Antimony is a toxic element which is mostly found in two oxidation states (III and V) in environmental, biological and geological samples. Antimony may form various inorganic and organic compounds that exhibit differences in analytical behavior, toxicity and mobility / inorganic compounds of antimony are more toxic than organic forms and toxicity of Sb(III) has been shown to be 10 times higher than that of Sb(V). Therefore selective determination of Sb(III) and Sb(V) is required in environmental and biological samples. Hydride generation atomic absorption spectrometry is a sensitive, fast and economical technique for the determination of antimony at trace level. A possible non-chromatographic method for antimony speciation is hydride generation atomic absorption spectrometry that is based on the relatively slow kinetics of hydride formation from Sb(V). In this study, continuous flow hydride generation method for the determination of antimony was developed and hydride generation conditions were optimized. Analyte solution was prepared in 0.050 mol/L HCl and 1.2% (w/v) NaBH4 stabilized in 0.30% (w/v) NaOH was used as a reductant solution. Inorganic antimony speciation conditions were determined by continuous flow HGAAS system. For the pre-reduction of Sb(V) to Sb(III), 8.0% (w/v) potassium iodide (KI) and 0.10% (w/v) ascorbic acid were used. Further speciation study was also carried out using Ir coated W-coil Atom Trap Hydride Generation Atomic Absorption Spectrometry. Tungsten coil atom trap was used to enhance the sensitivity. Tungsten coil surface was treated with Ir and totally 250 &amp / #956 / g 1000 mg/L Ir stock solution was used for coating of tungsten coil. LOD and LOQ values were calculated as 152 pg/mL and 508 pg/mL according to 120 seconds trapping. 128 and 37 fold enhancement were obtained for 120 seconds collection with respect to W-coil-ETAAS and ETAAS, respectively.

Hydride generation technique is frequently used for the detection of elements as As, Se, Sb, Sn, Bi, Ge, Te and Pb that form volatile hydrides in solution using a reductant. In this study, a novel quartz trap for on-line preconcentration of volatile analyte species was designed. Pb, Sb and Cd were selected as analyte elements and chemical vapour generation technique was employed for generation of their volatile species in flow systems. The trapping medium was formed by external heating of either the inlet arm of the quartz tube atomizer or a separate cylindirical quartz tube. Generated analyte species were trapped on quartz surface heated to the collection temperature and the collected species were revolatilized when the trap was heated further to releasing temperature and hydrogen gas was introduced in the trapping medium. The conventional quartz T-tube and multiple microflame quartz tube were employed as atomizers. The influence of relevant experimental parameters on the generation, collection and revolatilization efficiencies was investigated. Optimum conditions, performance characteristics of the trap and analytical figures of merit are presented. Experimental design was used for optimizations in some cases. Standard reference materials were analyzed to assess the accuracy of the proposed method. For a collection period of 1.0 minute for Pb, 2.0 minutes for Sb and 3.0 minutes for Cd, 3&amp / #963 / limit of detections, in pg ml-1, were 19, 3.9 and 1.8, respectively. In cases of Sb and Cd, the limits of detections obtained are the same as the best attained with in-situ trapping in graphite furnaces.

Vapor generation in atomic spectrometry is a well established technique for the determination of elements that can be volatilized by chemical reactions. In-situ trapping in graphite furnaces is nowadays one of the most popular methods to increase the sensitivity. In this study, resistively heated W-coil was used as an online trap for preconcentration and revolatilization of volatile species of Bi, Cd and Pb. The collected analyte species were revolatilized rapidly and sent to a quartz Ttube atomizer for AAS measurement. Although the nature of revolatilized species of Bi and Pb are not clear, they are probably molecular since they can be transported at least 45 cm without any significant decrease in the peak height values. However, cadmium is revolatilized from the trap surface as atoms. The experimental parameters were optimized for the highest vapor generation, trapping and revolatilization efficiencies. The concentration limits of detection calculated by the 3 of blank solution were found to be 0.0027, 0.0040 and 0.015 ng/mL for Bi (18 mL), Cd (4.2 mL) and Pb (2 mL), respectively / enhancement factors in the sensitivity were 130, 31 and 20, respectively. These values are comparable with those obtained by in-situ trapping in graphite furnaces or even ICP-MS found in the literature or better. Sensitivity can be improved further for Bi and Cd using larger sample volumes, but purification of blank is required for Pb. Certified standard reference materials were analyzed for the assessment of accuracy of developed method.

