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A LLE-GC-MS method was developed to detect PPCPs in surface water samples from Big Cypress National Park, Everglades National Park and Biscayne National Park in South Florida. The most frequently found PPCPs were caffeine, DEET and triclosan with detected maximum concentration of 169 ng/L, 27.9 ng/L and 10.9 ng/L, respectively. The detection frequencies of hormones were less than PPCPs. Detected maximal concentrations of estrone, 17β-estradiol, coprostan-3-ol, coprostane and coprostan-3-one were 5.98 ng/L, 3.34 ng/L, 16.5 ng/L, 13.5 ng/L and 6.79 ng/L, respectively. An ASE-SPE-GC-MS method was developed and applied to the analysis of the sediment and soil area where reclaimed water was used for irrigation. Most analytes were below detection limits, even though some of analytes were detected in the reclaimed water at relatively high concentrations corroborating the fact that PPCPs do not significantly partition to mineral phases. An online SPE-HPLC-APPI-MS/MS method and an online SPE-HPLC-HESI-MS/MS method were developed to analyze reclaimed water and drinking water samples. In the reclaimed water study, reclaimed water samples were collected from the sprinkler for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples. Coprostanol, bisphenol A and DEET’s maximum concentration exceeded 10 µg/L (ppb). The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%). In the study of drinking water, 54 tap water samples were collected from the Miami-Dade area. The maximum concentrations of salicylic acid, ibuprofen and DEET were 521 ng/L, 301 ng/L and 290 ng/L, respectively. The three most frequently detected compounds were DEET (93%), carbamazepine (43%) and salicylic acid (37%), respectively. Because the source of drinking water in Miami-Dade County is the relatively pristine Biscayne aquifer, these findings suggest the presence of wastewater intrusions into the delivery system or the onset of direct influence of surface waters into the shallow aquifer.

A method to detect nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in the air has been developed using gas chromatography with an atmospheric pressure chemical ionisation source, coupled to a triple quadrupole mass spectrometer (GC-APCI-MS/MS). An attempt to create a GC method using negative chemical ionisation (NCI) and a high-resolution mass spectrometer, Orbitrap, (GC-NCI-MS) was made as well without success. Nitro-PAHs are a group of widespread contaminants considered as possible mutagens and carcinogens. They are formed from incomplete combustion of organic matter as well as secondary reactions between PAHs and nitrogen dioxide (NO2) in the air. Three air samples (outdoor, in an air vent and indoor), both particulate and gaseous phase, collected in central Örebro during the spring were extracted and analysed for nitro-PAHs on GC-APCI-MS/MS and for PAHs on GC-MS in EI (electron ionisation) mode. Several studies have reported lower amounts of nitro-PAHs than PAHs in the air, which can be seen in this report as well. The levels of detected nitro-PAHs (1-nitronaphalene and 9-nitroanthracene) and PAHs (naphthalene, anthracene, fluoranthene and pyrene) in the different samples were 10.2-119 pg/m3 and 291-77700 pg/m3, respectively. Neither group of analytes were found in the particulate phase. The highest concentrations of both nitro-PAHs and PAHs were found indoors, suggesting that other sources than emissions from traffic are responsible.

Wax esters are substantial constituents of natural waxes, which can be found in many living organisms. Properties of lipids, including wax esters, may be significantly influenced by the position of double bond. In this diploma thesis the location of double bonds was determined by dimethyl disulfide (DMDS) derivatization followed by detection using tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). We managed to measure the APCI and ESI MS/MS spectra of 8 different wax esters with different position of double bond. Diagnostic ions determining double bond position were identified. This method could be used in HPLC/MS analysis of wax esters, which cannot be analyzed by GC/MS. It was shown that the DMDS derivatization reaction and mass detection with APCI ionization is also suitable for locating double bonds in alkenes.

