Comprehensive two-dimensional gas chromatography (GC×GC) is among the most powerful methods used to separate complex samples. Two columns of different selectivities are coupled in series through a special interface (modulator). The main role of the modulator is to trap and/or sample the primary column effluent and inject it into the secondary column. This results in an enhanced sensitivity, increased peak capacity and structured chromatograms. Practically all thermal modulators in use today are equipped with two trapping stages to prevent problems related to analyte breakthrough, which makes their design more complicated. In this work, The sensitivity of GC×GC coupled to two different detectors, time-of-flight mass spectrometer (GC×GC-TOFMS) and flame ionization detector (GC×GC-FID) was compared to the sensitivity of conventional one-dimensional gas chromatography (GC-TOFMS and GC-FID) by determining the limits of detection (LOD) for a series of different compounds such as n-alkanes and alcohols using both approaches. Different modulation periods were used for GC×GC ranging from 2 to 8 seconds. In addition, different types of inlet ferrules were used to study their effect on both systems. In general, the LODs in GC×GC were lower by at least an order of magnitude. A new liquid nitrogen-based single-stage cryogenic modulator was developed and characterized. In addition, a new liquid nitrogen delivery system was developed. Band breakthrough was prevented using changes in the carrier gas viscosity with temperature to reduce the carrier gas flow during desorption. Injection band widths for n-alkanes of 30-40 ms at half height were obtained. Most importantly, even the solvent peak could be perfectly modulated, which is impossible with any commercially available thermal modulator. Moreover, the newly developed liquid nitrogen supply system reduced liquid nitrogen consumption to ~30 L per day versus 50-100 L per day for commercially available modulators. Evaluation of the newly developed system for the GC×GC separation of some real samples such as regular gasoline and diesel fuel showed that the analytical performance of this single-stage modulator rivals that of the more complicated dual-stage designs. The technique was tested in various applications. Headspace solid phase microextraction in combination with GC×GC coupled to time-of-flight mass spectrometry (HS-SPME-GC×GC-TOFMS) were used for the detailed investigation of the impact of malolactic fermentation (MLF) using three commercial Oenococcus oeni strains on the volatile composition of Pinotage wines. The technique was also applied for the characterization of Pinotage wine volatiles and blue honeysuckle berries volatiles.

Comprehensive two-dimensional gas chromatography (GC×GC) is among the most powerful methods used to separate complex samples. Two columns of different selectivities are coupled in series through a special interface (modulator). The main role of the modulator is to trap and/or sample the primary column effluent and inject it into the secondary column. This results in an enhanced sensitivity, increased peak capacity and structured chromatograms. Practically all thermal modulators in use today are equipped with two trapping stages to prevent problems related to analyte breakthrough, which makes their design more complicated. In this work, The sensitivity of GC×GC coupled to two different detectors, time-of-flight mass spectrometer (GC×GC-TOFMS) and flame ionization detector (GC×GC-FID) was compared to the sensitivity of conventional one-dimensional gas chromatography (GC-TOFMS and GC-FID) by determining the limits of detection (LOD) for a series of different compounds such as n-alkanes and alcohols using both approaches. Different modulation periods were used for GC×GC ranging from 2 to 8 seconds. In addition, different types of inlet ferrules were used to study their effect on both systems. In general, the LODs in GC×GC were lower by at least an order of magnitude. A new liquid nitrogen-based single-stage cryogenic modulator was developed and characterized. In addition, a new liquid nitrogen delivery system was developed. Band breakthrough was prevented using changes in the carrier gas viscosity with temperature to reduce the carrier gas flow during desorption. Injection band widths for n-alkanes of 30-40 ms at half height were obtained. Most importantly, even the solvent peak could be perfectly modulated, which is impossible with any commercially available thermal modulator. Moreover, the newly developed liquid nitrogen supply system reduced liquid nitrogen consumption to ~30 L per day versus 50-100 L per day for commercially available modulators. Evaluation of the newly developed system for the GC×GC separation of some real samples such as regular gasoline and diesel fuel showed that the analytical performance of this single-stage modulator rivals that of the more complicated dual-stage designs. The technique was tested in various applications. Headspace solid phase microextraction in combination with GC×GC coupled to time-of-flight mass spectrometry (HS-SPME-GC×GC-TOFMS) were used for the detailed investigation of the impact of malolactic fermentation (MLF) using three commercial Oenococcus oeni strains on the volatile composition of Pinotage wines. The technique was also applied for the characterization of Pinotage wine volatiles and blue honeysuckle berries volatiles.

