Dissertations / Theses on the topic 'Td-Gc-Ms/ms'

Els compostos orgànics volàtils (COV) sorgeixen dels productes químics utilitzats en les diverses etapes del procés de fabricació del cuir. Un dels objectius de la industria del cuir es minimitzar o eliminar els COV, sense reduir la qualitat del cuir. Les emissions de COV estan controlades per la legislació mitjançant l’Annex VII de la Directiva 2010/75/UE, Activitat nº13; sent el límit de 75 a 150 g de dissolvent emes per m2 de cuir acabat. Els nivells d’emissió de COV per estar d’acord amb les Millors Tècniques Disponibles (MTD) per la producció de cuir a Europa estan entre 10-25 g/m2 expressats com valors promig anuals. Aquesta tesi té com a objectiu el desenvolupament de nous mètodes analítics per la identificació i quantificació de COV emesos per nous polímers dissenyats a escala pilot per l’acabat del cuir. Aquests, son resines de poliuretà formulades per reduir la concentració de COV durant el procés de síntesi. Els productes químics que son objecte d’estudi son els següents: dipropilenlicol monometil èter (DPGME), DBE-3 (una barreja d’esters dibàsics) i trimetilamina (TEA). Per portar a terme, les noves metodologies d’assaig, aquestes es divideixen segons la matriu de la mostra. Es a dir, que assagen les resines, el film resultant d’aquestes, el cuir acabat y també es realitza un estudi de l’ambient de treball quan l’operari esta manipulant les resines i aplicant l’acabat. La microextracció en fase sòlida (SPME), s’utilitza en mostres de resina i aquesta es una tècnica de preparació de mostres utilitzada per l’extracció de COV apta per moltes aplicacions, junt amb la cromatografia de gasos per eludir i determinar aquest tipus de compostos en mostres sòlides i líquides. Els avantatges principals d’aquesta tècnica son la velocitat i alta sensibilitat; no requereix de manipulació de les mostres o procediments d’extracció amb dissolvents, sent una tècnica d’extracció respectuosa amb el medi ambient, accelera la separació i augmenta el rendiment. A més a més, aquesta tècnica es rentable en comparació amb altres mètodes d’extracció alternatius. Es van analitzar 11 mostres de resines a escala de laboratori mitjançant HS-SPME seguit de cromatografia de gasos (GC-MS). S’han identificat amb èxit DPGME i DBE-3. Els compostos s’identifiquen mitjançant un mètode quantitatiu utilitzant corbes de calibratge extern pels components objectiu. La tècnica no es eficaç per determinar el compost TEA, ja que els cromatogrames van mostrar pics de baixa resolució pel patró. La Desorció Tèrmica (TD) acoblada a la GC-MS es la metodologia utilitzada per l’assaig de films i cuir acabat amb les resines poliuretaniques sintetitzades i l’aire de l’ambient de treball mentre es realitza el procés d’aplicació. Aquesta tècnica d’extracció d’analits es altament sensible el que implica una gran millora en aquest camp d’estudi. A més a més, aquesta tècnica també es respectuosa amb el medi ambient ja que minimitza l’ús de dissolvents orgànics per l’assaig de COV i la manipulació de la mostra es mínima. Es van assajar 11 mostres de films a nivell qualitatiu i es van identificar els 3 components objecte de l’estudi, per portar a terme això es van adaptar les normes ISO 12219-3 i ISO 16000-6. També es va assajar el cuir acabat a escala pilot amb el mètode d’adquisició de dades SCAN, tant a nivell qualitatiu como quantitatiu i com a resultat de l’estudi es va determinar que la metodologia es podia millorar realitzant un escombrat SIM, ja que un dels isòmers del dissolvent DPGME no va ser viable per l’assaig quantitatiu. Es van analitzar 4 mostres de cuir a escala industrial amb un escombrat SCAN- SIM amb el qual es van poder determinar amb èxit els analits d’interès. Pel que fa a l’anàlisi de COV en l’ambient de treball es va utilitzar la norma ISO 16017-2, es va realitzar a nivell qualitatiu utilitzant dos tipus diferents de tubs sorbents per la captació de COV.
