Valorisation of spent tire rubber as carbon adsorbents for Pb(II) and W(VI) in the framework of a Circular Economy.

Spent tire rubber-derived chars and their corresponding H3PO4 and CO2-activated chars were used as adsorbents in the recovery of Pb(II) ion and (W(VI)) oxyanion from synthetic solutions. The developed chars (both raw and activated) were thoroughly characterized to have insight about their textural and surface chemistry properties. H3PO4-activated chars presented lower surface areas than the raw chars and an acidic surface chemistry which affected the performance of these samples as they showed the lowest removals of the metallic ions. On the other hand, CO2-activated chars presented increased surface areas and increased mineral content compared to the raw chars, having presented higher uptake capacities for both Pb(II) (103-116 mg/g) and W(VI) (27-31 mg/g) ions. Cation exchange with Ca, Mg and Zn ions was appointed as a mechanism for Pb removal, as well as surface precipitation in the form of hydrocerussite (Pb3(CO3)2(OH)2). W(VI) adsorption might have been ruled by strong electrostatic attractions between the negatively charged tungstate species and the highly positively charged carbons' surface.The results shown in this work allow concluding that the valorisation of spent tire rubber through pyrolysis and the subsequent activation of the obtained chars is an alternative and a feasible option to generate adsorbent materials with a high uptake capacity of critical metallic elements.

Unraveling the reaction mechanism of silver ions reduction by chitosan from so far neglected spectroscopic features.

Metallic silver nanoparticles were synthesized in aqueous solution using chitosan, as both reducing and stabilizing agent, and AgNO3 as silver precursor aiming the production of solid ultra-thin films. A systematic characterization of the resulting system as a function of the initial concentrations was performed. The combination of UV-vis absorption - and its quantitative analysis - with X-ray photoelectron spectra, light scattering measurements and atomic force microscopy allowed obtaining a rational picture of silver reduction mechanism through the identification of the nature of the formed reduced/oxidized species. Nanoparticle mean sizes and sizes distributions were rather independent from the precursors initial absolute and relative concentrations ([AgNO3]/[chitosan]). This work clarifies some points of the mechanism involved showing experimental evidence of the early stages of the very fast silver reduction in chitosan aqueous solutions through the spectral signature of the smallest silver aggregate (Ag2+) even at room temperature. The characterized system is believed to be useful for research fields where silver nanoparticles completely exempt of harmful traces of inorganic ions, coming from additional reducing agents, are needed, especially to be used in biocompatible in films.

Adhesion of façade coating colonisers, as mediated by physico-chemical properties.

The adhesion of Klebsormidium flaccidum, Stichococcus bacillaris and Chlorella cf. mirabilis, three strains of green microalgae isolated from biofilms on façade coatings were investigated in a parallel plate flow chamber. The model surfaces tested were glass slides, and -CH(3) (mediated by octadecyltrichlorosilane [OTS] and hexamethyldisilazane [HMDZ] modification) and -NH(2) (aminopropyltriethoxysilane [APS] modification) terminated self-assembled monolayers. Algal physicochemical properties were evaluated by the microbial adhesion to solvents (MATS) assay and by contact angle measurements. The model surfaces were characterised by X-ray photoelectron spectroscopy analysis and by contact angle measurements. Predicted adhesion trends were then compared to in vitro measurements. The adhesion strength of the three algal strains followed the trend: APS > OTS > HMDZ > glass. The adhesion process thus seemed to be mediated by hydrophobic and electrostatic interactions, and was shown to be influenced by the algal culture age and the initial contact time.