Submitted by Gizele Lima (gizele.lima@inpa.gov.br) on 2016-08-31T13:21:43Z No. of bitstreams: 2 Tese de Doutorado_Angela Beth Jardine.pdf: 6114980 bytes, checksum: 07a301793e0522e5fb0084e12ee425fe (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-31T13:21:43Z (GMT). No. of bitstreams: 2 Tese de Doutorado_Angela Beth Jardine.pdf: 6114980 bytes, checksum: 07a301793e0522e5fb0084e12ee425fe (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-05-10 / 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.

Sökhundar är ett viktigt verktyg som används av polis och tullverksamhet, men deras detektionsmetodik är inte helt känd. En substans doftprofil är en viktig aspekt i sökhundars detektion, men de är svåra att forska på kemiskt då det finns en diskrepans mellan koncentration och bidrag till doftprofilen. Målet med den här forskningen var att öka förståelsen för sökhundars detektionsmetodik i relation till adsorberade föreningar på damm, samt hur marijuanas doftprofil skiljer sig från doftprofilen av damm som kontaminerats med marijuana. Citron och lime utnyttjades som modellsystem och bitar av deras skal analyserades även direkt. Terpener och terpenoider var de främsta komponenterna av intresse. Forskningen hade ett tvåfaldigt tillvägagångssätt och inkluderade termisk desorption gaskromatografi masspektrometri (TD-GC/MS) samt sökhundsanalys i form av urvalsövningar. Kontorsdamm och köpt standarddamm i storleken av luftburna partiklar (PM) med en aerodynamisk diameter av cirka 10 µm kontaminerades med marijuana, citron, lime och en cannabis-terpenmix i exsickatorer i 1, 3, samt 7 dagar. En sekundär kontaminering med marijuana utfördes också, där dammprovet som kontaminerats med marijuana i 1 dag användes för att vidare kontaminera nya damm- och PM-prover, och dammprov togs även i förvaringsskåp för packade illegala droger. Från TD-GC/MS analysen av laborativ kontaminering av marijuana detekterades totalt 25 föreningar av intresse i dammprovet, och 57 i PM-provet. Från TD-GC/MS analysen av citron framkom det att fler monoterpener (C10H18) än sesquiterpener (C15H24) detekterades i direktanalysen av citronskal, och det motsatta i analysen av de kontaminerade damm och PM-proverna. Utgående från detta är det troligt att doftprofilerna från ren marijuana samt marijuana kontaminerad på damm eller PM också skiljer sig åt. Sökhundarna markerade dock på båda proverna som kontaminerats med marijuana under 1 dag med stor säkerhet, och vissa markerade även på prover med kortare kontamineringstid och proverna från förvaringsskåpet. Inga eller få föreningar av intresse detekterades med TD-GC/MS i vissa av de prover som hundarna markerade på, vilket exemplifierar att hundarna har en högre sensitivitet vilket försvårar forskningen kring doftprofiler som hundarna kan detektera. Användningen av sökhundsanalys på dammprover som tagits från platser av intresse kan vara en möjlig metod för att detektera marijuana, och eventuellt även andra illegala substanser. / Detection dogs are an important tool utilized by police forces and customs, but their method of detection is not fully known. The odor profile of a substance is of major importance during dog detection, but they are difficult to research chemically due to the disconnection between concentration and contribution to the odor profile. The purpose of this research was to increase the knowledge regarding the mechanism of detection dogs in relation to adsorbed components on dust, as well as of how the odor profile of marijuana differs to that of dust contaminated with marijuana. Lemon and lime were utilized as model systems and pieces of peel were analyzed directly. Terpenes and terpenoids were the main compounds of interest. The research consisted of a dual approach, utilizing both thermal desorption gas chromatography mass spectrometry (TD-GC/MS), and detection dog analysis in the form of selection exercises. Office dust and bought particulate matter (PM)-like standard dust with an aerodynamic diameter of about 10 µm was contaminated with marijuana, lemon, lime, and a cannabis terpene mix in desiccators for 1, 3, and 7 days. A secondary marijuana contamination was also conducted, where the 1-day dust sample contaminated with marijuana was used to contaminate new dust and PM samples, and dust