Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.

Water reduction in waste-activated sludge by resettling and filtration in batch. Phase (1): pilot-scale experiments to optimize performance

This article describes an effective procedure for reducing the water content of excess sludge production from a wastewater treatment plant by increasing its concentration and, as a consequence, minimizing the volume of sludge to be managed. It consists of a pre-dewatering sludge process, which is used as a preliminary step or alternative to the thickening. It is made up of two discontinuous sequential stages: the first is resettling and the second, filtration through a porous medium. The process is strictly physical, without any chemical additives or electromechanical equipment intervening. The experiment was carried out in a pilot-scale system, consisting of a column of sedimentation that incorporates a filter medium. Different sludge heights were tested over the filter to verify the influence of hydrostatic pressure on the various final concentrations of each stage. The results show that the initial sludge concentration may increase by more than 570% by the end of the process with the final volume of sludge being reduced in similar proportions and hydrostatic pressure having a limited effect on this final concentration. Moreover, the value of the hydrostatic pressure at which critical specific cake resistance is reached is established.

Sol–gel copper chromium delafossite thin films as stable oxide photocathodes for water splitting

Significant effort is being devoted to the study of photoactive electrode materials for artificial photosynthesis devices. In this context, photocathodes promoting water reduction, based on earth-abundant elements and possessing stability under illumination, should be developed. Here, the photoelectrochemical behavior of CuCrO2 sol–gel thin film electrodes prepared on conducting glass is presented. The material, whose direct band gap is 3.15 eV, apparently presents a remarkable stability in both alkaline and acidic media. In 0.1 M HClO4 the material is significantly photoactive, with IPCE values at 350 nm and 0.36 V vs. RHE of over 6% for proton reduction and 23% for oxygen reduction. This response was obtained in the absence of charge extraction layers or co-catalysts, suggesting substantial room for optimization. The photocurrent onset potential is equal to 1.06 V vs. RHE in both alkaline and acidic media, which guarantees the combination of the material with different photoanodes such as Fe2O3 or WO3, potentially yielding bias-free water splitting devices.

From community approaches to single-cell genomics: the discovery of ubiquitous hyperhalophilic Bacteroidetes generalists

The microbiota of multi-pond solar salterns around the world has been analyzed using a variety of culture-dependent and molecular techniques. However, studies addressing the dynamic nature of these systems are very scarce. Here we have characterized the temporal variation during 1 year of the microbiota of five ponds with increasing salinity (from 18% to >40%), by means of CARD-FISH and DGGE. Microbial community structure was statistically correlated with several environmental parameters, including ionic composition and meteorological factors, indicating that the microbial community was dynamic as specific phylotypes appeared only at certain times of the year. In addition to total salinity, microbial composition was strongly influenced by temperature and specific ionic composition. Remarkably, DGGE analyses unveiled the presence of most phylotypes previously detected in hypersaline systems using metagenomics and other molecular techniques, such as the very abundant Haloquadratum and Salinibacter representatives or the recently described low GC Actinobacteria and Nanohaloarchaeota. In addition, an uncultured group of Bacteroidetes was present along the whole range of salinity. Database searches indicated a previously unrecognized widespread distribution of this phylotype. Single-cell genome analysis of five members of this group suggested a set of metabolic characteristics that could provide competitive advantages in hypersaline environments, such as polymer degradation capabilities, the presence of retinal-binding light-activated proton pumps and arsenate reduction potential. In addition, the fairly high metagenomic fragment recruitment obtained for these single cells in both the intermediate and hypersaline ponds further confirm the DGGE data and point to the generalist lifestyle of this new Bacteroidetes group.

