Bilateral project Italy-USA "Hydrogen transport through nano-structured electrodes for energy application" : progress report and perspectives

ENEA, the University of Missouri, NRL and SRI are cooperating within the frame of an International Project supported by the Italian Ministry of Foreign Affairs (Joint Declaration following the 10th Review Conference on Scientific and Technological Cooperation between Italy and the United States of America for the years 2011-2013). The research field is on Metal Hydrogen Systems for Energy Applications. The research project is oriented to improve the electrochemical processes involving hydrogen as energy vector. The functional effects of specific materials, characterized by a very high chemical activity and large mass transfer for hydrogen, have been investigated in order to have enhanced hydrogen kinetics . The material science involved in such a study is strongly in touch with the scientific program of ICC-18. The proposed approach is to develop properly shaped and structured layers of active metals to be nested on the electrodes, in order to optimize the effect of the surface morphology on the electrodes kinetics. The cooperation between ENEA and University of Missouri was officially activated by the Project. The exchange of scientist visits from the beginning of the Project up to now is quantified in more than 100 days by considering both Countries. The joint work performed within a stable cooperative frame, provided by the Project, gives the proper conditions for improving the technological and scientific relations between the Italian and American institutions

Light scattering from a rough metal surface: theory and experiment

There is still great interest in the determination of microtopographic properties of rough metallic surfaces from light scattering measurements. According to Beckmann–Kirchhoff theory a clear relationship is established between the in-plane angular scattered light intensity and the statistical properties of the surface. We discuss one way to invert this relationship, and we introduce a new iterative procedure to retrieve the height autocorrelation function even for a very rough metallic surface (rms surface roughness of the same order of the optical wavelength). The procedure is eventually applied to the experimental data of a known metallic surface for validation

On the forecasting accuracy of multivariate GARCH models

This paper addresses the question of the selection of multivariate GARCH models in terms of variance matrix forecasting accuracy with a particular focus on relatively large scale problems. We consider 10 assets from NYSE and NASDAQ and compare 125 model based one-step-ahead conditional variance forecasts over a period of 10 years using the model confidence set (MCS) and the Superior Predicitive Ability (SPA) tests. Model per- formances are evaluated using four statistical loss functions which account for different types and degrees of asymmetry with respect to over/under predictions. When consid- ering the full sample, MCS results are strongly driven by short periods of high market instability during which multivariate GARCH models appear to be inaccurate. Over rel- atively unstable periods, i.e. dot-com bubble, the set of superior models is composed of more sophisticated specifications such as orthogonal and dynamic conditional correlation (DCC), both with leverage effect in the conditional variances. However, unlike the DCC models, our results show that the orthogonal specifications tend to underestimate the conditional variance. Over calm periods, a simple assumption like constant conditional correlation and symmetry in the conditional variances cannot be rejected. Finally, during the 2007-2008 financial crisis, accounting for non-stationarity in the conditional variance process generates superior forecasts. The SPA test suggests that, independently from the period, the best models do not provide significantly better forecasts than the DCC model of Engle (2002) with leverage in the conditional variances of the returns.variance matrix, forecasting, multivariate GARCH, loss function, model confidence set, superior predictive ability

MOBILITY AND BIOAVAILABILITY OF HEAVY METALS AND METALLOIDS IN SOIL ENVIRONMENTS

In soil environments, sorption/desorption reactions as well as chemical complexation with inorganic and organic ligands and redox reactions, both biotic and abiotic, are of great importance in controlling their bioavailability, leaching and toxicity. These reactions are affected by many factors such as pH, nature of the sorbents, presence and concentration of organic and inorganic ligands, including humic and fulvic acid, root exudates, microbial metabolites and nutrients. In this review, we highlight the impact of physical, chemical, and biological interfacial interactions on bioavailability and mobility of metals and metalloids in soil. Special attention is devoted to: i) the sorption/desorption processes of metals and metalloids on/from soil components and soils; ii) their precipitation and reduction-oxidation reactions in solution and onto surfaces of soil components; iii) their chemical speciation, fractionation and bioavailability