Le développement des outils analytiques pour l'analyse de la matière organique complexe en géochimie organique a connu de nombreuses avancées ces dernières années. Ce développement a permis de répondre à un grand nombre de questions quant à la composition de la matière organique. Cependant, beaucoup des points restent encore à élucider comme notamment la caractérisation des fractions de hauts poids moléculaires ainsi que le suivi de la réactivité de la matière organique. Ce travail de thèse a eu pour objectif (i) d'adapter les techniques de spectrométrie de masse déjà existantes pour l'analyse de la matière organique fossile (notamment par la sélection de la source d'ionisation atmosphérique la plus adaptée) mais également (ii) de développer un nouveau type de couplage entre la chromatographie d'exclusion stérique (SEC) et la spectrométrie de masse APPI-QTOF pour l'analyse des fractions peu polaires de hauts poids moléculaires. L'adaptation du l'APPI-QTOF a tout d'abord permis de mieux comprendre la réactivité de contaminants organiques polyaromatiques en présence de phases minérales. Le couplage SEC-APPI-QTOF a, quant à lui, permis d'améliorer les connaissances sur la structure des asphaltènes. Cependant, malgré la « simplification » rendue possible par la SEC, la très grande quantité d'informations reste difficile à interpréter et prend beaucoup de temps. Un modèle mathématique a donc été développé basé sur des analyses numériques et statistiques des spectres de masse, permettant de les comparer entre eux afin de distinguer l'origine des échantillons et de suivre l'impact de processus physico-chimiques (altérations naturelles - traitements de remédiation). / The development of analytical tools for organic geochemistry analysis has increased these past years. This development has allowed answering many questions about organic matter composition. However, many issues remain to be clarified including the characterization of high molecular weight fractions and monitoring the reactivity of organic matter. This thesis has focused on both (i) existing method improvements for fossil organic geochemistry analysis but also on (ii) developing a new type of coupling between the size exclusion chromatography (SEC) and the APPI-QTOF mass spectrometry for high molecular weight weakly polar fractions. Adjustments on APPI-QTOF mass spectrometry have allowed a better understanding of polyaromatic organic contaminant reactivity in presence of mineral matrices. The success of this coupling has allowed a better understanding of the structure of asphaltenes. However despite the "simplification" obtained by the SEC, the large amount of information remains difficult to interpret and time-consuming. A mathematical model has been developed based on numerical and statistical analysis of mass spectra, allowing direct comparison of mass spectra and being able to identify several types of information such as origins of samples, monitoring of physico-chemical processes and also the efficiency of soil recovery treatments as well as the identification of analytical protocols.

Made available in DSpace on 2016-12-23T14:41:52Z (GMT). No. of bitstreams: 1 Thieres Magaive Costa Pereira.pdf: 7173330 bytes, checksum: 5a2aee56b5048351ab0fc838877f8030 (MD5) Previous issue date: 2013-08-23 / O petróleo é uma mistura complexa, sendo uma das misturas mais desafiadoras para as análises químicas. Muitas técnicas são empregadas para a caracterização dos constituintes do óleo. Entretanto, quando combinamos o altíssimo poder de resolução e exatidão da espectrometria de massas, em especial a Ressonância Ciclotrônica de Íons com Transformada de Fourier, (FT-ICR MS) com fontes de ionização a pressão atmosférica, uma atribuição precisa de mais de 20 000 compostos orgânicos do petróleo pode ser obtida. Na indústria do petróleo existe um grande interesse na análise de ácidos naftênicos e asfaltenos devido a problemas como corrosão e formação de depósitos, que aumentam os custos de produção. Portanto este trabalho tem como objetivo a avaliação da termodegradação de ácidos naftênicos, além do emprego das fontes de ESI, APCI, APPI, LDI e MALDI para aquisição de novos dados relativos a caracterização de asfaltenos. Dois petróleos foram utilizados nos ensaios de termodegradação, o petróleo A com acidez de 2,38 mg KOH g-1 e o petróleo B com 4,79 mg KOH g-1 os quais foram tratados a 280, 300 e 350 ºC pelo período de 2, 4 e 6 horas. De uma maneira geral, as principais classes identificadas para ambas às amostras