Le début du 21e siècle a vu naître un intérêt croissant pour la problématique des résidus de médicaments dans les milieux aquatiques. L’apparition de nouvelles technologies analytiques permettant la détection et la quantification de molécules à l’état d’ultra-traces a fortement contribué à cette expansion. Ces améliorations technologiques ont permis la recherche et la quantification de nombreux xénobiotiques dans les différents compartiments aquatiques. Depuis une quinzaine d’années, l’attention des équipes de recherche s’est ainsi portée sur les résidus de médicaments à usage humain ou vétérinaire. La faune et la flore aquatiques sont ainsi exposées à des mélanges de composés certes à très faibles doses (souvent de l’ordre de quelques ng à quelques centaines de ng) mais en continu et les effets de cette exposition sont très peu documentés. Ces contaminants font partie des polluants émergents et il n’existe actuellement pasde réglementation en Europe concernant leur présence dans l’environnement. La contamination des milieux aquatiques par les résidus de médicaments à usage humain est souvent le signe d’une urbanisation importante et les cours d’eau soumis à de fortes pressions domestiques sont des sitesd’étude privilégiés. Néanmoins, les données concernant les milieux ruraux sont encoreparcellaires bien qu’ils représentent les quatre cinquièmes du territoire français. Les travaux de cette thèse ont pour objectif premier d’établir un état des lieux des ressources en eau d’un territoire à dominante rurale, le département de la Dordogne. Pour répondre à cette problématique, la recherche de résidus de médicaments s'est orientée sur une liste de 40 molécules comprenant des hypolipidémiants, des antibiotiques, des béta-bloquants, des anti-inflammatoires non stéroïdiens, des anticancéreux, etc. Une méthode chromatographique multi-résidus (pré-concentration en ligne - LC-MS/MS) a été développée et validée pour les eaux de surface. En accord avec la Directive européenne Cadre sur l'Eau (DCE), des sites ont été échantillonnés tous les mois pendant un an (2011) sur six cours d'eau majeurs du département de la Dordogne de manière à déterminer leur état écologique (physico-chimique et biologique).Parallèlement, la caractérisation des résidus de médicaments a été réalisée sur ces mêmes échantillons. Les différentes campagnes de mesure ont permis d'identifier les principales zones impactées par les composés pharmaceutiques et ont également montré des corrélations linéaires avec d'autres paramètres (ions ammonium, phosphore, etc.).Suite aux premiers résultats obtenus lors de l'état des lieux du département de laDordogne, une étude complémentaire focalisée sur la présence des résidus de médicaments dansl'Isle a été menée en parallèle. Elle a permis de caractériser les voies d’introduction des résidus de médicaments et mieux comprendre l’impact de la ville de Périgueux sur l’Isle. Ainsi, un des objectifs a été de caractériser la présence de composés pharmaceutiques dans cette rivière et de comprendre l’origine de ces molécules par l’identification des effluents domestiques des stationsd’épuration présentes dans la zone urbaine. / The beginning of the 21th century saw a growing interest for pharmaceuticals in aquaticsystems. The development of new analytical technologies allowing detection and quantification ofcompounds at ultra-trace levels mostly contributed to this expansion. These technologicalimprovements allowed to evidence and quantify many xenobiotics in various aquaticcompartments. Since about fifteen years, research teams focused their attention to human orveterinary pharmaceuticals. These contaminants are among emerging pollutants and no regulationexists in Europe concerning their presence in the environment. The presence of few tenths ofpharmaceuticals has been demonstrated. Living organisms in aquatic bodies are thereforeexposed to mixtures of compounds certainly at low doses (often between few ng and fewhundreds of ng) but continuously and the effects of this exposure are few documented. Thecontamination of aquatic systems by pharmaceuticals is usually the sign of an importanturbanization and streams with strong domestic pressures are often chosen as sampling sites inscientific studies. Nevertheless, the data concerning rural areas are still scarce although theyrepresent four fifth of the French territory.This work aims to establish a current situation of water resources of a rural territory, theDordogne administrative department. The occurrence of 40 pharmaceuticals including lipidregulators, antibiotics, β-blockers, non-steroidal anti-inflammatories, anticancer drugs, etc inseveral streams has studied with a multi-residue analytical method involving an on-linepreconcentration, a chromatographic separation followed by tandem MS/MS detection. Themethod has been validated for surface waters according to COFRAC requirements.Many sites were sampled every month during one year (2011) on six major streams of theDordogne department. The various campaigns allowed identifying the main areas contaminatedby pharmaceuticals and some linear correlations with other parameters (ammonium ion,phosphorus, etc.) have been evidenced.Beside the results obtained over all the Dordogne department, a focus on the presence ofpharmaceuticals in Isle river, around Périgueux, the main urban area of Dordogne, was led. Thissurvey allowed characterizing the introduction ways of pharmaceuticals and better understandingthe impact of the city of Périgueux on the river Isle.