The submarine canyons of the Argentine Continental Margin: a review of their formation and sedimentary dynamics

Los cañones submarinos son los mayores rasgos erosivos de los márgenes continentales tanto activos como pasivos. Desde los albores del siglo XX, representan un fructífero tema de debate e investigación por su gran relevancia como agentes de transferencia de sedimento y materia orgánica de continente a océano, por ser lugar de surgencia de aguas profundas, elevada producción primaria y riqueza en biodiversidad, y por ser potenciales factores de riesgo en las rupturas de infraestructuras submarinas. El presente trabajo comprende una revisión de las principales teorías de formación y evolución de los cañones submarinos así como de los procesos de interacción entre dinámica oceanográfica, flujos sedimentarios y morfologías asociadas a los cañones. El objetivo es presentar una síntesis del estado del conocimiento sobre los cañones del Margen Continental Argentino (MCA), discutir su formación y evolución en el marco de los modelos genéticos más aceptados en la actualidad así como proponer una hipótesis de trabajo vinculada a la dinámica sedimentaria del Cañón Mar del Plata (MdP), el más estudiado del margen. Este cañón, como la mayoría de los del MCA, por un lado se desarrolla exclusivamente en el talud (cañón ciego) y por el otro interrumpe un gran sistema depositacional contornítico relacionado con la circulación oceanográfica regional. De aquí que su génesis en principio se explicaría por el modelo de erosión retrogradante a partir de fenómenos de inestabilidad del talud, pero además podría funcionar como trampa de sedimento captando el material transportado por el Agua Antártica Intermedia a lo largo del talud medio. Se propone que en la Terraza Ewing, donde el cañón tiene su cabecera, podrían generarse corrientes turbidíticas que afectarían a la evolución y dinámica del cañón. Estas corrientes se encauzarían cañón abajo contribuyendo a profundizar su valle y a conformar su trazado en parte sinuoso. En los sistemas de cañones Patagonia otros factores podrían activar la génesis de los cañones submarinos. Se ha sugerido la posibilidad que irregularidades morfológicas provocadas por la acción erosiva de las corrientes contorníticas sobre el fondo puedan dar origen a los cañones de esta zona. Este mecanismo podría no limitarse exclusivamente al sistema Patagonia sino aplicarse a los demás sistemas de cañones argentinos ya que el MCA está intersectado por intensas corrientes de contorno que operan a diferentes profundidades.Submarine canyons are the most outstanding geomorphologic features of continental margins. They play a fundamental role in transferring sediment and organic matter from shallow to deep waters. Also, they influence oceanographic and sedimentary processes, interact with productivity and benthic ecosystems, and pose a serious threat to seafloor infrastructures. Submarine canyons have been described as steep-walled, sinuous valleys with V-shaped cross sections, axes sloping outward as continuously as river-cut land canyons and relief comparable to even the largest of land canyons. The understanding of the origin and evolution of submarine canyons has been matter of intense debate since the first geologists observed them characterizing both passive and active margins. Canyons have been interpreted as (1) the off-shore prolongation of river systems that during low sealevel stages migrated seaward; (2) the product of the erosion caused by gravity dense flows- called turbidity currents- produced at the shelf-slope transition; (3) the deepening of pre-existing tectonic structures (e.g. faults) and (4) the result of slope instability combined with headward erosion. The first model only explains the genesis of the breaching-shelf canyons that connect with river systems, but does not resolve the formation of those that are unrelated to fluvial input. Turbidity currents take place at the shelf break when sufficient amount of sediment is injected into the water column by (re) suspension, resulting in a flow with higher density than the surrounding waters. These high-density flows, moving down-slope under the effect of gravity, cut the valleys that finally evolve into