A systematic procedure to enhance reproducibility of SWASV cycles in the determination of toxic metals in real samples

This work presents for the first time a systematic study on the optimization of the electrochemical cleaning time of a mercury film when it is used as a working electrode material in the analysis of toxic metals, such as Pb2+, used as model metal, in real samples by SWASV. The optimization study for the film’s cleaning time aimed at attaining a Pb2+ minimum value in the film after the re-oxidation step of the pre-concentrated metal, given the impossibility of complete removal of traces of the electroactive species from the film. This value was kept constant in each concentration range studied ensuring thus that all assays were performed in initial identical conditions. An assay performed on a synthetic sample was taken as reference. In it, given the absence of matrix effects, and after the electrochemical cleaning step, a direct proportionality was observed between the residual amounts of Pb2+ in the film (which for the cleaning time used was never completely removed) and Pb2+ concentration in the solution. This fact determined a high correlation between Pb2+ peak current and Pb2+ concentration which was not observed when real samples (tree leaves) were analyzed. This behavior may result from the presence of the interfering surfactants always present in real samples of complex matrix. Cleaning time optimization was performed for the following Pb2+ concentration ranges in the real samples of complex matrix: 0.006-0.020, 0.020-0.080, 0.060-0.200 and 0.100-0.600 ppb. As expected, in order to obtain identical levels of film’s cleaning efficiency, the need for longer cleaning times has been observed for higher concentrations. The optimized cleaning times for the concentration ranges under study were 120, 150, 180 e 300 s, respectively.

Toxicology of metals and metalloids

Metal toxicology is one of the oldest areas of study of toxicology and one of the oldest environmental problems. Metals and metalloids are toxic elements at the top of the priority list of hazardous substances of the Agency for Toxic Substances and Disease Registry (ATSDR). However, several gaps of knowledge still exist that are related to their toxicity, mainly concerning the mechanisms of action. This special issue affords the opportunity to bring together the results of nine papers covering several aspects of the toxicology of metals and metalloids in in vitro and in vivo experimental models, as well as in exposed populations.

Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

Diethydithiocarbamate complexes with metals used as food suplements show diferente effects in cancer cells

Diethyldithiocarbamate (ditiocarb), a metabolite of the old anti-alcoholic drug disulfiram (Antabuse), forms proteasome-inhibiting metal complexes with copper or zinc that suppress cancer cells both in vitro and in vivo. The drug has been used in a clinical trial (NCT00742911) along with copper gluconate as a dietary supplement in patients with cancer spreading to the liver. In this study, we demonstrate the effect of synthetic complexes of disulfiram with four various metals (Mn, Fe, Cr and Cu) used as food supplements. These complexes may be spontaneously formed in the blood during the use of disulfiram with divalent metals and thus may suppress the growth of cancer in vivo. The cytotoxic effect of the compounds and the compounds' ability to inhibit the cellular proteasome were tested in the osteosarcoma cell line U2OS. After 48 h, copper and manganese complexes exhibited cytotoxic effect on the cell line, in sharp contrast to both iron and chromium complexes. (C) 2014 Faculty of Health and Social Studies, University of South Bohemia in Ceske Budejovice. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Behaviour and fate of metals in urban wastewater treatment plants: a review

The concerns on metals in urban wastewater treatment plants (WWTPs) are mainly related to its contents in discharges to environment, namely in the final effluent and in the sludge produced. In the near future, more restrictive limits will be imposed to final effluents, due to the recent guidelines of the European Water Framework Directive (EUWFD). Concerning the sludge, at least seven metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) have been regulated in different countries, four of which were classified by EUWFD as priority substances and two of which were also classified as hazardous substances. Although WWTPs are not designed to remove metals, the study of metals behaviour in these systems is a crucial issue to develop predictive models that can help more effectively the regulation of pre-treatment requirements and contribute to optimize the systems to get more acceptable metal concentrations in its discharges. Relevant data have been published in the literature in recent decades concerning the occurrence/fate/behaviour of metals in WWTPs. However, the information is dispersed and not standardized in terms of parameters for comparing results. This work provides a critical review on this issue through a careful systematization, in tables and graphs, of the results reported in the literature, which allows its comparison and so its analysis, in order to conclude about the state of the art in this field. A summary of the main consensus, divergences and constraints found, as well as some recommendations, is presented as conclusions, aiming to contribute to a more concerted action of future research. © 2015, Islamic Azad University (IAU).