foram O2, N e NO2, respectivamente. Uma leve redução do NAT e da abundância relativa referente à classe O2 foram observado em função da temperatura e do tempo de envelhecimento (T = 280 → 300 oC e t = 2 → 6 h), sendo que a temperatura de tratamento térmico a 350 ºC demonstrou-se determinante na remoção de compostos da classe O2. O perfil químico de amostras de asfaltenos brasileiros foi avaliado utilizando-se cinco diferentes métodos de ionização em ambos os modos de ionização: positivo e negativo, depois, a distribuição de peso molecular, distribuição de classe, parcelas típicas de número de carbono contra DBE e diagramas van Krevelen foram obtidos e discutidos. Um comportamento atípico foi observado para a fonte de LDI e MALDI (±) FT-ICR MS. Um amplo perfil, de m/z 500-3000, apresentando espaçamento de 24 Da foi observado, e este corresponde a formas alotrópicas de fulereno, C60. Em geral, os asfaltenos apresentaram um elevada proporção de espécies heteroatómicas como: HC, HC [H], N, N [H], N2O, N2O [H], N2, N2 [H], O, O[H] para o modo (+) e N, N [H], NO, NO [H], NO, NO2[H], N2O, N2O[H] para o modo negativo. Nos diagramas de DBE contra o número de carbono, os asfaltenos mostraram para cada valor de DBE uma pequena amplitude de compostos com respeito à NC, proporcionando assim, imagens que formam uma linha de 45 ° entre os eixos CN e DBE. Isto indica que estes compostos não exibem grandes cadeias de alquílicas, sendo composta principalmente por anéis aromáticos. Em geral os diagramas de van Krevelen mostraram alta proporção de compostos com razão H/C ~0,7, corroborando com a existência de espécies altamente aromáticas / Petroleum is a complex mixture, being one of the most challenging mixtures for chemical analyzes. Many techniques are employed to characterize constituents of the oil. However , when we combine the highest resolving power and accuracy of mass spectrometry , especially Ion Cyclotron Resonance Fourier Transform ( FT - ICR MS ) with sources of atmospheric pressure ionization , an assignment need more than 20 000 organic compounds in the oil can be obtained. In the oil industry there is a great interest in the analysis of asphaltenes and naphthenic acids due to problems such as corrosion and deposit formation, which increases production costs. Therefore this study aims to evaluate the thermodegradation of naphthenic acids, besides the use of sources of ESI, APCI, APPI, MALDI and LDI for the acquisition of new data on the characterization of asphaltenes . Two test oils were used in thermodegradation of the oil with an acidity of 2.38 mg KOH g -1 and Oil B with 4.79 mg KOH g- 1 which were treated at 280 , 300 and 350 ° C for a period of 2 , 4 and 6 hours. Generally, the major classes identified for both samples O2, NO2, and C, respectively. A slight reduction of NAT and relative abundance refers to the class O2 were observed as a function of temperature and aging time (T = 280 → 300 ° C t = 2 → 6 h), and the heat treatment temperature at 350 ° C showed a determinant for the removal of class O2. The chemical asphaltenes Brazilian samples was evaluated using five different methods of ionization in both modes of ionization: positive and negative, then the molecular weight distribution, distribution class, typical plots versus carbon number and DBE van Krevelen diagrams were obtained and discussed. An unusual behavior was observed for the LDI and MALDI source ( ± ) FT - ICR MS . A comprehensive profile of m / z 500-3000, with spacing of 24 Da was observed, and this corresponds to allotropes of fullerene C60. In general, the asphaltenes had an heteroatómicas high proportion of species such as HC , HC [ H] , N, [ H] , N2O N2O [ H] N2, N2 [ M ] O O [ H] to mode (+) and N, [ H ] , NO [ H] , NO , NO2, [ H] , N2O N2O [ H ] for the negative mode . In the diagrams DBE against the carbon number , the asphaltenes shown for each value of DBE composed of a small amplitude with respect to NC, thus providing images that form a line of 45 ° between the axes CN and DBE. This indicates that these compounds do not exhibit large chain alkyl, composed mainly of aromatic rings. In general diagrams van Krevelen showed a high proportion of compounds ratio H / C ~ 0.7, confirming the existence of highly aromatic species

