Características estruturais e fotocatalíticas do compósito oxihidróxido de nióbio/vermiculita

The preparation of nanostructured materials using natural clays as support, has been studied in literature under the same are found in nature and consequently, have a low price. Generally, clays serve as supports for metal oxides by increasing the number of active sites present on the surface and can be applied for various purposes such as adsorption, catalysis and photocatalysis. Some of the materials that are currently highlighted are niobium compounds, in particular, its oxides, by its characteristics such as high acidity, rigidity, water insolubility, oxidative and photocatalytic properties. In this scenario, the study aimed preparing a composite material oxyhydroxide niobium (NbO2OH) / sodium vermiculite clay and evaluate its effectiveness with respect to the natural clay (V0) and NbO2OH. The composite was prepared by precipitation-deposition method and then characterized by X-ray diffraction, infrared spectroscopy (XRD), energy dispersive X-ray (EDS), thermal analysis (TG/DTG), scanning electron microscopy (SEM), N2 adsorption-desorption and investigation of distribution of load. The application of the material NbO2OH/V0 was divided in two steps: first through oxidation and adsorption methods, and second through photocatalytic activity using solar irradiation. Studies of adsorption, oxidation and photocatalytic oxidation monitored the percentage of color removal from the dye methylene blue (MB) by UV-Vis spectroscopy. The XRD showed a decrease in reflection d (001) clay after modification; the FTIR indicated the presence of both the clay when the oxyhydroxide niobium to present bands in 1003 cm-1 related to Si-O stretching bands and 800 cm-1 to the Nb-O stretching. The presence of niobium was also confirmed by EDS indicated that 17 % by mass amount of the metal. Thermal analysis showed thermal stability of the composite at 217 °C and micrographs showed that there was a decrease in particle size. The investigation of the surface charge of NbO2OH/V0 found that the material exhibits a heterogeneous surface with average low and high negative charges. Adsorption tests showed that the composite NbO2OH/V0 higher adsorption capacity to remove 56 % of AM, while the material removed from V0 only 13 % showed no NbO2OH and adsorptive capacity due to the formation of H-aggregates. The percent removal of dye color for the oxidation tests showed little difference from the adsorption, being 18 and 66 % removal of dye color for V0 and NbO2OH/V0 respectively. The NbO2OH/V0 material shows excellent photocatalytic activity managing to remove just 95,5 % in 180 minutes of the color of MB compared to 41,4 % and 82,2 % of V0 the NbO2OH, proving the formation of a new composite with distinct properties of its precursors.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Potencialidade do tratamento eletroquímico oxidativo associado à adsorção para remediação de corantes têxteis

This study aimed to evaluate the potential of oxidative electrochemical treatment coupled with adsorption process using expanded perlite as adsorbent in the removal of textile dyes, Red Remazol and Novacron Blue on synthetic effluent. Dyes and perlite were characterized by thermogravimetry techniques (TG), Differential Scanning Calorimetry (DSC), Spectroscopy infrared (IR), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Electrochemical treatments used as anodes, Ti/Pt and Pb/PbO2 under different conditions: 60 minutes, current density 20, 40 e 60 mAcm-2, pH 1, 4.5 e 8 and temperature variation 20, 40 e 60 ºC. In the case of adsorption tests, contact time of 30 minutes for the Remazol Red dye and 20 minutes for Novacron Blue were established, while pH 1, 4.5 e 8, 500 mg adsorbent and temperature variation 20, 40 e 60 ºC were used for both treatments. The results indicated that both treatments, electroxidation/adsorption and the adsorption/electroxidation, were effective for removing color from synthetic solutions. The consumption of electricity allowed to evaluate the applicability of the electrochemical process, providing very acceptable values, which allowed us to estimate the cost. Total organic carbon (TOC) and Gas Chromatography linked mass spectrometer (GC-MS) analyzes were performed, showing that the better combination for removing organic matter is by Pb/PbO2 and perlite. Meanwhile, GC-MS indicated that the by-products formed are benzoic acid, phthalic acid, thiocarbamic acid, benzene, chlorobenzene, phenol-2-ethyl and naphthalene when Remazol Red was degraded. Conversely, aniline, phthalic acid, 1, 6 - dimethylnaphthalene, naphthalene and ion hidroxobenzenosulfonat was detected when Novacron Blue was studied. Analyses obtained through atomic absorption spectrometry showed that there was release of lead in the electrochemical oxidation of analyzes that were performed with the anode Pb/PbO2, but these values are reduced by subjecting the effluent to adsorption analysis. According to these results, sequential techniques electroxidation/adsorption and adsorption/electroxidation are to treat solutions containing dyes.