Electrocatalytic reduction of CO2 to formate using particulate Sn electrodes: Effect of metal loading and particle size

The development of electrochemical processes for the conversion of CO2 into value-added products allows innovative carbon capture & utilization (CCU) instead of carbon capture & storage (CCS). In addition, coupling this conversion with renewable energy sources would make it possible to chemically store electricity from these intermittent renewable sources. The electroreduction of CO2 to formate in aqueous solution has been performed using Sn particles deposited over a carbon support. The effect of the particle size and Sn metal loading has been evaluated using cyclic voltammetry and chronoamperometry. The selected electrode has been tested on an experimental filter-press type cell system for continuous and single pass CO2 electroreduction to obtain formate as main product at ambient pressure and temperature. Experimental results show that using electrodes with 0.75 mg Sn cm−2, 150 nm Sn particles, and working at a current density of 90 mA cm−2, it is possible to achieve rates of formate production over 3.2 mmol m−2 s−1 and faradaic efficiencies around 70% for 90 min of continuous operation. These experimental conditions allow formate concentrations of about 1.5 g L−1 to be obtained on a continuous mode and with a single pass of catholyte through the cell.

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

Most of electrocatalytic reactions occur in an aqueous environment. Understanding the influence of water structure on reaction dynamics is fundamental in electrocatalysis. In this work, the role of liquid water structure on the oxygen reduction at Pt(1 1 1) electrode is analyzed in methanesulfonic (MTSA) and perchloric acids. This is because these different anions can exert a different influence on liquid water structure. Results reveal a lower ORR electrode activity in MTSA than in HClO4 solutions and they are discussed in light of anion's influence on water structural ordering. From them, the existence of an outer-sphere, rate determining, step in the ORR mechanism is suggested.

Pencil it in: pencil drawn electrochemical sensing platforms

Inspired by recent reports concerning the utilisation of hand drawn pencil macroelectrodes (PDEs), we report the fabrication, characterisation (physicochemical and electrochemical) and implementation (electrochemical sensing) of various PDEs drawn upon a flexible polyester substrate. Electrochemical characterisation reveals that there are no quantifiable electrochemical responses upon utilising these PDEs with an electroactive analyte that requires an electrochemical oxidation step first, therefore the PDEs have been examined towards the electroactive redox probes hexaammineruthenium(III) chloride, potassium ferricyanide and ammonium iron(II) sulfate. For the first time, characterisation of the number of drawn pencil layers and the grade of pencil are examined; these parameters are commonly overlooked when utilising PDEs. It is demonstrated that a PDE drawn ten times with a 6B pencil presented the most advantageous electrochemical platform, in terms of electrochemical reversibility and peak height/analytical signal. In consideration of the aforementioned limitation, analytes requiring an electrochemical reduction as the first process were solely analysed. We demonstrate the beneficial electroanalytical capabilities of these PDEs towards p-benzoquinone and the simultaneous detection of heavy metals, namely lead(II) and cadmium(II), all of which are explored for the first time utilising PDEs. Initially, the detection limits of this system were higher than desired for electroanalytical platforms, however upon implementation of the PDEs in a back-to-back configuration (in which two PDEs are placed back-to-back sharing a single connection to the potentiostat), the detection limits for lead(II) and cadmium(II) correspond to 10 μg L−1 and 98 μg L−1 respectively within model aqueous (0.1 M HCl) solutions.

Single photon emission mammography with convergent collimators

Tese de doutoramento, Engenharia Biomédica e Biofísica, Universidade de Lisboa, Faculdade de Ciências, 2016

Copyright in the EU Digital Single Market. Report of the CEPS Digital Forum. June 2013

The scope and enforcement of copyright in the digital environment have been among the most complex and controversial subjects tackled by lawmakers all over the world for the last decade. Due to the ubiquitous use of digital technology, modern regulation of copyright inherently touches on numerous areas of law and social and economic policy, including communications privacy and Internet governance. Modernising the EU’s copyright framework is considered a key step towards achieving the goal of an EU Digital Single Market in the context of the ‘Digital Agenda for Europe’, an initiative launched by the European Commission in May 2010. How can the EU make copyright fit for purpose in the Internet age? What are the most suitable and realistic policy options to achieve the objective of a Digital Single Market in the creative content sectors? To give comprehensive answers to these questions, the CEPS Digital Forum formed a Task Force on Copyright in the EU Digital Single Market to foster a multi-stakeholder dialogue on the major challenges for copyright law in the online content sector today. Drawing on the discussions and input gathered by the Task Force, this report contains the conclusions and policy recommendations organised around three main themes: licensing rules and practices in the online music and film sectors, the definition and implementation of copyright exceptions in the digital environment and the present and future of online copyright enforcement in Europe.

