Application of multivariate techniques in the optimization of a procedure for the determination of bioavailable concentrations of Se and As in estuarine sediments by ICP OES using a concomitant metals analyzer as a hydride generator

A procedure has been developed for the determination of bioavailable concentrations of selenium and arsenic in estuarine sediments employing inductively coupled plasma optical emission spectrometry (ICP OES) using a concomitant metals analyzer device to perform hydride generation. The optimization of hydride generation was done in two steps: using a two-level factorial design for preliminary evaluation of studied factors and a Doehlert design to assess the optimal experimental conditions for analysis. Interferences of transition metallic ions (Cd²⁺, Co²⁺, Cu²⁺, Fe³⁺ and Ni²⁺) to selenium and arsenic signals were minimized by using higher hydrochloric acid concentrations. In this way, the procedure allowed the determination of selenium and arsenic in sediments with a detection limit of 25 and 30 μg kg⁻¹, respectively, assuming a 50-fold sample dilution (0.5 g sample extraction to 25 mL sample final volume). The precision, expressed as a relative standard deviation (% RSD, n = 10), was 0.2% for both selenium and arsenic in 200 μg L⁻¹ solutions, which corresponds to 10 μg g⁻¹ in sediment samples after acid extraction. Applying the proposed procedure, a linear range of 0.08-10 and 0.10-10 μg g⁻¹ was obtained for selenium and arsenic, respectively. The developed procedure was validated by the analysis of two certified reference materials: industrial sludge (NIST 2782) and river sediment (NIST 8704). The results were in agreement with the certified values. The developed procedure was applied to evaluate the bioavailability of both elements in four sediment certified reference materials, in which there are not certified values for bioavailable fractions, and also in estuarine sediment samples collected in several sites of Guanabara Bay, an impacted environment in Rio de Janeiro, Brazil.     

Hybrid films of polyetherimide containing in situ grown Ag,Pd, and AgPd alloy nanoparticles: Synthesis route,morphology, and gas transport properties

In this study, bimetallic/polymer films are synthesized from polyetherimide (PEI), palladium acetate and silver nitrate for a wide range of total metal amount (from 0 to 30 wt %) and different Ag to Pd molar ratios. Hybrid precursor films are first prepared from polymer/metal complex solutions and the metal nanoparticles are then generated within the PEI matrix by annealing the precursor film under specific conditions. Reference neat PEI films and monometallic films are prepared in the same conditions. Interestingly, formation of AgPd alloys directly within the polymer films is for the first time obtained from a very simple and environmentally friendly route. Based on X‐ray diffraction and transmission electron microscopy analyses, a nanostructuration mechanism is proposed. The interactions of hydrogen towards the nanocomposites are investigated and discussed as a function of the nanoparticle composition. The impact of the nanostructuration is also studied on H₂, CO₂, and He permeation properties. Significant improvement of barrier properties is achieved. The pertinent parameters of the gas transport are identified and modelled for each gas/composite system. Finally, from both morphological and gas transport analyses, it is concluded that in situ generation AgPd alloys with Pd to Ag ratio above 1 leads to very interesting and promising materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1211–1220     

High-order Absorbing Boundary Conditions for anisotropic and convective wave equations

High-order Absorbing Boundary Conditions (ABCs), applied on a rectangular artificial computational boundary that truncates an unbounded domain, are constructed for a general two-dimensional linear scalar time-dependent wave equation which represents acoustic wave propagation in anisotropic and subsonically convective media. They are extensions of the construction of Hagstrom, Givoli and Warburton for the isotropic stationary case. These ABCs are local, and involve only low-order derivatives owing to the use of auxiliary variables on the artificial boundary. The accuracy and well-posedness of these ABCs is analyzed. Special attention is given to the issue of mismatch between the directions of phase and group velocities, which is a potential source of concern. Numerical examples for the anisotropic case are presented, using a finite element scheme.     

Who wants to break the hockey-stick sales pattern in the supply chain?

The hockey-stick pattern faced by suppliers consists of sales spikes at the end of each period. One of its causes is the information asymmetry that favors the retailer, who has better knowledge about the stochastic consumer demand. Because of delayed purchases, the supplier is induced to offer promotions, allowing the retailer to forward-buy at low prices. We model this situation as an infinitely repeated game, where each stage-game is subject to imperfect information. Drawing from the Nash equilibrium, we express sales and inventories in terms of demand, cost and the strategies players may adopt, and derive the conditions for a cooperative equilibrium.     

