Description of the behavior of dichloroalkanes-containing solutions with three [bXmpy][4] isomer, using the experimental information of thermodynamic properties, 1H-NMR spectral and the COSMO-RS methodology

[EN]This work studies the binaries of 1-butyl-X-methylpyridinium tetrafluoroborate [bXmpy][BF4] (X = 2, 3, and 4) with four 1,ω-dichloroalkanes, ω = 1−4, using the results obtained for the mixing properties hE and v E at two temperatures. The three isomers of the ionic liquid (IL) are weakly miscible with the 1,ω-dichloroalkanes when ω ≥ 5 and moderately soluble for ω = 4. The vE s of all the binaries present contractive effects, v E < 0, which are more pronounced with increasing temperature; the variation in vE with ω is positive, although this changes after ω = 4 due to problems of immiscibility

A dynamical system approach to data assimilation in chaotic models

The Assimilation in the Unstable Subspace (AUS) was introduced by Trevisan and Uboldi in 2004, and developed by Trevisan, Uboldi and Carrassi, to minimize the analysis and forecast errors by exploiting the flow-dependent instabilities of the forecast-analysis cycle system, which may be thought of as a system forced by observations. In the AUS scheme the assimilation is obtained by confining the analysis increment in the unstable subspace of the forecast-analysis cycle system so that it will have the same structure of the dominant instabilities of the system. The unstable subspace is estimated by Breeding on the Data Assimilation System (BDAS). AUS- BDAS has already been tested in realistic models and observational configurations, including a Quasi-Geostrophicmodel and a high dimensional, primitive equation ocean model; the experiments include both fixed and“adaptive”observations. In these contexts, the AUS-BDAS approach greatly reduces the analysis error, with reasonable computational costs for data assimilation with respect, for example, to a prohibitive full Extended Kalman Filter. This is a follow-up study in which we revisit the AUS-BDAS approach in the more basic, highly nonlinear Lorenz 1963 convective model. We run observation system simulation experiments in a perfect model setting, and with two types of model error as well: random and systematic. In the different configurations examined, and in a perfect model setting, AUS once again shows better efficiency than other advanced data assimilation schemes. In the present study, we develop an iterative scheme that leads to a significant improvement of the overall assimilation performance with respect also to standard AUS. In particular, it boosts the efficiency of regime’s changes tracking, with a low computational cost. Other data assimilation schemes need estimates of ad hoc parameters, which have to be tuned for the specific model at hand. In Numerical Weather Prediction models, tuning of parameters — and in particular an estimate of the model error covariance matrix — may turn out to be quite difficult. Our proposed approach, instead, may be easier to implement in operational models.

Modello bayesiano per la riduzione dell'incertezza nella previsione delle piene del fiume Reno

Many efforts have been devoting since last years to reduce uncertainty in hydrological modeling predictions. The principal sources of uncertainty are provided by input errors, for inaccurate rainfall prediction, and model errors, given by the approximation with which the water flow processes in the soil and river discharges are described. The aim of the present work is to develop a bayesian model in order to reduce the uncertainty in the discharge predictions for the Reno river. The ’a priori’ distribution function is given by an autoregressive model, while the likelihood function is provided by a linear equation which relates observed values of discharge in the past and hydrological TOPKAPI model predictions obtained by the rainfall predictions of the limited-area model COSMO-LAMI. The ’a posteriori’ estimations are provided throw a H∞ filter, because the statistical properties of estimation errors are not known. In this work a stationary and a dual adaptive filter are implemented and compared. Statistical analysis of estimation errors and the description of three case studies of flood events occurred during the fall seasons from 2003 to 2005 are reported. Results have also revealed that errors can be described as a markovian process only at a first approximation. For the same period, an ensemble of ’a posteriori’ estimations is obtained throw the COSMO-LEPS rainfall predictions, but the spread of this ’a posteriori’ ensemble is not enable to encompass observation variability. This fact is related to the building of the meteorological ensemble, whose spread reaches its maximum after 5 days. In the future the use of a new ensemble, COSMO–SREPS, focused on the first 3 days, could be helpful to enlarge the meteorogical and, consequently, the hydrological variability.