Assessing the Single Supervisory Mechanism: passing the point of no return for Europe's banking union. Egmont Paper No. 58, June 2013

From the Executive Summary. Europe’s financial and sovereign debt crises have become increasingly interconnected. In order to break the negative feedback loop between the two, the EU has decided to create a common supervisory framework for the banking sector: the Single Supervisory Mechanism (SSM). The SSM will involve a supervisory system including both the national supervisors and the European Central Bank (ECB). By endowing the ECB with supervisory authority over a major part of the European banking sector, the SSM’s creation will result in a shake-up of the way in which the European financial sector is being supervised. Under the right circumstances, this could be a major step forward in addressing Europe’s interconnected crises.

Atitude dos estudantes de enfermagem ao cuidar a pessoa com dor

Introdução: Cuidar da pessoa com dor é imprescindível à excelência dos cuidados de enfermagem. Refletindo sobre a natureza desses cuidados pelos estudantes, é possível promover atitudes de abertura ao sofrimento, para que como futuros profissionais respondam à necessidade de alívio. O comportamento humano é intencional, reflete preferências e para o prever podemos simplesmente examinar atitudes. Objectivo: Estimar a validade e confiabilidade da escala e analisar a atitude dos estudantes de enfermagem ao cuidar da pessoa com dor. Material e Método: Estudo analítico, correlacional e transversal, realizado com 255 estudantes da ESSV. Os dados recolhidos através de questionário autoaplicado que integra a escala: Atitude dos Estudantes de Enfermagem ao Cuidar a Pessoa com Dor. Resultados: Após o estudo psicométrico, a escala apresenta 17 itens e 2 fatores, fator 1 “Aptidão Terapêutico-Curativa” e fator 2 “Aptidão Centrada na Pessoa”. Os estudantes apresentam uma média de idade de 21.91 anos, 77.3% do sexo feminino, maioritariamente solteiros e 40.8% frequentam o 4º ano. Todos avaliam a dor nos ensinos clínicos, 86.4% com a EN e 94.9% conjuga intervenções farmacológicas e não farmacológicas, mais de 55% emprega a diminuição do ruído e luminosidade, aplicação do frio e massagem, havendo 87.5% que usa posicionamentos. Os do sexo masculino que aplicam exercícios de relaxamento e os do sexo feminino com idade ≥21 anos, do 3º ano, apresentam uma atitude mais adequada. Conclusão: A formação no tema dor ao longo do curso é preponderante no desenvolvimento de competências, mas também na aquisição de conhecimento e promoção de atitudes. Palavras chave: Estudantes de Enfermagem, Atitude; Dor; Cuidar.

