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

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

Determinació de concentracions de metall lliure amb AGNES

AGNES (absence of gradients and Nernstian equilibrium stripping) és una nova tècnica electroanalítica dissenyada per determinar concentracions de metall lliure. En aquest treball es descriuen els principis teòrics de la tècnica i quina és la metodologia necessària per analitzar diferents mostres aquoses. S'ha aplicat AGNES tant a medis sintètics (anàlisi d'àcids húmics, estudi de la solubilitat de nanopartícules de ZnO) com a medis naturals (determinació de Zn lliure en vins i mostres d'aigües de mar i rius).AGNES (absence of gradients and Nernstian equilibrium stripping) is a new electroanalytical technique developed for the determination of free metal ion concentrations. In this study, the theoretical principles of the technique will be presented as well as the appropriate methodology needed for the study of aqueous samples. AGNES has been applied in both synthetic systems (analysis of humic acids, study of ZnO nanoparticles dissolution) and in natural samples (determination of free Zn in wines and sea and river waters)