Los compuestos orgánicos volátiles (COV) surgen de los productos químicos utilizados en las diversas etapas del proceso de fabricación del cuero. Uno de los objetivos de la industria del curtido es minimizar o eliminar los COV, sin reducir la calidad del cuero. Las emisiones de COV están controladas por la legislación mediante el Anexo VII de la Directiva 2010/75/UE, Actividad nº 13; siendo el límite de 75 a 150 g de disolvente emitido por m2 de cuero acabado. Los niveles de emisión de COV para estar en conformidad con las Mejores Técnicas Disponibles (MTD) para la producción de cuero en Europa están entre 10-25 g / m2 expresados como valores promedio anuales. La presente tesis tiene como objetivo el desarrollo de nuevos métodos analíticos para la identificación y cuantificación de COV emitidos por nuevos polímeros diseñados a escala piloto para el acabado del cuero. Estos, son resinas de poliuretano formuladas para reducir la concentración de COV durante el proceso de síntesis. Los productos químicos que son objeto de estudio son los siguientes: dipropilenglicol monometil éter (DPGME), DBE-3 (una mezcla de ésteres dibásicos) y trimetilamina (TEA). Para llevar a cabo, las nuevas metodologías de ensayo, éstas se dividen según la matriz de la muestra. Es decir, que se ensayan las resinas, el film resultante de estas, el cuero acabado y también se realiza un estudio del ambiente de trabajo cuando el operario está manipulando las resinas y aplicando el acabado. La microextracción en fase sólida (SPME), se utiliza en las muestras de resina y ésta es una técnica de preparación de muestras utilizada para la extracción de COV apta para muchas aplicaciones, junto con la cromatografía de gases para eluir y determinar este tipo de compuestos en muestras sólidas y líquidas. Las principales ventajas de esta técnica son la velocidad y alta sensibilidad; no requiere manipulación de muestras o procedimientos de extracción con solventes, siendo una técnica de extracción respetuosa con el medio ambiente, acelera la separación y aumenta el rendimiento. Además, esta técnica es extremadamente rentable en comparación con los métodos de extracción alternativos. Se analizaron once muestras de resinas a escala de laboratorio mediante HS-SPME seguido de cromatografía de gases (GC-MS). Se han identificado eficazmente DPGME y DBE-3. Los compuestos se identifican mediante un método cuantitativo utilizando curvas de calibración externas para los compuestos objetivo. La técnica no es eficaz para determinar el compuesto TEA, ya que los cromatogramas mostraron picos de baja resolución para el estándar. La Desorción Térmica (TD) acoplada a la GC-MS es la metodología utilizada para el ensayo de films y cuero acabado con las resinas poliuretánicas sintetizadas y el aire del ambiente de trabajo mientras se realiza el proceso de aplicación. Esta técnica de extracción de analitos es altamente sensible por lo que conlleva una gran mejora en este campo de estudio. Además, esta técnica también es respetuosa con el medio ambiente ya que minimiza el uso de disolventes orgánicos para el ensayo de COV y la manipulación de la muestra es mínima. Se ensayaron 11 muestras de films a nivel cualitativo y se pudieron identificar los 3 componentes objeto del estudio, para ello se adaptaron las normas ISO 12219-3 e ISO 16000-6. También se ensayó cuero acabado a escala piloto con el método de adquisición de datos SCAN, tanto a nivel cualitativo como cuantitativo y como resultado del estudio se determinó que la metodología podía mejorar realizando un barrido SIM, ya que uno de los isómeros del disolvente DPGME no fue viable para el ensayo cuantitativo. Se analizaron 4 muestras de cuero a escala industrial con un barrido SCAN-SIM por lo que se pudieron determinar con éxito los analitos de interés. Por lo que se refiere al análisis de COV en el ambiente de trabajo se utilizó la norma ISO 16017-2, se realizó a nivel cualitativo utilizando dos tipos diferentes de tubos sorbentes para la captación de COV.
Volatile organic compounds (VOCs) and Semi-Volatile Organic Compounds (SVOCs) arises from the chemicals used in the various stages of the leather manufacturing process. An important aim of the tanning industry is to minimize or eliminate VOCs and SVOCs, without lowering the quality of leather. VOCs and SCOVs emissions are controlled by the legislation through the Annex VII of Directive 2010/75/EU, Activity No 13; being the limit from 75 to 150 g of solvent emitted per m2 of leather product produced. The VOC emission levels to be in conformity with the Best Available Techniques (BAT) for the leather production in Europe are between 10-25 g/m2 expressed as annual average values. The aim of this thesis is to develop new analytical methods for the identification and quantification of VOCs emitted by new polymers designed on a pilot scale for leather finishing. These are polyurethane resins formulated to reduce the concentration of VOCs during the synthesis process. The chemicals under study are the following: dipropyleneglycol monomethyl ether (DPGME), DBE-3 (a mixture of dibasic esters) and trimethylamine (TEA). To carry out the new test methodologies, these are divided according to the sample matrix. In other words, the resins, the film resulting of these resins, the finished leather are tested and a study of the work environment is also carried out when the operator is handling the resins and applying the finish. The solid phase micro extraction (SPME) is used in resin samples and this is a sample preparation technique used for the extraction of VOCs for many applications, coupled with gas chromatography to elute and determine these type of compounds in solid and liquid samples. The main advantages of this technique are speed, high sensitivity; it does not require sample handling or solvent extraction procedures being environmentally friendly extraction technique, speeds up the separation, and increases throughput. In addition, this technique is extremely cost-efficient in comparison to alternate extraction methods. Eleven samples of laboratory scale resins were tested by HS-SPME followed by gas chromatography (GC-MS). DPGME and DBE-3 have been identified effectively. The compounds are identified by a quantitative method using external calibration curves for the target compounds. The technique is not effective to determine the TEA compound, since the chromatograms shown poor resolution peaks for the standard. The Thermal Desorption (TD) coupled to GC-MS was the methodology used for testing films and finished leather with synthesized polyurethane resins and the air of the work environment while the application process is carried out. This analyte extraction technique is highly sensitive so it brings a great improvement in this field of study. Furthermore, this technique is also environmentally friendly as it minimizes the use of organic solvents for VOC testing and sample handling is minimal. Eleven film samples were tested at a qualitative level and the 3 components of the study could be identified, adapting the standards ISO 12219-3 and ISO 16000-6. Finished leather at pilot scale was also tested with SCAN data acquisition method, both qualitatively and quantitatively and as a result of the study it was determined that the methodology could be improved by performing a SIM acquisition method, since one of the isomers of the DPGME solvent wasn’t viable for quantitative testing. Four leather samples were analyzed on an industrial scale with a SCAN-SIM acquisition method so that the analytes of interest could be successfully determined. Regarding the analysis of VOC in the work environment, the ISO 16017-2 standard was used, it was carried out at a qualitative level using two different types of sorbent tubes for the capture of VOCs.

