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.     

Flow cytometric detection and enumeration of DNA and RNA viruses infecting marine eukaryotic microalgae

Sample preparation protocols for flow cytometry (FCM) analysis with five algal viruses were optimized: Heterocapsa circularisquama virus (HcV), Heterosigma akashiwo virus (HaV), Chaetoceros salsugineum nuclear inclusion virus (CsNIV), Rhizosolenia setigera RNA virus (RsRNAV) and H. circularisquama RNA virus (HcRNAV). The optimum staining protocols differed significantly among the viruses tested. FCM counts for the large DNA algal viruses HaV and HcV (∼0.2 μm in diameter) were similar to numbers determined by epifluorescence microscopy (EFM). In contrast, FCM counts of viruses smaller than 40 nm that harbor DNA (CsNIV) or RNA genomes (RsRNAV, HcRNAV) were comparable to or lower than most probable number (MPN) values, which indicate only infectious virus number, suggesting that the FCM counts were underestimates. This is presumably because their single particle fluorescence signals were below the detection limit for the flow cytometer. These results indicate that a large portion of the smaller viruses in the aquatic plankton virus community may be overlooked by FCM.     

Effects of irradiance on excystment of tintinnids from marine sediments

The effects of irradiance on the excystment of tintinids from marine sediments were examined by incubating sediment samples in filtered seawater under various light levels. The total incidence of tintinnid excystment over five days was significantly less at low irradiance at and less than 2.5 E m^–2sec^–1 comparing to that at higher irradiance, at and more than 6.9 E m^–2sec^–1 (p<0.01), indicating that excystment of tintinnids is inhibited under low irradiance conditions. These results imply that water depth, disturbance of surface sediments and vertical mixing of water influence the excystment of tintinnids in coastal areas because these factors determine the light levels to which the tintinnid cysts are exposed.     

Prograde P–T path of kyanite eclogites from Junan in the Sulu ultrahigh-pressure province, eastern China

Kyanite-bearing ultrahigh-pressure (UHP) eclogites occur as blocks in orthogneisses at Yangzhuang, in the Junan area of the southwestern Sulu province, eastern China. Eclogites have variable bulk rock compositions, with Al₂O₃ = 16–27 wt%, FeO* + MgO = 6–22 wt% and CaO = 9–13 wt%. Major minerals are garnet, omphacite, phengitic white mica, zoisite, kyanite, rutile and an SiO₂ phase. Fe-rich staurolite (Mg ? Mg# = 0.24 ± 0.01) and paragonite–margarite aggregates are rarely included in the cores of prograde zoned garnet. Metamorphic conditions ranged from 520 to 650°C and <1.4 GPa at an early prograde stage, and mostly reached 660–830°C and 2.7–3.5 GPa at the peak UHP stage. The estimated dP/dT of the prograde P–T path is less than 0.25 GPa/100°C at earlier stages and increases to 0.7–1.4 GPa/100°C just before the UHP stage. The kink of the prograde P–T path closely resembles the steady-state P–T paths proposed, assuming a two-parameter brittle-plastic shear stress model. The estimated P–T path adequately explains the absence of prograde lawsonite and sodic amphibole and the common occurrence of coexisting zoisite, kyanite and sodic-calcic amphibole in the UHP eclogites throughout the Sulu province. Simple clockwise prograde P–T paths for Sulu UHP eclogites proposed in earlier studies should be carefully re-examined.     

Crustal shortening of Southwest Japan in the Late Miocene

Abstract Tectonic deformation of an island arc is interpreted on the basis of geophysical data. Extensive reflection seismic, gravity, geomagnetic data around the back-arc region of Southwest Japan delineate east-west to northeast-southwest folding, and imply conspicuous compression on the southern margin of the Sea of Japan. Because geological data of exploration boreholes indicate that the coinpressive regime was dominant in the late Miocene, the tectonic event seems to be linked with coeval resumption of subduction of the Philippine Sea Plate. Strong coupling of the young buoyant oceanic plate brought about north-south shortening of the overriding continental lithosphere, and left wrench deformation at the southwestern corner of the Sea of Japan. Amount of shortening for the back-arc shelf and mountainous ranges of Southwest Japan is estimated to be ca 10 km, adopting a uniform ratio of shortening (0.944) since the Miocene determined on the shelf from depth-converted seismic profiles. Along the western side of a bend of boundary between the Eurasian Plate and Philippine Sea Plate, the middle Miocene and younger sediments upon the back-arc shelf are much less deformed than the northern equivalents, and the fore-arc Miocene strata are deformed by left wrenching, facts which are indicative of northerly initial convergence of the Philippine Sea Plate at the end of Miocene and crustal decoupling on the west of Kyushu Island.