DI-B experiment: planning, design and performance of an in situ diffusion experiment in the Opalinus Clay formation

The DI-B experiment is a long-term, natural-scale, in situ diffusion experiment, which is being performed in the Opalinus Clay formation at the Mont Terri Underground Rock Laboratory (URL), in Switzerland, employing nonradioactive tracers. One of the key aspects to be addressed for nuclear waste repository safety assessment purposes is the understanding of the transport mechanisms of the radionuclides contained in the radioactive waste. Consolidated clay formations display very low water hydraulic conductivities, so it is expected that the predominant transport process will be diffusion.The experimental set-up has been designed to withstand the site conditions and for monitoring and recording several physicochemical parameters (pH, conductivity, oxidation–reduction potential), as well as the pressures in the circuit and for the long-distance monitoring of the data acquisition system.The tracer selection has been made based on previous investigations carried out at CIEMAT, including a literature survey, laboratory sorption experiments and hydrogeochemical modeling for determining tracer stability under the physicochemical conditions to be expected in the site. The final selection includes ⁶Li, ⁸⁷Rb, D (as D₂O) and I (as I⁻). Hydrogeochemical modeling confirmed the stability of all the tracers selected. Batch sorption experiments showed that no sorption in the rock occurred in the case of ⁶Li, D and I (conservative tracers), whereas ⁸⁷Rb was 100% sorbed. However, ⁸⁷Rb was chosen because of its analogy with Cs, a relevant radionuclide commonly present in the nuclear spent fuel.Diffusion experiments have been carried out at laboratory scale with Opalinus Clay samples to provide diffusion parameters for modeling purposes. Effective diffusion coefficients, perpendicular and parallel to the bedding planes of the rock, respectively, were (1.68± 0.42)×10⁻¹¹ and (4.02± 0.30)×10⁻¹¹ m²/s for tritium, and (2.70± 0.27)×10⁻¹² and (1.38± 0.49)×10⁻¹¹ m²/s for iodide. Additional through-diffusion experiments (parallel to the bedding) were performed with the nonsorbing tracer ³⁶Cl⁻, in order to check the results obtained for iodide. The effective diffusion coefficient measured for chloride ions was (1.18± 0.27)×10⁻¹¹ m²/s, which is practically equal to the value obtained for iodide.Preliminary diffusion calculations have been carried out using two transport codes: GIMRT and CORE^2D, with conservative and nonconservative tracers, using effective diffusion coefficients (D_e) obtained experimentally in the laboratory (through-diffusion experiments) or selected from the literature. The diffusion profiles obtained from the calculations showed slight variations, which were consistent with the different modeling approaches employed. The predictive modeling results have been used to determine the initial tracer concentration that should be added to the circuit to assure well-defined profiles at the end of the experiment.This long-term in situ diffusion experiment will also provide useful data for the interpretation of previous diffusion experiments performed at the Mont Terri URL.     

Reductive Amination Without the Aldehyde: Use of a Ketolactol as an Aldehyde Surrogate

To overcome stability issues associated with the use of an aldehyde in a catalytic reductive amination reaction, a cyclic ketolactol (ω-hydroxylactone) was employed as an aldehyde surrogate to form a γ-aminoacid. The reaction proceeded most favorably over a Pt/C catalyst. The thermodynamics of each step were evaluated using density functional theory calculations, which correctly predicted the dominance of the ring-closed lactol reactant, yet suggested a preference for a ring-opened iminium intermediate upon the initial, slightly endoergic addition of amine substrate. Exoergic hydrogenation of this intermediate provided the thermodynamic driving force for the overall transformation. During development, the reaction was observed to depend significantly on the volumetric gas to liquid mass transfer coefficient (k_La) and this parameter was optimized to ensure successful scale up in a 400 L stirred tank reactor.     

Nano and micro architectures for self-propelled motors

Self-propelled micromotors are emerging as important tools that help us understand the fundamentals of motion at the microscale and the nanoscale. Development of the motors for various biomedical and environmental applications is being pursued. Multiple fabrication methods can be used to construct the geometries of different sizes of motors. Here, we present an overview of appropriate methods of fabrication according to both size and shape requirements and the concept of guiding the catalytic motors within the confines of wall. Micromotors have also been incorporated with biological systems for a new type of fabrication method for bioinspired hybrid motors using three-dimensional (3D) printing technology. The 3D printed hybrid and bioinspired motors can be propelled by using ultrasound or live cells, offering a more biocompatible approach when compared to traditional catalytic motors.     

