Simultaneous sample preparation and species-specific isotope dilution mass spectrometry analysis of monomethylmercury and tributyltin in a certified oyster tissue

cited By 58International audienceA rapid, accurate, sensitive, and simple method for simultaneous speciation analysis of mercury and tin in biological samples has been developed. Integrated simultaneous sample preparation for tin and mercury species includes open focused microwave extraction and derivatization via ethylation. Capillary gas chromatography-inductively plasma mass spectrometry (CGC-ICPMS) conditions and parameters affecting the analytical performance were carefully optimized both for species-specific isotope dilution analysis of MMHg and TBT and for conventional analysis of MBT and DBT. 201Hg-enriched monomethylmercury and 117Sn-enriched tributyltin were used for species-specific isotope dilution mass spectrometry (SIDMS) analysis. As important, accurate isotope dilution analysis requires equilibration between the spike and the analyte to achieve successful analytical procedures. Since the spike stabilization and solubilization are the most critical and time-consuming steps in isotope dilution analysis, different spiking procedures were tested. Simultaneous microwave-assisted spike stabilization and solubilization can be achieved within less than 5 min. This study originally introduces a method for the simultaneous speciation and isotope dilution of mercury and tin in biological tissues. The sample throughput of the procedure was drastically reduced by fastening sample preparation and GC separation steps. The accuracy of the method was tested by both external calibration analysis and species-specific isotope dilution analysis using the first biological reference material certified for multielemental speciation (oyster tissue, CRM 710, IRMM). The results obtained demonstrate that isotope dilution analysis is a powerful method allowing the simultaneous speciation of TBT and MMHg with high precision and excellent accuracy. Analytical problems related to low recovery during sample preparation are thus minimized by SIDMS. In addition, a rapid procedure allows us to establish a performant routine method using CGC-ICPMS technique

A Multiparametric Approach to Cerium Oxide Nanoparticle Toxicity Assessment in Non-Biting Midges

© 2019 SETAC Cerium oxide nanoparticles (CeO2 NPs) are included in the Organisation for Economic Co-operation and Development (OECD) priority list of engineered nanomaterials for assessment of their environmental impact. The present study was carried out to assess the CeO2 NP toxicity to the freshwater midge Chironomus riparius larvae at concentrations of 2.5, 25, 250, and 2500 mg of CeO2 NP/kg of sediment. Experiments were designed to assess the prolonged exposure of midges to CeO2 NPs while adhering to OECD test guideline 218. The following parameters were investigated: CeO2 NP uptake by larvae, oxidative stress parameters, in vivo genotoxic effects, and life trait parameters. Inductively coupled plasma–mass spectrometry analysis showed a significant positive correlation between the concentration of CeO2 NPs in the sediment and its uptake by the larvae. No significant mortality was observed in C. riparius, and oxidative stress was not detected. The only significantly induced sublethal effect was genotoxicity, which began to manifest at a lowest-observed-effect concentration of 25 mg kg–1 of sediment and progressively increased at higher concentrations. Our results indicate that exposure to CeO2 NP–contaminated freshwater sediments does not pose a risk to chironomids at environmentally realistic concentrations. However, the significant accumulation of CeO2 NPs by chironomid larvae may pose a risk through trophic transfer to organisms further up the food chain. Environ Toxicol Chem 2019;39:131–140. © 2019 SETAC

Modulation of Activity of Known Cytotoxic Ruthenium(III) Compound (KP418) with Hampered Transmembrane Transport in Electrochemotherapy In Vitro and In Vivo

To increase electrochemotherapy (ECT) applicability, the effectiveness of new drugs is being tested in combination with electroporation. Among them two ruthenium(III) compounds, (imH)[trans-RuCl4(im)(DMSO-S)] (NAMI-A) and Na[trans-RuCl4(ind)2] (KP1339), proved to possess increased antitumor effectiveness when combined with electroporation. The objective of our experimental work was to determine influence of electroporation on the cytotoxic and antitumor effect of a ruthenium(III) compound with hampered transmembrane transport, (imH)[trans-RuCl4(im)2] (KP418) in vitro and in vivo and to determine changes in metastatic potential of cells after ECT with KP418 in vitro. In addition, platinum compound cisplatin (CDDP) and ruthenium(III) compound NAMI-A were included in the experiments as reference compounds. Our results show that electroporation leads to increased cellular accumulation and cytotoxicity of KP418 in murine melanoma cell lines with low and high metastatic potential, B16-F1 and B16-F10, but not in murine fibrosarcoma cell line SA-1 in vitro which is probably due to variable effectiveness of ECT in different cell lines and tumors. Electroporation does not potentiate the cytotoxicity of KP418 as prominently as the cytotoxicity of CDDP. We also showed that the metastatic potential of cells which survived ECT with KP418 or NAMI-A does not change in vitro: resistance to detachment, invasiveness, and re-adhesion of cells after ECT is not affected. Experiments in murine tumor models B16-F1 and SA-1 showed that ECT with KP418 does not have any antitumor effect while ECT with CDDP induces significant dose-dependent tumor growth delay in the two tumor models used in vivo

Potential pathogenic role of beta-amyloid(1-42)-aluminum complex in Alzheimer's disease

The etiopathogenesis of Alzheimer's disease is far from being clearly understood. However, the involvement of metal ions as a potential key factor towards conformational modifications and aggregation of amyloid is widely recognized. The aim of the present study is to shed some light on the relationship between metal ions, amyloid conformation/aggregation, and their potential relationship with the conformational aspects of AD. We compare the effects of \u3b2-amyloid1-42 and its various metal complexes (\u3b2-amyloid-Al, \u3b2-amyloid-Zn, \u3b2-amyloid-Cu, \u3b2-amyloid-Fe) in human neuroblastoma cells in terms of cell viability, membrane structure properties, and cell morphology. No significant toxic effects were observed in neuroblastoma cells after 24 h treatment both with \u3b2-amyloid and \u3b2-amyloid-metals (\u3b2-amyloid-Zn, \u3b2-amyloid-Cu, \u3b2-amyloid-Fe); on the other hand, there was a marked reduction of cellular viability after treatment with \u3b2-amyloid-Al complex. In addition, treatment with \u3b2-amyloid-Al increased membrane fluidity much more than other \u3b2-amyloid-metal complexes, whose contribution was negligible. Furthermore, the cellular morphology, as observed by electron microscopy, was deeply altered by \u3b2-amyloid-Al. Importantly, \u3b2-amyloid-Al toxicity is closely and significantly associated with a great difference in the structure/aggregation of this complex with respect to that of \u3b2-amyloid alone and other \u3b2-amyloid-metal complexes. In addition, \u3b2-amyloid, as a consequence of Al binding, becomes strongly hydrophobic in character. These findings show a significant involvement of Al, compared to the other metal ions used in our experiments, in promoting a specific amyloid1-42 aggregation, which is able to produce marked toxic effects on neuroblastoma cells, as clearly demonstrated for the first time in this study