The structure of monomeric and dimeric uranyl adsorption complexes on gibbsite: A combined DFT and EXAFS study     

Tatsuya Hattori  Takumi Saito  Andreas C. Scheinost  Shinya Nagasaki 《Geochimica et cosmochimica acta》2009,73(20):5975-1439

We investigated the structure of uranyl sorption complexes on gibbsite (pH 5.6-9.7) by two independent methods, density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U-L_III edge. To model the gibbsite surface with DFT, we tested two Al (hydr)oxide clusters, a dimer and a hexamer. Based on polarization, structure, and relaxation energies during geometry optimization, the hexamer cluster was found to be the more appropriate model. An additional advantage of the hexamer model is that it represents both edges and basal faces of gibbsite. The DFT calculations of (monomeric) uranyl sorption complexes show an energetic preference for the corner-sharing versus the edge-sharing configuration on gibbsite edges. The energy difference is so small, however, that possibly both surface species may coexist. In contrast to the edge sites, sorption to basal sites was energetically not favorable. EXAFS spectroscopy revealed in all investigated samples the same interatomic distances of the uranyl coordination environment (R_U-Oax ≈ 1.80 Å, R_U-Oeq ≈ 2.40 Å), and towards the gibbsite surface (R_U-O ≈ 2.87 Å, R_U-Al ≈ 3.38 Å). In addition, two U-U distances were observed, 3.92 Å at pH 9.7 and 4.30 Å at pH 5.6, both with coordination numbers of ∼1. The short U-U distance is close to that of the aqueous uranyl hydroxo dimer, UO₂(OH)₂, reported as 3.875 Å in the literature, but significantly longer than that of aqueous trimers (3.81-3.82 Å), suggesting sorption of uranyl dimers at alkaline pH. The longer U-U distance (4.30 Å) at acidic pH, however, is not in line with known aqueous uranyl polymer complexes. Based on the EXAFS findings we further refined dimeric surface complexes with DFT. We propose two structural models: in the acidic region, the observed long U-U distance can be explained with a distortion of the uranyl dimer to form both a corner-sharing and an edge-sharing linkage to neighboring Al octahedra, leading to R_U-U = 4.150 Å. In the alkaline region, a corner-sharing uranyl dimer complex is the most favorable. The U-O path at ∼2.87 Å in the EXAFS spectra arises from the oxygen atom linking two Al cations in corner-sharing arrangement. The adsorption structures obtained by DFT calculations are in good agreement with the structural parameters from EXAFS analysis: U-Al (3.394 Å), U-U (3.949 Å), and U-O (2.823 Å) for the alkaline pH model, and U-Al (3.279 Å), U-U (4.150 Å), and U-O (2.743 Å) for the acidic pH model. This work shows that by combining EXAFS and DFT, consistent structural models for uranyl sorption complexes can be obtained, which are relevant to predict the migration behavior of uranium at nuclear facilities.  相似文献   

Sound velocity and density of liquid Ni68S32 under pressure using ultrasonic and X-ray absorption with tomography methods     

Hidenori Terasaki  Keisuke Nishida  Satoru Urakawa  Yusaku Takubo  Soma Kuwabara  Yuta Shimoyama  Kentaro Uesugi  Yoshio Kono  Akihisa Takeuchi  Yoshio Suzuki  Yuji Higo  Tadashi Kondo 《Comptes Rendus Geoscience》2019,351(2-3):163-170

