observed mainly for Mn, Cr, and Zn. High concentrations of Pb in the Capivara Bay and Cr in the river were attributed to contamination from a battery plant and a tannery, respectively. The concentrations of heavy metals in the deepest layers of the sediments remain high several years after deposition.     

Estrogen equivalent concentration of individual isomer-specific 4-nonylphenol in Ariake sea water, Japan

Concentrations of 4-nonylphenol (NP) were determined by isomer-specific quantification of individual NP isomers based on relative response factor (RRF) quantification with GC–MS in combination with steam distillation extraction. Concentrations of NP in the Ariake Sea decreased with distance from the river mouth (St.A; 49 ng NP/l) to offshore areas (St.C; 11 ng NP/l). Even the least concentration in water from St.C in Ariake Sea was sufficient to have adverse effects on barnacles. The isomers, NP1–NP14 were separated by GC–PFC and identified structurally with NMR. The isomers varied in estrogenic activity with NP7 exhibiting the greatest estrogenic activity with a potency that was approximately 1.9 × 10⁻³ that of 17β-estradiol (E2) in recombinant yeast screen system. The coefficient of variation (CV) of NP isomer’s concentrations among three samples at St.A, B and C were 4–75%. This suggests that NP isomers might be independently degraded in aquatic environmental samples. The predicted estrogenic activity of measured concentrations of NP in Ariake Sea was 2.7–3.0-fold greater than the measured estrogen agonist activity.     

Seafloor environmental changes resulting from nineteenth century reclamation in Mishou Bay, Bungo Channel, Southwest Japan

This study reconstructed environmental changes to the seafloor associated with reclamation in Mishou Bay, Bungo Channel, Japan, based on measurements of sediment grain size, organic matter and sulfur contents of surface sediments and data from sediment cores. Grain size within sediment cores from the middle of Mishou Bay decreased from the beginning of the 1800s to the 1900s. In contrast, a grain size profile from the river mouth shows a gradual increase in grain size up through the sediment core. These changes in grain size indicate a decrease in tidal current velocity within the middle of the bay and that the delta system is gradually prograding from the river mouth. Records of organic matter composition and sulfur contents indicate that the effect of the river on seafloor sedimentation became stronger during the nineteenth century. These changes are related to reclamation during the late 1700s and 1800s. The decrease in sea area resulting from reclamation probably led to a decrease in tidal prism and current velocity. It is likely that the increasing effect of river water on sedimentation is associated with reclamation-related progradation of the river delta system.     

The phase boundary between wadsleyite and ringwoodite in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between wadsleyite and ringwoodite in Mg₂SiO₄ has been determined in situ using a multi-anvil apparatus and synchrotron X-rays radiation at SPring-8. In spite of the similar X-ray diffraction profiles of these high-pressure phases with closely related structures, we were able to identify the occurrence of the mutual phase transformations based on the change in the difference profile by utilizing a newly introduced press-oscillation system. The boundary was located at ~18.9 GPa and 1,400°C when we used Shim’s gold pressure scale (Shim et al. in Earth Planet Sci Lett 203:729–739, 2002), which was slightly (~0.8 GPa) lower than the pressure as determined from the quench experiments of Katsura and Ito (J Geophys Res 94:15663–15670, 1989). Although it was difficult to constrain the Clapeyron slope based solely on the present data due to the kinetic problem, the phase boundary [P (GPa)=13.1+4.11×10⁻³×T (K)] calculated by a combination of a P–T position well constrained by the present experiment and the calorimetric data of Akaogi et al. (J Geophys Res 94:15671–15685, 1989) reasonably explains all the present data within the experimental error. When we used Anderson’s gold pressure scale (Anderson et al. in J Appl Phys 65:1535–1543, 1989), our phase boundary was located in ~18.1 GPa and 1,400°C, and the extrapolation boundary was consistent with that of Kuroda et al. (Phys Chem Miner 27:523–532, 2000), which was determined at high temperature (1,800–2,000°C) using a calibration based on the same pressure scale. Our new phase boundary is marginally consistent with that of Suzuki et al. (Geophys Res Lett 27:803–806, 2000) based on in situ X-ray experiments at lower temperatures (<1,000°C) using Brown’s and Decker’s NaCl pressure scales.     

Evaluation of Genetic Diversity in Zostera japonica (Aschers. et Graebn.) for Seagrass Conservation in Brackish Lower Reaches of the Hii River System, Japan

This study examined the genetic diversity and composition of 15 populations of Zostera japonica in the Hii River system, Japan. Genetic and genotypic diversity were consistently higher in populations in the Ohashi River than those in Lake Nakaumi, and the local tidal movements may explain the observed patterns of genetic diversity. Pairwise fixation index values among the populations in Lake Nakaumi were higher than among those in the Ohashi River, even though the ranges of the distances among the populations in the two locations were almost the same. The gene flow from the Ohashi River populations was important for some populations in Lake Nakaumi. The low genotypic diversity and gene flow in Lake Nakaumi seemed similar to those of marginal populations. If this low genotypic diversity and genetic differentiation were partly caused by human activities, the promotion of gene flow should be taken into account in conserving the populations in Lake Nakaumi.     

