Characterization of a redox-modified clay mineral with respect to its suitability as a barrier in radioactive waste confinement

Engineered barriers for high-level nuclear waste (HLW) consist of excavated repositories in sub-surface rock formations where canisters holding the radionuclide are stored. Clay minerals, particularly the swelling 2:1 types, are used as backfill material, both in the canisters and in the bore hole, in order to prevent radionuclide transport to surrounding groundwater. One of the most important risks that can occur is the corrosion of the canister, which could be coupled with reduction of iron (Fe) in the clay structure. Such changes could greatly decrease the long-term stability of the clay and, consequently, of the barriers themselves. In order to test the potential effects of such redox interactions, an Fe-bearing clay mineral from a commercial source located in the Kutch region, India, was selected for study. This particular mineral is one of the candidate clay minerals to serve as such a barrier material, and is the one with the largest structural Fe content. Results from it should, therefore, provide maximum insight into the potential effects of redox interactions between the barrier and its surroundings. The unaltered clay was characterized by X-ray powder diffractometry (XRD), thermal gravimetric analysis (TGA/DTGA), Fourier-transform infrared (FTIR) spectroscopy, and variable-temperature Mössbauer spectroscopy. The chemically reduced and reoxidized forms of the clay were characterized by variable-temperature Mössbauer spectroscopy and chemical analysis. In the unaltered state the clay is comprised of smectite, maghemite, superparamagnetic goethite, and hematite, with a possible trace of kaolinite. In the reduced state the Fe (oxyhydr)oxides were dissolved. Upon reoxidation no six-line pattern was observed, indicating that the Fe remained only in the structure of the silicates. The final structure of the reduced–reoxidized clay contained more defects than the original clay, as revealed by greater quadrupole splitting values for structural Fe(III) in the clay. These findings indicate that upon exposure to natural redox cycles the Kutch clay could undergo permanent changes in its mineralogical composition and clay mineral structure, but further study is required to ascertain the effects that such changes would have on its long-term stability as a barrier material.     

Adsorption of Alkanethiols on Gold Surfaces: PM-IRRAS Study of the Influence of Terminal Functionality on Alkyl Chain Orientation

The present paper focuses on a simplified method to study the orientation and the anisotropy of two different alkanethiols self-assembled monolayers on gold surfaces. The alkanethiols of interest vary only by their terminal functionalities (COOH and COOCH₃), thus allowing one to highlight the influence of these ending chemical groups on the final orientation of the adsorbed molecules. 11-Mercaptoundecanoic acid [HS-(CH₂)₁₀-COOH] and the methyl-11-mercaptoundecanoate [HS-(CH₂)₁₀-COOCH₃] were grafted under adequate conditions to obtain a high grafting density on gold substrates. These latter, before and after the alkanethiol adsorption, were analyzed mainly by the polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) technique to access orientation angles, and by atomic force microscopy (AFM) to check the homogeneity of the grafted layer.

By applying an original PM-IRRAS simplified method, the results showed an orientation closer to the normal of the surface plane in the case of the acid thiol compared with the ester one, which is probably because of the lateral hydrogen bonds established between the adjacent COOH functions. This method offers a direct and simple way to quantify the orientation angles in the alkanethiol nanofilms.     

A comparison of three turbulence models for the prediction of parallel lobed jets in perforated panel optimization

The general context of the present study is the design of high induction HVAC air diffusers by means of passive jet control. When the diffuser is a perforated panel with lobed orifices (Meslem et al. 2010), the optimization of jet induction consists in improving the orifice’s geometry, the spacing between orifices and their arrangement on the panel. In this study, the flow field of a turbulent twin cross-shaped jet is investigated numerically using the standard k-ε model, the Shear Stress Transport (SST) k-ω model and the Reynolds Stress Model (RSM). The results are compared with PIV measurements. The objective is to assess their capability and limitations to predict the significant features of twin jet flow when the flow is numerically resolved through a lobed diffuser. It is shown that the k-ε and RSM models are more appropriate for predicting potential jet core length, the change in jet centreline streamwise velocity, and flow expansion in the symmetry plane of the twin jet flow. However, these models overestimate the overall flow expansion and the jet volumetric flow rate. The SST k-ω model seems more appropriate for the prediction of such dynamic integral quantities. A high level of turbulent kinetic energy predicted by the k-ε and RSM models in the near field of jets is probably the reason for this overestimation of jet induction. The SST k-ω model would appear to be the most appropriate tool for optimizing orifice design, orifice to orifice spacing and relative orifice orientation on a perforated panel diffuser.     

Recovered memories in context: Thoughts and elaborations on Bowers and Farvolden (1996).

The recovered memory debate exposes several traditional and recent contradictions within psychology. Building on K. Bowers and P. Farvolden ( see record 83:27619), the nature of recovered memories has profoundly different meanings for therapeutic versus legal settings. Whereas memory can be distorted during the process of retrieval, certain techniques—such as nondirective writing—may be helpful in reducing suggestive influences in recall. Ironically, methods that have been found to produce the most accurate recollections of the past appear only subtly different from those that yield the greatest distortions. The recovered memory debate must ultimately be viewed within a cultural context, both in terms of the phenomenon and its treatment. The authors discuss parallels to other explanatory and therapeutic fads related to states of nonspecific distress. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Chemical composition,antimicrobial potential against cariogenic bacteria and cytotoxic activity of Tunisian Nigella sativa essential oil and thymoquinone

We investigate in this work the chemical composition by GC–EIMS, the antibacterial and the cytotoxic activities of Tunisian Nigella sativa essential oil and its bioactive compound, thymoquinone, were tested against various clinical cariogenic bacteria (n = 30). Eighty-four compounds were identified in the essential oil. The major one was p-cymene (49.48%) whereas thymoquinone represented only 0.79%. The essential oil (2.43 mg/disc) containing only 3.35 μg of thymoquinone showed pronounced dose dependant antibacterial activity against Streptococcus mitis, Streptococcus mutans, Streptococcus constellatus and Gemella haemolysans (15.5 ± 0.707 mm). However, pure thymoquinone compound (150 μg/disk) was active against all the studied strains especially S. mutans and S. mitis (24.5 ± 0.71 and 22 ± 1.41 mm inhibition zones, respectively).     

A matheuristic approach for optimizing mineral value chains under uncertainty

Optimization and Engineering - Mineral value chains, also known as mining complexes, involve mining, processing, stockpiling, waste management and transportation activities. Their optimization is...