Exhaled breath is a rich and complex matrix containing many hundreds of compounds. Every breath offers the potential of a non-invasive measurement of the biochemical processes occurring in the human body and it is this notion that has led to the application of breath analysis for the detection of disease. With the majority of research in the field being focused on the detection of biomarkers, little has been presented on how the seemingly homeostatic matrix of breath varies during the course of normal life events. The research in this thesis describes how a subject's emotional state, physical state, and daily activities can alter the composition of exhaled breath.

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Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq
Plants produce and emit a large array of volatile metabolites termed biogenic volatile organic compounds (BVOCs) as an integral part of primary and secondary metabolism. Monoterpenes are BVOCs from the largest family of plant natural products, the terpenoids. Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Using thermal desorption-gas chromatography-mass spectrometry techniques, twelve volatile monoterpenes were identified and quantified in a central Amazon terra firma rainforest including the first ambient air observations of the highly reactive cis-β-ocimene and trans-β- ocimene. At the ecosystem scale, monoterpene mixing ratios in the ambient air were greatest at the top of the canopy where light and temperatures are greatest. Leaf level monoterpene emissions were found to be light dependent among the Amazon trees sampled in the field. However, during drought stress conditions that led to leaf senescence, leaf monoterpene emissions were found to be first light dependent followed by temperature dependent and an acted as an early indicator of leaf lipid peroxidation. Further, leaf monoterpene emissions revealed a strong non-linear relationship with net photosynthesis (Pn), dedicating up to 2% of Pn to monoterpene emissions at leaf temperatures up to 30ºC and continuing to rise as leaf temperatures increased. These results suggest that highly reactive monoterpenes may play important roles as antioxidants protecting photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation reactions.
As plantas produzem e emitem uma grande variedade de metabólitos voláteis denominados compostos biogênicos orgânicos voláteis (BVOCs), como parte integrante do metabolismo primário e secundário. Monoterpenos são BVOCs de a maior família de plantas produtos naturais, os terpenóides. Apesar de diferenças das ordems de magnitude na reatividade atmosférica e grande diversidade em funcionamento biológico deles, pouco se sabe sobre a especiação dos monoterpenos em florestas tropicais. Usando tecnicas analiticas de desorpção termica-chromatografia gasosa-espetrometria (TD-GC-MS), doze monoterpenos voláteis foram identificados e quantificados numa floresta tropical de terra firma na Amazônia central, incluindo as primeiras observações no ar ambiente dos monoterpenos que são altamente reativos, cis-β-ocimeno e trans-β-ocimeno. Na escala do ecossistema, as taxas de mistura dos monoterpenos no ar ambiente foram maiores no topo do dossel onde a luz e as temperaturas são maiores. No nível das folhas, emissões dos monoterpenos foram dependente da luz para as avores foram amostradas em campo. No entanto, durante as condições de seca com estresses que levaram a senescência foliar, as emissões dos monoterpenos das folhas foram dependente primeiro da luz e depois a temperatura e agirem como um indicador da peroxidação lipídica folha. Além disso, as emissões dos monoterpenos das folhas revelou uma forte relação não-linear com fotossíntese líquida (Pn), dedicando-se a 2% do Pn para as emissões dos monoterpenos nas temperaturas das folhas até 30ºC e continuaram a aumentar com as temperaturas da folha. Estes resultados sugerem que os monoterpenos o que são altamente reativas podem ser importantes porque eles funçiõnam como antioxidantes que protegem a fotossíntese nas plantas e também podem ser fontes perto do dossel dos precursores dos aerossóis orgânicos secundários de fotooxidação na atmosfera.