Orientador: Fabio Augusto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T15:52:07Z (GMT). No. of bitstreams: 1 Lima_PaulaFelicianode_M.pdf: 3864135 bytes, checksum: c42784d53cede985603b04a4490ab760 (MD5) Previous issue date: 2014 / Resumo: O uso de compostos voláteis produzidos por fungos como parte das estratégias de biocontrole na prevenção de doenças ocasionadas por fitopatógenos vem impulsionando o mercado de biofungicidas. Neste cenário, a análise do metaboloma utilizando apenas uma técnica analítica é por vezes inviável devido à magnitude química dos compostos bem como de sua faixa de concentração. Desta forma, o trabalho utilizou a combinação de HS-SPME (Microextração em Fase Sólida) aliada à técnica GC×GC-qMS (Cromatografia Gasosa Bidimensional Abrangente acoplada à Espectrometria de Massas Quadrupolar) para a obtenção do perfil metabólico volátil inédito de duas espécies de fungos com potencial ação para biocontrole e indução de resistência a fitopatógenos na agricultura, Curvularia sp e Memnoniella sp. Através de modelagem MPCA e HCA foi possível a obtenção de um perfil cinético característico da produção de compostos voláteis das espécies que delimitou o processo de identificação tentativa destes metabólitos. Hidrocarbonetos e álcoois foram responsáveis pela maior produção volátil de ambas as espécies avaliadas, com destaque para a produção de lactonas como y-octalactona, y-hexalactona e y-hexalactona por Curvularia sp e sesquiterpenos como acoradieno, ß-chamigreno, a-chamigreno, ß-elemeno e valenceno por Memnoniella sp. A partir do perfil volátil das espécies, os estudos poderão ser direcionados à ação biocontrole e indução de resistência na agricultura / Abstract: Volatile compounds produced by fungi as part of biocontrol strategies in preventing diseases caused by pathogens has been stimulating the market of biofungicides. So, the analysis of the metabolome using only one analytic technique is sometimes not feasible due to chemical compounds as well as the magnitude of its concentration range. Thus, the study used a combination of HS-SPME technique (Solid-Phase Microextraction) coupled with GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography coupled to Quadrupole Mass Spectrometry) to obtain volatile metabolic profiles of two species of fungi with potential for biocontrol activity and induction of resistance to plant pathogens in agriculture, Curvularia sp and Memnoniella sp. Through modeling MPCA and HCA was possible to obtain a typical kinetic profile of volatile compounds from the production of species which delimited the process of identification of these metabolites. Hydrocarbons and alcohols were responsible for most volatile production of both studied species, with emphasis on the production of lactones such as y-octalactona, y-hexalactona e y-hexalactona by Curvularia sp and sesquiterpenes as acoradiene, ß-chamigrene, a-chamigrene, ß-elemene and valencene by Memnoniella sp. From the profile of volatile species, the studies may be related to the biocontrol activity and induction of resistance in agriculture / Mestrado / Quimica Analitica / Mestra em Química

GC×GC is an efficient tool for the analysis of volatile compound. However, improvements are still required on VOC extraction, GC×GC setup and data processing. Different sample preparation techniques and GC×GC setup were compared based on the literature study and experimental results. Each VOC extraction technology has its own drawbacks and needs new developments. There wasn’t an ideal sample preparation technique to recover all the VOCs from the beverage sample. Furthermore, the VOCs recovered by different techniques were very different. The discussion of the pros and cons of the different techniques in our study can serve as a guide for the further development and improvement of these techniques. Combining the results from different sample preparation techniques is necessary to achieve a higher coverage of global VOC profiling. For the known fermentative aromatic compounds, the best coverage can be reached by using SPME together with SPE for beer, and VALLME for wine and cider. A fine GC×GC method development involves modulator selection, column combination and parameter optimization. Thermal modulator provides high detection sensitivity and allow