Practical aspects of the uncertainty and traceability of spectrochemical measurement results by electrothermal atomic absorption spectrometry

The determination of trace elements concentration in water by electrothermal atomic absorption spectrometry (ETAAS) is a common and well established technique in many chemical testing laboratories. However, the evaluation of measurement uncertainty results is not systematically implemented. The paper presents an easy step-by-step example leading to the evaluation of the combined standard uncertainty of copper determination in water using ETAAS. The major contributors to the overall measurement uncertainty are identified due to amount of copper in water sample that mainly depends on the absorbance measurements, due to certified reference material and due to auto-sampler volume measurements. The practical aspects how the traceability of copper concentration in water can be established and demonstrated are also pointed out.     

Correlation between Small-Angle X-ray Scattering spectra and apparent diffusion coefficients in the study of structure and interaction of sodium taurodeoxycholate micelles

Small-Angle X-ray Scattering (SAXS) and Dynamic Light Scattering (DLS) measurements were carried out on aqueous micellar solutions of the ionic biological detergent sodium taurodeoxycholate (NaTDC). Apparent diffusion coefficients (D(app)) and SAXS spectra of NaTDC 0.1 M solutions at different ionic strengths (0.1-0.3 M NaCl) were reported. A comparative analysis of SAXS spectra and D(app) data was performed to infer information on particle structure and interaction potential. Uniform particles with a spherical, an oblate, and a prolate symmetry were used to model the micelles in the data interpretation. A hard-core interaction shell of suitable thickness and a screened Coulomb potential of the electric double layer (EDL potential) were alternatively used to represent the long-range repulsive tail of the interaction potential. The Percus Yevick and the Rescaled Mean Spherical Approximation were applied. To compare the data of the two techniques, for each sample, a D(app) was calculated from the SAXS best-fitting geometrical parameters and interparticle structure factor of the micelles. Hence, a fitting procedure involving both the scattering and D(app) data was performed. The interpretation of SAXS spectra does not allow the discrimination between the oblate and the prolate symmetries of the aggregates. On the other hand, the comparison of calculated and experimental D(app) values indicates that the prolate ellipsoid is better suited to represent the micelle shape. Moreover, the agreement between calculated and experimental D(app) values is sensitively better at the lowest NaCl concentration when the EDL potential is used. A rodlike micellar growth and a progressive screening of the electrostatic interactions is testified by the trends of best-fitting parameters as a function of the added electrolyte.     

1-Adamantanethiolate monolayer displacement kinetics follow a universal form

Alkanethiol molecules in solution displace 1-adamantanethiolate self-assembled monolayers on Au{111}, ultimately leading to complete molecular exchange. Specifically, here, fast insertion of n-dodecanethiolate at defects in the original 1-adamantanethiolate monolayer nucleates an island growth phase, which is followed by slow ordering of the n-dodecanethiolate domains into a denser and more crystalline form. Langmuir-based kinetics, which describe alkanethiolate adsorption on bare Au{111}, fail to model this displacement reaction. Instead, a Johnson-Mehl-Avrami-Kolmogorov model of perimeter-dependent island growth yields good agreement with kinetic data obtained by Fourier transform infrared spectrometry over 100-fold variation in n-dodecanethiol concentration. Rescaling the growth rate at each concentration collapses all the data onto a single universal curve, suggesting that displacement is a scale-free process. The rate of displacement varies as the square-root of the n-dodecanethiol concentration across the 0.01-1.0 mM range studied.     

Robust Contour Tracking Model Using a Variational Level-Set Algorithm

In this work, we provide a novel variational level-set based object contour tracking approach. Thus, a mathematically rigorous variant of the Chan-Vese algorithm for image segmentation via geometric active contour model is proposed here. With respect to the original contour detection algorithm, the level set function ?(t) defining the evolving contour S _t  = {x; ?(t, x) = 0} is iteratively computed from a nonlinear parabolic boundary value problem that is well posed in the space of functions with bounded variations. We provide a robust mathematical justification of the proposed level-set model.     

Nonlinear PDE Model for Image Restoration Using Second-Order Hyperbolic Equations

In this article we consider a novel nonlinear PDE-based image denoising technique. The proposed restoration model uses second-order hyperbolic diffusion equations. It represents an improved nonlinear version of a linear hyperbolic PDE model developed recently by the author, providing more effective noise removal results while preserving the edges and other image features. A rigorous mathematical investigation is performed on this new differential model and its well-posedness is treated. Next, a consistent finite-difference numerical approximation scheme is proposed for this nonlinear diffusion-based approach. Our successful image denoising experiments and method comparisons are also described.     

Ergodicity for Nonlinear Stochastic Equations in Variational Formulation

This paper is concerned with nonlinear partial differential equations of the calculus of variation (see [13]) perturbed by noise. Well-posedness of the problem was proved by Pardoux in the seventies (see [14]), using monotonicity methods. The aim of the present work is to investigate the asymptotic behaviour of the corresponding transition semigroup P_t. We show existence and, under suitable assumptions, uniqueness of an ergodic invariant measure ν. Moreover, we solve the Kolmogorov equation and prove the so-called "identite du carre du champs". This will be used to study the Sobolev space W^1,2(H,ν) and to obtain information on the domain of the infinitesimal generator of P_t.     

Existence and Ergodicity for the Two-Dimensional Stochastic Magneto-Hydrodynamics Equations

The paper proves the existence of solutions to the magneto-hydrodynamics equations driven by random exterior forcing terms both in the velocity and in the magnetic field. The existence and uniqueness of an invariant measure is also obtained via coupling methods.     

On a separation criterion for cohomology groups of (q, n - q)-coronae

We give a separation theorem for (q, n - q)-coronas improving a recent result due to Laurent-Thiébaut and Leiterer.     

Reliability and Survival Analysis for Drifting Markov Models: Modeling and Estimation

Methodology and Computing in Applied Probability - In this work we focus on multi-state systems modeled by means of a particular class of non-homogeneous Markov processes introduced in Vergne (Stat...