samples were also taken in storage units of packaged illicit drugs. From the laboratory contaminated samples with marijuana, a total of 25 compounds of interest were detected by TD-GC/MS from the dust samples, and 57 from the PM samples. From the direct TD-GC/MS analysis of lemon peel, it was evident that more monoterpenes (C10H18) than sesquiterpenes (C15H24) were detected, and the contrary was found for the lemon contaminated dust and PM samples. This entails that the odor profiles of marijuana as is and adsorbed on dust or PM is also likely to differ. Still, the detection dogs were able to detect the dust and PM samples which had been co-stored with marijuana for 1 day, and some also alerted to a few of the secondary contaminated marijuana samples as well as the samples from marijuana storages. None or only a few compounds of interest were detected by TD-GC/MS in some of the samples the detection dogs alerted to, which highlights the higher sensitivity of detection dogs, and thus the difficulty of chemically researching odor profiles the dogs can detect. All in all, detection dog analysis of dust collected at scenes of interest may be a viable method to detect marijuana, and perhaps other illicit drugs.

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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Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-09-17T15:13:51Z No. of bitstreams: 1 Fabio Neves Dissertação.pdf: 1617814 bytes, checksum: 880cf6fc37213ab6dcd60cf882b1ffb3 (MD5) / Approved for entry into archive by Fatima Cleômenis Botelho Maria (botelho@ufba.br) on 2014-09-19T12:31:43Z (GMT) No. of bitstreams: 1 Fabio Neves Dissertação.pdf: 1617814 bytes, checksum: 880cf6fc37213ab6dcd60cf882b1ffb3 (MD5) / Made available in DSpace on 2014-09-19T12:31:43Z (GMT). No. of bitstreams: 1 Fabio Neves Dissertação.pdf: 1617814 bytes, checksum: 880cf6fc37213ab6dcd60cf882b1ffb3 (MD5) / 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.

Les moisissures sont considérées comme un des facteurs affectant la qualité de l'air intérieur. L'exposition professionnelle aux moisissures peut affecter la santé des travailleurs. Selon l’espèce de moisissure, la dose d'exposition et la sensibilité individuelle, les effets peuvent être irritatifs, infectieux, immunologiques, toxiques ou cancérigènes. Les méthodes classiques, basées sur le bilan environnemental des moisissures cultivables dans l'air, souffrent d'inconvénients tels que le nombre élevé d'échantillons, les analyses coûteuses et la sous-estimation de l'exposition. La croissance des moisissures peut entraîner la production de métabolites, notamment des COVm. Ces derniers, lorsque inhalés, pourraient s’accumuler dans le corps et pourraient être détectés dans les matrices biologiques des travailleurs avant et après leur quart de travail. L'objectif principal de cette thèse est de développer une méthode permettant d’évaluer l'exposition aux moisissures en milieu de travail en exploitant les COVm comme biomarqueurs d'exposition. Le premier objectif spécifique est de développer une méthode analytique en utilisant la technique HS-SPME-CPG-SM/SM pour mesurer simultanément les 21 COVm dans le sang et l’urine. Le deuxième objectif est de développer une méthode analytique en se basant sur la technique DT-CPG-SM/SM pour analyser ces COVm dans l’air ambiant et exhalé. Le troisième objectif vise à optimiser la méthode développée dans l'air ambiant pour documenter les concentrations des COVm présents dans deux milieux de travail ayant des charges de moisissures différentes et évaluer leurs variations spatio-temporelles. Les 21 COVm sélectionnés dans cette thèse ont un potentiel comme biomarqueurs d’exposition aux moisissures. Leur sélection a été basée sur l’intérêt pour des effets sanitaires potentiels des espèces de moisissures, l’occurrence d’émission et les paramètres physicochimiques et pharmacocinétiques des COVm. Les paramètres d'extraction des COVm et les conditions analytiques ont été optimisés pour assurer une meilleure extraction et analyse des COVm dans le sang et l’urine. D’autre part, la méthode DT-CPG-SM/SM a été optimisée dans l’air ambiant et exhalé en testant plusieurs types d’adsorbant, débits et volumes d’air. Tenax TA/Carbograph a été sélectionné pour l’adsorption des COVm