exceptional trace analysis. Since the analytes coverage is the most important factor of in beverage VOC profiling, thermal modulation is a better choice. In fermented beverages, there are more polar compounds than non-polar compounds. The most suitable column combination is polar-semipolar. Same column diameters shall be used to minimize the column overloading. GC×GC parameters must be optimized. These parameters interact with each other therefore statistical prediction model is required. Response surface model is capable of doing this job while using a small number of experimental tests. The nearest neighbor distance was a suitable measurement for peak dispersion. Column and detector saturations are unavoidable if the metabolic sample is measured at one dilution level, incorrect peak deconvolution and mass spectrum construction may happen. Data processing results can be improved by a two-stage data processing strategy that will incorporate a targeted data processing and cleaning approach upstream of the “standard” untargeted analysis. Our experiments show a significant improvement in annotation and quantification results for targeted compounds causing instrumental saturation. After subtracting the saturate signal of targeted compounds, the MS construction was improved for co-eluted compounds. Incomplete signal subtraction may occur. It leads to the detection of false positive peaks or to interferences with the construction of mass spectra of co-diluted peaks. High-resolution MS libraries and more accurate peak area detection methods should be tested for further improvement.

<div>Determination of the chemical composition of liquid transportation fuels emerged as a novel and important field of study after the introduction of advanced analytical instruments, which are capable of very detailed chemical analyses of complex mixtures. Aviation fuels make up a crucial portion of liquid transportation fuels. There are several significant challenges in the field of aviation fuels, including the development of optimal analytical methods for the determination of the chemical compositions of the fuels, fuel properties measurements, and correlations between fuel properties and chemical composition. This dissertation explores possible correlations between fuel chemical composition and its properties and proposes novel approaches. First, a detailed description of a method for the determination of the detailed chemical composition of all middle distillate fuels (diesel and aviation fuels) is presented. Second, the density was correlated to fuel composition. Additionally, the approach of measuring the density, the hydrogen content, and the carbon content via a GC×GC-FID was introduced. Lastly, it was discovered that minute differences in chemical composition can influence fuel properties. This finding is described in the last chapter, where three HEFA samples were investigated. </div>

Les exsudats des plantes sont des substances naturelles complexes. Ils sont utilisés par plusieurs populations d’Afrique et trouvent de nombreuses applications : en thérapeutique, en pharmacie galénique, en parfumerie, etc. Au Congo, une grande majorité de ces substances est encore mal connue. Ce travail de thèse a consisté à inventorier les plantes à exsudats du Congo et à mettre au point une méthodologie d’analyse physico-chimique permettant la caractérisation des exsudats d’arbres d’origine botanique certifiée.La méthodologie d’inventaire adoptée nous a permis de recenser 135 plantes à exsudats appartenant à 87 genres. Il en ressort de cette étude que les exsudats des plantes inventoriées ont multiples usages (glu, insectifuge, allume-feu, antidouleur, etc.).La stratégie mise en place pour leur caractérisation fait appel à plusieurs techniques analytiques (SPIR, SMIR, CPG-SM, GCxGC-MS) et de traitement d’échantillon (Hs-SPME, hydrodistillation, extraction au Soxhlet, silylation, méthylation, pyrolyse). Dans le cadre de ce travail deux exsudats ont été caractérisés. L’exsudat de D. edulis (G. Don) K.J. Lam qui est constitué de monoterpènes hydrocarbonés et de triterpènes, dont les majeurs sont : 3-épi-α et -β-amyrine. L’exsudat de G. demeusei (Harms) J. Léonard dont la fraction volatile est constituée essentiellement de sesquiterpènes et la fraction peu-volatile d’acides