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   

Bayesian and Neural Network Approaches to Estimate Deep Temperature Distribution for Assessing a Supercritical Geothermal System: Evaluation Using a Numerical Model     

Ishitsuka  Kazuya  Kobayashi  Yosuke  Watanabe  Norihiro  Yamaya  Yusuke  Bjarkason  Elvar  Suzuki  Anna  Mogi  Toru  Asanuma  Hiroshi  Kajiwara  Tatsuya  Sugimoto  Takeshi  Saito  Ryoichi 《Natural Resources Research》2021,30(5):3289-3314

The temperature distribution at depth is a key variable when assessing the potential of a supercritical geothermal resource as well as a conventional geothermal resource. Data-driven estimation by a machine-learning approach is a promising way to estimate temperature distributions at depth in geothermal fields. In this study, we developed two methodologies—one based on Bayesian estimation and the other on neural networks—to estimate temperature distributions in geothermal fields. These methodologies can be used to supplement existing temperature logs, by estimating temperature distributions in unexplored regions of the subsurface, based on electrical resistivity data, observed geological/mineralogical boundaries, and microseismic observations. We evaluated the accuracy and characteristics of these methodologies using a numerical model of the Kakkonda geothermal field, Japan, where a temperature above 500 °C was observed below a depth of about 3.7 km. When using geological and geophysical knowledge as prior information for the machine learning methods, the results demonstrate that the approaches can provide subsurface temperature estimates that are consistent with the temperature distribution given by the numerical model. Using a numerical model as a benchmark helps to understand the characteristics of the machine learning approaches and may help to identify ways of improving these methods.

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Estimation of standing stock of chlorophylla and primary production from remote-sensed ocean color in the Oyashio region, the Western subarctic Pacific, during the spring bloom in 1997     

Hiromi Kasai  Hiroaki Saito  Atsushi Tsuda 《Journal of Oceanography》1998,54(5):527-537

In order to examine the applicability of remotely-sensed ocean color for the estimation of phytoplankton biomass and primary production in the Oyashio region, the western subarctic Pacific, vertical distributions of chlorophylla concentration and primary production were observed in April and May 1997. Spring bloom was observed in both April and May, and the surface concentration of chlorophylla exceeded 40 mg m⁻³. The relationship between the standing stocks of chlorophylla within the layer from the sea surface to one optical depth (0–1/k layer) and the surface chlorophylla concentration is expressed as a Michaelis-Menten equation. The mean ratio of the standing stock of chlorophylla in the euphotic layer to that in the 0–1/k layer was 4.41, this ratio did not significantly differ from 4.61 which was obtained at homogeneous distribution of chlorophylla within the euphotic layer. These facts suggest that the distribution of chlorophylla could be assumed to be homogeneous in the euphotic layer during the spring bloom. Results of primary production measurements by simulatedin situ method were compared with those by an algorithm with two variables; chlorphylla and non-spectral PAR. Daily primary production in the euphotic layer estimated by the algorithm varied in a range of 38–274% of that estimated by incubation, although the primary productions by the algorithm agreed with those by the incubation at a half of stations. Primary production within the euphotic layer calculated using simply the surface data was the same as that estimated using vertical distribution of chlorophylla. These results show that the primary production in the euphotic layer may be estimated from the remote sensed measurements during the spring bloom in the Oyashio region.  相似文献   

HST/FOS Eclipse mapping of IP Pegasi in outburst     

R. K. Saito  R. Baptista  K. Horne 《Astronomische Nachrichten》2004,325(3):213-213

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Mechanical properties and stress–dilatancy relationships of unsaturated soil under various cyclic loading conditions     

Tun Tun  Win  Sato  Tomotaka  Saito  Hirotaka  Kohgo  Yuji 《Acta Geotechnica》2020,15(7):1799-1813

Acta Geotechnica - Most studies investigating the effect of cyclic loading on soil properties have been conducted for saturated soils. Embankments such as fill dams, roads and railways are usually...  相似文献   

济州岛西南泥质区粒度组分变化的古环境应用   总被引：14，自引：1，他引：13  

向荣  杨作升  郭志刚  范德江  肖尚斌  陈木宏 《地球科学》2005,30(5):582-588

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．  相似文献   

Growth stimulation and inhibition of natural phytoplankton communities by model organic ligands in the western subarctic Pacific     

Yoshiko Kondo  Shigenobu Takeda  Jun Nishioka  Mitsuhide Sato  Hiroaki Saito  Koji Suzuki  Ken Furuya 《Journal of Oceanography》2013,69(1):97-115

The influence of organic ligands on natural phytoplankton growth was investigated in high-nitrate low-chlorophyll (HNLC) waters and during a phytoplankton bloom induced by a mesoscale iron enrichment experiment (SEEDS II) in the western subarctic Pacific. The growth responses of the phytoplankton in the treatments with iron complexed with model ligand were compared with those with inorganic iron or a control. Desferrioxamine B and protoporphyrin IX were used as models for hydroxamate-type siderophore and tetrapyrrole-type cell breakdown ligand, respectively. In the HNLC water, iron associated with protoporphyrin IX especially stimulated smaller phytoplankton (<10 μm) growth, 1.5-fold more than did inorganic iron. Surprisingly, only the addition of protoporphyrin IX stimulated small phytoplankton growth, suggesting that these cell breakdown ligands might be more bioavailable for them. The protoporphyrin IX’s stimulatory effect on small phytoplankton was not observed during bloom decline phase. The growth of phytoplankton was inhibited in the treatment with desferrioxamine B-complexed iron, suggesting its low bioavailability for the natural phytoplankton community. Its inhibitory effects were particularly pronounced in pico-eukaryotic phytoplankton. During the iron-induced bloom, the phytoplankton’s iron-stress response gradually increased with the desferrioxamine B concentration, suggesting that the competition for iron complexation between natural ligands and desferrioxamine B affected phytoplankton growth. However, the pico-eukaryotes did seem better able to utilize the desferrioxamine B-complexed iron during the bloom-developing phase. These results indicate that the iron bioavailability for phytoplankton differs between bloom-developing and bloom-decline phases.  相似文献   

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

Takeo Hama  Shoko Kawashima  Koichi Shimotori  Yuhi Satoh  Yuko Omori  Shigeki Wada  Taiki Adachi  Shun Hasegawa  Takashi Midorikawa  Masao Ishii  Shu Saito  Daisuke Sasano  Hiroko Endo  Tsuyoshi Nakayama  Isao Inouye 《Journal of Oceanography》2012,68(1):183-194

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.  相似文献   

Quasi-static analysis of strike fault growth in layered media     

Nobuki Kame  Shuji Saito  Kenji Oguni 《Geophysical Journal International》2008,173(1):309-314

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.  相似文献   

Strip Transect Sampling to Estimate Object Abundance in Homogeneous and Non-homogeneous Poisson Fields: a Simulation Study of the Effects of Changing Transect Width and Number     

Timothy C. Coburn  Sean A. McKenna  Hirotaka Saito 《Mathematical Geosciences》2009,41(1):51-70

This paper investigates the use of strip transect sampling to estimate object abundance when the underlying spatial distribution is assumed to be Poisson. A design-based rather than model-based approach to estimation is investigated through computer simulation, with both homogeneous and non-homogeneous fields representing individual realizations of spatial point processes being considered. Of particular interest are the effects of changing the number of transects and transect width (or alternatively, coverage percent or fraction) on the quality of the estimate. A specific application to the characterization of unexploded ordnance (UXO) in the subsurface at former military firing ranges is discussed. The results may be extended to the investigation of outcrop characteristics as well as subsurface geological features.  相似文献