submarine canyons. Turbidity currents, though effective agents of erosion, do not account for the formation of slopeconfined canyons. From the other side, tectonic control can apply for limited examples of canyons, which are located in specific geological contexts. Continental slopes often show scars that are left behind by instability events. Mass wasting processes may arise from fluid escape, sediment over pressure and steepening or be triggered by seismic shocks. These initial scars would evolve into rills and then into valleys by a process that combines localized slope failures, sediment funneling and headward erosion. According to this genetic model, slope-confined and shelf-breaching canyons are, respectively, the early and mature stages in the evolution of canyons, which starts with a pre-canyon rill that advances upslope by retrogressive failure and ends with the canyon cutting the shelf break. The objective of this contribution is to review the knowledge on the submarine canyons from the Argentine Continental Margin and to suggest a working hypothesis concerning the sedimentary dynamics of the Mar del Plata Canyon, by far the best known canyon of this margin. Four main systems have been described: La Plata River, Colorado-Negro (or Bahía Blanca), Ameghino (or Chubut) and Patagonia (or Deseado). Mar del Plata Canyon, belonging to the first of these systems, cuts the slope between ~1000 m (Ewing Terrace, middle slope) and ~3900 m (lower slope-continental rise transition) as a deep valley with steep walls. In its proximal sector, between 1100 and 3000 m, it shows a sinuous path whereas the thalweg is mostly linear between 3000 an 3900 m. Seismic profiles, obtained during the Meteor research cruise M78/3a, demonstrate no evidences of incisions that could suggest past fluvial connections with the canyon head. For this reason, the origin of this canyon has been explained as an example of headward erosion. During the Holocene, the sedimentation rate inside the canyon is much higher than outside. This occurs because the large amount of sediment mobilized by bottom currents along the Ewing Terrace is intercepted by the canyon. In contrast, during the Late Glacial and deglaciation phase, turbidite accumulation has been attributed to slope instability of the drift deposits at the southern flank of the canyon. In this study, we put forward the following working hypothesis: the canyon most probably generated from slope instability and retrogressive erosion. However, when the valley moved upslope and etched the Ewing Terrace (middle slope), turbidity currents might have been produced at this water depth (1000-1200 meters) by the peculiar oceanographic dynamics driven by the interaction between bottom currents and seafloor. If confirmed by future investigations, this hypothesis would account both for the turbidite deposition and the sinuous path of the canyon in its proximal sector, which is more typical, although not exclusive, for canyons routed by turbidity currents. The detailed morphological investigations, performed in the Patagonia Canyons system by a Spanish research group in 2011, add a stimulating source of discussion about canyon formation in the Argentine Margin. These authors have proposed that topographic irregularities shaped by scars resulting from the sea-floor erosion under strong contour currents and the step separating terraces located at different water depths, might be the precursors for a pre-canyon incision. This hypothesis, of great relevance in a continental margin where downslope and along-slope sedimentary processes often coexist and interact, probably apply not only to the Patagonia but also to the other, less investigated, canyons systems of the Argentine Margin.Fil: Bozzano, Graziella. Ministerio de Defensa. Armada Argentina. Servicio de Hidrografía Naval; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Martín de Nascimento, Jacobo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Austral de Investigaciones Científicas; ArgentinaFil: Spoltore, Daniela V.. Ministerio de Defensa. Armada Argentina. Servicio de Hidrografía Naval; ArgentinaFil: Violante, Roberto Antonio. Ministerio de Defensa. Armada Argentina. Servicio de Hidrografía Naval; Argentin