Sedimentology at the continental margin of the southern Weddell Sea

During four expeditions with RV "Polarstern" at the continental margin of the southern Weddell Sea, profiling and geological sampling were carried out. A detailed bathymetric map was constructed from echo-sounding data. Sub-bottom profiles, classified into nine echotypes, have been mapped and interpreted. Sedimentological analyses were carried out on 32 undisturbed box grab surface samples, as well as on sediment cores from 9 sites. Apart from the description of the sediments and the investigation of sedimentary structures on X-radiographs the following characteristics were determined: grain-size distributions; carbonate and Corg content; component distibutions in different grain-size fractions; stable oxygen and carbon isotopes in planktic and, partly, in benthic foraminifers; and physical properties. The stratigraphy is based On 14C-dating, oxygen isotope Stages and, at one site, On paleomagnetic measurements and 230Th-analyses The sediments represent the period of deposition from the last glacial maximum until recent time. They are composed predominantly of terrigenous components. The formation of the sediments was controlled by glaciological, hydrographical and gravitational processes. Variations in the sea-ice coverage influenced biogenic production. The ice sheet and icebergs were important media for sediment transport; their grounding caused compaction and erosion of glacial marine sediments on the outer continental shelf. The circulation and the physical and chemical properties of the water masses controlled the transport of fine-grained material, biogenic production and its preservation. Gravitational transport processes were the inain mode of sediment movements on the continental slope. The continental ice sheet advanced to the shelf edge and grounded On the sea-floor, presumably later than 31,000 y.B.P. This ice movement was linked with erosion of shelf sediments and a very high sediment supply to the upper continental slope from the adiacent southern shelf. The erosional surface On the shelf is documented in the sub-bottom profiles as a regular, acoustically hard reflector. Dense sea-ice coverage above the lower and middle continental slope resulted in the almost total breakdown of biogenic production. Immediately in front of the ice sheet, above the upper continental slope, a <50 km broad coastal polynya existed at least periodically. Biogenic production was much higher in this polynya than elsewhere. Intense sea-ice formation in the polynya probably led to the development of a high salinity and, consequently, dense water mass, which flowed as a stream near bottom across the continental slope into the deep sea, possibly contributing to bottom water formation. The current velocities of this water mass presumably had seasonal variations. The near-bottom flow of the dense water mass, in combination with the gravity transport processes that arose from the high rates of sediment accumulation, probably led to erosion that progressed laterally from east to West along a SW to NE-trending, 200 to 400 m high morphological step at the continental slope. During the period 14,000 to 13,000 y.B.P., during the postglacial temperature and sea-level rise, intense changes in the environmental conditions occured. Primarily, the ice masses on the outer continental shelf started to float. Intense calving processes resulted in a rapid retreat of the ice edge to the south. A consequence of this retreat was, that the source area of the ice-rafted debris changed from the adjacent southern shelf to the eastern Weddell Sea. As the ice retreated, the gravitational transport processes On the continental slope ceased. Soon after the beginning of the ice retreat, the sea-ice coverage in the whole research area decreased. Simultaneously, the formation of the high salinity dense bottom water ceased, and the sediment composition at the continental slope then became influenced by the water masses of the Weddell Gyre. The formation of very cold Ice Shelf Water (ISW) started beneath the southward retreating Filchner-Ronne Ice Shelf somewhat later than 12,000 y.B.P. The ISW streamed primarily with lower velocities than those of today across the continental slope, and was conducted along the erosional step on the slope into the deep sea. At 7,500 y.B.P., the grounding line of the ice masses had retreated > 400 km to the south. A progressive retreat by additional 200 to 300 km probably led to the development of an Open water column beneath the ice south of Berkner Island at about 4,000 y.B.P. This in turn may have led to an additional ISW, which had formed beneath the Ronne Ice Shelf, to flow towards the Filcher Ice Shelf. As a result, increased flow of ISW took place over the continental margin, possibly enabling the ISW to spill over the erosional step On the upper continental slope towards the West. Since that time, there is no longer any documentation of the ISW in the sedimentary Parameters on the lower continental slope. There, recent sediments reflect the lower water masses of the Weddell Gyre. The sea-ice coverage in early Holocene time was again so dense that biogenic production was significantly restricted.

Stable isotope analysis of foraminifera from sediment core V23-81 (Table 2)

Oxygen and carbon isotope records from benthic and planktonic foraminifera are presented for the past 35,000 years in the northeastern Atlantic. The results support the idea that the last deglaci-ation took place in two major steps (Duplessy et al., 1981 doi:10.1016/0031-0182(81)90096-1; Mix and Ruddiman, 1985 doi:10.1016/0277-3791(85)90015-0; Ruddiman, 1987; Fairbanks, 1989 doi:10.1038/342637a0), and conflict with theories calling for a strong reduction in North Atlantic deep-water formation to explain the abrupt cooling of the Younger Dryas cold period (Broecker et al., 1985 doi:10.1038/315021a0; Rind et al., 1986 doi:10.1007/BF01277044; Broecker et al., 1988 doi:10.1029/PA003i001p00001).