L’objectif de ce travail est de comprendre les effets d’un changement de composition des modèles fromagers sur la mobilité, la libération et la perception de molécules de la flaveur (sel, composés d’arôme). Six modèles fromagers aromatisés ont été formulés (3 ratios lipides/protéines (L/P) et 2 teneurs en sel). La microstructure et les propriétés rhéologiques des modèles fromagers ont été caractérisées respectivement par microscopie confocale et par compression uniaxiale. La mobilité des ions sodium a été analysée par RMN 23Na. La cinétique de libération des ions sodium a été suivie dans l’eau, puis dans la salive, en situation de consommation. La libération rétronasale des composés d’arôme a été suivie par nose-space APCI-MS, simultanément au suivi des déglutitions, et de la mastication par électromyographie. Enfin, les propriétés sensorielles des modèles fromagers (intensité salée, arôme, texture) ont été étudiées.Une diminution du ratio L/P et une diminution de la teneur en sel diminuent la taille des gouttelettes lipidiques et augmentent la fermeté. Cela conduit à une diminution de la mobilité des ions sodium, qui se traduit par une diminution de la quantité de sodium libéré dans la salive et une diminution de la perception salée. De plus, le maximum de libération d’arôme est atteint plus tard et la perception aromatique est diminuée. Ces effets peuvent être expliqués par la répartition lipides/protéines observée en microscopie, par une déglutition plus tardive et une plus grande activité masticatoire / The aim of this work is to understand the effects of changes in the composition of model cheeses on mobility, release and perception of flavor molecules (salt, aroma compounds). Six flavoured model cheeses were formulated (3 lipid/protein (L/P) ratios and 2 salt contents). The microstructure and the rheological properties of the model cheeses were characterized respectively by confocal microscopy and by uniaxial compression test. The mobility of sodium ions was analyzed by 23Na NMR. The kinetics of sodium release was followed in water and then in saliva during consumption of the model cheeses. The retronasal release of aroma compounds was followed by nose-space APCI-MS, simultaneously with the study of swallowing and chewing by electromyography. Then, the sensory properties of the model cheeses (saltiness, aroma, texture) were studied.A decrease in the L/P ratio and a decrease in salt content reduce the fat droplet size and increase the hardness. This leads to a decrease in sodium ion mobility, which results in a decrease in sodium release in saliva and a decrease in salty perception. Moreover, the maximum intensity of aroma release is reached later and the aroma perception is decreased. These effects can be explained by the observed lipid/protein distribution in microscopy, by the later swallowing and by the higher chewing activity

Although gas and liquid chromatography have emerged as dominant separation techniques in environmental analytical chemistry, these methods do not allow for the concurrent analysis of chemically diverse groups of persistent organic pollutants (POPs). There are also a small number of compounds which are not easily amenable to either of these traditional separation techniques. The main objective of this thesis was to address these issues by demonstrating the applicability of packed column supercritical fluid chromatography (pSFC) coupled to mass spectrometry (MS) in various aspects of environmental chemistry. First, pSFC/MS analytical methods were developed for legacy POPs (PCDDs, PCDFs, and PCBs) as well as the emerging environmental contaminant Dechlorane Plus (DP), and issues relating to the ionization of target analytes when pSFC was coupled to MS were explored. Novel APPI and APCI reagents (fluorobenzene and triethylamine) were optimized and real samples (water and soil) were analyzed to demonstrate environmental applicability. The possibility of chiral and preparative scale pSFC separations was then demonstrated through the isolation and characterization of thermally labile hexabromocyclododecane (HBCDD) stereoisomers. The analytical pSFC separation of the α-, β-, and γ-HBCDD enantiomers as well as the δ and ε meso forms was shown to be superior to results obtained using a published LC method. Finally, technical mixtures of phosphorus flame retardants (RBDPP, BPA-BDPP, and DOPO; a group of related compounds which are challenging to analyze concurrently) were examined using multiple analytical techniques and pSFC was found to be the only method which facilitated the accurate determination of the components of all 3 mixtures. This thesis confirms the potential of pSFC/MS as a fast, green, and cost effective means of separating and analyzing environmental contaminants.

