In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation

We present atomic-scale, video-rate environmental transmission electron microscopy and in situ time-resolved X-ray photoelectron spectroscopy of surface-bound catalytic chemical vapor deposition of single-walled carbon nanotubes and nanofibers. We observe that transition metal catalyst nanoparticles on SiOx support show crystalline lattice fringe contrast and high deformability before and during nanotube formation. A single-walled carbon nanotube nucleates by lift-off of a carbon cap. Cap stabilization and nanotube growth involve the dynamic reshaping of the catalyst nanocrystal itself. For a carbon nanofiber, the graphene layer stacking is determined by the successive elongation and contraction of the catalyst nanoparticle at its tip.     

Towards sensible toxicity testing for nanomaterials: proposal for the specification of test design

During the last decade, nanomaterials (NM) were extensively tested for potential harmful effects towards humans and environmental organisms. However, a sound hazard assessment was so far hampered by uncertainties and a low comparability of test results. The reason for the low comparability is a high variation in the (1) type of NM tested with regard to raw material, size and shape and (2) procedures before and during the toxicity testing. This calls for tailored, nanomaterial-specific protocols. Here, a structured approach is proposed, intended to lead to test protocols not only tailored to specific types of nanomaterials, but also to respective test system for toxicity testing. There are existing standards on single procedures involving nanomaterials, however, not all relevant procedures are covered by standards. Hence, our approach offers a detailed way of weighting several plausible alternatives for e.g. sample preparation, in order to decide on the procedure most meaningful for a specific nanomaterial and toxicity test. A framework of several decision trees (DT) and flow charts to support testing of NM is proposed as a basis for further refinement and in-depth elaboration. DT and flow charts were drafted for (1) general procedure—physicochemical characterisation, (2) choice of test media, (3) decision on test scenario and application of NM to liquid media, (4) application of NM to the gas phase, (5) application of NM to soil and sediments, (6) dose metrics, (S1) definition of a nanomaterial, and (S2) dissolution. The applicability of the proposed approach was surveyed by using experimental data retrieved from studies on nanoscale CuO. This survey demonstrated the DT and flow charts to be a convenient tool to systematically decide upon test procedures and processes, and hence pose an important step towards harmonisation of NM testing.     

Ecotoxicological evaluation of three tertiary wastewater treatment techniques via meta-analysis and feeding bioassays using Gammarus fossarum

Advanced treatment techniques, like ozone, activated carbon and TiO₂ in combination with UV, are proposed to improve removal efficiency of micropollutants during wastewater treatment. In a meta-analysis of peer-reviewed literature, we found significantly reduced overall ecotoxicity of municipal wastewaters treated with either ozone (n = 667) or activated carbon (=113), while TiO₂ and UV was not yet assessed. As comparative investigations regarding the detoxification potential of these advanced treatment techniques in municipal wastewater are scarce, we assessed them in four separate Gammarus-feeding trials with 20 replicates per treatment. These bioassays indicate that ozone concentrations of approximately 0.8 mg ozone/mg DOC may produce toxic transformation products. However, referred effects are removed if higher ozone concentrations are used (1.3 mg ozone/mg DOC). Moreover, the application of 1 g TiO₂/l and ambient UV consistently reduced ecotoxicity. Although activated carbon may remove besides micropollutants also nutrients, which seemed to mask its detoxification potential, this treatment technique reduced the ecotoxicity of the wastewater following its amendment with nutrients. Hence, all three advanced treatment techniques are suitable to reduce the ecotoxicity of municipal wastewater mediated by micropollutants and may hence help to meet the requirements of the European Water Framework Directive.     

Metal Oxide Nanowire and Thin-Film-Based Gas Sensors for Chemical Warfare Simulants Detection

This work concerns with metal oxide (MOX) gas sensors based on nanowires and thin films. We focus on chemical warfare agents (CWAs) detection to compare these materials from the functional point-of-view. We work with different chemicals including simulants for Sarin nerve agents, vescicant gases, cyanide agents, and analytes such as ethanol, acetone, ammonia, and carbon monoxide that can be produced by everyday activities causing false alarms. Explorative data analysis has been used to demonstrate the different sensing performances of nanowires and thin films. Within the chosen application, our analysis reveal that the introduction of nanowires inside the array composed by thin films can improve its sensing capability. Cyanide simulants have been detected at concentrations close to 1 ppm, lower than the Immediately Dangerous for Life and Health (IDLH) value of the respective warfare agent. Higher sensitivity has been obtained to simulants for Sarin and vescicant gases, which have been detected at concentrations close or even lower than 100 ppb. Results demonstrate the suitability of the proposed array to selectively detect CWA simulants with respect to some compounds produced by everyday activities.     