en échantillonnant 3 L d’air à 150 mL/min. Ces méthodes développées ont présenté de bonnes performances analytiques en termes de linéarité, précision, limites de détection et de quantification. Ceci a permis la quantification des COVm à faibles niveaux dans les matrices biologiques et l’air. Finalement, l’optimisation de l’analyse des prélèvements d’air d’un centre de tri des déchets et d’une université a été réalisée en utilisant la méthode DT-CPG-SM/SM. Un prélèvement de 2 heures a été sélectionné. Pour la majorité des COVm, aucune différence n’a été démontrée entre les périodes de la journée dans les milieux étudiés. À l’université, les concentrations des COVm étaient plus élevées dans les classes comparativement aux laboratoires munis d’un système de ventilation plus efficace. Au centre de tri, les concentrations des COVm étaient plus élevées dans la salle de pré-tri. Les résultats obtenus ont permis de sélectionner plusieurs COVm comme potentiels biomarqueurs d'exposition aux moisissures. Cette approche de biosurveillance pourrait donner un indice de la contamination fongique dans un milieu de travail, avant tout recours à l'approche classique, plus complexe et onéreuse. / Molds are one of the factors affecting indoor air quality. Occupational exposure to molds can have effects on workers' health. Depending on mold species, exposure dose and individual sensitivity, the health effects can be irritative, infectious, immunological, toxic, or carcinogenic. Conventional methods, based on the environmental assessment of cultivable molds in the air, have many drawbacks such as the high number of samples, the costly analyzes and the underestimation of exposure. Mold growth can lead to the production of metabolites, including mVOCs. The latter, when inhaled, could accumulate in the body, and could be detected in the biological matrices of workers before and after their shift. The main objective of this thesis is to develop a method to assess exposure to molds in the workplace by exploiting mVOCs as biomarkers of exposure. The first specific objective is to develop an analytical method using the HS-SPME-GC-MS/MS technique to simultaneously measure the 21 mVOCs in blood and urine. The second objective is to develop an analytical method based on the TD-GC-MS/MS technique to analyze these mVOCs in ambient and exhaled air. The third objective aims to optimize the method developed in ambient air to document the concentrations of mVOCs present in two workplaces with different mold loads and to assess their spatio-temporal variations. The 21 mVOCs selected in this thesis have potential as biomarkers of mold exposure. Their selection was based on the interest in potential health effects of the mold species, the occurrence of emission and their physicochemical and pharmacokinetic parameters of the mVOCs. Parameters influencing the extraction process and analytical conditions have been optimized to ensure better extraction and analysis of mVOCs in blood and urine. On the other hand, the TD-GC-MS/MS method has been optimized in ambient and exhaled air by testing several types of adsorbent and several flow rates and air volumes. Tenax TA/Carbograph was selected for mVOC adsorption by sampling 3 L of air at 150 mL/min. These developed methods exhibited good performance in terms of linearity, precision and detection and quantification limits. This allowed the quantification of mVOCs at relatively low levels in biological matrices and air. Finally, the optimization of mVOCs sampling from the air of a waste sorting centre and a university, was carried out using the TD-GC-MS/MS method. A sampling time of 2 hours was selected. For the majority of mVOCs, no difference was demonstrated between the periods of the day in the two environments studied. At university, the concentrations of mVOCs were higher in classrooms compared to laboratories equipped with a more efficient ventilation system. At the sorting centre, mVOCs’ concentrations were higher in the pre-sorting room. The results obtained made it possible to select several mVOCs as potential biomarkers of exposure to molds. This new biomonitoring approach could give an indication of fungal contamination in a workplace, before resorting to the traditional approach, which is more complex and expensive.