Metal contents in Porites corals: Anthropogenic input of river run-off into a coral reef from an urbanized area, Okinawa

In order to monitor pollutants from urban areas to coral reefs, metal contents in Porites coral samples collected from the Hija River mouth and at nearby sites from the estuary were analyzed. The corals were cleaned by oxidative and reductive treatments to effectively eliminate detritus and organic materials. Metal-to-calcium (Me/Ca) ratios in the samples were determined by ICP-MS. Filtered samples of river water were also measured similarly for metal concentrations. The extent of anthropogenic contribution by riverine input was assessed by comparing the Me/Ca values in corals to those of Rukan-sho, an unpolluted coral reef. High riverine inputs of Mn, Cd, Zn and Ag were observed from Me/Ca values in the coral samples. Manganese in the coral samples showed strong dependence on salinity, varying inversely to the distance from terrestrial sources. Considering a lead background of 25.0 nmol/mol measured in the Rukan-sho corals, Pb/Ca in corals of the Hija River estuary that are two and three times higher may indicate lead enrichment in the river mouth. Because Pb is only moderately high in the Hija River water compared to its concentration in surface seawater, lead may have accumulated in the estuarine water and sediments, resulting in an elevated concentration of lead available for coral uptake.     

Vertical heat transfer based on direct microstructure measurements in the ice-free Pacific-side Arctic Ocean: the role and impact of the Pacific water intrusion

This study quantifies diapycnal mixing and vertical heat transfer in the Pacific side of the Arctic Ocean, where sea-ice cover has disappeared between July and September in the last few decades. We conducted microstructure measurements in the open water region around the Canada Basin from late summer to fall in 2009 and 2010 using R/V Mirai. In the study domain, the dissipation rate of turbulent kinetic energy, ε, is typically as low level as O(10^?10) W kg^?1, resulting in vertical heat diffusivity of O(10^?7) m² s^?1, which is close to the molecular diffusivity of heat, suggesting comparatively little predominance of mechanical turbulent mixing. An exception is the case at the Barrow Canyon, where the strong baroclinic throughflow generates substantial vertical mixing, producing ε > O(10^?7) W kg^?1, because of the shear flow instability. Meanwhile, in the confluence region, where the warm/salty Pacific water and the cold/fresh Arctic basin water encounter, the micro-temperature profiles revealed a localized enhancement in vertical diffusivity of heat, reaching O(10^?5) m² s^?1 or greater. In this region, an intrusion of warm Pacific water creates a horizontally interleaved structure, where the double-diffusive mixing facilitates vertical heat transfer between the intruding Pacific water and the surrounding basin waters.     

Effects of pH and temperature on dimerization rate of glycine: Evaluation of favorable environmental conditions for chemical evolution of life

To evaluate favorable environmental conditions for the chemical evolution of life, we studied the effects of pH and temperature on the dimerization rate of glycine (Gly: NH₂-CH₂-COOH), one of the simplest amino acids. Gly dimerizes to form glycylglycine (GlyGly), and GlyGly further reacts to form diketopiperazine (DKP). Gly solutions with pH ranging from 3.1 to 10.9 were heated for 1-14 days at 140 °C, and changes in concentrations of Gly, GlyGly, and DKP were evaluated. At pH 9.8, the experiments were conducted at 120, 140, 160, and 180 °C. The dimerization rate of Gly was nearly constant at pH 3-7 and increased with increasing pH from 7 to 9.8 and then decreased with further increases in pH. To elucidate the reason for this pH dependency, we evaluated the role of the three dissociation states of Gly (cationic state: Gly⁺, zwitterionic state: Gly^±, and anionic state: Gly⁻). For pH >6, the dominant forms are Gly^± and Gly⁻, and the molar fraction of Gly^± decreases and that of Gly⁻ increases with increasing pH. The dimerization rate was determined for each dissociation state. The reaction between Gly^± and Gly⁻ was found to be the fastest; the rate constant of the reaction between Gly^± and Gly⁻ was 10 times the size of that between Gly⁻ and Gly⁻ and 98 times that between Gly^± and Gly^±. The dimerization rate became greatest at pH 9.8 because the molar fractions of Gly^± and Gly⁻ are approximately equal at this pH. The dimerization rate increased with temperature, and an activation energy of 88 kJ mol⁻¹ was obtained. Based on these results and previous reports on the stability of amino acids under hydrothermal conditions, we determined that Gly dimerizes most efficiently under alkaline pH (∼9.8) at about 150 °C.