(Table 2) Rate of reduction in cell size (apical length) and growth rate for seven Fragilariopsis kerguelensis strains sampled during POLARSTERN cruise ANT-XXI/3

The planktonic diatom Fragilariopsis kerguelensis plays an important role in the biogeochemical cycles of the Southern Ocean, where remains of its frustules form the largest deposit of biogenic silica anywhere in the world. We assessed the genetic identity of 26 strains, from cells collected at various sites in the Southern Ocean, using three molecular markers, LSU and ITS rDNA and rbcL. The LSU sequences were identical among the tested strains, ITS sequences were highly similar, and only one base pair difference was detected among the rbcL sequences. These results, together with a large number of successful mating experiments demonstrated that the strains belong to a single biological species. We investigated the mating system and life cycle traits of F. kerguelensis. Cell size diminished gradually in clonal strains. Gamete formation only occurred when strains of opposite mating type - within a cell size range of 7-36 µm - were mixed together. Two binucleate gametes were formed in each gametangium and gamete conjugation produced a zygote that had four nuclei and was surrounded by thin siliceous scales. Two out of the four nuclei subsequently degenerated and the zygote expanded to form an auxospore surrounded by a transverse and a longitudinal perizonium. Staining with the fluorochrome PDMPO provided for the first time a clear demonstration that the longitudinal perizonium is formed after auxospore expansion is complete. Initial cells produced within the mature auxospores were 78-101 µm in length. Various authors have shown that the average valve size of F. kerguelensis varies in sediment samples collected in regions and seasons with different primary production regimes and this parameter has thus been proposed as a biological proxy for palaeo-productivity. A better understanding of the life cycle of F. kerguelensis should help the design of future investigations aimed at testing the link between cell size distribution in the natural environment and the role that environmental factors might have in the regulation of population cell size.

An isotopic analysis of geothermal brine and calcite scaling from the Blue Mountain geothermal field, Winnemucca, Nevada

Understanding, and controlling, the conditions under which calcite precipitates within geothermal energy production systems is a key step in maintaining production efficiency. In this study, I apply methods of bulk and clumped isotope thermometry to an operating geothermal energy facility in northern Nevada to see how those methods can better inform the facility owner, AltaRock Energy, Inc., about the occurrence of calcite scale in their power plant. I have taken water samples from five production wells, the combined generator effluent, shallow cold-water wells, monitoring wells, and surface water. I also collected calcite scale samples from within the production system. Water samples were analyzed for stable oxygen isotope composition (d18O). Calcite samples were analyzed for stable oxygen and carbon (d13C) composition, and clumped isotope composition (D47). With two exceptions, the water compositions are very similar, likely indicating common origin and a well-mixed hydrothermal system. The calcite samples are likewise similar to one another. Apparent temperatures calculated from d18O values of water and calcite are lower than those recorded for the system. Apparent temperatures calculated from D47 are several degrees higher than the recorded well temperatures. The lower temperatures from the bulk isotope data are consistent with temperatures that could be expected during a de-pressurization of the production system, which would cause boiling in the pipes, a reduction in system temperature, and rapid precipitation of calcite scale. However, the high apparent temperature indicated by the D47 data suggests that the calcite is depleted in clumped isotopes given the known temperature of the system, which is inconsistent with this hypothesis. This depletion could instead result from disequilibrium isotopic fractionation during the aforementioned boil events, which would make both the apparent d18O-based and D47-based temperatures unrepresentative of the actual water temperature. This research can help improve our understanding of how isotopic analyses can better inform us about the movement of water through geothermal systems of the past and how it now moves through modern systems. Increased understanding of water movement in these systems could potentially allow for more efficient utilization of geothermal energy as a renewable resource.