Fe-speciation in kaolins : a diffuse reflectance study

Abstract--Diffuse r flectance spectra of kaolins have been recorded in samples from different environ-ments. They show the systematic presence of Fe-oxides, even in bleached kaolins, with no contribution from the Fe 3+ ions substituted in kaolinite. Second derivative spectra of various Fe-phases (hematite, goethite, lepidocrocite, maghemite, akaganeite, f rrihydrite and Fe-polymer) may be differentiated by the position of a diagnostic band corresponding tothe 2QA0 ~ 2(4T~(4G)) transition. The systematic com-parison of diffuse reflectance spectra of unbleached and bleached kaolins has demonstrated the differences between the Fe-oxides occurring as coatings and as occluded phases. The features observed in second derivative spectral curves are consistent with assignments ofcrystal field transitions togoethite, hematite, akaganeite, and aged hydrous ferric oxides. The optical determination f the Fe-phases associated to kaolins assists in the interpretation f the formation conditions of these minerals. Key Words--Diffuse r flectance spectroscopy, Fe-speciation, Kaolin, Second erivative spectra

Molecular dynamics simulation of radiation damage in glasses

Molecular dynamics simulations of the ballistic effects arising from displacement cascades in glasses have been investigated in silica and in a SiO 2 -B 2 O 3 -Na 2 O glass. In both glasses the T-O-T′ angle (where T and T′ are network formers) diminishes, despite radiation causes opposite effects: while the ternary glass swells and silica becomes denser. We show that radiation-induced modifications of macroscopic glass properties result from structural change at medium/range, reflecting an increasing disorder and internal energy of the system. A local thermal quenching model is proposed to account for the effects of ballistic collisions. The core of a displacement cascade is heated by the passage of the projectile, then rapidly quenched, leading to a process that mimics a local thermal quenching. The observed changes in both the mechanical and structural properties of glasses eventually reach saturation at 2 10 18 α/g as the accumulated energy increases. The passage of a single projectile is sufficient to reach the maximum degree of damage, confirming the hypothesis postulated in the swelling model proposed by J.A.C. Marples

X-ray Linear Dichroism in cubic compounds: the case of Cr3+ in MgAl2O4

The angular dependence (x-ray linear dichroism) of the Cr K pre-edge in MgAl2O4:Cr3+ spinel is measured by means of x-ray absorption near edge structure spectroscopy (XANES) and compared to calculations based on density functional theory (DFT) and ligand field multiplet theory (LFM). We also present an efficient method, based on symmetry considerations, to compute the dichroism of the cubic crystal starting from the dichroism of a single substitutional site. DFT shows that the electric dipole transitions do not contribute to the features visible in the pre-edge and provides a clear vision of the assignment of the 1s-->3d transitions. However, DFT is unable to reproduce quantitatively the angular dependence of the pre-edge, which is, on the other side, well reproduced by LFM calculations. The most relevant factors determining the dichroism of Cr K pre-edge are identified as the site distortion and 3d-3d electronic repulsion. From this combined DFT, LFM approach is concluded that when the pre-edge features are more intense than 4 % of the edge jump, pure quadrupole transitions cannot explain alone the origin of the pre-edge. Finally, the shape of the dichroic signal is more sensitive than the isotropic spectrum to the trigonal distortion of the substitutional site. This suggests the possibility to obtain quantitative information on site distortion from the x-ray linear dichroism by performing angular dependent measurements on single crystals

Early diagenetic vivianite [Fe-3(PO4)(2) center dot 8H(2)O] in a contaminated freshwater sediment and insights into zinc uptake: a mu-EXAFS, mu-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe3(PO4)2 · 8H2O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe3+ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption

Use of the gLite-WMS in CMS for production and analysis

The CMS experiment at LHC started using the Resource Broker (by the EDG and LCG projects) to submit Monte Carlo production and analysis jobs to distributed computing resources of the WLCG infrastructure over 6 years ago. Since 2006 the gLite Workload Management System (WMS) and Logging \& Bookkeeping (LB) are used. The interaction with the gLite-WMS/LB happens through the CMS production and analysis frameworks, respectively ProdAgent and CRAB, through a common component, BOSSLite. The important improvements recently made in the gLite-WMS/LB as well as in the CMS tools and the intrinsic independence of different WMS/LB instances allow CMS to reach the stability and scalability needed for LHC operations. In particular the use of a multi-threaded approach in BOSSLite allowed to increase the scalability of the systems significantly. In this work we present the operational set up of CMS production and analysis based on the gLite-WMS and the performances obtained in the past data challenges and in the daily Monte Carlo productions and user analysis usage in the experiment

Organisational participation and women - an attitude problem?

Employee participation is a dynamic and contested area of organisational behaviour, attracting continuing academic, practitioner and policy interest and debate. This chapter focuses on organisational participation and women