A benchmark for OCL engine accuracy, determinateness, and efficiency

Since several years, the Object Constraint Language (OCL) is a central component in modeling and transformation languages like the Unified Modeling Language, the Meta Object Facility, and Query View Transformation. Consequently, approaches MDE (Model-Driven Engineering) depend on this language. OCL is present not only in areas influenced by the OMG but also in the Eclipse Modeling Framework (EMF). Thus the quality of OCL and its realization in tools seems to be crucial for the success of model-driven development. Surprisingly, up to now a benchmark for OCL to measure quality properties has not been proposed. This paper puts forward in the first part the concepts of a comprehensive OCL benchmark. Our benchmark covers (1) OCL engine accuracy (e.g., for the handling of the undefined value, the use of variables and the implementation of OCL standard operations), (2) OCL engine determinateness properties (e.g., for the collection operations ??any?? and ??flatten??), and (3) OCL engine efficiency (for data type and user-defined operations). In the second part, this paper empirically evaluates the proposed benchmark concepts by examining several OCL tools. The paper clarifies a number of differences in handling particular language features and under specifications in the OCL standard.     

Spectral reflectance characterization of shallow lakes from the Brazilian Pantanal wetlands with field and airborne hyperspectral data

The relationships between field water reflectance spectra and physico-chemical data of seven freshwater and five saltwater lakes from the Brazilian Pantanal wetlands were characterized. Selection of the lakes was based on previous inspection of the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) images. Principal component analysis (PCA) was used to identify homogeneous groups of lakes, in which the regression relationships were evaluated. The continuum removal method was applied to characterize minor spectral variations in the depth of the absorption bands present in field and image spectra. The results showed lakes with very distinct spectral characteristics. The transition from the freshwater to the saltwater lakes was characterized by lower values of depth and Secchi depth, larger concentrations of dissolved organic carbon (DOC), total suspended sediments (TSS), calcium (Ca), magnesium (Mg), sodium (Na) and potassium (K), and higher values of pH and electrical conductivity. The saline lakes presented a higher overall reflectance in the 400–900?nm range than the freshwater lakes, as indicated by the first principal component. From the optically active constituents analysed, DOC better explained variations in water reflectance. The discrimination of the saltwater lakes along the second principal component was due to the decrease in the chlorophyll (Chl) and to the increase in the DOC concentrations from the greenish to the bluish saline lakes. The AVIRIS instrument was able to detect the narrow 630?nm absorption band present in field water reflectance spectra.     

Secondary hydriding during LOCA – Results from the QUENCH-L0 test

A shortened loss of coolant scenario was simulated experimentally at fuel rod bundle scale in the QUENCH-L0 test. All pressurized specimens burst at temperatures between 790 and 855 °C. The hydrogen distribution in the cladding of chosen fuel rod simulators was studied by neutron radiography and tomography. As the results of these investigations show, the inner oxidation level, depending on time between burst and cooling and the temperatures occurring during this time, are important parameters for the hydrogen uptake. No hydrogen uptake was measured for the specimen with less than 50 s between burst and quenching. For longer time intervals, hydrogen enriched bands were formed. These bended bands are oriented non-symmetrically to the tube axis. The width of the bands and the maximal hydrogen concentrations seem to increase with time between burst and quenching and with the temperatures during this period.     

Multicomponent Cascade Reactions: A Novel and Expedient Approach to Functionalized Indoles by an Unprecedented Nucleophilic Addition‐Heterocyclization‐Oxidative Alkoxycarbonylation Sequence

A novel multicomponent cascade process is reported, based on the sequential combination between an initial nucleophilic attack step to an imine moiety and a palladium‐catalyzed oxidative heterocyclization‐alkoxycarbonylation process. By this new process, five simple molecules [2‐alkynylaniline imines, alcohol (ROH), carbon monoxide (CO), alcohol (ROH), and oxygen (O₂)] are sequentially activated, selectively leading to high value‐added functionalized indole derivatives in a single operation.     

Spectral features associated with nitrogen,phosphorus, and potassium deficiencies in Eucalyptus saligna seedling leaves

Nitrogen (N), phosphorous (P) and potassium (K) deficiency symptoms were induced in Eucalyptus saligna seedlings. Leaves of these seedlings were measured radiometricaly in order to characterize spectrally the symptoms. It was used the SPECTRON SE-590, linked to a LICOR integrating sphere, running at 0.4 to 0.09 mu m spectral range. The results indicated that only the symptoms related with K deficiency could be spectrally detected in the visible region. The time lag from the beginning of the experiment was fundamental to characterize the symptoms, due to the synergism of the symptoms related with mineral deficiencies. The SPECTRON SE-590 fine spectral resolution proved unnecessary to spectrally characterize the symptoms.