La production de lavande concoure au rayonnement de la région Rhône-Alpes. Les applications de l'huile essentielle (HE) de lavande reposent sur la culture de 3 espèces (L. aangustifolia, L. latifolia et L. stoechas et d'un hybride L. x intermedia) aux chémotypes marqués. Le genre Lavandula est un modèle idéal pour comprendre la structuration et l'origine de la diversité des composés organiques volatils (COV) en particulier des terpènes. Les lavandes ont l'avantage d'avoir une aire de distribution large avec des régions bioclimatiques différentes, un nombre d'espèces limité (39) ayant des caractéristiques morphologiques et écologiques variées. Pour caractériser la diversité des COV accumulés dans les espèces du genre et envisager leur évolution, nous avons analysé (GC-MS) les COV de 29 espèces (certaines pour la première fois). Comme souvent chez les plantes, la production de COV dans les inflorescences de lavande est soumise à une régulation spatio-temporelle. L'émission différentielle de COV au cours du temps chez L. angustifolia a été relevée par les agriculteurs qui ont observé une qualité d'HE différente suivant la maturité des inflorescences au moment de la récolte. Pour modéliser ces variations et les corréler avec des étapes du développement de la plante, nous avons analysé, au niveau chimique (GC-FID) et moléculaire (qPCR), les variations temporelles des principaux COV dans les feuilles et les inflorescences (plusieurs années et cultivars). En amont de ces recherches sur les COV du genre Lavandula, différent outils de bioinformatique ont été développés. En particulier, le module " MSeasy " qui permet d'automatiser le rapatriement de données de GC-MS. Ceci constitue un pré-requis pour utiliser la lavande comme modèle d'étude des COV chez les Lamiacées

In this final thesis, an existing method for analysis of chlorophenols (CP) in bottom sediments has been updated and adjusted for analysis of chlorophenols in soil. The covalent bonds between the chlorophenols and the soil matrix were broken through basic hydrolysis and the chlorophenols were then separated from the water phase through addition of sulphuric acid followed by ether extraction. The chromatography was improved through extractive acetylation of the chlorophenols. The updated method was then applied on soil samples from a contaminated area (a former sawmill in Hyttsjö, Östergötland, Sweden). The analyse was preformed by GC/MS with respect to 2-MonoCP, 4-MonoCP, 2,4-DiCP, 2,6-DiCP, 2,4,6-TriCP, 2,3,4,6-TetraCP and pentachlorophenol (PCP). Contamination of chlorophenols in nature can be explained by the former use of wood preservative chemicals based on chlorophenols. In the 1960s and the 1970s these chemicals were used in Sweden, but due to their toxicity they were banned by the Swedish government in 1978. In Hyttsjö a pentachlorophenol-based product named Santobrite was used for several years. The concentration of PCP in the soil samples from Hyttsjö varied from 0.2->1.8 ng/mg dry substance. 2,3,4,6- Tetrachlorophenol was also detected in some of the soil samples.

One trend in the ‘omics’ sciences is the generation of increasing amounts of data, describing complex biological samples. To cope with this and facilitate progress towards reliable diagnostic tools, it is crucial to develop methods for extracting representative and predictive information. In global metabolite analysis (metabolomics and metabonomics) NMR, GC/MS and LC/MS are the main platforms for data generation. Multivariate projection methods (e.g. PCA, PLS and O-PLS) have been recognized as efficient tools for data analysis within subjects such as biology and chemistry due to their ability to provide interpretable models based on many, correlated variables. In global metabolite analysis, these methods have been successfully applied in areas such as toxicology, disease diagnosis and plant functional genomics. This thesis describes the development of processing methods for the unbiased extraction of representative and predictive information from metabolic GC/MS and LC/MS data characterizing biofluids, e.g. plant extracts, urine and blood plasma. In order to allow the multivariate projections to detect and highlight differences between samples, one requirement of the processing methods is that they must extract a common set of descriptors from all samples and still retain the metabolically relevant information in the data. In Papers I and II this was done by applying a hierarchical multivariate compression approach to both GC/MS and LC/MS data. In the study described in Paper III a hierarchical multivariate curve resolution strategy (H-MCR) was developed for simultaneously resolving multiple GC/MS samples into pure profiles. In Paper IV the H-MCR method was applied to a drug toxicity study in rats, where the method’s potential for biomarker detection and identification was exemplified. Finally, the H-MCR method was extended, as described in Paper V, allowing independent samples to be processed and predicted using a model based on an existing set of representative samples. The fact that these processing methods proved to be valid for predicting the properties of new independent samples indicates that it is now possible for global metabolite analysis to be extended beyond isolated studies. In addition, the results facilitate high through-put analysis, because predicting the nature of samples is rapid compared to the actual processing. In summary this research highlights the possibilities for using global metabolite analysis in diagnosis.

