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

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.     

Fluctuations of electron precipitation to the dayside auroral zone modulated by compression and expansion of the magnetosphere

Concurrent variations of CNA fluctuations and geomagnetic fluctuations are classified into Type 1 (substorm-type), Type 2 (Pc5-type), and Type 3 which is the object of the present study. Type 3 apparently has peculiar characteristics in that CNA fluctuations at a certain auroral-zone station show a pronounced positive correlation with magnetic fluctuations at distant low-latitude stations. The magnetic fluctuations of this type are identified to generalized Si which tends to take place much more frequently than the so-called Si. The CNA fluctuations of this type are found to take place on the dayside auroral zone only when preceded by a magnetic substorm on the night side. Considering the change of the growth rate of electron cyclotron instability and enhancement of pitch angle diffusion due to the change of magnetic field intensity, the following model is proposed to explain the occurrence mechanism of Type 3 concurrent variations. The CNA fluctuations take place only when two conditions are satisfied; generation of the accelerated electrons in association with substorm onset and modulation of the precipitation of the electrons by compression and expansion of the magnetosphere, in other words, by generalized Si.     

Tsunami damage to coastal defences and buildings in the March 11th 2011 M w 9.0 Great East Japan earthquake and tsunami

On March 11th 2011 a M _w 9.0 mega-thrust interface subduction earthquake, the Great East Japan Earthquake, occurred 130 km off the northeast coast of Japan in the Pacific Ocean at the Japan Trench, triggering tsunami which caused damage along 600 km of coastline. Observations of damage to buildings (including vertical evacuation facilities) and coastal defences in Tōhoku are presented following investigation by the Earthquake Engineering Field Investigation Team (EEFIT) at 10 locations in Iwate and Miyagi Prefectures. Observations are presented in the context of the coastal setting and tsunami characteristics experienced at each location. Damage surveys were carried out in Kamaishi City and Kesennuma City using a damage scale for reinforced concrete (RC), timber and steel frame buildings adapted from an earlier EEFIT tsunami damage scale. Observations show that many sea walls and breakwaters were overtopped, overturned, or broken up, but provided some degree of protection. We show the extreme variability of damage in a local area due to inundation depth, flow direction, velocity variations and sheltering. Survival of many RC shear wall structures shows their high potential to withstand local earthquake and significant tsunami inundation but further research is required into mitigation of scour, liquefaction, debris impact, and the prevention of overturning failure. Damage to steel and timber buildings are also discussed. These observations are intended to contribute to mitigation of future earthquake and tsunami damage by highlighting the key features which influence damage level and local variability of damage sustained by urban coastal infrastructure when subjected to extreme tsunami inundation depths.     

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2

We report the astronomical identification of the cyanomethyl radical, CH2CN, the heaviest nonlinear molecular radical to be identified in interstellar clouds. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1, where the abundance appears to be about 5 x 10(-9) relative to that of H2. This is significantly greater than the observed abundance of CH3CN (methyl cyanide) in TMC-1. In Sgr B2 the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident. Preliminary searches in other sources indicate that the distribution of CH2CN is similar to that for such carbon chain species as HC3N or C4H.     

Diel Patterns in Chlorophyll <Emphasis Type="Italic">a</Emphasis> Specific Absorption Coefficient and Absorption Efficiency Factor of Picoplankton

Diel patterns in the chlorophyll a specific absorption coefficient of surface picoplankton, a*_pico (γ) (m²·[mg chlorophyll a]⁻¹), were studied at 7 stations under daily cycle of in situ light condition in the western subarctic Pacific and Japan Sea. All the data were normalized by dividing the anomaly with daily averaged a*_pico (γ). Opposite diel patterns were observed for the normalized a*_pico (443) and a*_pico (675) with maximum toward dawn or dusk and minimum toward midday at 4 stations under low-irradiance (LI) conditions and vice versa at 3 stations under high-irradiance (HI) conditions. The absorption efficiency factors at red absorption peak, Q _a (675), were determined by reconstruction with intracellular chlorophyll a concentration and cell diameter. The normalized Q _a (675) also showed diel pattern with maximum toward midday and minimum toward dawn or dusk under LI. The diel pattern in a*_pico (675) and Q _a (675) were primarily caused by changes in intracellular chlorophyll a concentration due to photoadaptation under LI. The diel pattern in a*_pico (443) was influenced by pigmentation, as recognized by blue to red ratio [a*_pico (443)/a*_pico (675)] under HI. This study proposed that the opposite diel pattern in a*_pico (γ) might occur for a wide range of algal species. The results presented here have important consequences for the interpretation of diel variations in optical properties observed in the open ocean.     

Effect of ocean acidification on coastal phytoplankton composition and accompanying organic nitrogen production

The effect of ocean acidification, caused by the increase in pCO₂ in seawater, on phytoplankton population and on related organic nitrogen production was experimentally examined by use of a natural coastal microbial population. pCO₂ and pH were controlled by aeration with air in which pCO₂ was at the current level (control), for which ambient air was used, and with air in which pCO₂ was ??800?? and ??1200?? ppm, in 500-L culture vessels. The experiment was continued for 15?days after addition of the inorganic nutrients such as nitrate, phosphate, and silicate. During most of the experimental period, a minor increase in phytoplankton biomass was noted, probably because of low irradiance, an increase in phytoplankton biomass was observed at the end of the experiment. Flow cytometric and microscopic observations revealed that this increase was because of Chrysochromulina sp. (Haptophyceae). The growth of Chrysochromulina sp. was most obvious in the control vessel, and tended to be obscured by increasing pCO₂ (decrease in pH), indicating the possibility that ocean acidification inhibits the growth of specific phytoplankton groups, for example Chrysochromulina sp. Production of particulate organic nitrogen (PON), determined by the ¹⁵N tracer method, also diminished under acidified conditions compared with that at the current level.     

济州岛西南泥质区粒度组分变化的古环境应用

利用激光粒度仪对位于东海陆架济州岛西南泥质区的B2孔进行了沉积物粒度分析,根据标准偏差变化检出了B2孔含有4个粒度组分：〉65．6、65．6～10．5、10．5～1．3和〈1．3μm,其中〉65．6μm粗组分含量很低,主要是以底栖有孔虫为主的生源沉积．各组分平均粒径和粒度含量随孔深的变化显示了65．6～10．5μm组分在B2孔含量较高（21％～30％）,变化最明显,是该孔对环境变化最敏感的粒度组分．研究表明该敏感组分的粒度含量和平均粒径变化主要受东亚冬季风的强弱变化制约,其变化恢复的近2ka来东亚冬季风变化和中国东部气候变化序列具有很好的一致性,证明65．6～10．5μm粒度组分可以作为东亚冬季风的替代指标．     

Quasi-static analysis of strike fault growth in layered media

We study the effects of structural inhomogeneity on the quasi-static growth of strike-slip faults. A layered medium is considered, made up of an upper layer bounded by a free surface and welded to a lower half-space with different elastic property. Mode III crack is employed as a mathematical model of strike-slip fault, which is nucleated in the lower half-space and then propagates towards the interface. We adopt FEM-β, newly proposed analysis method for failure, to simulate the quasi-statistic crack growth governed by the stress distribution in layered media. Our results show that along planar traces across interfaces a compliant upper layer has significant effects on promoting/suppressing crack growth before/after its extension into the layer and vice versa for a rigid one. This proposes a possibility that surface breaks due to strike-slip faulting could be arrested by deposit layers at the topmost part of the Earth's crust.