Preparation, characterisation and testing of CuO/Ce0.8Zr0.2O2 catalysts for NO oxidation to NO2 and mild temperature diesel soot combustion

CuO/ceria-zirconia catalysts have been prepared, deeply characterised (N2 adsorption–desorption isotherms at −196 °C, XRD, Raman spectroscopy, XPS, TEM and H2-TPR) and tested for NO oxidation to NO2 in TPR conditions, and for soot combustion at mild temperature (400 °C) in a NOx/O2 stream. The behaviour has been compared to that of a reference Pt/alumina commercial catalyst. The ceria-zirconia support was prepared by the co-precipitation method, and different amounts of copper (0.5, 1, 2, 4 and 6 wt%) were loaded by incipient wetness impregnation. The results revealed that copper is well-dispersed onto the ceria-zirconia support for the catalysts with low copper loading and CuO particles were only identified by XRD in samples with 4 and 6% of copper. A very low loading of copper increases significantly the activity for the NO oxidation to NO2 with regard to the ceria-zirconia support and an optimum was found for a 4% CuO/ceria-zirconia composition, showing a very high activity (54% at 348 °C). The soot combustion rate at 400 °C obtained with the 2% CuO/ceria-zirconia catalyst is slightly lower to that of 1% Pt/alumina in terms of mass of catalyst but higher in terms of price of catalyst.

Formation of brominated pollutants during the pyrolysis and combustion of tetrabromobisphenol A at different temperatures

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Pollutant emissions during pyrolysis and combustion of waste printed circuit boards, before and after metal removal

The constant increase in the production of electronic devices implies the need for an appropriate management of a growing number of waste electrical and electronic equipment. Thermal treatments represent an interesting alternative to recycle this kind of waste, but particular attention has to be paid to the potential emissions of toxic by-products. In this study, the emissions from thermal degradation of printed circuit boards (with and without metals) have been studied using a laboratory scale reactor, under oxidizing and inert atmosphere at 600 and 850 °C. Apart from carbon oxides, HBr was the main decomposition product, followed by high amounts of methane, ethylene, propylene, phenol and benzene. The maximum formation of PAHs was found in pyrolysis at 850 °C, naphthalene being the most abundant. High levels of 2-, 4-, 2,4-, 2,6- and 2,4,6-bromophenols were found, especially at 600 °C. Emissions of PCDD/Fs and dioxin-like PCBs were quite low and much lower than that of PBDD/Fs, due to the higher bromine content of the samples. Combustion at 600 °C was the run with the highest PBDD/F formation: the total content of eleven 2,3,7,8-substituted congeners (tetra- through heptaBDD/Fs) was 7240 and 3250 ng WHO2005-TEQ/kg sample, corresponding to the sample with and without metals, respectively.

Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot

This work presents a comparative study between the catalytic performance of the 2% CuO/ceria-zirconia powder catalyst and the same catalyst supported on silicon carbide DPF (Diesel Particulate Filter) towards NO oxidation reaction and soot combustion reaction. The ceria-zirconia catalyst was prepared by the co-precipitation method and 2 wt% copper was incorporated by the incipient wetness impregnation method. The catalyst was incorporated onto the ceramic support using a simple and organic solvent-free procedure by a simply dipping the DPF into an aqueous solution of the catalyst. The powder catalyst has been characterized using N2 adsorption at −196 °C, XRD and Raman Spectroscopy; whereas the catalytic coating morphology has been evaluated by SEM and the mechanical stability by an adherence test. Both catalyst configurations were tested for NO oxidation to NO2 and for soot combustion under NOx/O2. The results revealed that incorporation of the very active copper/ceria-zirconia catalyst onto SiC-DPF has been successfully achieved by a simple coating procedure. Furthermore, the catalytic coating has shown suitable mechanical, chemical and thermal stability. A satisfactory catalytic performance of the catalytic-coated filter was reached towards the NO oxidation reaction. Moreover, it was proved that the catalytic coating is stable and the corresponding coated DPF can be reused for several cycles of NO oxidation without a significant decrease in its activity. Finally, it was verified that the loose-contact mode is a good choice to simulate the catalytic performance of this active phase in a real diesel particulate filter.

Mujeres empresarias en el uso de la web 2.0: discursos de un preludio

Este trabajo presenta los principales resultados de una investigación cuya finalidad es conocer la adopción de las redes sociales on-line en las pymes dirigidas por mujeres. Se parte de la base de que el uso de redes, como elemento estratégico de comunicación, se encuentra todavía en una fase incipiente de desarrollo, lejos aún de ser una práctica consolidada. Nuestro interés en este trabajo es conocer la predisposición y motivaciones de las empresarias hacia el uso estas redes, así como las utilidades y dificultades a las que han de enfrentarse. Nos interesa visibilizar el cambio actitudinal y competencial que las empresarias están imprimiendo en sus empresas dentro del marco competitivo en el que se encuentran. En definitiva, nos interesa estudiar la percepción que tienen las empresarias sobre el uso de las redes sociales online en la medida en que están insertas, como una herramienta más de gestión empresarial. Nos situamos ante un nuevo ámbito de conocimiento sobre el que apenas existen referencias bibliográficas ni se ha realizado apenas investigación; de ahí que la investigación tenga una finalidad fundamentalmente exploratoria y de carácter cualitativo. Para la obtención de la información se realizaron catorce entrevistas semi-estructuradas entre empresarias andaluzas de distintos sectores de actividad. Entre los principales resultados encontramos que algo menos de la mitad de ellas las utilizan, o están implantadas en sus empresas, como herramientas de comunicación. El resto, y relacionado con el tamaño de sus negocios, las utilizan como una prolongación del uso personal en el que se iniciaron.