Cette thèse porte sur une étude fondamentale sur le dépôt des couches minces d'organosiliciés par des Décharges à Barrière Diélectrique (DBD), un procédé très intéressant pour l'application aux textiles. La plupart des dépôts des couches d'oxyde de silicium sont déposées à partir du précurseur hexaméthyle silixone (HMDSO).De plus très peu d'études sont consacrées aux mécanismes de dépôt des couches à la pression atmosphérique. Dans cette étude les propriétés des couches minces déposées par DBD alimentées par Ar/HMDSO/O2, Ar/PMDSO (pentaméthyldisiloxane)/O2 et Ar/TMDSO (tetraméthyldisiloxane)/O2, avec différentes proportions de l'oxygène, ont été confrontées aux analyses, par GC-MS, des gaz sortant du réacteur. Nous avons trouvé que l'ajout d'O2 au gaz d'alimentation n'améliore pas l'activation du précurseur organosilicié, même s'il augmente la puissance injectée. En revanche il influence fortement la composition chimique des dépôts et favorise une forte réduction de la concentration des sous-produits dans le gaz sortant du réacteur. Sans ajout de l'O2, des couches minces obtenues contiennent beaucoup de carbone , avec rétention de la structure du précurseur de départ. En réduisant le nombre de -CH3 dans le précurseur (HMDSO>PMDSO>TMDSO), le nombre et l'abondance des sous-produits détectés dans le gaz sortant du réacteur diminuent fortement. Il semblerait que les unités de répétition diméthylsiloxane et hydrométhylsiloxane jouent un rôle important dans l'oligomérisation des trois précurseurs. Différents mécanismes d'activation, ainsi que différents procédés de formation des groupes Si-OH dans les dépôts, ont été proposés pour les trois précurseurs.