Uso de métodos ensemble para la predicción de la radiación solar

[EN]Se propone un modelo de radiación solar adaptativo como una nueva herramienta para la generación de mapas de radiación solar. Este introduce mejoras a los modelos existentes como la adaptación de la malla a la orografía y al albedo. Esta estrategia adaptativa nos permite generar un código eficiente que reduce el coste computacional para una precisión dada. La radiación global es obtenida como suma de sus tres componentes, la directa, la difusa y la reflejada, sobre una región de estudio bajo condiciones de cielo limpio. En este sentido, las superficies inclinadas tendrán un tratamiento diferente de las horizontales y se tendrá en cuenta el efecto de las zonas en sombra…

Desarrollo de un método ensemble para la predicción del viento a escala local usando elementos finitos

[EN]Los autores han desarrollado un modelo de viento de masa consistente especialmente diseñado para su aplicación en la escala local y en zonas de orografía compleja. Se ha dotado a este modelo de carácter predictivo usando como entrada resultados de HARMONIE. El HARMONIE es un modelo meteorológico predictivo de escala regional usado en la AEMET. Por otra parte, en los últimos años los métodos ensemble se han consolidado en la predicción meteorológica a escala regional…

Ensemble wind forecasting based on the HARMONIE model and adaptive finite elements in complex orography

[EN]Ensemble forecasting is a methodology to deal with uncertainties in the numerical wind prediction. In this work we propose to apply ensemble methods to the adaptive wind forecasting model presented in. The wind field forecasting is based on a mass-consistent model and a log-linear wind profile using as input data the resulting forecast wind from Harmonie, a Non-Hydrostatic Dynamic model used experimentally at AEMET with promising results. The mass-consistent model parameters are estimated by using genetic algorithms. The mesh is generated using the meccano method and adapted to the geometry…

Classification of suppressor additives based on synergistic and antagonistic ensemble effects

Three fundamental types of suppressor additives for copper electroplating could be identified by means of potential Transient measurements. These suppressor additives differ in their synergistic and antagonistic interplay with anions that are chemisorbed on the metallic copper surface during electrodeposition. In addition these suppressor chemistries reveal different barrier properties with respect to cupric ions and plating additives (Cl, SPS). While the type-I suppressor selectively forms efficient barriers for copper inter-diffusion on chloride-terminated electrode surfaces we identified a type-II suppressor that interacts non-selectively with any kind of anions chemisorbed on copper (chloride, sulfate, sulfonate). Type-I suppressors are vital for the superconformal copper growth mode in Damascene processing and show an antagonistic interaction with SPS (Bis-Sodium-Sulfopropyl-Disulfide) which involves the deactivation of this suppressor chemistry. This suppressor deactivation is rationalized in terms of compositional changes in the layer of the chemisorbed anions due to the competition of chloride and MPS (Mercaptopropane Sulfonic Acid) for adsorption sites on the metallic copper surface. MPS is the product of the dissociative SPS adsorption within the preexisting chloride matrix on the copper surface. The non-selectivity in the adsorption behavior of the type-II suppressor is rationalized in terms of anion/cation pairing effects of the poly-cationic suppressor and the anion-modified copper substrate. Atomic-scale insights into the competitive Cl/MPS adsorption are gained from in situ STM (Scanning Tunneling Microscopy) using single crystalline copper surfaces as model substrates. Type-III suppressors are a third class of suppressors. In case of type-land type-II suppressor chemistries the resulting steady-state deposition conditions are completely independent on the particular succession of additive adsorption. In contrast to that a strong dependence of the suppressing capabilities on the sequence of additive adsorption ("first comes, first serves" principle) is observed for the type-IIIsuppressor. This behavior:is explained by a suppressor barrier that impedes not only the copper inter-diffusion but also the transport of other additives (e.g. SPS) to the copper surface. (C) 2011 Elsevier Ltd. All rights reserved.

Potential drought stress in a Swiss mountain catchment-Ensemble forecasting of high mountain soil moisture reveals a drastic decrease, despite major uncertainties

Climate change is expected to profoundly influence the hydrosphere of mountain ecosystems. The focus of current process-based research is centered on the reaction of glaciers and runoff to climate change; spatially explicit impacts on soil moisture remain widely neglected. We spatio-temporally analyzed the impact of the climate on soil moisture in a mesoscale high mountain catchment to facilitate the development of mitigation and adaptation strategies at the level of vegetation patterns. Two regional climate models were downscaled using three different approaches (statistical downscaling, delta change, and direct use) to drive a hydrological model (WaSiM-ETH) for reference and scenario period (1960–1990 and 2070–2100), resulting in an ensemble forecast of six members. For all ensembles members we found large changes in temperature, resulting in decreasing snow and ice storage and earlier runoff, but only small changes in evapotranspiration. The occurrence of downscaled dry spells was found to fluctuate greatly, causing soil moisture depletion and drought stress potential to show high variability in both space and time. In general, the choice of the downscaling approach had a stronger influence on the results than the applied regional climate model. All of the results indicate that summer soil moisture decreases, which leads to more frequent declines below a critical soil moisture level and an advanced evapotranspiration deficit. Forests up to an elevation of 1800 m a.s.l. are likely to be threatened the most, while alpine areas and most pastures remain nearly unaffected. Nevertheless, the ensemble variability was found to be extremely high and should be interpreted as a bandwidth of possible future drought stress situations.