Moving from phenomenological to predictive modelling: Progress and pitfalls of modelling brain stimulation in-silico

Brain stimulation is an increasingly popular neuromodulatory tool used in both clinical and research settings; however, the effects of brain stimulation, particularly those of non-invasive stimulation, are variable. This variability can be partially explained by an incomplete mechanistic understanding, coupled with a combinatorial explosion of possible stimulation parameters. Computational models constitute a useful tool to explore the vast sea of stimulation parameters and characterise their effects on brain activity. Yet the utility of modelling stimulation in-silico relies on its biophysical relevance, which needs to account for the dynamics of large and diverse neural populations and how underlying networks shape those collective dynamics. The large number of parameters to consider when constructing a model is no less than those needed to consider when planning empirical studies. This piece is centred on the application of phenomenological and biophysical models in non-invasive brain stimulation. We first introduce common forms of brain stimulation and computational models, and provide typical construction choices made when building phenomenological and biophysical models. Through the lens of four case studies, we provide an account of the questions these models can address, commonalities, and limitations across studies. We conclude by proposing future directions to fully realise the potential of computational models of brain stimulation for the design of personalized, efficient, and effective stimulation strategies

Electrocatalytic properties of Pd-based nano-structured material for application in fuel cells

Fuel cells, especially low temperature fuel cells, are clean-energy devices that have high potentiality for use in electric power production and non-polluting vehicles. Platinum is commonly used as electrocatalysts in fuel cell electrodes, because of its excellent electrocatalytic activity and chemical stability. But, because of its high cost and limited resources, its use represents a bottleneck for large-scale application and commercialization of fuel cells. Palladium could be a good substitute for Pt, because of its similar chemical and physical properties, lower cost and higher abundance. Main challenges concern the development of Pd-based materials with high catalytic activity and durability at a reduced cost (i.e. metal content). Crucial technological issue is the optimization of the active surface of the catalysts, by the control of the morphology, shape and dispersion of the metal particles. The talk will describe the main results of the research activity carried out during the second year of the Italia-USA Bilateral Project in ENEA, concerning the fabrication and characterization of different kinds of nanostructured Pd-based electrocatalysts, by using both electrochemical and vacuum thin film deposition techniques

Search for Neutron Flux Generation in a Plasma Discharge Electrolytic Cell

Following some recent unexpected hints of neutron production in setups like high-voltage atmospheric discharges and plasma discharges in electrolytic cells, we present a measurement of the neutron flux in a configuration similar to the latter. We use two different types of neutron detectors, poly-allyl-diglicol-carbonate (PADC, aka CR-39) tracers and Indium disks. At 95% C.L. we provide an upper limit of 1.5 neutrons cm^-2 s^-1 for the thermal neutron flux at ~5 cm from the center of the cell. Allowing for a higher energy neutron component the largest allowed flux is 64 neutrons cm^-2 s^-1. This upper limit is two orders of magnitude smaller than what previously claimed in an electrolytic cell plasma discharge experiment. Furthermore the behavior of the CR-39 is discussed to point our possible sources of spurious signals.Comment: 4 pages, 3 figure

Scalable interconnections for remote indirect exciton systems based on acoustic transport

Excitons, quasiparticles consisting of electron-hole pairs bound by the Coulomb interaction, are a potential medium for the processing of photonic information in the solid state. Information processing via excitons requires efficient techniques for the transport and manipulation of these uncharged particles.We have carried out a detailed investigation of the transport of excitons in GaAs quantum wells by surface acousticwaves. Based on these results, we introduce here a concept for the interconnection of multiple remote exciton systems based on the long-range transport of dipolar excitons by a network of configurable interconnects driven by acoustic wave beams. By combining this network with electrostatic gates, we demonstrate an integrated exciton multiplexer capable of interconnecting, gating, and routing exciton systems separated by millimeter distances. The multiplexer provides a scalable platform for the manipulation of exciton fluids with potential applications in information processingFinancial support by DFG Project No. SA 598/

A low-cost stereo video system for measuring directional wind waves

Typical oceanographic instruments are expensive, complex to build, and hard to deploy and require constant and specialized maintenance. In this paper, we present a cheap and simple technique to estimate a three-dimensional surface elevation map, n (x, y, t), the directional spectrum, and the main sea state parameters using inexpensive smartphones. The proposed methodology uses Time Lagged Cross Correlation (TLCC) between the audio signals from two independent video records to perform the frame synchronization. This makes the system much easier to deploy, where the main requirement is a fixed or moving platform close to the sea. The time records are mostly limited by the equipment storage space and battery life, although it can be easily replaced or recharged. Here, we pose the basis for an inexpensive yet powerful stereo reconstruction device and discuss its capabilities and limitations. The smartphone system capabilities were illustrated here by near shore experiment, at Leme beach in the Southeast of Brazil, and the results were compared against a pressure sensor. For this particular setup, the root mean square error in terms of significant wave height is of the order of 11% with perfect estimation of the peak period. The results are promising and demonstrate the validity and applicability of the technique