Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10−6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni2+, Cs+ and Ln3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta 69, 4937–4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be double bond; length as m-dashAlOEu2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the double bond; length as m-dashAlOEu2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta 66, 2325–2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p]

Selective modulation of visual sensitivity during fixation

During periods of steady fixation, we make small amplitude ocular movements, termed microsaccades, at a rate of 1-2 every second. Early studies provided evidence that visual sensitivity is reduced during microsaccades - akin to the well-established suppression associated with larger saccades. However, the results of more recent work suggest that microsaccades may alter retinal input in a manner that enhances visual sensitivity to some stimuli. Here, we parametrically varied the spatial frequency of a stimulus during a detection task and tracked contrast sensitivity as a function of time relative to microsaccades. Our data reveal two distinct modulations of sensitivity: suppression during the eye movement itself, and facilitation after the eye has stopped moving. The magnitude of suppression and facilitation of visual sensitivity is related to the spatial content of the stimulus: suppression is greatest for low spatial frequencies while sensitivity is enhanced most for stimuli of 1-2 c/deg, spatial frequencies at which we are already most sensitive in the absence of eye movements. We present a model where the tuning of suppression and facilitation is explained by delayed lateral inhibition between spatial frequency channels. Our data show that eye movements actively modulate visual sensitivity even during fixation: the detectability of images at different spatial scales can be increased or decreased depending on when the image occurs relative to a microsaccade

Optical properties of perovskite alkaline earth titanates : a formulation

In this communication we suggest a formulation of the optical conductivity as a convolution of an energy resolved joint density of states and an energy-frequency labelled transition rate. Our final aim is to develop a scheme based on the augmented space recursion for random systems. In order to gain confidence in our formulation, we apply the formulation to three alkaline earth titanates CaTiO_3, SrTiO_3 and BaTiO_3 and compare our results with available data on optical properties of these systems.Comment: 19 pages, 9 figures, Submitted to Journal of Physics: Condensed Matte

Effect of nearest- and next-nearest neighbor interactions on the spin-wave velocity of one-dimensional quarter-filled spin-density-wave conductors

We study spin fluctuations in quarter-filled one-dimensional spin-density-wave systems in presence of short-range Coulomb interactions. By applying a path integral method, the spin-wave velocity is calculated as a function of on-site (U), nearest (V) and next-nearest (V_2) neighbor-site interactions. With increasing V or V_2, the pure spin-density-wave state evolves into a state with coexisting spin- and charge-density waves. The spin-wave velocity is reduced when several density waves coexist in the ground state, and may even vanish at large V. The effect of dimerization along the chain is also considered.Comment: REVTeX, 11 pages, 9 figure

Charge Ordering in Organic ET Compounds

The charge ordering phenomena in quasi two-dimensional 1/4-filled organic compounds (ET)_2X (ET=BEDT-TTF) are investigated theoretically for the $\theta$ and $\alpha$-type structures, based on the Hartree approximation for the extended Hubbard models with both on-site and intersite Coulomb interactions. It is found that charge ordered states of stripe-type are stabilized for the relevant values of Coulomb energies, while the spatial pattern of the stripes sensitively depends on the anisotropy of the models. By comparing the results of calculations with the experimental facts, where the effects of quantum fluctuation is incorporated by mapping the stripe-type charge ordered states to the S=1/2 Heisenberg Hamiltonians, the actual charge patterns in the insulating phases of $\theta$-(ET)_2MM'(SCN)_4 and $\alpha$-(ET)_2I_3 are deduced. Furthermore, to obtain a unified view among the $\theta$, $\alpha$ and $\kappa$-(ET)_2X families, the stability of the charge ordered state in competition with the dimeric antiferromagnetic state viewed as the Mott insulating state, which is typically realized in $\kappa$-type compounds, and with the paramagnetic metallic state, is also pursued by extracting essential parameters.Comment: 35 pages, 27 figures, submitted to J. Phys. Soc. Jp

