Development of efficient digestion procedures for quantitative determination of cobalt and molybdenum catalyst residues in carbon nanotubes

Whatever the method used for the synthesis of carbon nanotubes (CNTs), they always contain residual catalysts in variable amount. Many methods have been proposed in the literature to purify CNTs, but their efficiency strongly depends on the experimental conditions. Although the presence of residual catalysts in small amount is generally not a problem for many applications, this can become a critical issue when a high purity is required, typically for magnetic properties or for biomedical applications (because of the intrinsic toxicity of most catalysts). Quantification of the amount of residual catalysts is usually obtained by classical chemical analysis, which requires a preliminary digestion (complete mineralisation) of the CNT samples. In this work, we systematically compared 3 different digestion protocols and optimised one, reaching 100% dissolution within a very limited time (1 h) together with the requirement of only a few milligrams of sample, and safe experimental conditions. This method can be easily transferred for use in research laboratories, making accessible the quantitative analysis of CNT samples, and has been validated following ISO/ IEC 17025:2005 for linearity, specificity, intermediate precision, limits of detection and quantification

Développement de couplages chromatographie liquide -ICP-MS pour la spéciation de composés séléniés dans les compléments allimentaires

Le sélénium est un élément à la fois toxique et essentiel. Ses effets dépendent de sa teneur et de la forme chimique sous laquelle il est absorbé. Depuis des études démontrant ses bienfaits, la consommation de compléments alimentaires au sélénium a augmenté. Nous avons procédé à la spéciation des espèces séléniées dans ces produits par couplage HPLC-ICP-MS. Sept espèces séléniées, organiques et inorganiques, ont été séparées par couplage de la chromatographie échangeuse d anions à l ICP-MS. Deux types de méthodes d extraction ont été développés : l extraction en une seule étape et séquentielle. Les composés organiques, plus biodisponibles, ont été retrouvés en majorité : la sélénométhionine principalement et, à des teneurs plus faibles la sélénométhylcystéine et l acide méthaneséléninique qui ont des propriétés anticancéreuses. Parmi les espèces non identifiées, le MALDI-TOF-MS a permis de détecter des composés séléniés à m/z = 333 et m/z = 485 probablement des peptidesSelenium is both a toxic and essential element for organism. Its effects depend on the dose and the chemical form absorbed. The intake of selenium nutritional supplements has become important since a clinical study showing selenium positive effects. We develop selenium speciation analysis in nutritional supplements by coupling HPLC with ICP-MS. Seven selenized species, inorganic and organic, have been separated by coupling anion exchange chromatography with ICP-MS. Two kinds of extraction methods have been developed : the one step and the sequential protocols. Organic compounds, known to be more bioavailable, have been found in majority. Selenomethionine was the principal one and, at weaker contents, selenomethylcysteine and methanseleninic acid, which have anti-cancer properties, were found too. Among unidentified species, MALDI-TOF-MS enabled to detect selenized compounds at m/z = 333 and m/z = 485 which are propably peptidesLYON1-BU.Sciences (692662101) / SudocSudocFranceF

Determination of toxic elements (mercury, cadmium, lead, tin and arsenic) in fish and shellfish samples. Risk assessment for the consumers

International audienceAlthough fish intake has potential health benefits, the presence of metal contamination in seafood has raised public health concerns. In this study, levels of mercury, cadmium, lead, tin and arsenic have been determined in fresh, canned and frozen fish and shellfish products and compared with the maximum levels currently in force. In a further step, potential human health risks for the consumers were assessed. A total of 485 samples of the 43 most frequently consumed fish and shellfish species in Andalusia (Southern Spain) were analyzed for their toxic elements content. High mercury concentrations were found in some predatory species (blue shark, cat shark, swordfish and tuna), although they were below the regulatory maximum levels. In the case of cadmium, bivalve mollusks such as canned clams and mussels presented higher concentrations than fish, but almost none of the samples analyzed exceeded the maximum levels. Lead concentrations were almost negligible with the exception of frozen common sole, which showed median levels above the legal limit. Tin levels in canned products were far below the maximum regulatory limit, indicating that no significant tin was transferred from the can. Arsenic concentrations were higher in crustaceans such as fresh and frozen shrimps. The risk assessment performed indicated that fish and shellfish products were safe for the average consumer, although a potential risk cannot be dismissed for regular or excessive consumers of particular fish species, such as tuna, swordfish, blue shark and cat shark (for mercury) and common sole (for lead)

Investigation of the potential of the ICP-MS/MS for total and speciation analysis in petroleum fractions