Successional stage after land abandonment modulates fire severity and post-fire recovery in a Mediterranean mountain landscape

This study analyses the effect of successional stage after farmland terrace abandonment on post-fire plant recovery in a Mediterranean landscape. Specific objectives of the study were to (1) compare fuel characteristics and fire severity in three successional stages after farmland abandonment – dry grassland, dense shrubland and pine stands; (2) analyse the effect of pre-fire successional stage and fire severity on vegetation recovery and (3) analyse the relative vulnerability (i.e. potential for ecosystem shift and soil degradation) to wildfires of the successional stages. We assessed 30 abandoned terraces (15 unburned and 15 burned), with diverse successional stages, on the Xortà Range (south-east Spain). Post-fire recovery was measured 1, 4 and 7 years after fire. The successional stages varied in aboveground biomass, litter amount, vertical structure and continuity of plant cover, and flammability. Dry grassland showed the lowest fire severity, whereas no differences in severity were found between shrubland and pine stands. One year after fire, plant cover was inversely related to fire severity; this relationship attenuated with time after fire. Post-fire recovery of pine stands and shrubland led in both cases to shrublands, contributing to landscape homogenisation. The pine stands showed the largest changes in composition due to fire and the lowest post-fire plant recovery – a sign of high vulnerability to fire.

The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

EEAS 2.0. A legal commentary on Council Decision 2010/427/EU establishing the organisation and functioning of the European External Action Service. EIPA Working Paper, 2013

From the Preface. Pursuant to Article 13(3) of Council Decision 2010/427/EU of 26 July 2010 establishing the organisation and functioning of the European External Action Service, the High Representative is held to provide a review of the organisation and functioning of the EEAS by mid-­‐2013. This review will cover, inter alia, the implementation of Article 6(6), (8) and (11), so as to ensure an adequate geographical and gender balance and a meaningful presence of nationals from all member states in the EEAS. If necessary, the review will be accompanied by appropriate proposals for the revision of the 2010 Council Decision (e.g., suggestions for additional specific measures to correct possible imbalances of staffing). In that case, the Council will, in accordance with Article 27(3) TEU, revise the Decision in light of the review by the beginning of 2014. This short and user-­‐friendly legal commentary on the 2010 Council Decision is the first of its kind and is intended to inform those involved in the review process and to serve as a reference document for practitioners and analysts dealing with the EEAS. This commentary is not an elaborate doctrinal piece, but rather a textual and contextual analysis of each article, that takes account of i) other relevant legal provisions (primary, secondary, international), ii) the process leading to the adoption of the 2010 Council Decision (i.e. travauxpréparatoires), iii) the preamble of the Council Decision, and iv) insofar as it is possible at this stage, early implementation. Wherever relevant, cross-­‐references to other provisions of the EEAS Council Decision have been made so as to tie in the different commentaries and ensure overall consistency.

EEAS 2.0: A legal commentary on Council Decision 2010/427/EU establishing the organisation and functioning of the European External Action Service. CEPS Paperbacks. February 2013

This short and user-friendly legal commentary on the 2010 Council Decision establishing the organisation and functioning of the EEAS is the first of its kind. It is intended to inform those involved in the review process and to serve as a reference document for practitioners and analysts dealing with the EEAS. Rather than an elaborate doctrinal piece, this legal commentary is a textual and contextual analysis of each article that takes account of i) other relevant legal provisions (primary, secondary, international); ii) the process leading to the adoption of the 2010 Council Decision; iii) the preamble of the Council Decision and iv) insofar as it is possible at this stage, early implementation. Wherever relevant, cross-references to other provisions of the Council Decision have been made so as to tie in the different commentaries and ensure overall consistency.