diterpéniques de type labdane (acide éperuique, cativique, copalique, ozique, etc.).Pour exploiter l’efficacité de séparation élevée de la GCxGC-MS, nous nous sommes confronté aux problèmes de la non-répétabilité des cartes chromatographiques obtenues en 2D. Nous avons alors mis en place une méthodologie permettant de vérifier l’épaisseur de film et l’homogénéité des dépôts de phases stationnaires afin de sélectionner des colonnes courtes identiques pour la GCxGC. Cependant, les résultats préliminaires ont montré que même avec des colonnes de deuxième dimension identiques, on pouvait avoir des différences au niveau de carte 2D. / Plant exudates are natural complex substances. They are used by several populations in Africa and have many applications: in therapeutics, in galenic pharmacy, in perfumery, etc. In Congo, a great majority of these substances are not yet well known. This thesis work aimed to make an inventory of plant exudates from Congo and to develop a methodology for performing physico-chemical analysis which may enable characterization of exudates from botanical certified trees.Through the methodology that we developed, 135 plant exudates belonging 87 genera were registered. It was observed in this study that these exudates are used for many purposes (glue, insect repellent, making fire, anti-pain, etc).The strategy implemented for characterizing the exudates included several analytical (SNIR, SMIR, GC-MS, GCxGC-MS) and sample processing (Hs-SPME, hydrodistillation, extraction using the Soxhlet, silylation, methylation pyrolyse) techniques. With regard to this work, two exudates were characterized. The exudates from D. edulis (G. Don) K.J. Lam which contained monoterpene hydrocarbons and triterpenes, with the major constituents being: 3-epi-α and -β-amyrine. The exudates from G. Demeusei (Harms) J. Léonard was found to have the sesquiterpenes as major constituents of the volatile fraction and the labdane-type diterpenes (eperuique acide, cativique acid, copalique acid, ozique acid, etc) as major constituents of the poor-volatile fraction.To explore the efficacy of elevated separation of the GCxGC-MS, we faced some problems related to the non-repeatability of chromatographic cards obtained in 2D. Therefore, we put in place a methodology which enables us to verify the film thickness and homogeneity of layers of stationary phases in order to select identical short columns for GCxGC. However, the preliminary results have shown that even using second identical dimension columns, we could observed differences in 2D cards

La pyrolyse rapide de biomasse lignocellulosique produit des bio-huiles avec des rendements élevés mais ces liquides contiennent de nombreux composés oxygénés, une acidité élevée et de ce fait sont instables. Un hydrotraitement poussé de ces huiles est nécessaire avant qu'elles puissent être utilisées comme combustibles liquides. Afin de réduire le coût et d'améliorer les performances de l'hydrotraitement ultérieur, plusieurs stratégies ont été proposées pour réduire les teneurs en oxygène et en acides, comme l'ajout d'un lit catalytique après la pyrolyse. La conversion catalytique des vapeurs de pyrolyse permet une désoxygénation partielle avant la condensation des vapeurs. Dans ce contexte, nous avons étudié la conversion de molécules modèles, l'acide acétique et le gaïacol, sur différents catalyseurs acides afin d'identifier des phases actives performantes et de comprendre les mécanismes réactionnels. Dans un deuxième temps, un test de pyrolyse semi-continu combiné avec un réacteur catalytique a été conçu et mis en place et les meilleurs catalyseurs acides sélectionnés pour les molécules modèles ont été testés pour la conversion de bois de hêtre. Après conversion, un protocole de séparation des fractions a été appliqué et les fractions gaz, liquide et solide ont été caractérisées par différentes méthodes (?