Potencialidade do tratamento eletroquímico oxidativo associado à adsorção para remediação de corantes têxteis

This study aimed to evaluate the potential of oxidative electrochemical treatment coupled with adsorption process using expanded perlite as adsorbent in the removal of textile dyes, Red Remazol and Novacron Blue on synthetic effluent. Dyes and perlite were characterized by thermogravimetry techniques (TG), Differential Scanning Calorimetry (DSC), Spectroscopy infrared (IR), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Electrochemical treatments used as anodes, Ti/Pt and Pb/PbO2 under different conditions: 60 minutes, current density 20, 40 e 60 mAcm-2, pH 1, 4.5 e 8 and temperature variation 20, 40 e 60 ºC. In the case of adsorption tests, contact time of 30 minutes for the Remazol Red dye and 20 minutes for Novacron Blue were established, while pH 1, 4.5 e 8, 500 mg adsorbent and temperature variation 20, 40 e 60 ºC were used for both treatments. The results indicated that both treatments, electroxidation/adsorption and the adsorption/electroxidation, were effective for removing color from synthetic solutions. The consumption of electricity allowed to evaluate the applicability of the electrochemical process, providing very acceptable values, which allowed us to estimate the cost. Total organic carbon (TOC) and Gas Chromatography linked mass spectrometer (GC-MS) analyzes were performed, showing that the better combination for removing organic matter is by Pb/PbO2 and perlite. Meanwhile, GC-MS indicated that the by-products formed are benzoic acid, phthalic acid, thiocarbamic acid, benzene, chlorobenzene, phenol-2-ethyl and naphthalene when Remazol Red was degraded. Conversely, aniline, phthalic acid, 1, 6 - dimethylnaphthalene, naphthalene and ion hidroxobenzenosulfonat was detected when Novacron Blue was studied. Analyses obtained through atomic absorption spectrometry showed that there was release of lead in the electrochemical oxidation of analyzes that were performed with the anode Pb/PbO2, but these values are reduced by subjecting the effluent to adsorption analysis. According to these results, sequential techniques electroxidation/adsorption and adsorption/electroxidation are to treat solutions containing dyes.

MID-IR luminosities and UV/optical star formation rates at z < 1.4

Ultraviolet (UV) nonionizing continuum and mid-infrared (IR) emission constitute the basis of two widely used star formation (SF) indicators at intermediate and high redshifts. We study 2430 galaxies with z < 1.4 in the Extended Groth Strip with deep MIPS 24 μm observations from FIDEL, spectroscopy from DEEP2, and UV, optical, and near-IR photometry from the AEGIS. The data are coupled with dust-reddened stellar population models and Bayesian spectral energy distribution (SED) fitting to estimate dust-corrected star formation rates (SFRs). In order to probe the dust heating from stellar populations of various ages, the derived SFRs were averaged over various timescales—from 100 Myr for "current" SFR (corresponding to young stars) to 1-3 Gyr for long-timescale SFRs (corresponding to the light-weighted age of the dominant stellar populations). These SED-based UV/optical SFRs are compared to total IR luminosities extrapolated from 24 μm observations, corresponding to 10-18 μm rest frame. The total IR luminosities are in the range of normal star-forming galaxies and luminous IR galaxies (10^10-10^12 L_☉). We show that the IR luminosity can be estimated from the UV and optical photometry to within a factor of 2, implying that most z < 1.4 galaxies are not optically thick. We find that for the blue, actively star-forming galaxies the correlation between the IR luminosity and the UV/optical SFR shows a decrease in scatter when going from shorter to longer SFR-averaging timescales. We interpret this as the greater role of intermediate age stellar populations in heating the dust than what is typically assumed. Equivalently, we observe that the IR luminosity is better correlated with dust-corrected optical luminosity than with dust-corrected UV light. We find that this holds over the entire redshift range. Many so-called green valley galaxies are simply dust-obscured actively star-forming galaxies. However, there exist 24 μm detected galaxies, some with L_IR>10^11 L_☉, yet with little current SF. For them a reasonable amount of dust absorption of stellar light (but presumably higher than in nearby early-type galaxies) is sufficient to produce the observed levels of IR, which includes a large contribution from intermediate and old stellar populations. In our sample, which contains very few ultraluminous IR galaxies, optical and X-ray active galactic nuclei do not contribute on average more than ~50% to the mid-IR luminosity, and we see no evidence for a large population of "IR excess" galaxies.

Interactions between Paramoeba perurans, the causative agent of amoebic gill disease, and the blue mussel, Mytilus edulis

Acknowledgements The authors would like to thank staff at Marine Scotland Science Patricia White, Rebecca McIntosh, Julia Black and Mark Fordyce for their technical assistance and invaluable feedback on the project. Thanks also go to Alex Douglas at the University of Aberdeen for his advice on data analysis and statistics. For feedback on the manuscript thanks to Lesley McEvoy and Rhiannon Inkster at the NAFC Marine Centre. The study was supported by the Marine Collaborations Forum (MarCRF) which aims to develop cross-disciplinary research between the University of Aberdeen and Marine Scotland Science. Finally, thanks are also due to Scottish Fishermen's Trust for a student support bursary.