Stage-Specific Plasticity in Ovary Size Is Regulated by Insulin/Insulin-Like Growth Factor and Ecdysone Signaling in Drosophila

Animals from flies to humans adjust their development in response to environmental conditions through a series of developmental checkpoints, which alter the sensitivity of organs to environmental perturbation. Despite their importance, we know little about the molecular mechanisms through which this change in sensitivity occurs. Here we identify two phases of sensitivity to larval nutrition that contribute to plasticity in ovariole number, an important determinant of fecundity, in Drosophila melanogaster. These two phases of sensitivity are separated by the developmental checkpoint called "critical weight"; poor nutrition has greater effects on ovariole number in larvae before critical weight than after. We find that this switch in sensitivity results from distinct developmental processes. In precritical weight larvae, poor nutrition delays the onset of terminal filament cell differentiation, the starting point for ovariole development, and strongly suppresses the rate of terminal filament addition and the rate of increase in ovary volume. Conversely, in postcritical weight larvae, poor nutrition affects only the rate of increase in ovary volume. Our results further indicate that two hormonal pathways, the insulin/insulin-like growth factor and the ecdysone-signaling pathways, modulate the timing and rates of all three developmental processes. The change in sensitivity in the ovary results from changes in the relative contribution of each pathway to the rates of terminal filament addition and increase in ovary volume before and after critical weight. Our work deepens our understanding of how hormones act to modify the sensitivity of organs to environmental conditions, thereby affecting their plasticity.

Intraperitoneal bevacizumab for control of malignant ascites due to advanced-stage gastrointestinal cancers: A multicentre double-blind, placebo-controlled phase II study - AIO SUP-0108

PURPOSE: Malignant ascites is debilitating for patients with advanced cancer. As shown previously, tumour cell production of vascular endothelial growth factor might be a major cause of the formation of malignant ascites. Intraperitoneal bevacizumab could therefore be an option for symptom control in refractory ascites. PATIENTS AND METHODS: Patients with advanced gastrointestinal cancer and malignant ascites who had undergone paracentesis at least twice within the past 4 weeks were randomly assigned in a 2:1 ratio to intraperitoneal bevacizumab (400 mg absolute) or placebo after paracentesis. During the 8-week treatment period, a minimum interval of 14 d was kept between the applications of the study drug. Primary end-point was paracentesis-free survival (ParFS). RESULTS: Fifty-three patients (median age 63 years) were randomised. Forty-nine patients received at least one study drug application and qualified for the main analysis. The proportion of patients with at least one common toxicity criteria grade III-V event was similar with 20/33 (61%) on bevacizumab and 11/16 (69%) on placebo. Median ParFS was 14 d (95% confidence interval [CI]: 11-17) in the bevacizumab arm and 10.5 d (95% CI: 7-21) on placebo (hazard ratio 0.74, 95% CI: 0.40-1.37; P = 0.16). The longest paracentesis-free period was 19 d on bevacizumab (range 6-66 d) and 17.5 d in the placebo arm (range 4-42) (P = 0.85). Median overall survival was 64 d (95% CI: 45-103) on bevacizumab compared to 31.5 d (95% CI: 20-117) on placebo (P = 0.31). CONCLUSION: Intraperitoneal bevacizumab was well tolerated. Overall, treatment did not result in a significantly better symptom control of malignant ascites. However, patients defined by specific immune characteristics may benefit.

Abundance of copepods from multinet samples during POLARSTERN cruise ANT-XXII/2 (ISPOL)

The mesozooplankton community, with special emphasis on calanoid copepods, was studied with respect to its species composition, abundance, vertical distribution and developmental structure during the ISPOL expedition to the ice covered western Weddell Sea. Stratified zooplankton tows were carried out nine times between December 1, 2004 and January 2, 2005 with a multiple opening-closing net between 0 and 1000 m depth. Copepods were by far the most abundant taxon contributing more than 94% of the total mesozooplankton. Numerical dominants were cyclopoid copepods, mostly Oncaea spp. A total of 66 calanoid copepod species were identified, but the calanoid copepod community was characterised by the dominance of only a few species. The most numerous species was Microcalanus pygmaeus, which comprised on average 70% of all calanoids. Calanoides acutus and Metridia gerlachei represented other abundant calanoid species contributing an average of 8 and 7%, respectively. All other species comprised less than 3%. The temporal changes in the abundance and population structure of M. pygmaeus and M. gerlachei were small while a shift in the stage frequency distribution of C. acutus was observed during the study: CIV dominated the C. acutus population with 48 to 50% during the first week of December, while CV comprised 48% in late December. CI and CII of C. acutus were absent in the samples and males occurred only in very low numbers in greater depths. In M. gerlachei, CI was not found, whereas all developmental stages of M. pygmaeus occurred throughout the study. All three species showed migratory behaviour, and they occurred in upper water layers towards the end of the investigation. This vertical ascent was most pronounced in C. acutus and relatively weak in the other two species. In M. pygmaeus and M. gerlachei, copepodite stages were responsible for the upward migration in late December, while the vertical distribution of adults did not change. In C. acutus all abundant developmental stages (CIV, CV and females) ascended to upper water layers. Almost exclusively (93%) medium- and semi-ripe females of C. acutus and M. gerlachei were found, and only 3 - 4% of the ovaries were ripe. The absence of CI and the low number of ripe females indicate that the main reproductive period had not started in C. acutus and M. gerlachei until the end of our study in early January. In contrast, the high portion of CI and CII of M. pygmaeus suggests that reproduction of this species had started in October-November and hence, before the onset of the phytoplankton bloom in the water. The community structure did not differ between stations with one exception on December 26, when the station was strongly influenced by the continental shelf.