Control of Immobilization and Hybridization on DNA Chips by Fluorescence Spectroscopy

A new methodology for the analysis of DNA polymorphisms has been developed using specific oligonucleotide strand arrays bound to a solid silicon support recovered by a thin layer of silica. Arrays of directly synthesized oligonucleotides covalently fixed on Si/SiO₂ wafers have been designed at the macroscopic scale. Using suitable nucleotide-labeled units, the fluorescence emission technique has been used as an experimental control of the molecular network bound to the support and as a method for analyzing the hybridizing abilities of the corresponding oligonucleotide array. Fluorescein has allowed us to control the molecular density of the DNA strand resulting from a complete synthetic growing process. A specific protocol using both complementary and noncomplementary units labeled with two probes, Cy3 and Cy5, was used to distinguish clearly nucleotide units fixed on the array either as hybridized sequences or by the unavoidable adsorption process. The present performance of this fluorescence detection procedure will now be used with a scanning fluorescence device to perform the analysis at the microscopic scale.     

Determination of total arsenic by batch hydride generation atomic absorption spectrometry in injectable drugs containing high levels of Sb(V) as N-methylglucamine antimonate

A procedure for the determination of arsenic by batch hydride generation atomic absorption spectrometry (HG AAS) in commercial samples of injectable drugs, containing high concentrations of Sb(V), is described. The procedure is based on the complexing effect for Sb of citric, oxalic and acetic acids as reaction media. Aqua regia was used for sample digestion prior to As determination by HG AAS. The following experimental conditions for the determination of total As, as As(V), were evaluated: the acid medium and its concentration, sodium tetrahydroborate concentration, purge time, and influence of the different oxidation states of As. The effect of the delay time after mixing of sample and acid solution was also studied. Optimized conditions were: 10% (m/v) citric acid, 1.5% (m/v) sodium tetrahydroborate solution and 30 s for purge time. A delay time of 1 h was required after the digested sample had been mixed with citric acid, before As determination could be carried out. No interference on As(III) and As(V) signals was observed in the presence of up to 1 mg Sb(V). The tolerance limits for Ni(II), Cu(II) and Pb(II) were 1 mg, 100 μg and 100 μg, respectively. Recovery tests for As(III) and As(V) resulted in values between 97 and 101%. Characteristic mass and detection limit (3σ), using the recommended conditions, were 0.52 and 0.8 ng, respectively, for total As.     

About negative efficiencies in Cross Evaluation BCC input oriented models

It will be shown in this paper that the input oriented DEA BCC model can generate negative efficiencies that are usually hidden in the model. The impact of these negative efficiencies becomes obvious when using input oriented Cross Evaluation models. With the help of an example with one input and one output, the conditions for the possible occurrence of negative efficiencies will be shown. Furthermore, we will show that a small intuitive change in the BCC multipliers model, previously presented in other papers, corrects this situation. We show why this change is used and compared it with an alternative formulation, which avoid negative efficiencies, namely the Non-Decreasing Returns to Scale (NDRS) model. We also show that the formulation studied in this paper is less restrictive than the NDRS model. The study of this variation in the DEA BCC model will be complemented with the formulation of the dual envelope model. This model changes the original frontier. Using the concept of non-observed DMUs, those variations can be graphically analyzed. We have also carried out some algebraic studies concerning benchmarks, multipliers and returns to scale.     

Numerical simulation of soot optical diagnostics in non-optically thin media

The global aim of this paper consists of quantifying the effect of optically thick media on LII measurements. The paper emphasises in a simple, general two-phase case, the potential “signal trapping” due to the multiple scattering of light by soot particles. A statistical Monte Carlo approach has been used in the frame of a parametric study. This method allows testing separately the distinct influences of parameters like soot volume fraction, sphere diameter, optical path length or aggregate shape. As a first result of this numerical study, the theoretical validity range of experimental techniques can be determined when applied to a larger domain than the strictly optically thin one. A numerical tool for a better understanding of mixed and complex phenomena has been realised. Here the approach is validated on the simplest geometrical configuration; it will be applied to a real combustion chamber configuration later. PACS 78.70.-g