-GC, GC×GC, GPC, RMN…). Une attention particulière a été portée à la quantification des monomères dans la fraction liquide par GC×GC. Les bilans massiques atteignent plus de 90% et des bilans carbones ont été également réalisés dans les différentes fractions. L'ensemble des caractérisations et la comparaison entre pyrolyse avec et sans étape catalytique permet d'améliorer la compréhension du rôle du catalyseur dans la conversion des vapeurs de pyrolyse / Fast pyrolysis of biomass yields bio-oils with high levels of oxygen-containing components, high acidity and low stability. Further upgrading of these oils is necessary before they can be used as liquid fuels. Several low-cost strategies have been proposed for reducing the oxygen and acid contents including the catalytic conversion of pyrolytic vapors before vapor condensation. In this context, a first step in this work was the study of model molecules conversion, acetic acid and guaiacol, on different acid catalyst to understand reaction mechanisms and determine the best catalyst. In a second time, a semi-continuous pyrolysis test combined with a catalytic reactor was built and use to test the best acid catalysts found on model molecules, for the conversion of beech wood chips. A product recovery protocol was implanted to recover all the gas, liquid and solid fractions. Those fractions were characterized in depth by various techniques (?-GC, GC×GC, GPC, RMN…). A special focus was made on the quantification of monomers in the bio-oils by GC×GC. Mass balance reached 90% and carbon balance were established for some experiments. The performed characterizations as well as the comparison between catalytic and thermal experiments allowed to get more insights in the role of the catalyst on pyrolytic vapors conversion

Polychlorinated Biphenyls (PCBs) are a group of 209 ‘man-made’ chlorinated organic compounds that were widely used in the 20th century for a variety of industrial uses. PCBs were first commercially produced in the 1929 and were manufactured until the 1980s when their use was phased out due to environmental and human health risks. However, due to their widespread use and persistence they are ubiquitous in the environment and remain a contaminant of concern. The structural properties that determine the persistence of PCBs in humans were therefore elucidated by statistical analysis of data from the National Health and Nutrition Examination Survey (NHANES). PCBs with chlorine bonding in the 2,5-and 2,3,6- positions (and 2- in di- and tri-chlorinated congeners) were rapidly biotransformed and so can be classed as episodic congeners whereas PCBs with chlorine bonding in the 2,3,4-, 2,4,5-, 3,4,5-, and 2,3,4,5- positions were more resistant to biotransformation and can therefore be classed as steady state congeners. A fundamental requirement of using PCB signatures for environmental fingerprinting is an effective analytical method capable of producing high resolution signatures from biological samples. An extraction and clean-up method was developed that was successfully applied to different biological matrices (blood and tissues). A two dimensional gas chromatography with time of flight mass spectrometry (GCxGC-ToFMS) method was designed and optimised to provide a congener specific method capable of identifying 200 out of the 209 PCBs, with detection limits in human serum in the range of 1 to 10 ng g-1 lipid. The extraction and detection methods were used to determine the source of PCB contamination and age date exposure in workers at a transformer dismantling plant. A total of 84 different PCB congeners were identified in the sera of 30 workers with concentrations of the 7 indicator PCBs ranging from 1.2 - 39 μg g-1 lipid. Analysis of PCB signatures was able to distinguish recent from prolonged exposure and also identified an additional source of inhalation exposure in a subgroup of workers. Analysis of 12 different tissue types obtained from the common guillemot (Uria aalge) suggested a high degree of perpetuation between the PCB signature in different tissue types. This shows that comparative assessments can be undertaken between animals using different tissue types and that small (1 g) samples of blood can be used as a non-lethal sampling technique. The regional provenance of 25 wrecked Leach’s storm petrels (Oceanodroma leucorhoa) was also determined using PCB signatures. Results from GCxGC-ToFMS analysis revealed distinctively different PCB signatures in birds from Canada and Europe. The findings reported in this thesis enhance our understanding of PCB signatures in the environment and show how they can be used effectively to age date and identify the source of exposure in humans and animals.