Les emballages alimentaires existent depuis la nuit des temps, depuis que l'homme transporte des aliments solides ou liquides. Comme tous les matériaux destinés à entrer au contact des aliments, le bois peut être une source de contaminations chimiques et/ou biologiques, il est donc soumis au règlement (CE) 1935/2004 du parlement européen. Cependant en France, la réglementation spécifique « bois » date de novembre 1945. Elle définit les espèces autorisées pour le contact alimentaire. Il existe également une note d'information « bois » de l'agence sanitaires française « DGCCRF » qui détaillent quelques phénomènes de migration entre le bois et l'aliment mais elles sont très peu développées. L'objectif de cette thèse est d'étudier les différents facteurs qui influencent la migration des composés organiques du bois après un contact alimentaire afin de développer une méthodologie d'analyse simple applicable par les industriels de l'emballage. A l'échelle locale, ce projet innovant apporte une réponse auprès des autorités sanitaires françaises et auprès de la filière française emballages bois et palettes. Et fournira des éléments nécessaires pour la mise à jour de la fiche « matériau bois n°2012-93 » et permettront aux industries agroalimentaires d'avoir à disposition une méthode d'analyse de référence
Food packaging has existed for millennia; ever since man wished to transport solid or liquid foods that were gathered previously. As in the case most materials, wood could be a source of contamination by chemical or biological products. To date, there are no studies available that assess the migration potential of wood components in to food. Food in contact with materials, like wood, is subject to the European Regulation (EC) 1935/2004. In contrast to other materials, there is no specific directive for wooden food contact packaging. In France, the only specific regulation concerning "wood" dates from November 1945 and is very underdeveloped. This thesis aims to study various factors that influence the migration of organic compounds from wood to food when in direct or indirect contact with one another. The final outcome will be a simple methodology that can be applied to industrial packaging. At the national level, this innovative project is in response to the needs of both the French health authorities and the French wood packaging industry. And provide the information necessary to update the information contained in "wood material No. 2012-93” which will, in turn, give the food industry an analytical method and a point of reference

Certain oxygen free radicals are produced constantly in cells by metabolism and exogenous agents. Some, such as the hydroxyl radical, may react with various biomolecules like DNA, lipids or proteins, and thus be involved in the pathogenesis of various diseases. It is often difficult to detect oxygen free radicals due to their relatively short half-life. This problem may be overcome, however, using the spin trapping technique. In this technique, the spin-trap compound is used to trap free radicals, making them stable enough to be analysed using techniques like Electron Paramagnetic Resonance (EPR) spectroscopy or Mass Spectrometry (MS). In the current study, Fenton chemistry has been used to generate hydroxyl radicals. Since the hydroxyl radical adduct of the spin-trap N-tert-butyl-α-phenylnitrone (PBN) is shortlived at room temperature a secondary trapping technique is employed. The resulting spin-trapped species have been sampled using solvent-free extraction approaches i.e. Headspace Solid Phase Microextraction (HS-SPME) or Thermal desorption (TD), and the extracted products then detected and identified by using gas chromatography-mass spectrometry (GC-MS). GC-MS provides an alternative to other traditional techniques like EPR spectroscopy, as it provides more detailed information about structure of the radical adduct. Aldehydes are some of the most important products of oxidative stress, mostly produced through lipid peroxidation, and potentially may be used as biomarkers for different diseases. Their reactivity, production in low quantities and need of derivatisation are some of the challenges faced by analytical chemists to detect them. In the current research, aldehydes are used as secondary source of radicals in the Fenton reaction to produce aldehyde related free radicals. The developed method is not only a solvent free approach but also there is no need of derivatisation. It has the potential to be used as a biomarker assay of oxidative stress.

À l’heure actuelle, la contamination des sols est une problématique majeure. En France, un peu plus de 10 045 sites et sols pollués ont été recensés à la mi-2022. D’après une étude de 2018, les hydrocarbures aromatiques polycycliques (HAP) et les éléments traces métalliques (ETM) étaient responsables de cette pollution à hauteur de 14% et 23%, respectivement. La pollution des sols a un impact significatif sur la biodiversité des écosystèmes et la santé humaine. Dans le cadre des politiques d’urbanisation et d’une « zéro artificialisation nette » des sols, la restauration des friches industrielles présente un grand interêt, mais la dépollution de sols co-contaminés en HAP et ETM reste un défi. La mycoremédiation, procédé utilisant les capacités naturelles de souches fongiques afin d’éliminer ou de transformer certains polluants présents dans une matrice environnementale, suscite un intérêt grandissant de par la résistance de certaines souches fongiques à la co-contamination et à leur capacité à coloniser les sols par leur réseau mycélien. Ces travaux de thèse ont permis d’amorcer le développement de nouveaux outils analytiques pour l’analyse des HAP et de certains métabolites oxygénés (cétones, quinones, hydroxylés) de manière semi-automatisée par thermodésorption couplée à la GC-MS/MS en tandem. Une nouvelle méthode, utilisant un polymère de cyclodextrine, a été appliquée pour évaluer