Theoretical Aspects of Charge Ordering in Molecular Conductors

Theoretical studies on charge ordering phenomena in quarter-filled molecular (organic) conductors are reviewed. Extended Hubbard models including not only the on-site but also the inter-site Coulomb repulsion are constructed in a straightforward way from the crystal structures, which serve for individual study on each material as well as for their systematic understandings. In general the inter-site Coulomb interaction stabilizes Wigner crystal-type charge ordered states, where the charge localizes in an arranged manner avoiding each other, and can drive the system insulating. The variety in the lattice structures, represented by anisotropic networks in not only the electron hopping but also in the inter-site Coulomb repulsion, brings about diverse problems in low-dimensional strongly correlated systems. Competitions and/or co-existences between the charge ordered state and other states are discussed, such as metal, superconductor, and the dimer-type Mott insulating state which is another typical insulating state in molecular conductors. Interplay with magnetism, e.g., antiferromagnetic state and spin gapped state for example due to the spin-Peierls transition, is considered as well. Distinct situations are pointed out: influences of the coupling to the lattice degree of freedom and effects of geometrical frustration which exists in many molecular crystals. Some related topics, such as charge order in transition metal oxides and its role in new molecular conductors, are briefly remarked.Comment: 21 pages, 19 figures, to be published in J. Phys. Soc. Jpn. special issue on "Organic Conductors"; figs. 4 and 11 replaced with smaller sized fil

The Spatial and Temporal Deployment of Voluntary Attention across the Visual Field

Several studies have addressed the question of the time it takes for attention to shift from one position in space to another. Here we present a behavioural paradigm which offers a direct access to an estimate of voluntary shift time by comparing, in the same task, a situation in which subjects are required to re-engage their attention at the same spatial location with a situation in which they need to shift their attention to another location, all other sensory, cognitive and motor parameters being equal. We show that spatial attention takes on average 55 ms to voluntarily shift from one hemifield to the other and 38 ms to shift within the same hemifield. In addition, we show that across and within hemifields attentional processes are different. In particular, attentional spotlight division appears to be more difficult to operate within than across hemifields

Human Visual Search Does Not Maximize the Post-Saccadic Probability of Identifying Targets

Researchers have conjectured that eye movements during visual search are selected to minimize the number of saccades. The optimal Bayesian eye movement strategy minimizing saccades does not simply direct the eye to whichever location is judged most likely to contain the target but makes use of the entire retina as an information gathering device during each fixation. Here we show that human observers do not minimize the expected number of saccades in planning saccades in a simple visual search task composed of three tokens. In this task, the optimal eye movement strategy varied, depending on the spacing between tokens (in the first experiment) or the size of tokens (in the second experiment), and changed abruptly once the separation or size surpassed a critical value. None of our observers changed strategy as a function of separation or size. Human performance fell far short of ideal, both qualitatively and quantitatively

ERRα promotes breast cancer cell dissemination to bone by increasing RANK expression in primary breast tumors

Bone is the most common metastatic site for breast cancer. Estrogen-related-receptor alpha (ERRα) has been implicated in cancer cell invasiveness. Here, we established that ERRα promotes spontaneous metastatic dissemination of breast cancer cells from primary mammary tumors to the skeleton. We carried out cohort studies, pharmacological inhibition, gain-of-function analyses in vivo and cellular and molecular studies in vitro to identify new biomarkers in breast cancer metastases. Meta-analysis of human primary breast tumors revealed that high ERRα expression levels were associated with bone but not lung metastases. ERRα expression was also detected in circulating tumor cells from metastatic breast cancer patients. ERRα overexpression in murine 4T1 breast cancer cells promoted spontaneous bone micro-metastases formation when tumor cells were inoculated orthotopically, whereas lung metastases occurred irrespective of ERRα expression level. In vivo, Rank was identified as a target for ERRα. That was confirmed in vitro in Rankl stimulated tumor cell invasion, in mTOR/pS6K phosphorylation, by transactivation assay, ChIP and bioinformatics analyses. Moreover, pharmacological inhibition of ERRα reduced primary tumor growth, bone micro-metastases formation and Rank expression in vitro and in vivo. Transcriptomic studies and meta-analysis confirmed a positive association between metastases and ERRα/RANK in breast cancer patients and also revealed a positive correlation between ERRα and BRCA1mut carriers. Taken together, our results reveal a novel ERRα/RANK axis by which ERRα in primary breast cancer promotes early dissemination of cancer cells to bone. These findings suggest that ERRα may be a useful therapeutic target to prevent bone metastases