Thesis (PhD)--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: The analysis of Fischer–Tropsch–derived (FT–derived) synthetic crude and derived products is very challenging because of the highly complex nature of these products. In this study, the use of comprehensive multidimensional gas chromatography (GCxGC) with time-of-flight mass spectrometry (TOF-MS) and flame ionisation detection (FID) was investigated for the analysis of these products and the technique was found to be invaluable for the analysis of these complex mixtures. The compositions of FT synthetic crude, produced at low temperature (LT–FT) and high temperature (HT–FT) processes were compared and the effect that changes in FT reaction temperature has on product formation was investigated. Results for conventional onedimensional GC (1D-GC) and GCxGC were compared. It was found that conventional 1D–GC does not have sufficient peak capacity to separate the thousands of compounds in the HT FT products. GCxGC provides a huge peak capacity of tens-of-thousands to separate highly complex mixtures. Structured chromatograms, where groups of compounds with similar properties are grouped together, aid in peak identification. Moreover, sensitivity at low microgram per milliliter levels is obtained. These attributes enabled accurate analysis of various complex feed and product streams in the FT refinery, and also various final fuel products. The use of GCxGC alone was demonstrated, and also combined with high performance liquid chromatography (HPLC), supercritical fluid chromatography (SFC) and nuclear magnetic resonance (NMR) when even more separation power was needed. HPLC–GCxGC enabled the separation of alkene and cyclic alkane compound classes in oligomerisation products. These compound classes have similar mass spectra, elute in adjacent regions and co–elute even to some extent on the GCxGC contour plot, making differentiation difficult. SFC is a good replacement for HPLC for these applications because it does not use solvents as mobile phases. CO2 is easily evaporated after the separation and does not interfere with the GCxGC separation of the analytes. SFC is also a very good technique to separate the compound classes of alkanes, alkenes, aromatics and oxygenates, and is therefore highly complementary to GCxGC. The combination of GCxGC with NMR data was also found to be very valuable for the identification of branched alkane isomers in LT–FT diesels. GCxGC provides excellent separation of individual compounds but the identification of isomers (except for mono–methyl branching) is difficult because the mass spectra of most of these isomers are similar and not all compounds are in the mass spectral libraries. NMR, on the other hand, is able to distinguish between the individual types of branched isomers but has limited separation power for the complex mixtures. By combining the two techniques, the best of both was obtained. The study found GCxGC to be invaluable for the analysis of the highly complex FT–derived products, while its combination with other techniques such as HPLC, SFC and NMR provided even more separation power. / AFRIKAANSE OPSOMMING: Die hoogs komplekse samestelling van sintetiese ru–olie en afgeleide produkte, afkomstig van Fischer–Tropsch (FT) sintese, bied groot uitdagings aan die analis. Die studie het die gebruik van GCxGC met ’n TOF-MS en FID bestudeer vir die analise van FT produkte en het bevind dat die tegniek van onskatbare waarde is vir die analise van die hoogs komplekse mengsels. Die samestellings van produkte van lae- en hoë-temperatuur FT prossesse is vergelyk en die effek van ’n verhoging in die reaksie–temperatuur op die produk samestelling is ondersoek. Resultate vir 1D–GC and GCxGC is vergelyk en dit was duidelik dat 1D-GC nie naastenby voldoende piekkapasiteit het om al die komponente van die produkte wat tydens die hoëtemperatuur prosses gevorm word, te kan skei nie. Die GCxGC se piekkapasiteit daarteenoor is in die orde van tienduisende wat die skeiding van hoogs komplekse mensels moontlik maak terwyl die tegniek hoogs gestruktureerde kontoerplotte verskaf wat help met identfikasie van komponente. Die tegniek is verder ook baie sensitief en kan komponente op lae μg/mL vlakke waarneem. Hierdie eienskappe het akkurate analise van verskeie FT produkstrome moontlik gemaak. Die kombinasie van GCxGC met HPLC, SFC en KMR het selfs meer skeidingskrag verskaf waar nodig. HPLC–GCxGC het die skeiding van alkene en sikliese alkane moontlik gemaak. Hierdie komponent klasse se massaspektra is feitlik dieselfde en terselfdertyd elueer die twee groepe reg langs mekaar, en