la bioaccessibilité des HAP dans le sol industriel d’étude. Une étude en microcosmes de sol d’une durée de 6 mois a permis d’exclure l’utilisation de la souche modèle Absidia cylindrospora pour la mycoremédiation du sol étudié : les fortes concentrations et disponibilités de certains ETM (Pb, Cu, Zn), la très faible bioaccessibilité des HAP, n’ont pas permis à la souche fongique de contribuer significativement à la biodégradation des HAP. De nouvelles souches fongiques ont été isolées à partir du sol industriel. Une souche indigène de Penicillium annulatum résistante aux Cu, Pb et Zn et capable de biodégrader les HAP a été sélectionnée pour une étude à plus grande échelle, en bac pouvant contenir 2 kg de sol. Après inoculation sur un support solide original, un développement fongique important a été observé dans le sol ainsi que la dégradation significative des polluants organiques (en moyenne 22% pour les HAP et 33% pour les polychlorobiphényles (PCB)) en moins de 4 mois
Soil contamination is a major issue today. In France, over 10,045 polluted sites and soils had been identified by mid-2022. According to a 2018 study, polycyclic aromatic hydrocarbons (PAHs) and trace metals (TMEs) were responsible for 14% and 23% of this pollution, respectively. Soil pollution has a significant impact on the biodiversity of ecosystems and human health. In the context of urbanisation policies and ‘zero net artificialisation’ of soils, the restoration of brownfield sites is of great interest, but the decontamination of soils co-contaminated with PAHs and TMEs remains a challenge. Mycoremediation, a process that uses the natural capacities of fungal strains to eliminate or transform certain pollutants present in an environmental matrix, is attracting growing interest due to the resistance of certain fungal strains to co-contamination and their ability to colonise soils through their mycelial network. This thesis work led to the development of new analytical tools for the semi-automated analysis of PAHs and certain oxygenated metabolites (ketones, quinones, hydroxylates) using thermodesorption coupled with tandem GC-MS/MS. A new method, using a cyclodextrin polymer, was applied to assess the bioaccessibility of PAHs in the industrial studied soil. A 6-month study in soil microcosms ruled out the use of the model strain Absidia cylindrospora for the mycoremediation of the studied soil: the high concentrations and availability of certain TMEs (Pb, Cu, Zn) and the very low bioaccessibility of PAHs meant that the fungal strain could not make a significant contribution to PAH biodegradation. Then new fungal strains were isolated from the industrial soil. An indigenous strain of Penicillium annulatum, resistant to Cu, Pb and Zn and capable of biodegrading PAHs, was selected for a larger-scale study, in a container that could hold 2 kg of soil. After inoculation thanks to an original solid support, significant fungal growth was observed in the soil, as well as significant degradation of organic pollutants (22% for PAHs and 33% for polychlorinated biphenyls (PCBs) on average) in less than 4 months

Nonylphenol (NP) and its ethoxylates are used in formulation of pesticides and detergents, production of personal care products and many industrial sectors such as textile, metal plating, plastic, paper and energy. They are also used in the formulation of household cleaning agents. Industrial uses in the production line make up 55% of the total use
whereas industrial and domestic cleaning processes constitute 30 and 15%, respectively. Since they are widely used in industry and households, NP compounds enter the environment mainly by industrial and municipal wastewater treatment plant effluents. NP is considered strongly toxic and has adverse effects even with short term exposures. Moreover, with its similarities to natural hormones, NP and its ethoxylates are considered as endocrine disrupter compounds. In studies conducted with human cells, chicken embryo, trout and mice eostrogen receptors, positive responses were observed. Due to their lipophilic and hydrophobic characteristics they accumulate in cells, tissues and organic materials such as sludge. For these reasons, fate of NP and its v ethoxylates in wastewater treatment plants and in sludge treatment processes gained importance. Nonylphenol polyethoxylates (NPnEO) are degraded in microbial media and lose their ethoxylates to nonylphenol diethoxylate (NP2EO), nonylphenol monoethoxylate (NP1EO) and NP. Moreover, nonyl phenoxycarboxylic acids (NPnEC) can be formed during some of these reactions. Because the first degradation reactions are fast, concerns and studies are focused mainly on NP2EO, NP1EO, NP, NP1EC and NP2EC. Even though these general degradation information is available, studies on sludge are very rare. In this study, treatability and toxicity of NP2EO in anaerobic batch reactors is investigated. First, with the use of Anaerobic Toxicity Assay (ATA) test, toxic doses of NP2EO which was added to the reactor as the parent component, were determined. Moreover, the degradation of these chemicals were studied in larger scale batch anaerobic digesters. The aim of this part was to observe the degradation patterns and products. Throughout the study the fate of NP and its ethoxylates was followed in aqueous and solid phases by the use of Gas Chromatography / Mass Spectrometry system (GC/MS). ATA tests showed that NP2EO was not toxic to anaerobic microorganisms at the doses investigated in this study. It was rather stimulating and caused an increase in methane production in the reactors. On the other hand the spiked NP2EO&rsquo
s at 0.5 and 2.5 mg/L concentration were completely degraded in the larger scale batch reactors. At the same time, an increase in the concentrations of NP and NP1EO was observed which supported the fact that NP2EO was degraded into NP1EO and NP under anaerobic conditions. Abiotic degradation was not observed.

