Chemical generation of arsane and methylarsanes with amine boranes. Potentialities for nonchromatographic speciation of arsenic.

The efficiency of chemical generation of arsanes from inorganic arsenic, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), to arsane, AsH3, monomethylarsane, CH3AsH2 (MMA), and dimethylarsane, (CH3)2AsH (DMA), has been investigated in different reaction media with the aim to better elucidate the mechanisms controlling their generation process and to find the experimental conditions to implement a nonchromatographic arsenic speciation analytical method, which is based on the selective determination of some arsenic species. Studies were performed by continuous flow hydride generation coupled with atomic spectrometry (CF-HG-AS), using different reductants such as borane-ammonia (AB), borane-tert-butylamine (TBAB), and sodium tetrahydridoborate (THB) in HCl and HClO4 media, in the presence or absence of L-cysteine (Cys). The efficiency of HG processes for MMA and DMA is mainly controlled by the reactivity of the substrates with the borane, which could be strongly influenced by the formation of ion couples. The protonation of arsane did not play a significant role in the employed reaction system. By taking advantage of the different reactivity pattern of As species in selected generation conditions, DMAA and MMAA could be selectively determined in 0.5 and 10 M HClO4 solutions, respectively, in the presence of Cys, with AB as the reducing agent. The presence of Cys as a masking agent and the peculiar reducing properties of AB ensured a good control of interferences, as far as it has been observed for Co(II), Ni(II), Cu(II), Fe(II), Fe(III). The overall time needed to complete the prereduction step has been verified for MMAA and DMAA at different acidities in order to achieve the best selectivity. The selective determination of DMAA with AB/Cys in HClO4 has been optimized and applied to certified reference materials (CRMs) of natural waters CASS-4, SLRS-4, and NASS-4 (NRCC). The estimation of DMAA concentration allows us to correct the concentration of As(III) for the interference of DMAA in the selective determination of As(III) according to a selective HG method recently reported.

Determination of thiomersal by flow injection coupled with microwave-assisted photochemical online oxidative decomposition of organic mercury and cold vapor atomic fluorescence spectroscopy.

We developed a flow injection (FI) method for the determination of thiomersal (sodium ethylmercurithiosalicylate, C9H9HgNaO2S) based on the UV/microwave (MW) photochemical, online oxidation of organic mercury, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. Thiomersal was quantitatively converted in the MW/UV process to Hg(II), with a yield of 97±3%. This reaction was followed by the reduction of Hg(II) to Hg(0) performed in a knotted reaction coil with NaBH4 solution, and AFS detection in an Ar/H2 miniaturized flame. The method was linear in the 0.01-2 µg mL(-1) range, with a LOD of 0.003 µg mL(-1). This method has been applied to the determination of thiomersal in ophthalmic solutions, with recoveries ranging between 97% and 101%. We found a mercury concentration in commercial ophthalmic solutions ranging between 7.5 and 59.0 µg mL(-1).

A multidisciplinary approach for assessing the toxicity of marine sediments: analysis of metal content and elutriate bioassays using metal bioavailability and genotoxicity biomarkers.

The goal of this article is to verify the applicability of two different biological assays for studying a coastal area that is subject to anthropogenic inputs. Phytochelatins in the marine diatom Thalassiosira weissflogii were used as a biomarker of metal bioavailability. The frequency of genetic damage in the sensitive D7 strain of the yeast Saccharomyces cerevisiae was used to estimate the mutagenic potential. Biological assays were carried out using sediment elutriates. Sediments were collected at three selected sites located in the Gulf of Follonica (Tuscany, Italy), during a 2-year sampling period: Cala Violina (reference site) and the mouths of the rivers Pecora and Cornia, named sites V, P and C, respectively. The chemical characterization of each site was determined in terms of metal concentrations (As, Cd, Cr, Cu, Ni, Pb), measured in 11 sediment samples for each site. The results showed that metal concentrations in sediments from sites C and P were 2-10 times higher than the reference values (site V, year 2004). In addition, we found generally higher metal concentrations in the 2007 sediments than in the 2008 ones, including those of site V, due to the occurrence of an unexpected pollution event. This enabled us to obtain a pollution gradient to validate the proposed bioassays. In fact, the bioassays showed a potential biological hazard in the 2007 elutriates. Significant mutagenic effects were found in samples exhibiting higher concentrations of Cd and Cr. The induction of phytochelatins in T. weissflogii correlated positively with the Cd concentration in the elutriates.

Biosynthesis of phytochelatins and arsenic accumulation in the marine microalga Phaeodactylum tricornutum in response to arsenate exposure.

The arsenate-induced synthesis of phytochelatins (PC), intracellular cysteine-rich metal-binding peptides, and its relationship with toxicity and with As accumulation in the cell have been studied in laboratory cultures of the marine microalga Phaeodactylum tricornutum. The time course of cellular PC and As in short-term exposures showed that the involvement of PC in the As detoxification as well as the pathway of cellular As depend on the extent of As accumulation and on the rate of PC synthesis. At arsenate concentrations causing As accumulation at a rate exceeding that of PC synthesis, cells seem to activate a mechanism of release of As mainly in a chemical form not complexed with PC. At arsenate concentrations at which the synthesis of PC occurs at a rate sufficient to allow a significant portion of As accumulated in the cell to be bound, the fate of cellular As seems to be mainly controlled by PC. The occurrence of these different pathways of As detoxification was discussed to explain the pattern of cellular As and PC in cells grown for three days at growth-inhibitory and at no growth-inhibitory concentration of arsenate.