oorvleuel soms selfs tot ’n mate, op die GCxGC kontoerplot, sodat dit moeilik is om daartussen te onderskei. SFC is ’n goeie alternatief vir HPLC in meeste toepassings aangesien die tegniek net CO2 gebruik, wat maklik verdamp by kamertemperatuur en nie oplosmiddels gebruik wat se pieke steur met die van die laekookpunt komponente op die GCxGC kontoerplot nie. Skeidings van die komponentgroepe alkane, alkene, aromate en oksigenate is moontlik met SFC en daarom komplimenteer dit die GCxGC skeiding goed aan. Die kombinasie van GCxGC met kern–magnetiese resonansie (KMR) is van waarde gevind om die verskillende tipes vertakkings in ’n lae-temperatuur FT diesel te identifiseer. GCxGC verskaf uitstekende skeiding van individuele komponente maar die identifikasie van die verskilende isomere, behalwe vir die mono-metiel vertakkings, is moeilik aangesien die massaspektra van baie van die komponente soortgelyk is en die komponente nie in die massa spektrum–biblioteke voorkom nie. KMR, aan die ander kant, kan tussen die individuele vertakkings onderskei maar het beperkte skeidingskrag vir komplekse mensels. Deur die twee tegnieke te kombineer is die beste van albei tegnieke bekom. Die studie het bevind dat GCxGC van onskatbare waarde is vir die analise van die komplekse sintetiese FT produkte terwyl die kombinasie met ander tegnieke soos HPLC, SFC and KMR selfs meer skeidingskrag verskaf.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants and are mostly products of the incomplete combustion of organic material. PAHs are often found in environmental samples as a complex mixture of isomers. In addition, the same sources that produce complex PAH mixtures also produce other poorly characterized mixtures of organic compounds, commonly referred to as an unresolved complex mixture (UCM), that act as matrix interferences in the chromatographic analysis of samples. Conventional one-dimensional chromatographic techniques, such as gas chromatography coupled to mass spectrometry (GC/MS), are not sufficient for the analysis and quantitation of complex PAH mixtures present in environmental samples due to the high degree of overlap in compound vapor pressures, boiling points, and mass spectral fragmentation patterns. Therefore, the separation and quantitation of complex mixtures of individual PAH compounds in environmental samples requires high chromatographic resolution. Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC��GC/ToF-MS) was used for this study. GC��GC/ToF-MS uses two different gas chromatographic columns, with different separation mechanisms, for the analysis of complex environmental samples. In theory, the peak capacity in GC��GC/ToF-MS is equivalent to the product of the individual peak capacities of each column used. However, in practice, this is rarely obtained because of the existing correlation between the two GC columns used. This dissertation is a compilation of three studies related to analytical method development for the identification and quantitation of complex PAH mixtures (including parent-PAHs, alkyl-PAHs, oxy-PAHs, nitro-PAHs, thio-PAHs, chloro-PAHs, bromo-PAHs and PAHs with molecular weight higher than 300 Da) that may be present in environmental samples using novel column combinations in GC��GC/ToF-MS. The use of a liquid crystal column (LC-50) in the first dimension, followed by a nano-stationary phase column (NSP-35) in the second dimension, was evaluated for the separation of a standard PAH mixture containing 97 different PAHs. Two standard reference materials purchased from NIST (NIST SRM1650b ��� Diesel Particulate Matter and NIST SRM1975 ��� Diesel Extract) were used, after extraction and cleanup, for method validation and comparison between the commonly used non-polar �� polar column combination and the LC-50 �� NSP-35 column combination with high orthogonality. As part of the method validation, an aliquot of NIST SRM1975 (Diesel extract), without sample cleanup was also analyzed for PAHs, showing that the LC-50 �� NSP-35 column combination was accurate (with an average absolute percent difference of approximately 30%) for the identification and quantitation of complex PAH mixtures in environmental samples, with reduced sample preparation prior to analysis. In addition, the LC-50 �� NSP-35 column combination was used for the analysis of PAHs sorbed to polystyrene pellets deployed in an urban bay area as passive water samplers because one-dimensional GC/MS was ineffective due to the presence of a strong unresolved complex mixture (UCM) and matrix interferences. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Dec. 27, 2012 - June 27, 2013