In this Masters Thesis emissions to water from diesel engines in pleasure boats when driven with alternative fuels have been investigated. Two alternative fuels, Fischer-Tropsch-diesel (FT-diesel) and a blend of FT-diesel and rapeseed methyl ester (RME) have been compared with diesel of Swedish environmental class 1 (diesel EC1). The alternative fuels have been compared using two older marine diesel engines, and water samples have been taken from the water in the exhaust system before the exhaust compounds reaches the recipient. The water samples have been analysed with gas chromatography (GC) and mass spectrometry (GC/MS), to analyse volatile and semi volatile compounds including aldehydes and ketons. To investigate the acute toxicity of the exhaust water a 24 h ecotoxicological test was preformed with the crustacean Artemia fransiscana. The results showed considerable differences in emissions of poly aromatic hydrocarbons (PAHs) and alkylated benzenes. From diesel EC1, the amounts of PAHs and alkylated benzenes were significantly higher than from pure FT-diesel and FT-diesel containing 20 % of RME. Pure FT-diesel generated the lowest amounts of PAH and alkylated benzenes. The FT-diesel containing 20 % RME generated higher amounts of benzene than diesel EC1. FT-diesel and FT-diesel with a 20 % blend of RME generated the same amount of acetone, which in turn was higher than the concentration of acetone in the exhaust water, using diesel EC1. Based on the analysis, FT-diesel is the best alternative from an exhaust emission point-of-view, concerning both the amounts and the difference in chemical composition of the combustion products released into the water. The ecotoxicological test showed no effect on the test organism using either of the samples. / Fritidsbåtsintresset är stort i Sverige och båtlivet betyder mycket för många svenskar. Tyvärr är användningen av fritidsbåtar förknippad med en rad miljöproblem. Avgasutsläpp till vatten och luft från fritidsbåtsmotorer påverkar den lokala miljön avsevärt. Gammal teknik med dålig förbränning används fortfarande i stor utsträckning. På kort sikt, innan den gamla tekniken är utbytt, är det viktigt att den äldre motorparken använder miljöanpassade bränslen för att utsläppen till sjöar och hav ska bli så skonsamma som möjligt. Det är dock viktigt att utvärdera miljöpåverkan av dessa alternativa bränslen, så att det verkligen är ett bättre alternativ ur miljösynpunkt. I detta examensarbete har utsläpp till vatten från dieselinombordsmotorer vid drift med olika bränslen undersökts. Två miljöanpassade dieselbränslen; FT-diesel (Fischer-Tropsch) och en procentinblandning av rapsmetylester (RME) i FT-diesel, har jämförts med diesel av svensk miljöklass 1 (MK1). Bränslena har testkörts i två äldre, marina dieselmotorer och prover har tagits på det avgasblandade kylvattnet innan det når recipienten. Det avgasblandade kylvattnet har analyserats med avseende på delvis flyktiga och flyktiga föreningar, aldehyder samt ketoner. Analyserna har skett med gaskromatografi och masspektormetri (GC/MS-screening) på externt laboratorium. För att testa avgasvattnets akuta giftighet har även ett akut (24h) ekotoxikologiskt test utförts på kräftdjuret Artemia fransiscana. Analysresultatet visade skillnad i utsläpp av polyaromatiska kolväten (PAH) och alkylbensener. Vid körning med diesel MK1 genererades betydligt högre halter av PAH:er och alkylbensener, än vid körning med FT-diesel och FT-diesel med 20 % inblandning av RME. Ren FT-diesel gav de lägsta halterna av PAH:er och alkylbensener. Utsläppshalterna av bensen uppvisade inte lika stor skillnad mellan de olika bränslena. Blandningen FT-diesel med 20 % RME gav lite högre halter bensen än vad diesel MK1 gjorde. Ren FT-diesel uppvisade lägst halt bensen. Utsläpp av aceton visade sig vara lika för FT-diesel och FT-diesel med 20 % RME och gav högre halter än vad diesel MK1 gjorde. Baserat på analysresultaten är FT-diesel det bästa bränslet ur emissionssynpunkt med avseende på vilka ämnen som hamnar i vattenfasen. Det ekotoxikologiska testet visade ingen skillnad mellan de olika bränslena. Avgasvatten från bränslena hade inte någon akut toxisk effekt på testdjuret.

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<p>A solid phase extraction (SPE) method was developed for simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. The developed SPE method and subsequent GC-MS analysis were used to extract, identify and quantify low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS) during aging in aqueous media. The combination of SPE and GC-MS proved to be a sensitive tool, able to detect small differences in the degradation rate during early stages of hydrolysis before any significant differences were observed by weight loss and molecular weight measurements. The detected low molecular weight products included monomers i.e. adipic acid and 1,4-butanediol for the PBA polymers and succinic acid and 1,4-butanediol for PBS. Several dimers and trimers i.e. hydroxybutyl adipate, hydroxybutyl succinate, di(hydroxybutyl) adipate, di(hydroxybutyl) succinate and hydroxybutyl disuccinate were also detected. Best extraction efficiency for 1,4-butanediol and succinic acid was achieved with a hydroxylated polystyrene-divinylbenzene resin as solid phase. Linear range for the extracted analytes was 1-500 ng/ml for adipic acid and 2-500 ng/ml for 1,4-butanediol and succinic acid. Detection and quantification limits for all analytes were between 1-2 ng/ml (S/N=3) and 2-7 ng/ml (S/N=10) respectively. Relative standard deviations were between 3 % and 7 %. Comparison of measured weight loss and the amount of monomeric products showed that weight loss during early stages of hydrolysis was mainly caused by the release of water-soluble oligomers that on prolonged ageing were further hydrolyzed to monomeric species. Significant differences in degradation rate could be assigned to degree of branching, molecular weight, aging temperature and degradation medium.</p><p>Linear and branched PBA was mixed with PVC in solution cast films to study the effects of molecular weight and branching on plasticizer efficiency. Used as polymeric plasticizer, PBA formed a semi-miscible two-phase system with PVC where the amorphous part exhibited one single glass transition temperature and the degree of polyester crystallinity was dependent on molecular weight, degree of branching and blend composition. Plasticizing efficiency was favored by higher degree of branching and a 40 weight-percent polyester composition.</p>