Synergistic hydrogen generation from aluminum, aluminum alloys and sodium borohydride in aqueous solutions

A new method to produce high purity hydrogen using reactions of aluminum and sodium borohydride with aqueous alkaline solutions is described. This process mainly consumes water and aluminum (or its alloys) which are cheaper raw materials than the borohydride. As a consequence, this process could be competitive for in situ production of hydrogen. Moreover, a synergistic effect has been observed in hydrogen production rates and yields combining aluminum or aluminum alloys with sodium borohydride in aqueous solutions. Good results have been obtained for powders of Al, Al/Si and Al/Co alloys. The development of this idea could improve yields and reduce costs in power units based on fuel cells which use borohydride as raw material for hydrogen production.     

Aluminum and aluminum alloys as sources of hydrogen for fuel cell applications

Production of hydrogen using aluminum and aluminum alloys with aqueous alkaline solutions is studied. This process is based on aluminum corrosion, consuming only water and aluminum which are cheaper raw materials than other compounds used for in situ hydrogen generation, such as chemical hydrides. In principle, this method does not consume alkali because the aluminate salts produced in the hydrogen generation undergo a decomposition reaction that regenerates the alkali. As a consequence, this process could be a feasible alternative for hydrogen production to supply fuel cells. Preliminary results showed that an increase of base concentration and working solution temperature produced an increase of hydrogen production rate using pure aluminum. Furthermore, an improvement of hydrogen production rates and yields was observed varying aluminum alloys composition and increasing their reactive surface, with interesting results for Al/Si and Al/Co alloys. The development of this idea could improve yields and reduce costs in power units based on fuel cells which use hydrides as raw material for hydrogen production.     

Technique based on LED multispectral imaging and multivariate analysis for monitoring the conservation state of the Dead Sea Scrolls

The aim of this project is the development of a noninvasive technique based on LED multispectral imaging (MSI) for monitoring the conservation state of the Dead Sea Scrolls (DSS) collection. It is well-known that changes in the parchment reflectance drive the transition of the scrolls from legible to illegible. Capitalizing on this fact, we will use spectral imaging to detect changes in the reflectance before they become visible to the human eye. The technique uses multivariate analysis and statistical process control theory. The present study was carried out on a "sample" parchment of calfskin. The monitoring of the surface of a commercial modern parchment aged consecutively for 2 h and 6 h at 80 °C and 50% relative humidity (ASTM) was performed at the Imaging Lab of the Library of Congress (Washington, DC, U.S.A.). MSI is here carried out in the vis-NIR range limited to 1 μm, with a number of bands of 13 and bandwidths that range from about 10 nm in UV to 40 nm in IR. Results showed that we could detect and locate changing pixels, on the basis of reflectance changes, after only a few "hours" of aging.     

Pixel selection for near-infrared chemical imaging (NIR-CI) discrimination between fish and terrestrial animal species in animal protein by-product meals

This paper proposes a method based on near-infrared hyperspectral imaging for discriminating between terrestrial and fish species in animal protein by-products used in livestock feed. Four algorithms (Mahalanobis distance, Kennard-Stone, spatial interpolation, and binning) were compared in order to select an appropriate subset of pixels for further partial least squares discriminant analysis (PLS-DA). The method was applied to a set of 50 terrestrial and 40 fish meals analyzed in the 1000-1700 nm range. Models were then tested using an external validation set comprising 45 samples (25 fish and 20 terrestrial). The PLS-DA models obtained using the four subset-selection algorithms yielded a classification accuracy of 99.80%, 99.79%, 99.85%, and 99.61%, respectively. The results represent a first step for the analysis of mixtures of species and suggest that NIR-CI, providing valuable information on the origin of animal components in processed animal proteins, is a promising method that could be used as part of the EU feed control program aimed at eradicating and preventing bovine spongiform encephalopathy (BSE) and related diseases.