Cardanols are more and more used in the industry of polymers, resins, coatings, friction materials, etc. At right conditions, these lipid-like chemicals can undergo metathesis reaction. The main aim of the diploma thesis is an analysis of products of cardanol metathesis by HPLC-MS/MS. Standard 3,3'-hexadec-8-en-1,16-diyldiphenol, one of the main products of cardanol metathesis, was prepared for quantitative HPLC analysis. The standard was prepared in two steps. The first step was cardanol ethenolysis to give 3-(non-8-enyl)phenol. The second step was self-metathesis of 3-(non-8- enyl)phenol to give 3,3'-hexadec-8-en-1,16-diyldiphenol. The standard was characterised by HPLC/MS, MS/MS, EI-MS, UV/VIS, IR, Raman a NMR spectroscopy. The second part of the thesis is dedicated to the study of a mechanism of double-bond localization method in long chain hydrocarbons by acetonitrile APCI-MS. The formation of adducts [M + 55]+ , which are the key substances of this method, was studied using simple alkene models by MS and MS/MS. At the end, the structure and the mechanism of the formation of adducts [M + 55]+ were suggested. Key words: Cardanol, olefin metathesis, HPLC-MS, double-bond localization, APCI, acetonitrile

La perception aromatique d’un aliment résulte de l’intégration par le cerveau d’un ensemble complexe de stimuli (texture, saveurs, arômes) qui évoluent au cours de la consommation. Elle nécessite, entre autre, la stimulation des récepteurs olfactifs, par les composés d’arôme contenus dans les aliments qui sont libérés lors de la déstructuration de l’aliment en bouche. Dans ce contexte de compréhension de la perception aromatique, ce travail de thèse avait pour objectif de mieux comprendre les mécanismes régissant la libération des composés d’arôme. Il visait plus précisément à mieux comprendre de quelle manière les caractéristiques des aliments et celles du sujet interviennent et interagissent lors du process de déstructuration en bouche de l’aliment et comment elles affectent la libération des composés d’arôme. Pour cela, ce travail de thèse s’est organisé selon trois étapes : 1- développer une gamme de 6 produits fromagers variant en texture et en teneur en matière grasse mais avec une même composition aromatique, 2- sélectionner 50 sujets caractérisés physiologiquement (flux salivaires, efficacité masticatoire,…); 3- mesurer et analyser la libération des composés d’arôme lors de la consommation par les 50 sujets sélectionnés des 6 produits développés. Simultanément le processus de transformation en bouche (« food oral processing ») a été suivi par des mesures de l’activité masticatoire, de la rhéologie du bol alimentaire ainsi que du taux de salive incorporée juste avant déglutition et du tapissage en bouche après déglutition. Ce travail met en évidence le rôle majeur de la fermeté et de la teneur en matière grasse de l’aliment qui influencent davantage la libération des composés d’arôme que les caractéristiques physiologiques des individus. Il montre également que le rôle respectif de ces caractéristiques de l’aliment est fonction de la nature des composés d’arôme. Les caractéristiques physiologiques mises en jeu lors du « food oral processing » influencent la libération de manière directe et au travers de la déstructuration de l’aliment en fonction de sa composition et sa texture. De plus, l’étude de la variabilité inter individuelle en termes de quantités de composés d’arôme libérée a permis d’établir l’existence de faibles et forts libérateurs. / Pas de résumé en anglais.