Dissolution and phosphate-induced transformation of ZnO nanoparticles in synthetic saliva probed by AGNES without previous solid-liquid separation. Comparison with UF-ICP-MS

The variation over time of free Zn2+ ion concentration in stirred dispersions of ZnO nanoparticles (ZnO NPs) prepared in synthetic saliva at pH 6.80 and 37 degrees C was followed in situ (without solid liquid separation step) with the electroanalytical technique AGNES (Absence of Gradients and Nernstian Equilibrium Stripping). Under these conditions, ZnO NPs are chemically unstable due to their reaction with phosphates. The initial stage of transformation (around 5-10 h) involves the formation of a metastable solid (presumably ZnHPO4), which later evolves into the more stable hopeite phase. The overall decay rate of ZnO NPs is significantly reduced in comparison with phosphate-free background solutions of the same ionic strength and pH. The effective equilibrium solubilities of ZnO (0.29-0.47 mg.L-1), as well as conditional excess-ligand stability constants and fractional distributions of soluble Zn species, were determined in the absence and presence of organic components. The results were compared with the conventional ultrafiltration and inductively coupled plasma-mass spectrometry (UF-ICP-MS) methodology. AGNES proves to be advantageous in terms of speed, reproducibility, and access to speciation information. KeywordsThis work was supported by the Spanish Ministry MINECOunder Grant No. CTM2016-78798 and European UnionSeventh Framework Programme FP7-NMP.2012.1.3-3 underGrant No. 310584 (NANoREG). FQ gratefully acknowledgesa grant from AGAUR

Ampliació i remodelació del Presbiteri de la Catedral de Girona

Nau gòtica de la Catedral de Girona. Degut a l’adaptació a les prescripcions del Concili Vaticà II, es va ampliar el presbiteri de la Catedral de Girona fins al límit de les tres naus, i situar-hi les peces històriques (Ara romànica s. XI; Baldaquí del mestre Bartomeu, 1320-1362; Retaule 1320-1380), mantenint la Cadira de Carlemany s.XI, ideant un Ambó a partir d’un fragment de la portalada romànica, i integrant-hi la resta de mobiliari litúrgic (cadiram dels canonges, ciri pasqual, etc.). El projecte es planteja des de l’austeritat, simplicitat de línies i materials, i amb la disposició òptima de les peces de la litúrgica, tot mantenint al màxim la relació entre elles. Els condicionants de la intervenció són la reversibilitat, la desmuntabilitat dels materials (la base sobre la que es construeix està ocupada per una sèrie de làpides), així com la visibilitat tant de les peces com dels celebrants. Per les condicions abans descrites, es proposa una intervenció amb un únic material (fusta de roure massís tenyit color noguera) i a manera de gran catifa sobre l’enllosat de la nau, en la que se situen l’ambó, l’ara romànica i el baldaquí; i el nou mobiliari format pel cadiram per a canonges i sacerdots concelebrants, que s’integra amb la base general de fusta. Per al suport de la resta d’elements de la litúrgia, sols s’empra l’acer, material la neutralitat del qual, dóna més rellevància als elements històrics de pedra.Peer Reviewe

Computing steady-state metal flux at microorganism and bioanalogical sensor interfaces in multiligand systems. A reaction layer approximation and its comparison with the rigorous solution

In complicated environmental or biological systems, the fluxes of chemical species at a consuming interface, like an organism or an analytical sensor, involve many coupled chemical and diffusion processes. Computation of such fluxes thus becomes difficult. The present paper describes an approximate approach, based on the so-called reaction layer concept, which enables one to obtain a simple analytical solution for the steady-state flux of a metal ion at a consuming interface, in the presence of many ligands, which are in excess with respect to the test metal ion. This model can be used for an unlimited number of ligands and complexes, without limit for the values of the association/dissociation rate constants or diffusion coefficients. This approximate solution is compared with a rigorous approach for the computation of the fluxes based on an extension of a previously published method (J. Galceran, J. Puy, J. Salvador, J. Cecília, F. Mas and J. L. Garcés, Phys. Chem. Chem. Phys., 2003, 5, 50915100). The comparison is performed for a very wide range of the key parameters: rate constants and diffusion coefficients, equilibrium constants and ligand concentrations. Their combined influence is studied in the whole domain of fully labile to non-labile complexes, via two combination parameters: the lability index, L, and the reaction layer thickness, μ. The results show that the approximate solution provides accurate results in most cases. However, for particular combinations of metal complexes with specific values of L or μ, significant differences between the approximate and rigorous solutions may occur. They are evaluated and discussed. These results are important for three reasons: (i) they enable the use of the approximate solution in a fully reliable manner, (ii) when present, the differences between approximate and rigorous solution are largely due to the coupling of chemical reactions, whose importance can thus be estimated, (iii) due to its simple mathematical expression, the individual contribution of each metal species to the overall flux can be computed

Dynamics of trace metal sorption by an ion-exchange chelating resin described by a mixed intraparticle/film diffusion transport model. The Cd/Chelex case

The time-evolution of Cd2+ ion sorption by Chelex 100 resin was studied in batch experiments as a function of time, pH, ionic strength, stirring rate, mass of resin and initial metal ion concentration. In the experimental conditions, the amount of resin sites are in excess with respect to the amount of metal ion, leading to extensive depletion of metal in bulk solution when equilibrium is reached. The data were described using a mixed control mass transport model in finite volume conditions (MCM) that includes explicitly both intraparticle and film diffusion steps. Exact numerical computations and a new approximate analytical expression of this model are reported here. MCM successfully predicts the influence of pH and ionic strength on the experimental Cd(II)/Chelex kinetic profiles (which cannot be justified by a pure film diffusion controlled mechanism) with a minimum number of fitting parameters. The overall diffusion coefficient inside the resin was modelled in terms of the Donnan factor and the resin/cation binding stability constant. The values of the latter coefficient as a function of pH and ionic strength were estimated from the Gibbs-Donnan model. Even though MCM is numerically more involved than models exclusively restricted to film or intraparticle diffusion control, it proves to be accurate in a wider range of values of the mass transfer Biot number and solution/resin metal ratios.The authors gratefully acknowledge support for this research from the Spanish Ministry MINECO (Projects CTM2013-48967 and CTM2016-78798) and by the “Comissionat d'Universitats i Recerca de la Generalitat de Catalunya” (2014SGR1132). FQ acknowledges a grant from AGAUR