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O monômero cloreto de vinila (MVC) é a principal matéria-prima utilizada na produção do Policloreto de vinila (PVC). Sendo assim, o controle da pureza do MVC é fundamental para o controle da reação de polimerização, bem como para as propriedades do PVC, visto que alguns contaminantes orgânicos reagem como co-monômeros. Portanto, faz-se necessário o desenvolvimento de metodologias para identificação das substâncias presentes como contaminantes do MVC. Neste trabalho, foram desenvolvidos métodos de identificação dos contaminantes, baseados na sua pré-concentração por adsorção em Tenax-TA e Tenax- TA/Carboxen1000/CarbosieveSIII, seguidos de dessorção térmica e análise por cromatografia gasosa acoplada à espectrometria de massas (TD-GC-MS). A otimização desses métodos foi realizada utilizando-se planejamento fatorial de experimentos completo e fracionário. Os métodos otimizados foram utilizados na identificação dos contaminantes do MVC nas etapas do processo de obtenção, armazenamento e recuperação do monômero, correspondendo a quatro pontos distintos de coleta das amostras. Foram identificadas ao todo dezenove substâncias dentre as quais hidrocarbonetos alifáticos e aromáticos, organoclorados, alcoóis, fenóis e fenonas. Destas, doze estavam presentes no MVC virgem, treze no MVC da esfera de armazenamento, doze no MVC da entrada dos reatores de polimerização e dezesseis no MVC recuperado. Os contaminantes presentes com as maiores concentrações relativas nos diferentes pontos foram estireno, aromático C6, tolueno, naftaleno, 1-octanol e 1,3- butadieno. Destes, estireno e 1,3-butadieno tem sido relatados na literatura como sendo fortes inibidores de polimerização para o MVC. Através da análise de componentes principais foi possível comprovar que há diferenças nas características do MVC, a depender do ponto do processo de onde ele é captado. Além disso, foi possível classificar as amostras de MVC, provenientes de diferentes pontos do processo, em três agrupamentos distintos, bem como identificar em cada agrupamento os principais contaminantes responsáveis pelas diferenciações. Considerando que o controle da pureza do monômero é fundamental para a qualidade do PVC, estes resultados demonstram a importância de realizar experimentos em escala de laboratório com o MVC proveniente de cada ponto, a fim de verificar a influência dos seus contaminantes característicos sobre as propriedades do PVC produzido. Com essas informações será possível buscar estratégias para a eliminação ou redução dos principais contaminantes responsáveis pelas alterações nas propriedades do produto final.
The Vinyl Chloride Monomer (MVC) is the main raw material used in the production of Poly (Vinyl Chloride) (PVC). Thus, the control of MVC purity is essential to control polymerization reaction, as well as the properties of PVC, since some organic contaminants react as co-monomers. Therefore, it is necessary to develop methodologies for the identification of substances as contaminants MVC. In this work, we developed methods for identifying contaminants, based on your pre- concentration by adsorption on Tenax-TA and Tenax- TA/Carboxen1000/CarbosieveSIII, followed by thermal desorption and analysis by Gas Chromatography-Mass Spectrometry (TD-GC-MS). The optimization of these methods was performed using full factorial design of experiments and fractional. The optimized methods were used in the identification of contaminants in the MVC stages of acquisition, storage and retrieval of the monomer, corresponding to four distinct points of sample collection. We identified a total of nineteen substances among which aliphatic and aromatic hydrocarbons, organochlorine, alcohols, phenols and fenonas. Of these, twelve were present in virgin MVC, MVC thirteen in the storage sphere, twelve in MVC input of polymerization reactors and sixteen in MVC recovered. Contaminants with higher relative concentrations in different points were styrene, benzene, toluene, naphthalene, 1-octanol and 1,3-butadiene. Of these, 1,3-butadiene and styrene have been reported in the literature as strong polymerization inhibitors for MVC. Through Principal Component Analysis was possible to prove that there are differences in the characteristics of the MVC, depending on the point in the process where it is captured. Moreover, it was possible to classify the samples MVC from different points of the process in three distinct clusters and identify each cluster major contaminants responsible for differentiation. Whereas the control of the purity of the monomer is critical to the quality of the PVC, these results demonstrate the importance of conducting experiments on a laboratory scale with the MVC from each point, in order to check the influence of its contaminants on the characteristic properties of PVC produced. With this information you can find strategies for elimination or reduction of major pollutants responsible for changes in the properties of the final product.

A wide range of organic compounds are released from building and furnishing products and these have the potential to adversely affect indoor air quality. There are growing international requirements for testing and controlling these emissions for the protection of public health. The test methods require specialist analytical chemistry facilities based on thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). This project has addressed the need for better performance and greater automation of the analysis, as well as development of simpler screening tests. A variety of products were tested using screening techniques, with an emission cell method being used as a reference test. Short duration tests, using a micro-scale chamber at slightly elevated temperature, were shown to have the potential to predict emissions occurring during longer term reference tests. Multi-sorbent air sampling tubes, that have the potential to extend the volatility range of compounds determined by a single TD/GC/MS analysis, were compared with Tenax TA tubes specified by current standard methods. This showed no difference in performance for the range of compounds for which Tenax is optimal, with improved performance for a number of more volatile compounds. The determination of formaldehyde was investigated using 2-hydroxymethylpiperidine as a derivatising agent, followed by TD/GC/MS. The results showed the possibility of this method being developed as an alternative to the current standard method that involves solvent elution and liquid chromatography. The performance of a newly developed time-of-flight mass spectrometer was compared with a standard quadrupole instrument. This showed its potential, with the use of re-collection, to extend the concentration range of compounds quantified from a single air sample, of particular benefit for the determination of carcinogens. New compound identification software was applied to increase automation of analysis of the TD/GC/MS data. Good correlation with manual processing was achieved, demonstrating the possibility of routine application to material emissions testing.