A new experimental setup for simultaneous P-wave velocity (V_P) and density (ρ) measurements for liquid alloys is developed using ultrasonic and X-ray absorption methods combined with X-ray tomography at high pressures and high temperatures. The new setup allows us to directly determine adiabatic bulk moduli (K_S) and to discuss the correlation between the V_P and ρ of the liquid sample. We measured V_P and ρ of liquid Ni₆₈S₃₂ up to 5.6 GPa and 1045 K using this technique. The effect of pressure on the V_P and ρ values of liquid Ni₆₈S₃₂ is similar to that of liquid Fe₅₇S₄₃. (Both compositions correspond to near-eutectic ones.) The obtained K_S values are well fitted to the finite strain equation with a $K_{{\text{S}}_0}$ value (K_S at ambient pressure) of 31.1 GPa and a dK_S/dP value of 8.44. The measured V_P was found to increase linearly with increasing ρ, as approximated by the relationship: V_P [m/s] = 1.29 ρ [kg/m³] – 5726, suggesting that liquid Ni–S follows an empirical linear relationship, Birch's law. The dV_P/dρ slope is similar between Ni₆₈S₃₂ and Fe₅₇S₄₃ liquids, while the V_P–ρ plot of liquid Ni–S is markedly different from that of liquid Fe–S, which indicates that the effect of Ni on Birch's law is important for understanding the V_P–ρ relation of planetary and Moon's molten cores.  相似文献   

Diets of Steller sea lions off the coast of Hokkaido,Japan: An inter‐decadal and geographic comparison          下载免费PDF全文

Yoko Goto  Akihiko Wada  Noboru Hoshino  Takahiro Takashima  Masaki Mitsuhashi  Kaoru Hattori  Orio Yamamura 《Marine Ecology》2017,38(6)

Inter‐decadal and geographic variations in the diets of Steller sea lion, Eumetopias jubatus, were examined based on the contents of 408 stomachs collected from coastal areas around Hokkaido Island during the periods 1994–1998 and 2005–2012. The most important prey species in the 1990s were gadid fishes (walleye pollock [Gadus chalcogrammus], Pacific cod [Gadus microcephalus] and saffron cod [Eleginus gracilis]). The frequency of occurrence and gravimetric contribution of gadids decreased in the 2000s latter period at three study sites (Rausu, Shakotan and Rebun) and were replaced by Okhotsk Atka mackerel (Pleurogrammus azonus) and smooth lumpsucker (Aptocyclus ventricosus). However, analysis based on gravimetric composition indicated that the dietary diversity of prey showed only a slight inter‐decadal difference, reflecting the wide diversity of prey ingested during both study periods. These results indicate that Steller sea lions along the Hokkaido coast are opportunistic feeders that utilize a wide variety of prey, and appear to feed mainly upon prey that is easily obtained.  相似文献   

How hydrological factors initiate instability in a model sandy slope   总被引：1，自引：1，他引：0       下载免费PDF全文

Tomomi Terajima  Ei‐ichiro Miyahira  Hiroyuki Miyajima  Hirotaka Ochiai  Katsumi Hattori 《水文研究》2014,28(23):5711-5724

Knowledge of the mechanisms of rain‐induced shallow landslides can improve the prediction of their occurrence and mitigate subsequent sediment disasters. Here, we examine an artificial slope's subsurface hydrology and propose a new slope stability analysis that includes seepage force and the down‐slope transfer of excess shear forces. We measured pore water pressure and volumetric water content immediately prior to a shallow landslide on an artificial sandy slope of 32°: The direction of the subsurface flow shifted from downward to parallel to the slope in the deepest part of the landslide mass, and this shift coincided with the start of soil displacement. A slope stability analysis that was restricted to individual segments of the landslide mass could not explain the initiation of the landslide; however, inclusion of the transfer of excess shear forces from up‐slope to down‐slope segments improved drastically the predictability. The improved stability analysis revealed that an unstable zone expanded down‐slope with an increase in soil water content, showing that the down‐slope soil initially supported the unstable up‐slope soil; destabilization of this down‐slope soil was the eventual trigger of total slope collapse. Initially, the effect of apparent soil cohesion was the most important factor promoting slope stability, but seepage force became the most important factor promoting slope instability closer to the landslide occurrence. These findings indicate that seepage forces, controlled by changes in direction and magnitude of saturated and unsaturated subsurface flows, may be the main cause of shallow landslides in sandy slopes. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