International audienceThe capability of inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) to achieve total concentration and speciation using direct injection of petroleum products after solvent dilution for severely interfered isotopes was demonstrated here with different applications cases. For the direct determination of heavy elements (Z > 70) in organic matrices, the ICP-MS/MS was less sensitive than the ICP-HRMS. For light elements (Z < 40), the sensitivity was similar or better using ICP-MS/MS and for interfered elements (Si, S, Ca, Fe), the use of the two quadrupoles combined to the octopole reaction/collision cell (ORC) with He, O2 or H2 gave similar or better detection limits (LOD) than the ICP-HRMS in medium resolution. Comparable or better sensitivity were obtained replacing the 1.5 mm by the 1 mm injector diameter and especially for lighter elements (Z < 30) using the ICP-MS/MS. LOD in xylene were ranging from 0.004 μg/kg (V) to 0.9 μg/kg (Al) and appeared in the lowest values published in the literature using ICP-MS/MS in hydrocarbons. To demonstrate the performance of the ICP-MS/MS using direct injection of petroleum products after dilution in hydrocarbon solvent, three application cases were presented.Sulfur at very low levels in reformates was successfully monitored in oxygen mode using the oxide ion (32S → 48SO). The background equivalent concentration (BEC) origin was attributed to solvent contamination by sulfur and was confirmed by ultra-violet fluorescence (UVF) method. Using H2 for Ni (58Ni → 58Ni) and O2 for V (51V → 67VO) as reactant gas, the direct injection ICP-MS/MS method easily confirmed Ni and V concentrations measured using wavelength dispersive X-rays fluorescence (WDXRF) and allowed the determination of 14 elements in the asphaltene fraction, with concentrations ranging from 0.3 mg/kg (Al and Pb) to 37.4 mg/kg for Fe.For speciation of Ni, V and S, gel permeation chromatography (GPC) hyphenated to ICP-MS/MS is particularly powerful using O2 (2.5 mL/min) both for vacuum residue and hydrotreated (HDT) vacuum residue. Contrary to GPC-ICP-HRMS where two injections of sample were required (medium resolution for S and V and low resolution for Ni), GPC-ICP-MS/MS easily allowed the acquisition of the 3 elements in one mode during the same run and considerably reduce the analysis cost and time. Both for total and speciation analysis, the direct injection of petroleum products after solvent dilution ICP-MS/MS method is a significant advantage and appealing in high-volume petroleum laboratories

Biomonitoring chronic lead exposure among battery manufacturing workers in Tunisia

International audienc

Two-year survey of specific hospital wastewater treatment and its impact on pharmaceutical discharges

International audienceIt is well known that pharmaceuticals are not completely removed by conventional activated sludge wastewater treatment plants. Hospital effluents are of major concern, as they present high concentrations of pharmaceutically active compounds. Despite this, these specific effluents are usually co-treated with domestic wastewaters. Separate treatment has been recommended. However, there is a lack of information concerning the efficiency of separate hospital wastewater treatment by activated sludge, especially on the removal of pharmaceuticals. In this context, this article presents the results of a 2-year monitoring of conventional parameters, surfactants, gadolinium, and 13 pharmaceuticals on the specific study site SIPIBEL. This site allows the characterization of urban and hospital wastewaters and their separate treatment using the same process. Flow proportional sampling, solid-phase extraction, and liquid chromatography coupled with tandem mass spectrometry were used in order to obtain accurate data and limits of quantification consistent with ultra-trace detection. Thanks to these consolidated data, an in-depth characterization of urban and hospital wastewaters was realized, as well as a comparison of treatment efficiency between both effluents. Higher concentrations of organic carbon, AOX, phosphates, gadolinium, paracetamol, ketoprofen, and antibiotics were observed in hospital wastewaters compared to urban wastewaters. Globally higher removals were observed in the hospital wastewater treatment plant, and some parameters were shown to be of high importance regarding removal efficiencies: hydraulic retention time, redox conditions, and ambient temperature. Eleven pharmaceuticals were still quantified at relevant concentrations in hospital and urban wastewaters after treatment (e.g., up to 1 μg/L for sulfamethoxazole). However, as the urban flow was about 37 times higher than the hospital flow, the hospital contribution appeared relatively low compared to domestic discharges. Thanks to the SIPIBEL site, data obtained from this 2-year program are useful to evaluate the relevance of separate hospital wastewater treatment

Speciation of metals by sequential extractions of agricultural soils located near a dumpsite for prediction of element availability to vegetables

International audienc

Analyse de nanoparticules par Single Particle ICP MS en milieux organiques

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Experimental analysis of the solidification of Sn-3 wt.%Pb alloy under natural convection

International audienceA quasi-two-dimensional solidification benchmark experiment with controlled thermal boundary conditions is proposed. The experiment consists in solidifying a rectangular ingot of Sn-3 wt.%Pb alloy using two lateral heat exchangers to extract the heat flux from one or two sides of the sample. The temperature difference between the two sides of the heat exchangers may vary from 0 to 40 K and the cooling rate from 0.02 to 0.04 K/s. This slow-cooling condition has been used to promote segregation formation. An array of fifty thermocouples placed on the corresponding sample walls is used to determine the instantaneous temperature distribution. During the solidification process, the temperature field is recorded versus time and analyzed. This makes it possible to estimate the change in temperature due to natural convection, the velocity field and the solidification macrostructure and segregation behavior. After each experiment, the segregation patterns are obtained by X-ray analysis and confirmed by eutectic fraction measurements. The local solute distribution is determined by means of induction coupled plasma analysi

Recent improvements of the ICP/MS capabilities of the 8800 for the petroleum industry

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