2008/2009
I consumi energetici europei si basano per oltre un terzo su prodotti petroliferi, di cui circa il 60% viene importato1. Trieste è tra i primi porti petroliferi italiani ed i petroli rappresentano oltre l’80 % dei circa 46 milioni di tonnellate di merci sbarcati annualmente. Le operazioni di sbarco, stoccaggio e pompaggio dei greggi nell’oleodotto transalpino TAL vengono effettuate nel rispetto delle normative nazionali e di standard internazionali di sicurezza, che hanno fatto sì che dal 1967 ad oggi, a fronte di una movimentazione di oltre un miliardo e 200 milioni di tonnellate di greggio, non si siano verificati incidenti rilevanti con l’eccezione dell’attentato terroristico del 4 Agosto 1972. Una gestione attenta di impianti e processi di queste dimensioni richiede tuttavia continui adattamenti ed indirizzi rispetto alle evoluzioni normative, tecniche e del contesto sociale in cui gli impianti sono inseriti. Risulta indubbio in questo senso evidenziare come la sensibilità nei confronti degli impatti reali o percepiti delle attività produttive sull’ambiente sia aumentata nelle società europee proprio a partire dagli anni settanta del secolo scorso. Il presente lavoro di tesi di dottorato mira a proporre metodi analitici e modellistici per la caratterizzazione degli impatti associati alle emissioni nell’ambiente originate da impianti di stoccaggio/pompaggio di idrocarburi, nel caso di rilasci di lieve entità; i metodi risultano indispensabili anche per l’ottimizzazione di soluzioni tecnologiche volte a rimuovere o minimizzare gli impatti ambientali. Bisogna ricordare come la composizione chimica e le proprietà chimico fisiche dei petroli greggi, miscele naturali, siano variabili e dipendano dai giacimenti d’origine degli stessi, comportando mobilità, persistenza, tossicità e rilevabilità diverse per eventuali rilasci nell’ambiente. In alcuni casi i greggi sono presenti come blend provenienti da giacimenti diversi e quindi a composizione non strettamente definita. Le attività intraprese si articolano in studi (capitolo 1) di caratterizzazione analitica dei petroli, volte a determinare componenti alifatiche ed aromatiche che li caratterizzano come contaminanti, e composti particolarmente persistenti come gli opani spesso impiegati come marker di contaminazione ed indicatori per seguire processi di degradazione. Si sono quindi impostati e condotti esperimenti in condizioni controllate, allestendo microcosmi costituiti da suoli contaminati artificialmente, in presenza ed assenza di fenomeni di biodegradazione. 1 European Commission’s Market Observatory for Energy (2009) Europe’s energy position, markets and supply (http://ec.europa.eu/energy/observatory/annual_reports/doc/2009_annual_report.pdf) L’obiettivo è quello di raccogliere indicazioni e parametri utili per la realizzazione di interventi di bonifica con approcci di attenuazione naturale monitorata, land farming o di allestimento di biopile nel caso di contaminazioni accidentali che si dovessero verificare. Un’ulteriore tipologia emissiva da considerare nell’esercizio di impianti di questa natura è quella che riguarda i composti organici volatili (COV) che possono evolvere dai serbatoi durante le operazioni di riempimento, svuotamento e manutenzione o dalle navi cisterna che alimentano il tankfarm. Si sono messi a punto (capitolo 2) metodi per il campionamento passivo ed attivo di COV, includendo sia composti normati quali benzene, toluene, etilbenzene e xileni (BTEX), quanto idrocarburi alifatici volatili, che possono evolvere in atmosfera durante le operazioni di movimentazione dei greggi o di trattamento suoli. I campionatori passivi consentono di ottenere, a costi contenuti, informazioni su concentrazioni medie di BTEX nell’aria ambiente, mentre i campionatori attivi si prestano a campionamenti di breve durata. In considerazione delle segnalazioni di molestie olfattive in prossimità del tankfarm si è affrontato uno studio(capitolo 3) di correlazione tra la concentrazione di odore associata a una serie di campioni di greggi e la loro composizione chimica, con particolare riferimento alla presenza di composti solforati. La natura transitoria delle emissioni di COV in atmosfera e dei fenomeni di molestia olfattiva rende i campionamenti discreti (non continui) dell’aria relativamente poco efficaci, per cui le simulazioni modellistiche possono fornire un valido complemento alle valutazioni ambientali ed all’ottimizzazione delle strategie di controllo. Si è quindi affrontato (capitolo 4)l’allestimento di catene modellistiche che valutano le emissioni dai serbatoi, anche grazie ai dati sperimentali raccolti negli studi precedenti, e la loro dispersione sul territorio. Tali valutazioni possono consentire di posizionare in maniera ragionata centraline di monitoraggio o nasi elettronici sul territorio, tenendo conto quantitativamente dei dati meteorologici e della specifica orografia. Nel caso di emissioni di origine sconosciuta che giungano ad un sito recettore, i modelli possono essere impiegati per valutare la provenienza delle masse d’aria, ricostruendo i campi meteorologici nel dominio spaziale d’interesse e trovando eventuali correlazioni sorgente/recettore. Gli strumenti individuati e sviluppati costituiscono gli elementi che possono essere integrati in un sistema di monitoraggio e retroazione, utile per una gestione ambientale basata su dati quantitativi, comunicabili e su un approccio razionale.