Characteristics of precipitation in northern Mauritania and its links with sea surface temperature     

O.C.A. Ahmedou  H. Yasuda  K. Wang  K. Hattori 《Journal of Arid Environments》2008,72(12):2243-2250

This paper deals with the periodic fluctuation of precipitation at three meteorological stations (Atar, Chenguitti, and Akjoujt) in the Adrar and Inchiri provinces in northern Mauritania and its links with sea surface temperature (SST). Trends for these three meteorological stations were evaluated using the Mann–Kendall (MK) nonparametric test, regression analysis, and autocorrelation for persistence analysis. The MK test showed a significant decreasing trend for Akjoujt and an insignificant trend for the other rainfall time series. However, the decreasing linear regression trends were highly significant for the different time series. On the other hand, persistence analysis indicated the presence of a linear Markov type. The cycles found by power spectrum analysis ranged from 0.5 years to about 11 years. The possibility of a connection between precipitation in this region and sunspot numbers was suggested. SST of the Atlantic Ocean, Indian Ocean, and Mediterranean Sea have significant cross-correlations with precipitation in the study area. The El Niño-Southern Oscillation effect was found to be marginal.  相似文献   

Investigation of ULF Seismo-Magnetic Phenomena in Kanto, Japan During 2000–2010: Case Studies and Statistical Studies     

Katsumi Hattori  Peng Han  Chie Yoshino  Febty Febriani  Hiroki Yamaguchi  Chieh-Hung Chen 《Surveys in Geophysics》2013,34(3):293-316

In order to clarify the ultra low frequency (ULF) seismo-magnetic phenomena, a sensitive geomagnetic network has been installed in Kanto, Japan. In this study, we have analyzed geomagnetic data observed during the past decade in Izu and Boso Peninsulas. Energy of ULF geomagnetic signals at the frequency around 0.01 Hz has been investigated by wavelet transform analysis. To identify anomalous changes in ionospheric disturbances, the station Memabutsu has been chosen as a reference station. Case studies of magnitude 6 class earthquakes have demonstrated that there are unusual geomagnetic energy enhancements in the vertical component before the main shocks. Statistical studies by superposed epoch analysis have indicated that, before a sizeable earthquake, there are clearly higher probabilities of ULF anomalies than after the earthquake: statistical results of daily counts were found significant at about 3–4 weeks before, 1 week before, few days before, and 1 day after the event for Seikoshi station in Izu and around 2 weeks before, few days before, and 1 day after the event for Kiyosumi station in Boso, respectively.  相似文献   

Biogenic carbon flows through the planktonic food web of the Amundsen Gulf (Arctic Ocean): A synthesis of field measurements and inverse modeling analyses   总被引：1，自引：0，他引：1  

Alexandre Forest  Jean-Éric Tremblay  Yves Gratton  Johannie Martin  Jonathan Gagnon  Gérald Darnis  Makoto Sampei  Louis Fortier  Mathieu Ardyna  Michel Gosselin  Hiroshi Hattori  Dan Nguyen  Roxane Maranger  Dolors Vaqué  Cèlia Marrasé  Carlos Pedrós-Alió  Amélie Sallon  Christine Michel  Colleen Kellogg  Jody Deming  Elizabeth Shadwick  Helmuth Thomas  Heike Link  Philippe Archambault  Dieter Piepenburg 《Progress in Oceanography》2011,91(4):410-436