An Exploration of Fairness in International Law through the Blue Nile and GERD

Peer reviewed

System operational costs reduction with non-conventional reactive power sources

Wind energy installations are increasing in power systems worldwide and wind generation capacity tends to be located some distance from load centers. A conflict may arise at times of high wind generation when it becomes necessary to curtail wind energy in order to maintain conventional generators on-line for the provision of voltage control support at load centers. Using the island of Ireland as a case study and presenting commercially available reactive power support devices as possible solutions to the voltage control problems in urban areas, this paper explores the reduction in total generation costs resulting from the relaxation of the operational constraints requiring conventional generators to be kept on-line near load centers for reactive power support. The paper shows that by 2020 there will be possible savings of 87€m per annum and a reduction in wind curtailment of more than a percentage point if measures are taken to relax these constraints.

Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.

Extractions and analyses of reactive phosphorus in the Bering Sea from IODP Holes 323-U1341A and 323-U1341B

To reconstruct the cycling of reactive phosphorus (P) in the Bering Sea, a P speciation record covering the last ~ 4 Ma was generated from sediments recovered during Integrated Ocean Drilling Program (IODP) Expedition 323 at Site U1341 (Bowers Ridge). A chemical extraction procedure distinguishing between different operationally defined P fractions provides new insight into reactive P input, burial and diagenetic transformations. Reactive P mass accumulation rates (MARs) are ~ 20-110 µmol/cm2/ka, which is comparable to other open ocean locations but orders of magnitude lower than most upwelling settings. We find that authigenic carbonate fluorapatite (CFA) and opal-bound P are the dominant P fractions at Site U1341. An overall increasing contribution of CFA to total P with sediment depth is consistent with a gradual "sink switching" from more labile P fractions (fish remains, Fe oxides, organic matter) to stable authigenic CFA. However, the positive correlation of CFA with Al content implies that a significant portion of the supposedly reactive CFA is non-reactive "detrital contamination" by eolian and/or riverine CFA. In contrast to CFA, opal-bound P has rarely been studied in marine sediments. We find for the first time that opal-bound P directly correlates with excess silica contents. This P fraction was apparently available to biosiliceous phytoplankton at the time of sediment deposition and is a long-term sink for reactive P in the ocean, despite the likelihood for diagenetic re-mobilisation of this P at depth (indicated by increasing ratios of excess silica to opal-bound P). Average reactive P MARs at Site U1341 increase by ~ 25% if opal-bound P is accounted for, but decrease by ~ 25% if 50% of the extracted CFA fraction (based on the lowest CFA value at Site U1341) is assumed to be detrital. Combining our results with literature data, we present a qualitative perspective of terrestrial CFA and opal-bound P deposition in the modern ocean. Riverine CFA input has mostly been reported from continental shelves and margins draining P-rich lithologies, while eolian CFA input is found across wide ocean regions underlying the Northern Hemispheric "dust belt". Opal-bound P burial is important in the Southern Ocean, North Pacific, and likely in upwelling areas. Shifts in detrital CFA and opal-bound P deposition across ocean basins likely occurred over time, responding to changing weathering patterns, sea level, and biogenic opal deposition.

Impacts of seawater acidification on mantle gene expression patterns of the Baltic Sea blue mussel: implications for shell formation and energy metabolism, link to supplementary material

Marine organisms have to cope with increasing CO2 partial pressures and decreasing pH in the oceans. We elucidated the impacts of an 8-week acclimation period to four seawater pCO2 treatments (39, 113, 243 and 405 Pa/385, 1,120, 2,400 and 4,000 µatm) on mantle gene expression patterns in the blue mussel Mytilus edulis from the Baltic Sea. Based on the M. edulis mantle tissue transcriptome, the expression of several genes involved in metabolism, calcification and stress responses was assessed in the outer (marginal and pallial zone) and the inner mantle tissues (central zone) using quantitative real-time PCR. The expression of genes involved in energy and protein metabolism (F-ATPase, hexokinase and elongation factor alpha) was strongly affected by acclimation to moderately elevated CO2 partial pressures. Expression of a chitinase, potentially important for the calcification process, was strongly depressed (maximum ninefold), correlating with a linear decrease in shell growth observed in the experimental animals. Interestingly, shell matrix protein candidate genes were less affected by CO2 in both tissues. A compensatory process toward enhanced shell protection is indicated by a massive increase in the expression of tyrosinase, a gene involved in periostracum formation (maximum 220-fold). Using correlation matrices and a force-directed layout network graph, we were able to uncover possible underlying regulatory networks and the connections between different pathways, thereby providing a molecular basis of observed changes in animal physiology in response to ocean acidification.

"A noite branca", between the Documentary and Fictional: the Silenced Account of the Blue Division

The article explores the ambiguous phenomenological status of the novel A noite branca (The White Night) by Francisco Fernández Naval, published in Galician in 2012. This ambiguity is produced by the discursive hybridity of the novel and by the vague ontological status of facts narrated and by several characters. The clarification of the strategies of the said ambiguity, and the originality of the subject, in the whole of Galician narrative about the memory of Civil War and Postwar can tightly evaluate the literary merits of the novel.

Correlation between the photocatalysed oxidation of methylene blue in solution and the reduction of resazurin in a photocatalyst activity indicator ink (Rz Paii)