XXII Ciclo
1974

碩士
國立清華大學
工程與系統科學系
107
Human exhaled breath test is more and more important for non-invasive health monitoring and detecting method nowadays. Patients with Obstructive sleep apnea (OSA) disease are difficult to be distinguished from the normal people clinically. Because of these two reasons, in this research, a method of thermal desorption (TD) tendon with gas chromatography–mass spectrometry (GC-MS) system has been developed for distinction of OSA patients and normal people. In this research, first we create a standard which called Reliable Number(N).And we detected the volatile organic compounds (VOCs) from the tubes and bags which we used in the experiments, then we compared those VOCs with normal people’s VOCs and OSA patients VOCs in order to find out the marker. When reliable number is ≧50% , we found 8 markers of OSA patients which are (Pentane) (Cyclopentyl acetylene) (Toluene) (Heptane, 2,4-dimethyl-) (Octane, 4-methyl-) (Propanamide, 2-methyl-) (2H-Azepin-2-one, hexahydro-1-methyl-) (2H-Azepin-2-one, hexahydro-7-methyl-). But if we cut down reliable number to ≧30%, there are 9 markers more than ≧50%. In contrast, if we raise reliable number to ≧70%, we only have 3 markers remaining. Based on this result, we also discussed the different marker or peak intensity of the compounds between different levels of the disease from OSA patients.

碩士
國立清華大學
奈米工程與微系統研究所
102
This research was to demonstrate the TD-GC-MS system and realize the idea of gas measurement and analysis, roasted coffee beans were chosen as our study target. Tenax-TA adsorbent tubes and a low flow rate pump were used to collect the coffee beans aroma. Then the adsorbent tube was submitted to TD-GC-MS for analysis. Different roasting conditions would give the coffee beans aroma various smells and taste characteristics. This is due to the complex chemical reactions occurred during the roasting process. 17 major components have been identified by GC-MS. Results showed that most components in coffee beans aroma increased with roast levels, while furfurals family had a downward tendency. A mechanism of the formation of furfural was proposed to explain the decrease in furfural. Storage time and monitoring intervals were also two factors that can affect the measurement results. Components had their own specific trends of change in their intensity over the storage period. This can be due to the molar mass, boiling points, and chemical structures. As the monitoring intervals prolonged, which means less sampling frequency, we found that the intensity of 2-methyl-furan significantly decayed at a slower rate.

碩士
國立清華大學
化學系
94
Abstract Dry-process photocopy was reported to emit volatile organic compounds (VOCs), O3 and particulates. Raw materials used in dry-process photocopy include toners and plain papers, and would emit VOCs when being heated to fuser temperature (180~200 ℃). We mimic fusing process in dry-process photocopy by TD-GC/MS and set up on-line method to analyze VOCs emitted from heated toner and plain paper. Compared to off-line method which may lose VOCs during the analysis, on-line method is advantageous to capture and introduce all released VOCs into TD-GC/MS for subsequence. We found more VOCs emitted from toners than plain paper. One toner cartridge was estimated to emit 1~8 mg VOCs; whereas one package of plain papers (500 sheets) will emit 3~10 ng VOCs emitted from. This method was also applied to analyze newspapers. One copy of newspaper (ex. 10 sheets) was estimated to emit 14 mug VOCs. Indoor air quality (IAQ) has effect on people ease and working efficiency. We use the analytical method based on U.S. Environmental Protection Agency (EPA) TO-17 using Tenax GR as absorbent to sample indoor air in photocopy shops. Qualitative and quantitative analysis was performed using TD-GC/MS. The method detection limits (MDL) and average recoveries for the target analytes were in the range 0.17~0.39 ppbv and 96~113 %, respectively. The method shows good linearity (R2 ≧0.995) and precision (＜10 %). About 80% VOCs were emitted from toners in the indoor air photocopy shop. We also quantified nine of VOCs including BETEX etc. Total volatile organic compounds (TVOC) in two photocopy shops were 0.09 and 0.08 mg/m3, individually. The highest concentration was toluene 9.05 ppbv. Isovaleric acid used as cleaning reagent was measured in one photocopy shop at a concentration of 16.47 ppbv.

碩士
國立清華大學
工程與系統科學系
104
Human exhaled breath measurement is one of important non-invasive health monitoring methods. The symptoms of bronchial asthma (BA) and chronic obstructive pulmonary disease (COPD) are similar, but different treatments for these two diseases. In this research, thermal desorption (TD) tendon with gas chromatography–mass spectrometry (GC-MS) system has been used to develop a screen method for the COPD patients, BA patients, and normal people. In this research, “Cyclotrisiloxane, hexamethyl-“has been used as an internal standard for the evaluation of the relative concentration for all the detected volatile organic compounds (VOCs). First, we compare the relative concentration of VOCs from empty airbags and from the samples that were exhaled from COPD, BA patients, and normal people. Then, decision tree with deliberately ordered VOCs is used to identify the situation of every object. Cross validation is used to verify the data between the certain groups of samples. The breath from these three kinds of people could be simply distinguished and the average classification accuracy of normal people, COPD patients and BA patients are 100%, 94% and 70% respectively.