Major pathways of biogenic carbon (C) flow are resolved for the planktonic food web of the flaw lead polynya system of the Amundsen Gulf (southeast Beaufort Sea, Arctic Ocean) in spring-summer 2008. This period was relevant to study the effect of climate change on Arctic marine ecosystems as it was characterized by unusually low ice cover and warm sea surface temperature. Our synthesis relied on a mass balance estimate of gross primary production (GPP) of 52.5 ± 12.5 g C m⁻² calculated using the drawdown of nitrate and dissolved inorganic C, and a seasonal f-ratio of 0.64. Based on chlorophyll a biomass, we estimated that GPP was dominated by phytoplankton (93.6%) over ice algae (6.4%) and by large cells (>5 μm, 67.6%) over small cells (<5 μm, 32.4%). Ancillary in situ data on bacterial production, zooplankton biomass and respiration, herbivory, bacterivory, vertical particle fluxes, pools of particulate and dissolved organic carbon (POC, DOC), net community production (NCP), as well as selected variables from the literature were used to evaluate the fate of size-fractionated GPP in the ecosystem. The structure and functioning of the planktonic food web was elucidated through inverse analysis using the mean GPP and the 95% confidence limits of every other field measurement as lower and upper constraints. The model computed a net primary production of 49.2 g C m⁻², which was directly channeled toward dominant calanoid copepods (i.e. Calanus hyperboreus 20%, Calanus glacialis 10%, and Metridia longa 10%), other mesozooplankton (12%), microzooplankton (14%), detrital POC (18%), and DOC (16%). Bacteria required 29.9 g C m⁻², a demand met entirely by the DOC derived from local biological activities. The ultimate C outflow comprised respiration fluxes (82% of the initial GPP), a small sedimentation (3%), and a modest residual C flow (15%) resulting from NCP, dilution and accumulation. The sinking C flux at the model limit depth (395 m) supplied 60% of the estimated benthic C demand (2.8 g C m⁻²), suggesting that the benthos relied partly on other C sources within the bottom boundary layer to fuel its activity. In summary, our results illustrate that the ongoing decline in Arctic sea ice promotes the growth of pelagic communities in the Amundsen Gulf, which benefited from a ∼80% increase in GPP in spring-summer 2008 when compared to 2004 – a year of average ice conditions and relatively low GPP. However, 53% of the secondary production was generated within the microbial food web, the net ecological efficiency of zooplankton populations was not particularly high (13.4%), and the quantity of biogenic C available for trophic export remained low (6.6 g C m⁻²). Hence it is unlikely that the increase in lower food web productivity, such as the one observed in our study, could support new harvestable fishery resources in the offshore Beaufort Sea domain.  相似文献   

Building damage characteristics based on surveyed data and fragility curves of the 2011 Great East Japan tsunami   总被引：4，自引：2，他引：2  

Anawat Suppasri  Erick Mas  Ingrid Charvet  Rashmin Gunasekera  Kentaro Imai  Yo Fukutani  Yoshi Abe  Fumihiko Imamura 《Natural Hazards》2013,66(2):319-341

A large amount of buildings was damaged or destroyed by the 2011 Great East Japan tsunami. Numerous field surveys were conducted in order to collect the tsunami inundation extents and building damage data in the affected areas. Therefore, this event provides us with one of the most complete data set among tsunami events in history. In this study, fragility functions are derived using data provided by the Ministry of Land, Infrastructure and Transportation of Japan, with more than 250,000 structures surveyed. The set of data has details on damage level, structural material, number of stories per building and location (town). This information is crucial to the understanding of the causes of building damage, as differences in structural characteristics and building location can be taken into account in the damage probability analysis. Using least squares regression, different sets of fragility curves are derived to demonstrate the influence of structural material, number of stories and coastal topography on building damage levels. The results show a better resistant performance of reinforced concrete and steel buildings over wood or masonry buildings. Also, buildings taller than two stories were confirmed to be much stronger than the buildings of one or two stories. The damage characteristic due to the coastal topography based on limited number of data in town locations is also shortly discussed here. At the same tsunami inundation depth, buildings along the Sanriku ria coast were much greater damaged than buildings from the plain coast in Sendai. The difference in damage states can be explained by the faster flow velocities in the ria coast at the same inundation depth. These findings are key to support better future building damage assessments, land use management and disaster planning.  相似文献   

Geometry of the Nojima Fault at Nojima-Hirabayashi, Japan – II. Microstructures and their Implications for Permeability and Strength     

