917 research outputs found

    2013 LLNL Nuclear Forensics Summer Program

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    Enhancement of the ferromagnetic order of graphite after sulphuric acid treatment

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    We have studied the changes in the ferromagnetic behavior of graphite powder and graphite flakes after treatment with diluted sulphuric acid. We show that this kind of acid treatment enhances substantially the ferromagnetic magnetization of virgin graphite micrometer size powder as well as in graphite flakes. The anisotropic magnetoresistance (AMR) amplitude at 300 K measured in a micrometer size thin graphite flake after acid treatment reaches values comparable to polycrystalline cobalt.Comment: 3.2 pages, 4 figure

    Dinuclear Tb and Dy complexes supported by hybrid Schiff-base/calixarene ligands: synthesis, structures and magnetic properties

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    The synthesis of the new lanthanide complexes [HNEt3_{3}][Dy2_{2}(HL1^{1})(L1^{1})] (5), and [Ln2_{2}(L2_{2})2_{2}] (Ln = TbIII^{III} (7), DyIII^{III} (8)) supported by the hybrid Schiff-base/calix[4]arene ligands H4_{4}L1^{1} (25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and H3_{3}L2^{2} (25-[2-((2-methylpyridine)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) are reported. Spectroscopic data (for 5) and X-ray crystallographic analysis (for 7·4MeCN, 8·4MeCN) reveal the presence of dimeric structures, featuring doubly-bridged NO4_{4}Ln(μ-O)2_{2}LnO4_{4}N (5) or N2_{2}O3_{3}Ln(μ-O)2_{2}LnO3_{3}N2_{2} cores (7, 8) with seven-coordinated Ln3+^{3+} ions. The magnetic properties of polycrystalline samples of 5, 7 and 8 were studied by variable temperature dc and ac magnetic susceptibility measurements. The χ′′(T) vs. T plots show no maxima in zero field, but the maxima can be detected under a 3 kOe dc field. The relaxation times τ obey the Arrhenius law above 5 K. Anisotropy barriers of ∼18 cm−1^{-1} (26 K) for 5 and ∼23 cm−1^{-1} (33 K) for 8 were determined

    Effect of Aging on the Reversibility of Pu(IV) Sorption to Goethite

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    Designing safe remediation and disposal strategies for plutonium (Pu) requires understanding the sorption affinity of Pu for soil minerals. Sorption of Pu(IV) was examined with respect to aging for a goethite system using batch sorption experiments. Sorption of Pu(IV) to iron oxides has been observed to be strong, rapid, and possibly irreversible or hysteretic. These observations may be explained by aging, a surface chemical process happening after initial sorption which causes a change in contaminant surface speciation over time. Measurements of Pu(IV) sorption are often complicated by oxidative leaching of Pu(IV) as Pu(V). Desferrioxamine B (DFOB) is a complexant capable of competing with the proposed strong surface complexes. Additionally, DFOB minimizes oxidative leaching by forming strong Pu(IV)-DFOB complexes, thereby stabilizing Pu(IV) as the dominant aqueous oxidation state. Pu(IV) was reacted in suspensions of 0.1g/L goethite and 10mM NaCl spanning pH 4–7 for various lengths of time (1,6,15,34 and 116 days). Supernatant was replaced with a 1.7µM DFOB solution and, after 34 more days, analyzed for aqueous Pu by liquid scintillation counting. Modeling sorption curves in FITEQL yielded logK values which increased from 0.078 to 0.953 over 116 days, indicating Pu(IV) sorption onto goethite becomes less reversible with aging

    Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates

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    Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006) and upscaled for use in CAU models (Stoller-Navarro, 2008) includes surface complexation constants for U, Am, Eu, Np and Pu (Zavarin and Bruton, 2004). Generally, between 15 to 30 datasets were used to develop the constants for each radionuclide. However, the constants that describe Pu sorption to aluminosilicates were developed using only 10 datasets, most of which did not specify the oxidation state of Pu in the experiment. Without knowledge or control of the Pu oxidation state, a high degree of uncertainty is introduced into the model. The existing Pu surface complexation model (e.g. Zavarin and Bruton, 2004) drastically underestimates Pu sorption and, thus, will overestimate Pu migration rates (Turner, 1995). Recent HST simulations at Cambric (Carle et al., 2006) suggest that the existing surface complexation model may underpredict Pu K{sub d}s by as much as 3 orders of magnitude. In order to improve HST and CAU-scale transport models (and, as a result, reduce the conservative nature Pu migration estimates), sorption experiments were performed over a range of solution conditions that brackets the groundwater chemistry of the Nevada National Security Site. The aluminosilicates examined were gibbsite, silica, and montmorillonite

    Coping with anxiety: Brain structural correlates of vigilance and cognitive avoidance

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    Background: Individuals differ in their dispositional coping behavior when they are confronted with anxiety-provoking situations. Cognitive avoidance is characterized by a withdrawal from threatening information, whereas vigilance denotes the intensive search for threat-related information. Functional neuroimaging studies indicate alterations in brain responsivity to emotional stimuli as a function of cognitive avoidant and vigilant coping, but findings are partially discrepant. Studies on structural correlates of coping styles are scarce. Materials and Methods: By using structural magnetic resonance imaging, the present study examined the relationship between brain gray matter volume and coping strategies in 114 healthy individuals. Individual differences in vigilance and cognitive avoidance were measured by the Mainz Coping Inventory. Results: Exploratory whole-brain analyses were conducted. Cognitive avoidant coping significantly predicted reduced gray matter volume in the bilateral thalamus, whereas vigilant coping was associated with volumetric increases in the bilateral thalamus. These relationships remained significant when controlling for a potential influence of age, sex, depressive symptoms, and trait anxiety. Discussion: Our findings indicate that dispositional strategies to deal with anxiety-provoking situations are related to volumetric alterations in the thalamus, a brain structure that has been implicated in the mediation of attentional processes and alertness, and the anticipation of harm. The dispositional tendency to monitor the environment for potential threats (i.e., vigilance), appears to be associated with volumetric increases in the thalamus, whereas the dispositional inclination to divert one’s attention away from distressing stimuli (i.e., cognitive avoidance) seems to go along with reductions in thalamic gray matter density

    Sorption Behavior and Morphology of Plutonium in the Presence of Goethite at 25 and 80C

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    In this study, we examined the sorption behavior of Pu at elevated temperatures in the presence of one relevant mineral, goethite ({alpha}-FeOOH), over a range of concentrations that span solubility-controlled to adsorption-controlled concentrations. We focused on the sorptive behavior of two common forms of Pu: aqueous Pu(IV) and intrinsic Pu(IV) nano-colloids at 25 and 80 C in a dilute pH 8 NaCl/NaHCO{sub 3} solution. The morphology of Pu sorbed to goethite was characterized using transmission electron microscopy (TEM). We examined the relative stability of PuO{sub 2} precipitates, PuO{sub 2} nano-colloids, Pu{sub 4}O{sub 7} surface precipitates, and monomeric sorbed Pu as a function of temperature and over a time scale of months
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