<p>In this final thesis, an existing method for analysis of chlorophenols (CP) in bottom sediments has been updated and adjusted for analysis of chlorophenols in soil. The covalent bonds between the chlorophenols and the soil matrix were broken through basic hydrolysis and the chlorophenols were then separated from the water phase through addition of sulphuric acid followed by ether extraction. The chromatography was improved through extractive acetylation of the chlorophenols.</p><p>The updated method was then applied on soil samples from a contaminated area (a former sawmill in Hyttsjö, Östergötland, Sweden).</p><p>The analyse was preformed by GC/MS with respect to 2-MonoCP, 4-MonoCP, 2,4-DiCP, 2,6-DiCP, 2,4,6-TriCP, 2,3,4,6-TetraCP and pentachlorophenol (PCP).</p><p>Contamination of chlorophenols in nature can be explained by the former use of wood preservative chemicals based on chlorophenols. In the 1960s and the 1970s these chemicals were used in Sweden, but due to their toxicity they were banned by the Swedish government in 1978.</p><p>In Hyttsjö a pentachlorophenol-based product named Santobrite was used for several years. The concentration of PCP in the soil samples from Hyttsjö varied from 0.2->1.8 ng/mg dry substance. 2,3,4,6- Tetrachlorophenol was also detected in some of the soil samples.</p>

Evaluation of solid-phase microextraction as an alternative official method for analysis of polymers migration. The objective this study was to compaire the official methods with solid-phase microextraction (SPME)for the analysis of compounds migrating from cross-linked polyethylene into water. A medium polarity polydimethylsiloxane/divinylbenzene (PDMS/DVB)was proved most efficient for the SPME extraction. However, when applied to water samples in contact with polyethylene, SPME proved to be immensely more sensitive and have a greater extraction range than liquid-liquid extraction (LLE). It was proved the migration of Phenol, 2,4-bis(1,1-dimethylethyl). Concentration of this compound 0,6-0,15mg/l.It was proved the migration of Cyclohexadiene-1,4-dione, 2,6-bis(1,1-dimethylethyl).

Aujourd'hui, la gestion du risque en milieu profesionnel ainsi que l'évaluation de l'exposition aux polluants, tels que les Composés Organiques Volatils (COV) présents dans l'air deviennent une nécessité tant la qualité de l'air des lieux de travail peut être à l'origine de problèmes de santé ou de maladies professionnelles reconnues. Dans le but de répondre à ces exigences de sécurité, l'Université Claude Bernard Lyon 1 a institutionnalisé et développé une Cellule Analyse Hygiène Sécurité et Environnement en lien direct avec le service SHS préexistant. Cette cellule est chargée de la mise en place d'une méthodologie de surveillance de la qualité de l'air intérieur de l'ensemble des locaux de l'université (14 sites, environ 80 laboratoires) en accord avec le code du travail et de l'environnement. Afin de pouvoir assurer l'ensemble des analyses inhérentes aux lieux de travail, le SHS a défini 45 composés comme prioritaires ajoutés à la liste du SHS et portent à 93 le nombre de COV identifiés et quantifiés. La méthode de séparation et d'identification mise en place permet d'atteindre des limites de quantification largement inférieures aux VLCT et VLEP 8 heures fixées par la législation. Des campagnes de prélèvement ont pu ainsi être organisées en collaboration avec le SHS et être lancées au sein de l'université