Diane E. Moore  David A. Lockner  Hisao Ito  Riuji Ikeda  Hidemi Tanaka  Kentaro Omura 《Pure and Applied Geophysics》2009,166(10-11):1669-1691

Samples of damage-zone granodiorite and fault core from two drillholes into the active, strike-slip Nojima fault zone display microstructures and alteration features that explain their measured present-day strengths and permeabilities and provide insight on the evolution of these properties in the fault zone. The least deformed damage-zone rocks contain two sets of nearly perpendicular (60–90° angles), roughly vertical fractures that are concentrated in quartz-rich areas, with one set typically dominating over the other. With increasing intensity of deformation, which corresponds generally to increasing proximity to the core, zones of heavily fragmented rock, termed microbreccia zones, develop between prominent fractures of both sets. Granodiorite adjoining intersecting microbreccia zones in the active fault strands has been repeatedly fractured and locally brecciated, accompanied by the generation of millimeter-scale voids that are partly filled with secondary minerals. Minor shear bands overprint some of the heavily deformed areas, and small-scale shear zones form from the pairing of closely spaced shear bands. Strength and permeability measurements were made on core collected from the fault within a year after a major (Kobe) earthquake. Measured strengths of the samples decrease regularly with increasing fracturing and fragmentation, such that the gouge of the fault core and completely brecciated samples from the damage zone are the weakest. Permeability increases with increasing disruption, generally reaching a peak in heavily fractured but still more or less cohesive rock at the scale of the laboratory samples. Complete loss of cohesion, as in the gouge or the interiors of large microbreccia zones, is accompanied by a reduction of permeability by 1-2 orders of magnitude below the peak values. The core samples show abundant evidence of hydrothermal alteration and mineral precipitation. Permeability is thus expected to decrease and strength to increase somewhat in active fault strands between earthquakes, as mineral deposits progressively seal fractures and fill pore spaces.  相似文献   

SHRIMP zircon and EPMA monazite dating of granitic rocks from the Maizuru terrane, southwest Japan: Correlation with East Asian Paleozoic terranes and geological implications   总被引：1，自引：0，他引：1  

Masahiro  Fujii  Yasutaka  Hayasaka  Kentaro  Terada 《Island Arc》2008,17(3):322-341

Abstract The Maizuru terrane, distributed in the Inner Zone of southwest Japan, is divided into three subzones (Northern, Central and Southern), each with distinct lithological associations. In clear contrast with the Southern zone consisting of the Yakuno ophiolite, the Northern zone is subdivided into the western and eastern bodies by a high-angle fault, recognized mainly by the presence of deformed granitic rocks and pelitic gneiss. This association suggests an affinity with a mature continental block; this is supported by the mode of occurrence, and petrological and isotopic data. Newly obtained sensitive high mass-resolution ion microprobe (SHRIMP) zircon U–Pb ages reveal the intrusion ages of 424 ± 16 and 405 ± 18 Ma (Siluro–Devonian) for the granites from the western body, and 249 ± 10 and 243 ± 19 Ma (Permo–Triassic) for the granodiorites from the eastern body. The granites in the western body also show inherited zircon ages of around 580 and 765 Ma. In addition, electron probe microanalysis (EPMA) monazite U–Th–total Pb dating gives around 475–460 Ma. The age of intrusion, inherited ages, mode of occurrence, and geological setting of the Siluro–Devonian granites of the Northern zone all show similarities with those of the Khanka Massif, southern Primoye, Russia, and the Hikami granitic rocks of the South Kitakami terrane, Northeast Japan. We propose that both the Siluro–Devonian and Permo–Triassic granitic rocks of the Northern zone are likely to have been juxtaposed through the Triassic–Late Jurassic dextral strike-slip movement, and to have originated from the Khanka Massif and the Hida terrane, respectively. This study strongly supports the importance of the strike-slip movement as a mechanism causing the structural rearrangement of the Paleozoic–Mesozoic terranes in the Japanese Islands, as well as in East Asia.  相似文献