Search

International audience; RATIONALE: This paper investigates the validity of the transfer of a liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the determination of veterinary medicinal products in honey and compares it with an LC/linear ion trap/Orbitrap mass spectrometry method. A descriptive statistical approach was used in order to assess whether such a transfer would succeed or fail. This approach is based on the simultaneous evaluation of the trueness and of the intermediate precision for each compound at a 95% interval of confidence of both analytical techniques. METHODS: Two grams of honey were placed in a centrifuge tube and diluted with 2.5 mL of ultra-pure water and 2.5 mL of acidified methanol with hydrochloric acid at 2 mol.mL-1 . The extract was purified with 50 mg of primary secondary amine and then analyzed using LC/MS/MS in multiple reaction monitoring (MRM) mode and LC/orbitrap high-resolution mass spectrometry in full scan mode. Both analytical techniques were compared by using the descriptive statistical approach for the determination of antimicrobial residues in honey. RESULTS: The transfer of the method showed that the Orbitrap system provides the same accurate analytical results compared with the LC/MS/MS method except for 4-epitetracycline, anhydroerythromycin A, erythromycin A enol ether, and dihydrostreptomycin. Furthermore, the LC/LTQ-Orbitrap system is capable of successfully competing with the LC/MS/MS method by additional provision of high mass resolution and mass accuracy even though it shows less sensitivity compared with the LC/MS/MS instrument. CCalpha levels for most analytes were 1.3 times higher by LC/MS/MS than those observed by LC/LTQ-Orbitrap. The method was assessed in terms of relative bias through analysis of a reference material provided by FAPAS (Food Analysis Performance and Assessment Scheme) and also through the control of several contaminated honey samples from local Lebanese markets. Satisfactory relative bias was below 22% except for tetracycline found in one sample that showed a higher bias at 29%. CONCLUSIONS: The LC/LTQ-Orbitrap method offers adequate performance in comparison with previously validated method on a LC/MS/MS system resulting in acceptance of the transfer of the method from LC/MS/MS to LC/LTQ-Orbitrap.

A new multi-residue method based on solid-phase extraction (SPE) with centrifugation was developed for determination and quantitation of 67 pesticides in water samples. Two SPE cartridges were tested: Chromabond C18 and Oasis HLB. Parameters that influence the extraction efficiency such as the eluent volume, the sample loading volume, the addition of organic solvent to water sample, sorbent drying and elute concentration were optimized. The innovation of this work was the examination of the use of a centrifugation technique in both the drying and elution steps. When combined with centrifugation, the volume of the elution solvent was reduced to 2 mL and the time for sorbent drying decreased also to 10 min under vacuum. Under the optimized conditions, this method showed good recoveries higher than 65% - 68% for the 67 analyzed pesticides using the C18 and HLB cartridges with relative standard deviations lower than 9.7% - 12.3%. Limits of quantification were between 2 and 20 ng.L–1. The simplicity of the described method, use of less of organic solvent, short procedure time, and good recoveries demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.

Antibiotics and psychiatrics residues are dumped into the environment due to their massive and inappropriate use in human and veterinary medicine either to an incomplete metabolism into organism. Surface waters and ground waters are the major receptacles of these pollutants and also represent sources of water used for human consumption. This study was specifically focused on photolysis of four pharmaceuticals compounds: two antibiotics and two psychiatrics (sulfamethazine, sulfamethoxypyridazine, amitriptyline and clomipramine) also on their oxidation by chlorine and hydroxyl radicals, two processes mainly used in water treatment.First, kinetic studies were conducted and rate constants were determined. For each pharmaceutical, different rates of degradation were observed depending on photolysis or oxidation process. To better assess pharmaceutical removal under water treatment conditions, an estimation of pharmaceutical removal in natural water was undertaken. Secondly, several degradation products formed during chlorination and photolysis were identified by LC/MS/MS and degradation pathways were proposed, Les résidus d'antibiotiques et de psychotropes sont déversés dans l'environnement, en conséquence d'une utilisation massive et souvent inadaptée de ces substances dans les domaines médicaux et vétérinaires et d’une métabolisation incomplète dans l’organisme. Les eaux de surface et les eaux souterraines sont les réceptacles majeurs de ces polluants et représentent également les sources d'eau utilisées pour la consommation humaine. Notre recherche s’est focalisée sur la phototransformation et l’oxydation par le chlore et le peroxyde d’hydrogène de quatre composés : deux antibiotiques et deux psychotropes : sulfaméthazine, sulfaméthoxypyridazine, amitriptyline et clomipramine). Ces deux derniers processus sont utilisés fréquemment dans les filières de traitement de l’eau.D’abord, une étude cinétique nous a permis à déterminer des constantes cinétiques. Pour chaque composé, une dégradation plus ou moins rapide a été observée suivant le procédé de photolyse ou d’oxydation employé. L’étude cinétique a été appliquée également sur des eaux naturelles pour prévoir le devenir des composés pharmaceutiques et estimer leur dégradation après photoréaction et chloration. Puis, de nombreux sous produits de chloration et de photolyse ont été identifiés par LC/MS/MS et des mécanismes réactionnels ont été proposés.

Antibiotics are pollutants present in aquatic ecosystems ultimate receptacles of anthropogenic substances. These compounds are studied as their persistence in the environment or their effects on natural organisms. Numerous efforts have been made worldwide to assess the environmental quality of different water resources for the survival of aquatic species, but also for human consumption and health risk related. Towards goal, the optimization of analytical techniques for these compounds in aquatic systems remains a necessity. Our objective is to develop extraction and detection methods for 12 molecules of aminoglycosides and colistin in sewage treatment plants and hospitals waters. The lack of analytical methods for analysis of these compounds and the deficiency of studies for their detection in water is the reason for their study. Solid Phase Extraction (SPE) in classic mode (offline) or online followed by Liquid Chromatography analysis coupled with Mass Spectrometry (LC/MS/ MS) is the most method commonly used for this type of analysis. The parameters are optimized and validated to ensure the best conditions for the environmental analysis. This technique was applied to real samples of wastewater treatment plants in Bordeaux and Lebanon.; Les antibiotiques sont des polluants présents dans les écosystèmes aquatiques, réceptacles ultimes des substances anthropiques. L’étude de ces composés porte sur leur rémanence dans le milieu ou leurs effets sur des organismes naturels. De nombreux efforts ont été faits à l’échelle mondiale pour l’évaluation de la qualité environnementale des différentes ressources en eau pour la survie des espèces aquatiques mais aussi pour la consommation humaine et le risque sanitaire lié. Dans ce but, l’optimisation des techniques analytiques pour ces composés dans les systèmes aquatiques demeure une nécessité. Notre objectif est de développer des méthodes d’extraction et de détection pour 12 molécules appartenant à la famille des aminoglycosides et de la colistine dans les eaux des stations d’épuration et les eaux hospitalières. L’absence des méthodes d’analyse pour ces composés ainsi que le manque des études permettant leur détection dans l’eau sont les raisons de leur étude. L’Extraction sur Phase Solide (SPE) en mode classique (hors ligne) ou en ligne, suivie d’une analyse par la Chromatographie Liquide couplée à la Spectrométrie de Masse (LC/MS/MS) est la méthode la plus couramment employée pour ce type d’analyse. Les paramètres sont optimisés et validés afin d’assurer les meilleures conditions utilisées dans les analyses environnementales. Cette technique a été appliquée sur des échantillons réels des eaux des stations d’épuration à Bordeaux et au Liban.